United States
          Environmental Protection
          Agency
            Environmental Monitoring
            Systems Laboratory
            P.O. Box 93478
            Las Vegas NV 89193-3478
EPA 600/R-94/031
March 1994
          Research and Development
EPA
Application of Microwave
Energy to the Extraction
of Organic Compounds
from Solid Samples
                                         0174qad94.cov

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APPLICATION OF MICROWAVE ENERGY
   TO THE EXTRACTION OF ORGANIC
   COMPOUNDS FROM SOLID SAMPLES
                         By
             Viorica Lopez-Avila* and Richard Young
                 Midwest Research Institute
                   California Operations
                   625-B Clyde Avenue
               Mountain View, California 94043
                        USA
                 Contract Number 68-C1-0029
               Project Officer:  Werner F. Beckert
         Quality Assurance and Methods Development Division
            Environmental Monitoring Systems Laboratory
                  Las Vegas, Nevada 89119
     ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
          OFFICE OF RESEARCH AND DEVELOPMENT
         U.S. ENVIRONMENTAL PROTECTION AGENCY
                LAS VEGAS, NEVADA 89119

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                                       NOTICE
        The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development (ORD),  partially funded and managed the extramural  research described here.  It has
been peer reviewed by the Agency and approved as an EPA publication.

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                                       PREFACE
        This is the final report for research performed under Work Assignment 3-18, EPA Contract
68-C1-0029, conducted by the Midwest Research Institute, California Operations (MRI-CO).  The
MRI-CO project was directed by Dr. Viorica Lopez-Avila.

        This report was written by Dr. Lopez-Avila. Technical support for the project was provided
by Richard Young.  Nikhil Shah and Robert Kim were involved with some early experiments under
this work assignment.

        The authors would like to thank the CEM Corporation (Matthews, NC) for the loan of the
microwave unit used in this  study  and  Bob Revesz from CEM Corporation for helpful technical
discussions. The  authors  also acknowledge Steven Hawthorne of the Energy & Mineral Research
Center of the  University  of North  Dakota (Grand Forks,  ND)  for reviewing this report and for
providing helpful comments.
                                            111

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                                         ABSTRACT
        As part of  an ongoing  evaluation  of novel sample-preparation techniques  by  the  U.S.
Environmental Protection Agency (EPA), especially techniques that minimize generation of waste solvents,
we  evaluated microwave-assisted extraction (MAE) of organic compounds from  solid materials (or
"matrices"). Six certified reference materials containing polynuclear aromatic hydrocarbons (PAHs) and
some base/neutral/acidic compounds, all of which are pollutants of interest to the EPA, were subjected to
MAE in a  closed-vessel microwave system with hexane-acetone (1:1) at different temperatures (80°C,
115°C, or  145°C) and for different periods of time (5,  10, or 20 min).  For comparison, the same samples
were subjected to room-temperature extraction by allowing the same solvent mixture to stay in contact with
the solid matrix the same amount of time as the microwave-extracted sample (including any cooling time).
Two matrices were also heated in a convection oven at 115°C, for different periods of time, with the same
solvent and in the same vessel as the microwave-extracted samples.  Whereas  the average recovery at room
temperature was about 54 percent, the MAE recoveries for 17  PAHs (three of which  were deuterated
PAHs that were spiked into the matrices) from the six  matrices were 72 percent at  80°C, 78  percent at
115CC, and 77 percent at  145'C.  The  recoveries  for the oven-heated samples  were similar to those
obtained by MAE.  MAE was,  however,  exclusively used in this study because of its easy controllability
and convenience. Although the average  recoveries by MAE increased slightly with extraction time, the
increase was not statistically significant.  The performance of the MAE technique varied with the matrix
and  the analytes.  Eleven  PAHs had average recoveries  in the 65- to  111-percent range,  and three
compounds [benzo(a)pyrene, benzo(ghi)perylene, and fluorene] had recoveries of 51 percent, 64 percent,
and 62 percent,  respectively.  The spiked-compound recoveries by MAE were 77 percent for anthracene-
d,0, 104 percent for benzo(a)anthracene-d,2, and 84 percent for fluoranthene-d,0. Additional experiments
with  14 phenols and 20 organochlorine pesticides indicated that  MAE  is a viable alternative to the
conventional Soxhlet/Soxtec and sonication extraction  techniques.   MAE requires smaller amounts  of
organic solvents, and sample throughput is increased by shorter extraction  times (10 min) and  because
simultaneous extraction of up to 12 samples is possible.
                                               IV

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                                       CONTENTS
Notice	      ii
Preface  	      iii
Abstract	      iv
Tables	      vi
Figures  	     viii

    1.  Introduction	       1
    2.  Conclusions	      2
    3.  Recommendations	      3
    4.  Experimental	      4
    5.  Results and Discussion	      16

References	      43
Appendices

    A. Percent-recovery results of the GC/MS analyses for the six certified reference
       materials	      44

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                                        TABLES

Number                                                                             Page

   1     Compounds investigated in this study  	    5

   2     Certified values and concentrations measured in this study by sonication-
           GC/MS and Soxtec-GC/MS for compounds known to be present in the HS-3,
           HS-4, and HS-5 marine sediments	    7
   3     Certified values and concentrations measured in this study by sonication-
           GC/MS for compounds known to be present in the SRM1941 marine sediment .  .    8

   4     Certified values and concentrations measured in this study by Soxtec-
           GC/MS  for compounds known to be present in the SRS 103-100 soil	   9

   5     Time required to reach the maximum temperature under various extraction
           conditions   	   17

   6     Recoveries of pesticides from freshly spiked sand using MAE and room-
           temperature extraction with hexane-acetone (1:1)	   18

   7     Average recoveries and percent RSDs for dry and wet SRS 103-100 soil	  26

   8     Percent recoveries of "native" and spiked compounds from ERA soil
           Lot No.  321  with hexane-acetone (1:1) using room-temperature extraction
           and MAE at different temperatures and pressures   	  30

   9     Average recoveries and percent RSDs for dry and wet ERA soil Lot
           No. 323	  32

  10     Average recoveries and percent RSDs for phenols after microwave heating - solvent
           versus solvent/soil suspension	  33

  11     Average recoveries and percent RSDs for organochlorine pesticides after microwave
           heating - solvent versus solvent/soil suspension  	'	  34

  12     Average recoveries and percent RSDs for PAHs and selected base/neutral
           compounds after microwave heating -  solvent versus solvent/soil suspension  ...  35

  13     Comparison of analyte concentrations in  extracts generated by sonication, Soxtec,
           and MAE with the certified values for  the HS-3 marine sediment	  37

                                           vi

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                                    TABLES (concluded)


Number                                                                               Page
   14    Comparison of analyte concentrations in extracts generated by sonication, Soxtec,
           and MAE with the certified values for the HS-4 marine sediment	   38

   IS    Comparison of analyte concentrations in extracts generated by sonication and MAE
           with the certified values for the HS-5 marine sediment	   39

   16    Comparison of analyte concentrations in extracts generated by sonication and MAE
           with the certified values for the SRM1941 marine sediment	   40

   17    Comparison of analyte concentrations in extracts generated by Soxtec and MAE with
           the certified values for the SRS103-100 soil	   41

   18    Correlation of the data obtained from MAE extracts for different matrices with  the
           certified values and the values obtained from sonication or Soxtec extracts	   42
                                            VII

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                                        FIGURES


Number                                                                             Page

   1     Schematic diagram of the temperature/pressure control system for the MDS-2000
          microwave system 	   11

   2     View of the  12 lined digestion vessels, containment vessel, and temperature and
           pressure probes  	   12

   3     (a) Lined digestion vessel with the temperature and pressure control; (b) lined
           digestion vessel without the temperature and pressure control	    13

   4     Percent recovery  as a function of temperature for the  17 PAH compounds  	   20

   5     Percent recovery  as a function of time for the 17 PAH compounds	   21

   6     Percent recovery  as a function of matrix for the 17 PAH compounds	   22

   7     Spiked versus native compound percent recoveries  	   23

   8     Percent recovery  as a function of compound for the 17 PAH compounds   	   25

   9a    GC/MS chromatogram of the extract obtained by MAE of the HS-3 marine sediment
           with hexane-acetone (1:1)	   27

   9b    GC/MS chromatogram of the extract from  a second extraction performed on the
           HS-3 marine sediment using microwave energy and fresh solvent	   28

   9c    GC/MS chromatogram of the sonication extract from the HS-3 marine sediment that
           was first extracted using microwave energy before extraction with fresh solvent
           using a sonic probe	   29
                                           vui

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                                          SECTION 1

                                       INTRODUCTION
         Use of microwave energy to enhance extraction of organic compounds from solid matrices such as
soil, seeds, foods, and feeds was reported by Ganzler and coworkers in two publications in 1986 and 1987
(1,2).  These researchers used a conventional, household microwave oven to irradiate solvent/sample
suspensions for 30 sec up to seven times each. They reported that the microwave extraction method was more
efficient than Soxhlet extraction for polar compounds (1).  Recently, Onuska and Terry (3) used microwave
energy to extract organochlorine pesticides in open vessels from spiked sediment samples; they reported
quantitative recoveries and no compound breakdown due to exposure to microwaves.  Extraction of essential
oils and other oils from biological materials such as plant and fish tissue by exposure to microwave energy
was recently described in a patent application (4).  In a U.S. patent (5), use of microwave energy for the
extraction of natural  products from mint,  sea parsley, cedar foliage, and garlic with hexane, methylene
chloride, or ethanol in open vessels in two or more stages is described. Other researchers have reported use
of microwave energy to extract stabilizers from polyolefins (6).

         As part of an ongoing U.S. Environmental Protection Agency (EPA) program addressing sample
preparation techniques that prevent or minimize pollution and  generation of waste solvents  in analytical
laboratories, this study, which was started in mid-1992 by the Environmental Monitoring Systems Laboratory,
Las Vegas (EMSL-LV), addresses the extraction of organic compounds using a closed-vessel microwave-
assisted extraction (MAE) technique.  Six  standard reference soils and sediments containing polynuclear
aromatic hydrocarbons (PAHs) and some other base/neutral/acidic compounds of interest to the EPA were
subjected  to MAE in hexanc-acctone (1:1) at various temperatures and for different periods of time to
establish whether this technology has merit as a method to extract such pollutants from solid samples.  For
comparison, extractions were performed using conventional techniques (e.g., Soxhlet/Soxtec and sonication
extraction), room-temperature extraction (as defined  later), and simple heating with solvent in  a closed
container  using a convection oven. The results indicated that MAE could  be a viable alternative  to the
conventional Soxhlet and sonication methods. This technique uses smaller amounts of organic solvents, and
sample throughput is increased because shorter extraction times (10 min) are required, and simultaneous
extraction of up to 12 samples is possible (in this study, up to six samples were extracted simultaneously).

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                                        SECTION 2

                                     CONCLUSIONS
        A MAE technique for extracting organic compounds from soils and sediments was developed
and evaluated  with representative matrices  and compounds of environmental  significance (PAHs,
selected base/neutral compounds, phenols,  and organochlorine pesticides).   All  extractions  were
performed with  hexane-acetone (1:1)  in  a  closed-vessel  microwave  system  that is commercially
available.  Our results indicated that recoveries of 17 PAHs (three of which were deuterated spikes)
from six matrices averaged 72 percent  at 80°C, 78 percent at 115°C, and 77 percent  at 145°C. The
average recoveries increased slightly  with  extraction time, and a 10-min  extraction at  115°C  is
recommended  for these types of compounds and matrices  when hexane-acetone (1:1) is used  as the
extraction  solvent.

        Other solvent mixtures that appeared to work well include methylene chloride-acetone (1:1)
and toluene-methanol (1:10).  Methylene chloride alone and toluene-methanol (10:1) take 10 to 14 min
for 30 mL solvent to heat to maximum temperature in the  microwave system.

        A 5- to  10-g soil or sediment  sample and 30 mL solvent seem  to work  well when  a 110-mL
closed extraction vessel is used since the mixture reaches  the maximum  operating temperature of 151°
to 157°C (at 100 percent power) in about 2 min, regardless of matrix.

        From all compounds investigated in this study (17 PAHs,  13 base/neutral compounds, 14
phenols, and 20 organochlorine pesticides), only two compounds (2,4-dinitrophenol and 2-methyl-4,6-
dinitrophenol) exhibited low recoveries  when  soil/solvent suspensions were heated for 10 min at 115°C.
We concluded that catalytic reactions in the  presence of soil or strong  adsorption of  the compounds
on soil  may have been the cause of low recoveries.   Since the temperatures used during  MAE are
typically close to and above 100°C, very temperature-sensitive compounds may partially decompose.
Stability of the target analytes under MAE conditions  must therefore be demonstrated.

        MAE of organic compounds from soil and sediment samples seems to be a viable alternative
to the conventional Soxhlet and  sonication extraction techniques since MAE recoveries are  in general
equal to or better than those achieved with conventional extraction techniques.  The main advantages
of MAE over the conventional Soxhlet and sonication methods or the simple heating of sample/solvent
suspensions in a closed container are the ease with which uniform conditions can be maintained in the
microwave system (temperature  and pressure are being continously monitored), the reduced  extraction
time (typical sample preparation time for this technique is 10 min for extraction and 40 min for extract
cooling, centrifugation, and extract concentration), and  reduced solvent use (30 mL in the MAE versus
300  mL in the Soxhlet extraction).  Up  to 12 samples can be extracted simultaneously in a few
minutes, resulting in increased sample  throughput compared to Soxhlet and sonication extraction.

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                                          SECTION 3

                                    RECOMMENDATIONS
        The data presented in this report were obtained in a single-laboratory study and \vith a few relevant
solid materials. MAE should now be evaluated with additional matrices and target analytes and then subjected
to an intcrlaboratory performance study.

        MAE of other classes of compounds, including organophosphorus pesticides, chlorophenoxy acid
herbicides, and carbamate pesticides, should be investigated.  It may be possible to extract the compounds
with a buffer solution (e.g.,  0.2 M KC1/0.2 M KOH buffer at pH 12 for the chlorophenoxy acid herbicides)
thus eliminating or further  minimizing the use of organic solvents in the extraction process.

        Future studies should also address the effect of moisture upon compound recovery.

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                                        SECTION 4

                                    EXPERIMENTAL
Standards

        Analytical  reference standards  of  14 non-labeled  PAHs (concentration:   2 mg/mL  per
compound; solvent: methylene chloride-benzene, 50:50), 14 phenols (concentration:  1 mg/mL per
compound; solvent:  acetonitrile), and 20 organochlorine pesticides (concentration:  2 mg/mL per
compound; solvent: toluene-hexane, 50:50) (Table 1) were purchased as composite solutions from
Supelco, Inc. (Bellefonte, PA).  The three deuterated PAHs  were purchased as neat materials from
Cambridge Isotope  Laboratory (Woburn, MA).  The base/neutral compounds  in Table I (except
dibenzofuran, which was bought from  Supelco as neat material) were purchased as  individual stock
solutions from ChemService (West Chester, PA) and Supelco, Inc., and were combined with the PAH
stock solution to make the working calibration  standards for the GC/MS analysis. Dibenzofuran was
dissolved separately in methanol at 5 mg/mL and was combined with the PAH stock solution to make
the working calibration  standards.  The purities of all compounds were stated to  be  greater than
96 percent.  The  spiking solution and the working calibration standards  were prepared by serial
dilution of the  composite stock solution containing either the phenols,  organochlorine pesticides,
PAHs, or base/neutral compounds; for the analysis of the ERA soil samples (defined below), the
calibration standards contained the PAHs, the base/neutral compounds, and selected phenols.

Standard Reference Materials

        Six standard reference marine sediments and soils were used in this study. The HS-3, HS-4,
and HS-5 marine sediments,  collected from three harbors in  Nova Scotia, were purchased from the
National Research  Council  of Canada,  Atlantic  Research  Laboratory (Halifax,  Nova  Scotia).
According to the certificate of analysis, these materials had been freeze-dried, sieved to pass a 125-/*m
sieve, homogenized in a cement mixer, and then subsampled into 200-g portions. The certified values
for the  16 compounds found in these  samples are  shown in Table 2, together with the values we
obtained in our  study after extracting 10-g portions of these materials with hexane-acetone (1:1) in a
Soxtec extractor or 5-g  portions with methylene chloride-acetone (9:1)  using a sonic probe.  The
SRS1941 marine sediment, purchased from NIST (Gaithersburg, MD), is a sediment collected from
the Chesapeake Bay at the mouth of the  Baltimore Harbor.  According to  NIST, this sediment was
air-dried,  pulverized, sieved (<150/*m), homogenized, and subsampled into 70-g  portions.  The
bottled samples  were sterilized by ^Co radiation. Table 3 identifies the compounds certified by NIST
in this sample  and  the values that we obtained by extracting a 5-g portion of this material  with
methylene chloride-acetone (9:1) using a  sonic probe.  Additional information about this sediment is
reported on the  NIST Certificate of Analysis.  The SRS103-100 standard reference material is a soil
contaminated with PAHs (natural material) and  was purchased from Fisher Scientific (Fair Lawn, NJ);
the material  was prepared by RT Corporation  in Laramie, WY.  The certified values and the values

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TABLE 1.  COMPOUNDS INVESTIGATED IN THIS STUDY
          Compound
              no.
          PAHs
Compound name
               1        Acenaphthene
               2        Acenaphthylene
               3        Anthracene
               4        Anthracene-d,0
               5        Benzo(a)anthracene
               6        Benzo(a)anthracene-d12
               7        Benzo(a)pyrene
               8        Benzo(b+k)fluoranthene
               9        Benzo(ghi)perylene
              10       Chrysene
              11       Fluoranthene-d10
              12       Fluorene
              13       Fluoranthene
              14       Indeno(l,2,3-cd)pyrene
              15       Naphthalene
              16       Phenanthrene
              17       Pyrene
          Base/Neutral Compounds

              18      Dibenzofuran
              19      1,2-Dichlorobenzene
              20      1,3-Dichlorobenzene
              21      N-Nitroso-di-n-propylamine
              22      Nitrobenzene
              23      1,2,4-TrichIorobenzene
              24      2,4-Dinitrotoluene
              25      9H-Carbazole
              26      Di-n-butylphthalate
              27      Bis(2-ethylhexyl)phthalate
              28      Isophorone
              29      4-Chlorophenyl phenyl ether
              30      Butyl benzyl phthalate

                                      (continued)

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         TABLE 1 (Concluded)
 Compound        Compound name
    no.

Phenols

     31       Phenol
     32       2-Chlorophenol
     33       2-Methylphenol
     34       3-Methylphenol
     35       2-Nitrophenol
     36       2,4-Dimethylphenol
     37       2,4-Dichlorophenol
     38       4-Chloro-3-methylphenol
     39       2,4,6-Trichlorophenol
     40       2,4-Dinitrophenol
     41       4-Nitrophenol
     42       2,3,4,5-Tetrachlorophenol
     43       2-Methyl-4,6-dinitrophenol
    44       Pentachlorophenol

Organochlorine pesticides

    45       alpha-BHC
    46       beta-BHC
    47       gamma-BHC
    48       delta-BHC
    49       Heptachlor
    50       Aldrin
    51       Heptachlor epoxide
    52       gamma-Chlordane
    53       Endosulfan-I
    54       aJpha-Chlordane
    55       Dieldrin
    56       4,4'-DDE
    57       Endrin
    58       Endosulfan-II
    59       4,4'-DDD
    60       Endrin aldehyde
    61       Endosulfan sulfate
    62       4,4'-DDT
    63       Endrin ketone
    64       Methoxychlor

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TABLE 2.    CERTIFIED VALUES AND CONCENTRATIONS MEASURED IN THIS STUDY BY SONICAT1ON-GC/MS
            AND SOXTEC-GC/MS FOR COMPOUNDS KNOWN TO BE PRESENT IN THE HS-3, HS-4, AND HS-5
            MARINE SEDIMENTS
Compound name

Certified
value
(rag/kg)'
HS-3
Concentration
measured by
sonication
extraction and
GC/MS (mg/kg)b

Concentration
measured by
Soxtec extraction
and GC/MS
(rag/kg)b

Certified
value

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TABLE 3.    CERTIFIED VALUES AND CONCENTRATIONS MEASURED IN THIS
            STUDY BY SONICATION-GC/MS FOR COMPOUNDS KNOWN TO BE
            PRESENT IN THE SRM1941 MARINE SEDIMENT
Compound name
Acenaphthenec
Acenaphthylenec
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Chrysenec
Fluorene6
Fluoranthene
Indeno(l,2,3-cd)pyrene
2-Methylnaphthalenec
Naphthalene6
Perylene
Phenanthrene
Pyrene
Concentration
measured by
sonication
Concentration extraction and
(mg/kg)a GC/MS (mg/kg)b
0.052 ±
0.115 ±
0.202 ±
0.55 ±
0.67 ±
0.78 ±
0.444 ±
0.516 ±
0.702 ±
0.104 ±
1.22 ±
0.569 ±
0.406 ±
1.322 ±
0.422 ±
0.577 ±
1.08 ±
0.002
0.010
0.042
0.079
0.13
0.19 \
0.049 /
0.083
0.016
0.005
0.24
0.040
0.036
0.014
0.033
0.059
0.20
d
0.041
0.109
d
0.294
0.835

0.135
d
d
0.950
0.285
d
0.147
e
0.344
0.915
           a Value reported by NIST.
           b Single determinations.
           c Concentration reported for this compound is not certified by NIST.
           d ND - not detected; detection limit is approximately 0.1 mg/kg.
           e NA - not analyzed for perylene.

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we measured after using Soxtec extraction are reported in Table 4. The ERA soils (Lot No. 321 and
323) are spiked materials and were purchased from Environmental Resource Associates (Arvada, CO).
The certified values for these materials are  included in Tables 8 and 9  in the Results section.

              The soil used in the preliminary experiments was a sandy  loam soil (0.1 percent organic
matter)  and  was obtained from Sandoz Crop Protection (Gilroy, CA).

Solvents

              All  solvents used in this study were distilled-in-glass, pesticide grade.  The solvent
mixture chosen for the MAE was hexane-acetone (1:1). Other solvents evaluated for the MAE include
tetrachloroethylene, methylene chloride-acetone (1:1), toluene-methanol (10:1), methylene chloride,
and toluene-methanol (1:10).  The solvent mixture used for Soxtec extraction was hexane-acetone (1:1)
and that for  sonication extraction was  methylene chloride-acetone (9:1).

MAE Procedure

              A 5-g portion of the sample  was accurately  weighed into an aluminum dish and  was
transferred quantitatively to one of die Teflon-lined extraction vessels.  To prepare the wet samples,
the calculated  volume of water  was added and allowed to  equilibrate with the sample  for
approximately 10 min. A solution containing the three deuterated PAHs was added to each sample
immediately before adding the hexane-acetone (1:1) solvent mixture (30 mL).  The extraction vessel
was closed,  after  ensuring  that a new  rupture membrane  was installed before each extraction.
Extractions were performed  at 80°C,  115°C, or 145°C for 5, 10, or  20 min at 50 percent power.
After extraction, the vessels were allowed  to cool to room temperature (approximately 20 min without
external cooling) before rney were opened.  The  supernatant and  a 2- to 3-mL hexane-acetone rinse
of the Teflon extraction vessel containing the soil were combined and were filtered through precleaned
glass wool.    The extract was  concentrated to approximately  5  mL  using  nitrogen blowdown
evaporation, and then centrifuged twice for 10 min at 2,300  rpm to separate any fine particulates.  The
extract was finally either concentrated to  1 mL or diluted for GC/MS analysis.

              All MAEs were performed  with a 950-watt MDS-2000 Microwave Sample Preparation
System  (CEM Corporation, Matthews, NC) shown in Figure 1.  This system was equipped with an
inboard pressure  and  fluoroptic" temperature  control system  for  regulating sample  extraction
conditions via magnetron power output control.  Temperature- and pressure-control set points could
be  programmed in five  separate heating  stages.   The instrument controlled  either pressure or
temperature,  depending on which parameter reached its control set-point first.

              The MAEs  were performed in  110-mL lined digestion vessels.  The turntable shown
in Figure 2  contained a control vessel and  11 standard vessels.  The control vessel is  illustrated in
Figure 3a. The outer body and cap consisted of microwave-transparent Ultem  polyedierimide.  The
removable inner liner,  the liner cover, and the safety rupture membrane were made of Teflon  PFA.
Gases could escape through  the exhaust port if the safety rupture membrane broke or if the vessel
were hand-vented by turning the vent fitting. The liner cover of the control vessel had Teflon PFA
fittings to allow for pressure tubing connection and  for insertion of a Pyrex tube that ran through the
cap into the vessel  and  ended close to the bottom of the vessel.  The Pyrex tube, which housed the

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TABLE 4.   CERTIFIED VALUES AND CONCENTRATIONS MEASURED IN THIS STUDY
           FOR COMPOUNDS KNOWN TO BE PRESENT IN THE SRS103-100 SOIL
Compound name
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(k + b)fluoranthene
Chrysene
Fluorene
Fluoranthene
2-Methylnaphthalene
Naphthalene
Phenanthrene
Pyrene
Dibenzofuran
Pentachlorophenol
Concentration
Certified measured by
value Soxtec extraction and
(mg/kg)» GC/MS (mg/kg)b
591
16.3
425
249
97.5
156
310
475
1,307
56.7
23.6
1,450
961
306
884
± 104
± 11.1
± 67.5
± 56.8
± 26.6
± 40.1
± 62.9
± 101
± 396
± 21.0
± 28.1
± 570
± 428
± 74.8
± 692
683
21.0
553
240
78.0
179
272
456
1,041
78.9
41.1
1,315
714
378
1,070
         a Value reported by Fisher Scientific.
         b Single determinations.
                                    10

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                                                 Fiberoptic
                                               Temperature
                                                  Probe
 II
 II
 n
 ii
 n
 n
 n
 n
 II
 M
 n
 n
n
n
n
vi
                   Water Flush
                 'System


»h


i
t
LCD
t
Temperature
Control
Board
^m
^m
^m

1
Magn

CPU Board
                              Manual
                              Two-way
                              Valve
J
Signal
                                          Pressure
                                          Transducer
                                                                            Printer
                                                                            or PC
Figure 1.
        Schematic diagram of the temperature/pressure control system for the MDS-2000
        microwave system.
                                      11

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0
   Figure 2.   View of the 12 lined digestion vessels, containment  vessel, and temperature and
               pressure probes.

                                               12

-------
                                           Temperature Port
             Rupture Membrane


       Vent Fitting
Exhaust Port
                                                     Prauuro Port
                                                                                         Backup Ring
                                                                                        Cov»r
                                                        Uiwr
                                                        Vessel Body
                                                     Teflon* Coated
                                                     Pyrex* Thermowell
                                                                                                                                 V«nt Tub*
                                                                                                                               Rupture M«nbran«
                                                                                                                                 Lbwr
                                                                                                                                 VeuelBody
                     Figure 3.
(a) Lined digestion vessel with  the temperature  and  pressure  control.;  (h)  lined
digestion vessel without the temperature and pressure control.

-------
fluoroptic™ probe, provided a seal in the cap and protected the fluoroptic" probe from solvent attack.
The standard vessels, one of which is shown in Figure 3b, did not have temperature and pressure ports
but had only rupture membranes and vent stems. These vessel assemblies were rated for operation
up to 175 psi and 200°C.

        All vessels shown in Figure 2 were connected to a containment vessel (shown in the center
of Figure 2) via  1/8-in Teflon tubes. The control vessel's temperature and pressure were monitored
for control  purposes. The fluoroptic™  probe extended down through the center of the turntable and
was  inserted into the control vessel. The 1/4-in diameter Teflon tube from the sealed containment
vessel passed through the oven cavity wall to provide a safe exhaust of any solvent vapor in case the
rupture membrane broke.

Other  Extraction Procedures

        Extractions  using a Soxtec apparatus  (Tecator,  Silver Springs,  MD) were performed by
extracting 10-g portions of the  reference materials with 50 mL hexane-acetone (1:1); the immersion
time and the extraction time were 45 min each. The solvent was evaporated directly in the Soxtec
apparatus.  Details of this procedure can be found elsewhere (7, 8).

        Extractions  using a sonic probe (Sonifier 450, Branson Ultrasonics, Danbury, CT) were
performed using 5-g portions of each reference material (except for the NIST 1941  material where
3.4 g was used). The solvent-soil suspensions were sonicated for 3 min at 50 percent power (output
setting  3.5) with 20 mL methylene chloride-acetone (9:1)  and then again  with another  10 mL
methylene chloride-acetone (9:1).  The  extracts were combined, the solvent was exchanged to hexane,
and the hexane solution was concentrated to 1 mL.  A silica gel procedure using 1.8 g silica gel (100-
200 mesh, EM Science, Gibbstown, NJ), activated for 16 hrs at 130°C prior to use, was used to clean
up the extracts. The first fraction that was eluted with 10 mL hexane was discarded. PAHs were then
eluted from the silica gel column with  10 mL hexane-methylene chloride (60:40).

        The  room-temperature extractions of the reference soils and sediments  were performed by
allowing the solvent mixture to stay in contact with the solid matrix the same amount of time that was
required for the temperature in the microwave-heated vessel (i) to reach the set point, (ii) to be
maintained  at the set point (5,  10, or 20 min),  and (iii) then to cool to room temperature.

        The extractions using a convection oven were performed as described above for MAE except
that the vessels were heated in  a convection oven (Baxter Scientific Products, McGaw Park, IL) for
15, 30, 60, and  120 min.  Two matrices including SRS103-100 soil and the HS-5 marine sediment
were used in  these experiments.

Analysis of Extracts

        Analyses of the extracts from the reference soil and sediment samples and from those samples
containing  PAHs and selected base/neutral compounds  were performed  on  a  5890 Series II gas
chromatograph interfaced to an HP 5971A mass spectrometer  MSD/DOS Chemstation (Hewlett-
Packard Company,  Palo Alto, CA) and equipped with a 5973A autoinjector.   The samples were
introduced via a  30-m length x  0.25-mm ID x 0.25-/xm film thickness PTE-5 fused-silica open tubular
column (Supelco, Inc.) with helium carrier gas at  a linear velocity of 39 cm/sec.  The column
temperature was held at 75°C for 3 min, then programmed to the final  temperature of 300°C at

                                             14

-------
 12°C/min, where it was  held  for  13 min.  The injection volume  was 2 /xL, and the injector
temperature was 250°C. The injector was set in the splitless mode for  1 min after the injection.  The
electron energy was set at 70 eV and the electron multiplier voltage was set at 2,160 V.  Spectral data
were acquired at a rate of 1.2 sec/scan (scanning  range was 40 to 500 amu).  The instrument was
tuned daily with PFTBA introduced via the calibration gas valve; the ion intensity was verified using
DFTPP introduced via the GC inlet.  A 5-point internal standard calibration was performed initially
to establish the GC/MS linear range.  Six internal standards including 1,4-dichlorobenzene-d4 (IS-1),
naphthalene-d8 (IS-2), acenaphthene-d10 OS-3),  phenanthrene-d,0 (IS-4), chrysene-d,2 (IS-5), and
perylene-d12 (IS-6) were spiked into every extract that was analyzed by GC/MS.

        Analyses of the extracts containing the 14 phenols or the 20 organochlorine pesticides were
performed by gas chromatography. For phenol analysis, we used a 5890 Series II gas chromatograph
equipped with a flame ionization detector and a 5973A autoinjector.  Samples were introduced via a
15-m length x 0.53-mm ID x 0.88-fun film thickness HP-5 fused-silica open tubular column (Hewlett-
Packard Company) with helium carrier gas at a flow rate of 7.1 mL/min.  The column temperature
was held at 65°C for 3 min, then programmed to  185°C (1-min hold) at 10°C/min, then to 275°C
(5-min hold) at 30°C/min.  The injection volume was 2 /iL, and the injector temperature was 200°C.

        For organochlorine pesticide analysis, we used a 5890 Series II gas chromatograph equipped
with an electron capture detector and a 5973A autoinjector.  Samples were introduced via a  15-m
length  x  0.53-mm ID x 0.88-/im film thickness HP-5 fused-silica open  tubular column  (Hewlett-
Packard Company) with helium carrier gas at a flow rate of 7.5 mL/min.  The column temperature
was held at 150°C for 0.5 min, then programmed  to 275°C  at 5°C/min.  The injection volume was
1 /xL, and the  injector temperature was 200°C.

Safety

        The microwave unit should be operated in accordance with CEM's recommended operating
safety  instructions.   The  MDS-2100  microwave  unit used in this study was  modified by CEM
Corporation to  incorporate additional safety  features:   (a) a  Teflon ceiling, held  in place with
polypropylene clips,  was mounted in the cavity underneath the mode stirrer so that any sparks from
the stirrer would not ignite organic vapors that might leak into the cavity;  (b) an air-flow sensor was
installed in the exhaust line from the  microwave unit (should the sensor detect a decrease in the air
flow, then the  microwave energy would be shut off); (c) the  maximum operating pressure was set to
150 psi; and (d) the lined digestion vessels were modified so that in case  of membrane rupture, the
solvent vapors would be retained in the containment vessel and  would  not escape  into  the cavity.
                                             15

-------
                                       SECTION 5

                               RESULTS AND DISCUSSION
Preliminary Experiments

        Pure hydrocarbon solvents (e.g., hexane) do not absorb microwave energy.  Therefore,  a
certain percentage (> 10 percent) of a polar component (e.g.,  acetone) must be  added.   In our
preliminary MAE experiments, we tried several solvents and solvent mixtures that are commonly used
with conventional extraction techniques using the control vessel to establish the time required to reach
the maximum temperature.   Methylene chloride-acetone (1:1),  hexane-acetone (1:1), and toluene-
methanol (1:10) reached maximum temperature within 1 to 3 min (Table 5). We chose hexane-acetone
(1:1) in subsequent experiments since this solvent mixture  was compatible with electron capture
detection.   Next, we investigated the effect of solvent volume by varying the volume of hexane-
acetone (1:1) from 5 to 30 mL.  The results indicated that a  30-mL volume was desirable since the
solvent could reach the maximum temperature (156-160°C) in 2.5 min (Table  5).  Various solid
matrices were added to the  solvent, but the effect of the matrix on the heating rate appeared to be
insignificant; the time required for the temperature to reach maximum was still about 2 min (Table 5).

        When both the solvent volume and the mass of the sample were varied, while keeping their
ratio constant, we found that a 30-mL volume and a 6-g sample were giving the shortest heating time
(Table 5). When the water content of the sample was adjusted to  10 or 30 percent, the time required
to reach the maximum temperature almost doubled, and the Tmax was about 15 °C lower than in the
case of the dry matrix.  When we performed experiments using solvent only, with 6 and 12 vessels,
we found  that the time required to heat the solvent in the vessels to Tmax  increased to 5 min for  6
vessels and to 9.5 min for 12 vessels (Table 5).

        Sand freshly spiked  with seven of the organochlorine  pesticides listed in  Table 1 was
extracted for 5, 10, or 20 min using microwave energy; another spiked sand sample was left in contact
with the solvent at room temperature (no microwave energy)  for about 5  min.  Recoveries (Table 6)
were all above 95 percent, and we could not draw conclusions about how well the MAE technique
performed because simple soaking of the sample with solvent  also resulted in quantitative recoveries.
The results indicated, however, that the spiked compounds did not degrade when microwave  energy
was applied.  The recoveries ranged from 95 to 134 percent; the high  values may have been due to
partial evaporation of the solvent upon opening the vessel too soon after extraction. In subsequent,
more carefully monitored experiments, we measured the volume of the solvent after extraction and
found no changes in the solvent volume when we extracted dry  matrices and allowed adequate time
for cooling.
                                             16

-------
TABLE 5. TIME (MIN) REQUIRED TO REACH THE MAXIMUM TEMPERATURE UNDER
         VARIOUS EXTRACTION CONDITIONS
Solvent type
Effect of solvent
Tetrachloroethylene
Methylene chloride-acetone (1:1)
Hexane-acetone (1:1)
Toluene-methane! (10: 1)
Methylene chloride
Toluene-methanol (1:10)
Effect of solvent volume
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Effect of matrix
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Effect of solvent
volume and sample weight
Hexane-acetone (1:1)
Hexane-acetone (1 : 1)
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Effect of number of vessels
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Effect of sample moisture
Hexane-acetone (1:1)
Hexane-acetone (1:1)
Solvent
volume
(mL)

10, 20, 30
30
30
30
30
30

5
10
15
20
30

30
30
30
30


10
15
20
30

30
30
30

30
30
Matrix type

Solvent only
Solvent only
Solvent only
Solvent only
Solvent only
Solvent only
*
Solvent only
Solvent only
Solvent only
Solvent only
Solvent only

Sand
Sediment
Sandy loam
Clay loam


Clay loam
Clay loam
Clay loam
Clay loam

Solvent only
Solvent only
Solvent only

Sand (10% water)
Sand (30% water)
Sample
weight
(g)

0
0
0
0
0
0

0
0
0
0
0

10
5
10
6


2
3
4
6

0
0
0

5
5
Number
of
vessels

1
1
1
1
1
1

1
1
1
1
1

1
1
1
I


1
1
1
1

1
6
12

1
1
Time required to
reach maximum
temperature
(min)

a
1:15
2:30
13:45
9:45
1:15

17:00
7:45
7:30
5:00
2:30

2:30
2:00
1:45
2:15


14:00
8:30
4:45
2:15

2:30
5:00
9:30

4:30
3:30
*max
CO

—
160-161
157-159
110-112
135-136
146-147

146
147-148
145
145
156-160

156-157
154-155
152-153
151-152


155
153
152
151

156-160
156-160
156-160

142-143
137-138
a Temperature did not exceed 70°C.
                                  17

-------
TABLE 6.  RECOVERIES OF PESTICIDES FROM FRESHLY SPIKED SAND USING
           MAE AND ROOM-TEMPERATURE EXTRACTION WITH HEXANE-
           ACETONE (!:!)•
Compound name
                             MAE recoveries (percent)
5 min
10 min
20 min
Room temperature
    extraction
recoveries (percent)
      5 min
alpha-BHC
gamma-BHC
Heptachlor
Aldrin
4,4'-DDE
Endosulfan II
4,4'-DDT
99.2
96.8
94.6
102
106
97.0
100
116
116
117
120
130
122
134
108
107
111
107
125
116
129
96.6
95.0
96.2
95.4
103
102
114
a Single determinations.  The spike level was 600 ng/g. The sample weight was 5 g; the extraction
  was performed with 30 mL hexane-acetone (1:1) at 155°C and 100 percent power.
                                      18

-------
MAE of PAHs from Standard Reference Materials

        Four standard reference marine sediments (HS-3, HS-4, HS-5, and NIST SRM1941) and two
certified contaminated soils (SRS103-100 and ERA Lot No. 321) were subjected to MAE with hexane-
acetone (1:1) for 5, 10, or 20 min after reaching the set temperature (80°C, 115°C, or 145°C).  In
parallel, we performed room-temperature extractions of the same materials by allowing the solvent
mixture to stay in contact with the solid matrix for the same  combined amounts of time that were
required for the temperature in the microwave-heated vessel to reach  the set point, to  be maintained
at the set  point (5, 10, or 20 min), and then to cool to room temperature.  Before extraction, three
deuterated compounds were spiked  onto  these samples at  levels comparable to those  of their
undeuterated counterparts. This allowed us to compare the recoveries of the "native" compounds and
the spiked compounds.

        The recovery data for the 17 compounds listed under PAHs in Table  1 (14 of which were
native compounds and three were spikes) are summarized in Figures 4 through 8. These recoveries
were determined from the values obtained from the  analysis of the extracts by  GC/MS in relation to
the certified values provided by the  manufacturers.  Not  all  reference materials contained  all  17
compounds; therefore, the  summarized recovery data pertain  to recovery results from four  to six
matrices,  depending on the  compound.

        Figure 4 shows the average recoveries and  the 95-percent confidence intervals as a  function
of temperature across the  17  compounds  and the  six  matrices.  The average recovery  at room
temperature was approximately 54 percent,  which was significantly lower than the average recoveries
achieved  at 80°C,  115°C, and 145°C (72 percent, 78 percent,  and 77 percent,  respectively).  Since
the average recoveries  at  115°C  and  145°C were almost  identical, subsequent experiments  to
determine method precision and accuracy were carried out at 115°C.

        Figure 5 shows  the average recoveries (for data  generated  for four to six  matrices per
compound and at  three temperatures,  80°C,  115°C,  and 145°C) and the 95-percent confidence
intervals as a function of time.  The average recovery increased slightly with extraction time, but the
increase was not statistically significant.  Thus, a 5-min extraction (at  115°C) was deemed sufficient
for recovering 11 "native" PAHs from a soil or sediment matrix.

        Figure 6 shows the average  recoveries  (for data generated for the 17 compounds  at three
temperatures and three extraction times) and  the 95-percent  confidence intervals as  a function  of
matrix. These data indicate that, just as with other extraction methods,  method performance was also
a function of the matrix.  It is difficult to establish whether the recovery was also a function of analyte
concentration; the results in Figure 6  did not support this.  For example, the HS-4 marine sediment
matrix  had the lowest PAH concentrations (ranging from 0.15 to  1.25 mg/kg), yet the  average
recovery  across the 17 compounds was higher than for the HS-5 marine sediment where the PAH
concentrations ranged from  0.2 to 8.4 mg/kg.  The  NIST sediment material, which had some  PAHs
at levels that were comparable to those in the HS-4 marine sediment,  gave even higher recoveries.
The ERA soil, which is  not a naturally occurring  soil material, but a soil that has  been spiked,
homogenized,  and weathered, exhibited recoveries  averaging 83 percent, which were approaching
those measured for the spikes (Figure  7). This seems to indicate that even after weathering, the ERA
spikes behaved almost like fresh spikes.
                                             19

-------
               81
               78
              71
          g   68
          u
          V
          at
              81
              SB
              51
                               29
                                              95 Percent LSD


                                         Intervals for Factor Means
                                                        115          145
                                           Temperature (°C)
Figure 4.    Percent recovery as a function of temperature for the 17 PAH compounds (four to

             six matrices).
                                            20

-------
              78
              78
             74
             72
             78
                                              95 P«pc«nt LSO

                                         Intervals •for Factor H«*n»
                                                  10              20

                                               Time (min)
Figure 5.    Percent recovery as a function of time  for the 17 PAH compounds (four to six
             matrices).
                                            21

-------
                                                95 P«rc«nt LSO

                                          Intervals for Factor Mean*
               184
               94
               84
          31

          I
              74
              64
              54
                                                           I         I
I	I
                                                                            I
                            HS3              SRS103188             HS4

                                   NIST1941              HSS                ERft

                                                 Matrix
Figure 6.    Percent recovery as a function of matrix for the 17 PAH compounds (four to six
             matrices).
                                             22

-------
          95
          91
         87
     31
     C
     u
     £
         83
         79
         75
         71
                                          95 Percent LSD


                                     Interval* for Factor Means
                                 Nat i ve
                                                        SP i ked
                                        Compound state
Figure 7.  Spiked versus native compound percent recoveries (four to six matrices).
                                        23

-------
        Figure 8 shows  the average recoveries (for data generated from four to six matrices per
compound at three temperatures and three extraction times)  and the 95-percent confidence intervals
as a function of compound.  Of  the native  compounds,  11 gave average recoveries within 65 to
111 percent, and three compounds [benzo(a)pyrene, benzo(ghi)perylene, and fluorene] had recoveries
of 51 percent,  64 percent, and 62 percent, respectively.   The spiked-compound recoveries were
77 percent (compound no. 4), 104 percent (compound no. 6), and 84 percent (compound no. 11).

        To determine method accuracy and precision, six 5-g portions of the SRS103-100 standard
reference soil were extracted simultaneously for 10  min at 115°C. The average recoveries and percent
RSDs for the 16 compounds known to be present in  the  sample  are presented in Table 7.  The
repeatability  of the  injection technique  was  1.3 percent or better (as determined from  the six
consecutive injections of a calibration standard at a concentration of 50 ng//*L).  When one of the soil
extracts was injected six times, the percent RSDs were comparable to those obtained for the calibration
standard with the exception of pentachlorophenol (percent RSD  11.9).  The percent RSDs calculated
for the  six extracts were higher, as expected; but they were  under 10 percent for  14 of the  16
compounds.   Naphthalene and pentachlorophenol  were the  two compounds for which  we obtained
percent  RSDs in the  12 to 14 percent range.  Percent recoveries established relative to the certified
values were greater than 80 percent and did not appear to be affected by the presence of water in the
sample.   The high recoveries of naphthalene and phenanthrene that we found for the MAE may be
due to a certified value that is biased low, since in both cases the standard deviation for the certified
concentration is quite high (Table  4).

        To verify that a 10-min MAE was sufficient to extract the compounds of interest from a soil
or sediment matrix, we reextracted the material (remaining after the first extraction) with fresh solvent
using the same conditions. Figures 9a and 9b show GC/MS chromatograms of the HS-3 extracts from
the first and  second extraction, respectively.  Since we did not recover any compounds in the second
extraction, we reextracted a separate portion of the material (that had already been extracted once
using microwave energy) with methylene chloride-acetone (9:1) using sonication extraction.  A
GC/MS chromatogram of the extract obtained by sonication extraction is shown in Figure 9c.  Except
for three compounds  (phenanthrene, fluoranthene, and pyrene) that represented  less than 5 percent of
their original concentrations, the extract was clean.  Thus,  we concluded that a  10-min MAE was
sufficient for the types of matrices we  investigated.

Extraction of Other Organic Compounds

        The recovery data for 20 compounds of interest to  the EPA that were known to be present
in the ERA soil Lot No. 321 are included in Table 8. The recoveries follow the same trend as in the
case of the PAHs.  The recoveries obtained at room temperature were significantly lower than those
achieved using microwave energy; the 5-min,  10-min, and 20-min extraction results were very similar;
and there was a significant improvement in recovery when extractions were done at either 115°C or
145°C as compared with the 80°C extraction.  Compounds that gave recoveries above 80 percent at
115°C/10min  included  naphthalene,  dibenzofuran,  N-nitroso-di-n-propylamine, nitrobenzene,
2,4-dichlorophenol, 2,4,6-trichlorophenol, fluoranthene, chrysene, 2,4-dinitrotoluene, carbazole, and
di-n-butylphthalate. Pentachlorophenol gave a  recovery of 67 percent and bis(2-ethylhexyl)phthalate
a recovery of 79 percent.  1,2,4-Trichlorobenzene recovery was only 56 percent, and the more volatile
compounds such as 1,2-dichlorobenzene and 2-methylphenbl gave low recoveries, even when extracted
at room temperature.
                                             24

-------
                                               95 Ptrccnt LSD

                                         Intervals for Factor rt««n»
               125
               IBS
               85
               65
               45
                         I   I    I   I    I   I
               I    I   I
                       I
i   i    i   i    i   i
                  i   i    i
                  _L
                        1234

                       (4) (4)  (6) -
   5

   (5)
6789

-  (5)  (6) (4)
10

(5)
11   12 13  14  15  16   17

-   (4) (6)  (4) (5)  (5)  (6)
                                              Compound
Figure 8.    Percent recovery as a function of compound for the 17 PAH compounds (four to
            six matrices). Refer to Table 1 for compound number and to Tables 2 through 4
            for the list of certified  compounds  in each matrix.  The numbers in parentheses
            indicate the number of matrices that contained the individual compounds.
                                           25

-------
              TABLE 7. AVERAGE RECOVERIES AND PERCENT RSDs FOR DRY AND WET SRSI03-100 SOIL
to
MAE'
Compound name
Naphthalene
2-Methylnaphthalene
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a + k)fluoranihene
Benzo(a)pyrene
Chrysene
Fluorene
Fluoranlhene
Phenanthrene
Pyrene
Dibenzofuran
Penlachlorophenol
Certified
value
(mg/kg)
23.6
56.7
590.9
16.3
424.8
249.4
156.1
97.5
310.4
475.5
1,306.6
1,449.5
961.2
305.6
884.0
Dry matrix percent
recovery
(percent RSD)b
150
98.0
112
80.9
107
87.9
114
93.3
95.5
97.3
109
137
117
109
80.3
(11.7)
(6.4)
(4.6)
(5.9)
(4.5)
(6.2)
(5.0)
(4.6)
(6.3)
(4.4)
(4.8)
(4.5)
(4.0)
(4.6)
(14.3)
Wet matrix percent
recovery
(percent RSD)b
143
95.0
111
79.0
105
84.2
111
87.3
92.8
96.3
106
135
115
108
104
(13.5)
(6.8)
(6.9)
(6.0)
(7.6)
(6.4)
(7.6)
(7.0)
(7.6)
(6.3)
(8.0)
(7.5)
(7.5)
(6.5)
(11.8)
Percent RSD for
extract injection
0.3
0.5
0.6
0.9
1.4
1.5
1.4
2.2
1.8
1.8
0.7
0.3
0.7
0.6
11.9
Percent RSD for
standard injection**
0.5
NAC
1.1
0.8
0.3
1.0
0.4
0.6
1.2
1.3
0.5
0.3
1.0
1.0
1.1
       * Six vessels were extracted simultaneously for 10 min at 115°C. The wet matrix contained 20 percent water.
       b The number of determinations was six.
       c Data not available.

-------
 Abundance


 I 2.46+07



 ' 2.26+07
 I
 i

 :   26+07



  1.86+07



 | 1.66+07
 i
 j
 • 1.46+07



 I 1.26+07

 !

    16+07
 i
 i

 j 8000000



 | 6000000



: 4000000 -


i         |
| 2000000 -j
                                     TIC: MWEHS33A.D
                            IS-3
                    IS-2
                                     IS-4
                                                 IS-S
                                                        IS-6
.Time — >    5.00
                       10.00
15.00
                                           20.00     25.00
                                                                30.00
Figure 9a.   GC/MS chromatogram of the extract obtained by MAE  of the HS-3 marine
            sediment with hexane-acetone (1:1) (1S-1 through IS-6 are internal standards).
                                       27

-------
   Abundance
    6500000 -•
                            IS-3
TIC: MWEHS35.D
    6000000 -
1
5500000 -
| 5000000 -
4500000 -
4000000 -
3500000
I
3000000 -

2500000 -
2000000 -
)
; 1500000 -
IS
1000000 -
1
500000 -j
1
J
j
Time — > 5.






IJ





-1


V
00






5-2









10.00
















1
15.
IS-4














.. L i i
00 20. 0(


IS-5












1 . .
) 2








IS-6



1



5.00 30.00
Figure 9b.    GC/MS chromatogram of the extract from a second extraction performed on the
             HS-3 marine sediment using microwave energy and fresh solvent (IS-1 through
             IS-6 are internal standards).
                                        28

-------
   Abundance
                                         TIC:  SONHS31.D

; eoooooc

1
! 5500000
i
i
J 5000000
i
i
i 4500000
1
i
i
I
1 4000000
i
i
i
! 3500000
1
: 3000000

2500000
I
2000000
1
1
1500000
I
1000000 -
500000-
0 -
Time — >



















IS




5.












I!






-1



\
00
IS-











5-2











10.00
3






















, L
15.


IS-




















^
00


4




















x.
























jLJ
2o:oc






IS-5
















t 	 u
) 2














IS-6

t







5.00 30.00
Figure 9c.    GC/MS chromatogram of the sonication extract from the HS-3 marine sediment
             that was first  extracted  using microwave energy before extraction with fresh
             solvent using a sonic probe (IS-1 through IS-6 are internal standards).
                                         29

-------
TABLE 8. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM ERA SOIL LOT NO. 321
         WITH HEXANE-ACETONE (1:1) USING ROOM TEMPERATURE EXTRACTION AND MAE AT
         DIFFERENT TEMPERATURES AND PRESSURES"
Compound name
"Native" compounds
Anthracene
Benzo(b)fluoranlhene
1 ,2-Dicblorobenzene
Chrysene
Fluoranlhene
Naphthalene
Dibenzofuran
Pyrene
2-Methylphenol
N-Nitroso-di-n-propylamine
Nitrobenzene
2,4-Dichlorophenol
1 ,2,4-Trichlorobenzene
2,4,6-Trichlorophenol
2,4-Dinitrotoluene
Carbazole
Di-n-butyl-phthalate
Bis(2-ethylhexyl)phlhalate
Penlachlorophenol
Spikes
Anthracene-d|o
Fluoranthene-d|0
Benzo(a)anth race ne-d ( 2
Certified
value
(mg/kg)

3.52
2.03
10.0
4.47
8.09
2.96
1.70
3.78
5.46
5.01
7.87
5.52
9.36
2.82
4.86
5.00
3.43
7.62
6.68

5.00
5.00
5.00
Room temperature
5 min

44.0
44.6
33.4
70.7
65.2
58.6
67.4
48.7
20.3
93.7
90.2
65.0
52.5
59.1
139
79.4
129
53.5
36.3

87.6
98.8
99.2
10 min

41.6
43.4
30.5
65.5
62.7
50.5
59.9
48.5
19.2
89.2
87.9
64.0
49.4
58.2
123
74.8
121
51.4
34.1

86.4
89.0
94.5
20 min

39.6
47.6
25.5
61.6
61.1
46.4
53.8
44.6
16.7
79.7
74.7
57.8
43.7
48.6
112
65.6
112
54.9
35.3

89.2
105
103
80°C/22 psi
5 min

49.3
50.0
31.3
66.0
70.2
53.9
71.4
55.6
20.7
78.0
79.4
78.7
53.0
71.1
123
87.6
113
59.7
47.6

86.2
95.2
98.2
10 min

48.9
51.0
33.8
69.3
72.3
56.8
74.1
55.6
21.1
81.9
83.7
80.9
54.6
70.8
122
95.3
117
62.2
45.7

82.3
91.3
91.6
20 min

54.5
62.1
32.4
83.7
83.5
64.9
80.7
66.7
23.2
84.3
84.3
79.6
55.7
82.4
140
107
141
73.2
56.8

84.4
97.1
97.7
US°C/72 psi
5 min

64.5
74.7
37.6
106
102
71.4
91.6
81.2
25.4
98.7
104
112
67.0
94.8
143
136
166
92.4
52.5

83.9
92.6
98.2
10 min

61.3
68.9
32.7
87.2
89.3
105
82.2
78.8
17.9
80.7
82.6
87.1
55.7
90.9
142
113
125
79.1
67.5

87.9
98.0
96.8
20 min

64.8
73.4
33.4
100
96.6
113
84.4
79.4
23.8
85.6
88.6
93.2
59.4
100
144
120
145
88.6
76.6

88.4
101
96.6
145'C/ISO
5 min

69.5
74.8
29.6
89.7
91.1
160
83.6
78.3
24.5
85.9
96.3
96.4
54.1
109
140
125
134
85.7
76.8

96.0
104
99.6
10 min

78.9
80.9
32.3
104
102
69.3
92.7
92.1
28.0
85.7
98.2
103
61.9
129
159
142
146
89.8
83.6

93.8
100
101
psi
20 min

63.6
68.8
27.6
84.3
89.4
66.8
81.3
79.7
20.6
74.9
83.4
85.7
52.5
91.1
125
118
130
76.7
76.0

85.7
93.1
92.2
 1 Single determinations. The sample size was 5 g; the solvent volume was 30 mL. The extracts were concentrated 30-fold prior to GC/MS
  analysis.

-------
        The average recoveries and the percent RSDs were also determined for this matrix using six
5-g portions of the ERA soil Lot No. 323 (both dry and wet).  We could not use material from Lot
No. 321, since it was no longer available from ERA.  However, the ERA soil Lot No. 321 matrix
was the same as  in the new Lot No. 323, and the spike levels (certified values) were comparable to
those in Lot No. 321.  Table 9 identifies the 20  compounds known to be present in  ERA soil Lot
No. 323  and gives their certified values, the typical  recoveries achieved using the EPA-approved
methodology (Soxhlet or sonication techniques), and the recoveries that we achieved using MAE. In
addition, the percent RSDs are shown for six consecutive injections of one of the extracts and of a
calibration standard.  The repeatability of the injection technique was better than 1.4 percent (except
for two of the 23 values at 2.9 percent) for the calibration standard and better than 1.1 percent for the
ERA extract (except for two of the 23 values at 4.3 and 5.3 percent).  There was more spread in the
average recoveries for the ERA soil since the compounds covered a wider range of volatilities.
However, the recoveries that we achieved  using MAE were for the most part higher than those
achieved by the EPA-approved methodology.  When comparing  the typical recoveries  achieved with
the EPA-approved methodology and those achieved with the MAE for the dry sample  (Table 9), we
found that 11 compounds exhibited an increase in recovery greater than 10 percent (the range was 10
to 56 percent), two compounds exhibited a 6 to 7 percent increase, two compounds showed no change
in recovery, and five compounds exhibited a decrease  in recovery (10 to  15 percent).  In the case of
the wet matrix, the recoveries for the MAE were higher than those for conventional extraction for 14
of the 20 compounds and lower (but not exceeding 15 percent) for six compounds.

Stability Studies

        To test for possible compound degradation during the extraction, we performed experiments
in which we heated solvent (hexane-acetone, 1:1) and solvent-soil suspensions, spiked with the target
compounds, at 115°C for 10 min  using microwave  energy at  50 percent power.  To account for
possible losses during the nitrogen blowdown evaporation, we took an equivalent volume of hexane-
acetone (1:1) and spiked it with the target compounds at the same concentrations as the samples
subjected to MAE. The spiked solvent was then concentrated to 1 mL for phenols and PAHs and was
analyzed as is  for organochlorine pesticides.  The results are presented in Tables 10 through 12.

        For the 14 phenols tested  (Table 10), we did not find any degradation when using solvent
only (recoveries  ranged from 80.3 to 111 percent). When soil was present, we found  slightly lower
but acceptable recoveries (> 70 percent) for 10 compounds, two compounds had borderline recoveries
(2-nitrophenol  at  66.7 percent  and   pentachlorophenol  at 55 percent),  and  two  compounds
(2,4-dinitrophenol and 2-methyl-4,6-dinitrophenol) appeared to have degraded since their recoveries
were 9.4 percent and  17.1 percent,  respectively.  Catalytic  reactions in  the presence  of the soil or
simply strong adsorption to soil particles may have been the cause for these low recoveries.

        In the case of the organochlorine pesticides (Table 11), we did not find any degradation when
using solvent only (recoveries ranged from  83 to 117 percent).  When soil was present,  recoveries
were still quantitative for all compounds but gamma-chlordane (recovery 74 percent). We found some
losses for three of the four BHC isomers; however, their recoveries were still almost quantitative (the
range was 82 to  88 percent).

        In the case of the PAHs and a few  base/neutral compounds (Table 12), we did not find any
degradation when using solvent only (recoveries ranged from 85.2 to 135 percent). When soil was
present, five compounds exhibited no change in recoveries but 21 compounds showed  approximately

                                            31

-------
           TABLE 9. AVERAGE RECOVERIES AND PERCENT RSDs FOR DRY AND WET ERA SOIL LOT NO. 323
to
MAE'
Certified Typical recovery Dry matrix
value using approved percent recovery
Compound name (mg/kg)bEPA methodology6 (percent RSD)C
"Native" compounds
Anthracene
Benzo(a)anthracene
Benzo(k)fluoranthene
Chrysene
Naphthalene
Pyrene
Dibenzofuran
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
2-Methylphenol
3-MelhyIphenol
1 ,2,4-Trichlorobenzene
2,4,6-Trichlorophenol
2,4-Dinitrotoluenc
Bis(2-ethylhexyl)phthalate
Isophorone
4-Chlorophenyl phenyl ether
Butyl benzyl phthalate
Phenol
Penlachlorophenol
Spikes
Anihracene-d|0
Fluoranlhene-d|o
Benzo(a)anthracene-d|2

6.97
5.16
2.35
9.45
7.77
6.32
650
13.0
8.58
3.41
4.62
1.87
9.36
4.82
1.54
4.75
3.40
8.48
3.94
9.63

5.60
5.60
5.60

62
66
63
64
58
66
73

.6
.1
.4
.0
.7
0
.7
43.5
30
46
64
57
57
79
89
67
80
73
65
42

—
—
—
.5
6
9
.2
.1
.7
6
.2
6
6
0
7





72.6
74.2
49.1
85.2
60.3
74.7
80.8
39.1
26.2
34.6
72.2
59.2
89.0
106
74.7
76.5
79.4
90.0
72.2
646

83.1
82.4
85.2

(11.0)
(10.3)
(8.6)
(10.5)
(13.2)
(9.7)
(8.8)
(18.3)
(15.8)
(15.4)
(13.9)
(13.1)
(14.3)
(14.3)
(10.0)
(11.9)
(9.3)
(11.5)
(18.9)
(39.0)

(11.6)
(8.6)
(9.1)
Wet matrix
percent recovery
(percent RSD)"*

72.0
81.3
52.3
836
59.0
85.9
86.1
28.8
17.7
36.3
74.6
55.5
89.7
117
81.5
78.1
87.0
100
72.7
96.8

91.4
96.3
102

(2.7)
(5.3)
(4.0)
(2.8)
(6.1)
(4-9)
(2.9)
(9.6)
(13-5)
(5.1)
(2.9)
(5.7)
(21.8)
(9.2)
(5.8)
(2.4)
(4.3)
(8.1)
(3.8)
(9.4)

(2.7)
(5.0)
(8.7)
Percent
extract

0
0
RSD for
analysis0

.5
.3
0.6
0
0
0
0.
0
0
0
.7
4
9
5
.2
4
6
0.6
0.
1.
0.
0.
0.
1.
0.
0.
5.

0.
0.
4.
7
1
7
9
6
1
9
4
3

6
7
3
Percent RSD for
standard analysis1

0
1

.3
.0
2.9
1
.2
0.5
1
1
0
0
0
.4
0.3
0
.5
0.9
0
1
0
0
0
0
0
0
1.

2.
0
1.
3
0
5
4
5
3
9
g
1

9
5
4
             * Samples in five to six vessels were extracted simultaneously for 10 min at 115°C. The wet matrices contained 20 percent water.
             b Reported by ERA.
             0 The number of determinations was six.
             d The number of determinations was five.

-------
TABLE 10.   AVERAGE RECOVERIES AND PERCENT RSDs FOR PHENOLS  AFTER
           MICROWAVE  HEATING  -  SOLVENT   VERSUS   SOLVENT/SOIL
           SUSPENSION"



Compound name
Phenol
2-Chlorophenol
2-Methylphenol
3-Methylphenol
2-Nitrophenol
2,4-DimethyIphenol
2,4-Dichlorophenol
4-Chloro-3-methylphenol
2,4,6-Trichlorophenol
2,4-Dinitrophenol
4-Nitrophenol
2,3,4,6-Tetrachlorophenol
2-Methyl-4,6-dinitrophenol
Pentachlorophenol
Solvent
Percent
average
recovery
80.3
87.4
85.0
91.1
100
86.9
87.2
89.4
90.4
106
86.7
91.1
111
93.4
only

Percent
RSD
22.9
14.6
12.5
11.5
20.9
7.0
9.3
8.0
8.8
21.0
10.8
8.9
18.7
9;8
Solvent
Percent
average
recovery
74.9
76.7
75.9
79.1
66.7
76.4
75.2
78.8
76.9
9.4
74.2
73.9
17.1
55.0
and soil

Percent
RSD
7.6
8.9
7.4
8.2
9.2
9.7
6.4
4.6
5.5
20.2
6.7
5.6
34.6
7.3


Slowdown
evaporation
84.5
87.1
83.0
86.9
85.4
71.3
84.1
85.2
84.7
82.7
82.6
84.4
85.7
81.6
a The number of determinations was three. The amount spiked was 50 ng per compound.
                                  33

-------
TABLE 11.  AVERAGE RECOVERIES AND PERCENT RSDs FOR ORGANOCHLORINE
           PESTICIDES AFTER  MICROWAVE  HEATING - SOLVENT  VERSUS
           SOLVENT/SOIL SUSPENSION"
Compound name
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
gamma-Chlordane
Endosulfan-I
aJpha-Chlordane
Dieldrin
4,4'-DDE
Endrin
Endosulfan-II
4,4'-DDD
Endrin aldehyde
Endosulfan sulfate
4,4'-DDT
Endrin ketone
Methoxychlor
Solvent
Percent
average
recovery
104
103
104
107
105
107
107
83.0
110
99.3
108
107
109
106
111
117
109
105
107
115
only
Percent
RSD
1.6
1.5
1.7
1.5
1.5
1.3
2.3
2.3
4.0
0.5
2.7
0.9
0.6
1.4
2.0
1.0
1.5
1.0
1.2
6.0
Solvent
Percent
average
recovery
82.4
81.9
88.0
95.5
108
92.5
100
74.0
98.2
86.9
125
93.9
123
99.6
118
92.6
101
114
123
169
and soil
Percent
RSD
8.4
9.3
8.5
9.5
12.2
8.4
11.5
ll.O
11.4
9.6
14.8
9.6
14.4
8.4
15.4
11.9
11.0
22.7
14.9
17.4
     a The number of determinations was three.  The amount spiked was 1.5 /xg per
      compound.  The hexane-acetone extracts were not concentrated.
                                    34

-------
TABLE 12.  AVERAGE RECOVERIES AND PERCENT RSDs FOR PAHs AND SELECTED BASE/NEUTRAL
          COMPOUNDS AFTER MICROWAVE HEATING - SOLVENT VERSUS SOLVENT/SOIL SUSPENSION*
Compound name
PAHs
Acenaphthene
Acenaphthylene
Anthracene
Anthracene-dlo
Benzo(a)anthracene
Benzo
-------
a 30-percent loss.  Considering that losses during the blowdown step could be as high as 15 percent
for some of these compounds and that the measurement error could also be as high as 15 percent, we
concluded that the 30-percent loss is not unreasonable for these types of compounds.  We believe some
of the more volatile compounds (e.g., chlorinated benzenes, naphthalene)  may be partially lost during
the filtration step.

Comparison of MAE with Other Extraction Techniques

        To compare MAE with other extraction techniques, we summarized in Tables 13 through 17
the concentrations of the various compounds (known to be present in each sample) in each matrix that
was extracted by sonication, Soxtec, and MAE at 115°C for 10 min.  The data for the ERA soil are
not presented since we did  not have enough material  to extract by sonication or Soxtec extraction.
The Soxtec extractions and MAEs were performed with  hexane-acetone (1:1), and  the sonication
extractions were performed  with methylene chloride-acetone (9:1); thus,  the sonication data may not
be comparable to MAE data.  In Table 18, we report the correlation coefficients and the regression
equations for each matrix.

        Overall, the data indicate that there is significant correlation at  the 95-percent significance
level between the MAE and the other extraction techniques. The slopes of the regression equations
ranged from 0.653 to 1.934.  The various slopes indicated that the extraction efficiencies by MAE
were higher than those achieved by sonication  for two matrices (HS-3 marine sediment and SRS103-
100 soil), almost identical for the HS-5 marine sediment, slightly lower for the HS-4 marine sediment,
and still reasonable for the SRM1941 marine sediment. MAE gave higher recoveries than Soxtec for
the HS-3 marine sediment and lower recoveries for the HS-4 marine sediment.   When comparing
MAE data with the certified  values (that were obtained either by sonication and/or Soxhlet extraction),
we found that MAE recoveries ranged from 70 percent for the HS-5 marine sediment to 112 percent
for the SRS103-100 soil.

        The encouraging results obtained in this study with MAE indicate that efficient extraction of
analytes from a solid matrix could be achieved by heating the sample/solvent suspension in a  closed
vessel for  a defined period of time using microwave energy.   Heating the sample/solvent  in a
convection oven would  undoubtedly  be sufficient as we  have seen  from the  two preliminary
experiments (data not shown) conducted here.  However, the purpose of this study was not to develop
an extraction technique using a closed-vessel system in a convection oven but rather to evaluate the
use of a microwave system  because of its easy controllability and convenience.
                                             36

-------
TABLE 13.   COMPARISON  OF  ANALYTE  CONCENTRATIONS  IN  EXTRACTS
            GENERATED BY SONICATION, SOXTEC,  AND  MAE WITH  THE
            CERTIFIED VALUES FOR THE HS-3 MARINE SEDIMENT
Certified
value
Compound name
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Chrysene
Dibenzo(ah)anthracene
Fluorene
Fluoranthene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
(mg/kg)
4
0
13
14
7
7
2
5
14
1
13
60
5
9
85
39
.5
.3
.4
.6
.4
.7
.8
.0
.1
.3
.6

.4
.0
±
±
+
±
±
±
±
±
±
±
±
±
±
±
a
1.
0.
0.
2.
3.
1.
2.
2.
2.
0.
3.
9
1.
0.

5
1
4
0
6
2
0
0
0
5
1

3
7
± 20

±
9

Concentration
Concentration measured by
measured by Soxtec
sonication extraction and
extraction and
GC/MS
1
0
3
7
2
1 7
1
1
8
0
4
34
2
1
(mg/kg)b
.8
.18
.5
.6
.7
Q 1
J
.8
.8
.74
.9
.7
.2
.8
46.8
21
.6
GC/MS
(mg/kg)b
5
0
10
8
3
10

2
8
1
7
30
2
4
38
16
.8
.5
.1
.2
.6
.4

.8
.1
.2
.3
.8
.8
.3
.2
.8
Concentration
measured by
MAE and
GC/MS
(mg/kg)b
3.
0.
7.
10.
3.
1 11
J
3.
10.
2.
6.
53.
3.
7.
74.
32.
,c
4
38
0
8
7
3

9
8
0
7
0
8
7
2
7
a Value reported by the National Research Council of Canada.
b Single determinations.
c MAE at 115°Cfor 10 min.
                                   37

-------
TABLE 14.   COMPARISON  OF   ANALYTE  CONCENTRATIONS   IN  EXTRACTS
            GENERATED  BY SON1CATION,  SOXTEC, AND  MAE  WITH  THE
            CERTIFIED VALUES FOR THE HS-4 MARINE SEDIMENT





Compound name
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Chrysene
Dibenzo(ah)anthracene
Fluorene
Fluoranthene
Indeno(l ,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene



Certified
value
(mg/kg)a
0.15d
0.15d
0.14 ±0.07
0.53 ±0.05
0.65 ±0.08
0.70 ±0.15
0.36 ±0.05
0.58 ±0.22
0.65 ± 0.08
0.12 ±0.05
0.15d
1.25 ±0.10
0.51 ±0.15
0.15d
0.68 ±0.08
0.94 ±0.12

Concentration
measured by
sonication
extraction and
GC/MS (mg/kg)b
e
e
0.06
0.32
0.28
1 059
J
0.21
0.44
e
e
0.75
0.24
e
0.34
0.61
Concentration
measured by
Soxtec
extraction and
GC/MS
(mg/kg)b
e
e
0.18
0.38
0.38
1 0.98 1
I J
e
0.50
e
e
1.1
e
e
0.58
0.90

Concentration
measured by
MAE and
GC/MS
(mg/kg)b-c
0.02
0.06
0.10
0.75
0.29
0.58

0.48
0.41
d
0.04
0.92
0.57
0.06
0.43
0.82
a Value reported by the National Research Council of Canada.
b Single determinations.
c MAE at 115°C for 10 min.
d Upper limit; the amount present is not greater than 0.15 mg/kg.
e Not detected; the approximate detection limit was 0.1 mg/kg.
                                     38

-------
TABLE 15.   COMPARISON  OF  ANALYTE  CONCENTRATIONS  IN  EXTRACTS
            GENERATED BY SONICATION AND MAE WITH THE CERTIFIED VALUES
            FOR THE HS-5 MARINE SEDIMENT
Concentration Concentration
measured by measured by
Certified sonication MAE and
value extraction and GC/MS
Compound name
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Chrysene
Dibenzo(ah)anthracene
Fluorene
Fluoranthene
Indeno(l ,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
(mg/kg)a GC/MS (mg/kg)b (mg/kg)b'c
0.23 ±0.10
d
0.38 ±0.15
2.9 ± 1.2
1.7 ±0.8
2.0 ± 1.0 1
1.0 ±0.4 {
1.3 ±0.3
2.8 ±0.9
0.2 ±0.1
0.4 ±0.10
8.4 ±2.6
1.3 ±0.7
0.25 ± 0.07
5.2 ± 1.0
5.8 ± 1.8
0.03
0.06
0.16
1.1
0.58
1.9 1
I
0.19
1.9
0.12
0.11
5.5
0.55
0.04
2.8
3.2
0.04
0.45
0.25
2.2
0.38
1.3

0.47
1.4
d
0.13
5.9
0.66
0.15
3.2
3.8
       a Value reported by the National Research Council of Canada.
       b Single determinations.
       c MAE at 115°Cfor 10 min.
       d Not detected; the approximate detection limit was 0.1 mg/kg.
                                    39

-------
TABLE 16.   COMPARISON  OF  ANALYTE  CONCENTRATIONS  IN  EXTRACTS
            GENERATED BY SONIC ATION AND MAE WITH THE CERTIFIED VALUES
            FOR THE SRM1941 MARINE SEDIMENT
Concentration Concentration
measured by measured by


Compound name
Acenaphthened
Acenaphthylened
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Chrysened
Fluorene
Fluoranthene
Indeno(l,2,3-cd)pyrene
2-MethyInaphthaIened
Naphthalene*1
Perylene
Phenanthrene
Pyrene
Certified
value
(mg/kg)»
0.052 ± 0.002
0.115 ±0.010
0.202 ± 0.042
0.55 ±0.079
0.67 ±0.13
0.78 ±0.19
0.444 ± 0.049
0.516 ±0.08
0.702 ±0.016
0.104 ±0.005
1.22 ±0.24
0.569 ± 0.04
0.406 ± 0.036
1.322 ±0.014
0.422 ± 0.03
0.577 ± 0.059
1.08 ±0.20
sonication
extraction and
GC/MS (mg/kg)b
e
0.041
0.109
d
0.294
1 0.835 1
J I
0.135
e
e
0.950
0.285
e
0.147
f
0.344
0.915
MAE and
GC/MS
(mg/kg)b'c
0.042
0.098
0.186
0.376
0.396
0.990

0.454
0.454
0.056
1.03
0.398
0.254
f
f
0.494
0.604
       8 Value reported by the National Research Council of Canada.
       b Single determinations.
       c MAE at 115°Cfor 10 min.
       d Concentration reported for this compound is not certified by NIST.
       e Not detected; the approximate detection limit was 0.1 mg/kg.
       f Data not available.
                                     40

-------
TABLE 17.    COMPARISON  OF  ANALYTE  CONCENTRATIONS  IN  EXTRACTS
            GENERATED BY SOXTEC AND MAE WITH THE CERTIFIED VALUES
            FOR THE SRS103-100 SOIL
Certified
value
Compound name
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(ajpyrene
Benzo(k + b)fluoranthene
Chrysene
Fluorene
Fluoranthene
2-Methylnaphthalene
Naphthalene
Phenanthrene
Pyrene
Dibenzofuran
Pentachlorophenol
Concentration
measured by
sonication
extraction and
(mg/kg)" GC/MS (mg/kg)b
591
16.3
425
249
97.5
156
310
475
1,307
56.7
23.6
1,450
961
306
884
± 104
± 11.1
± 67.5
± 56.8
± 26.6
± 40.1
± 62.9
± 101
± 396
± 21.0
± 28.1
± 570
±428
± 74.8
±692
683
21.0
553
240
78.0
179
272
456
1,041
78.9
41.1
1,315
714
378
1,070
Concentration
measured by
MAE and
GC/MS
(mg/kg)b'c
556
19.4
450
210
79.2
142
277
441
1,320
53.5
32.1
1,798
980
279
858
     a Value reported by Fisher Scientific.
     b Single determinations.
     c MAE at 115°C for 10 min.
                                  41

-------
TABLE 18. CORRELATION OF THE DATA OBTAINED FROM MAE EXTRACTS FOR DIFFERENT MATRICES
         WITH THE CERTIFIED VALUES AND THE VALUES OBTAINED FROM SONICATION OR SOXTEC
         EXTRACTS
Type of extraction
Reported certified value

Sonication extraction

Soxtec extraction


r
y
r
y
r
y
HS-3 marine
sediment
= 0.996
= -1.263+0.884x
= 0.997
= 0.436 +1.539x
= 0.983
= 4.026+1.934x

r
y
r
y
r
y
HS-4 marine
sediment
= 0.876
= -0.006 + 0.739x
= 0.779
= 0.183 + 0.916x
= 0.767
= 0.129 + 0.653x

r
y
r
y
a

HS-5 marine
sediment
= 0.985
= -0.285 +0.70U
= 0.969
= -0.099 +1.045x



r
y
r
y
a

SRMI94I marine
sediment
= 0.962
= -0.009 + 0.747x
= 0.889
= 0.178 + 0.779x


SRS103-100 soil
r
y
r
y
a

= 0.989
= -47.2+1.
= 0.954
= -75.9+1



122x

.2l3x


" Data not available.

-------
REFERENCES

1.      Ganzler, K.; Salgo, A.; Valko, K. "Microwave Extraction - A Novel Sample Preparation
        Method for Chromatography," J. Chromatogr. 371, 299-306 (1986).

2.      Ganzler, K.; Salgo, A.  "Microwave Extraction - A New Method Superseding
        Traditional Soxhlet Extraction,"  Z. Lebensm.-Unters. Forsch. 184, 274-276 (1987).

3.      Onuska, F.  E.; Terry,  K.A.  "Extraction of Pesticides from Sediments Using a Microwave
        Technique," Chromatographia 36, 191-194 (1993).

4.      Pare, J. R. J., et al.  "Microwave Extraction of Volatile Oils and Apparatus Therefor,"
        Eur. Pat. Appl.  EP485668 Al (1992).

5.      Pare, J. R. J., et al.  "Microwave-Assisted Natural Products Extraction," U. S. Patent
        5,002,784 (1991).

6.      Freitag, W.; John, O.  "Fast  Separation of Stabilizers from Polyolefins by Microwave
        Heating," Angew. Makromol. Chem. 175,  181-185 (1990).

7.      Lopez-Avila, V.; Bauer, K.; Milanes, J.; Beckert, W.  F.  "Evaluation of a Soxtec
        Extraction Procedure for Extracting Organic Compounds from Soils and Sediments,"
        J. AOAC Internal. 76, 864-880 (1993).

8.      Lopez-Avila, V.  "Development of a Soxtec Extraction Procedure for Extracting Organic
        Compounds from Soils and Sediments," EPA Report 600/X-91/140, Environmental
        Monitoring Systems  Laboratory, Las Vegas, NV, October 1991.
                                           43

-------
                     APPENDIX A

PERCENT-RECOVERY RESULTS OF THE GC/MS ANALYSES FOR THE
           SIX CERTIFIED REFERENCE MATERIALS
                          44

-------
TABLE A-l. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
           THE HS-3 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) AT ROOM
           TEMPERATURE"
Compound name
"Native" compounds
Naphthalene
Acenaphthyleneb
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l ,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d10
Fluoranthene-dj0
Benzo(a)anthracene-d t 2
Certified value
(mg/kg)

9.0 ±0.7
0.3 ±0.1
4.5 ± 1.5
13.6 ±3.1
85 ± 2.0
13.4 ±0.5
60 ±9.0
39 ±9.0
14.6 ±2.0
14.1 ±2.0
7.7 ± 1.2
2.8 ±2.0
7.4 ±3.6
5.4 ±1.3
1.3 ±0.5
5.0 ±2.0

25
25
25
Percent recovery
5 min

28.6
97.3.
47.1
33.8
53.8
32.9
54.7
50.3
40.6
49.4
1 67.1
38.1
43.1
97.7
49.0

55.6
68.7
60.4
10 min

29.0
101
44.7
31.8
49.0
33.9
49.1
45.8
36.8
46.4
1 59.9
33.1
40.7
85.4
45.2

48.5
55.1
49.2
20 min

44.6
101
54.9
40.7
62.1
39.9
67.3
59.8
48.4
56.1
1 77.6
38.9
49.4
106
54.4

70.0
83.1
69.4
a Cinnln Hatorminatir\ri Tho camnla CITO u/ac ^ O- fhp «r\lupnt Vf\llim<» U/3Q ^fl ml Thp
  extract was concentrated sixfold prior to GC/MS analysis.
 b The extract was concentrated 30-fold prior to GC/MS analysis.
                                    45

-------
TABLE A-2.  PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
            THE HS-3 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) USING MAE
            (TEMPERATURE 80°C; PRESSURE 22 PSI)a
Compound name
"Native" compounds
Naphthalene
Acenaphthyleneb
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d10
FluoranthenendjQ
Benzo(a)anthracene-d12
Certified value
(mg/kg)

9.0 ± 0.7
0.3 ± 0.1
4.5 ± 1.5
13.6 ± 3.1
85 ± 2.0
13.4 ± 0.5
60 ± 9.0
39 ± 9.0
14.6 ± 2.0
14.1 ± 2.0
7.7 ± 1.2
2.8 ± 2.0
7.4 ± 3.6
5.4 ± 1.3
1.3 ± 0.5
5.0 ± 2.0

25
25
25
Percent recovery
5 min

41.6
105
63.6
41.9
64.6
45.4
70.8
65.2
57.9
58.9
1 83.2
47.7
53.5
118
62.6

68.3
82.6
81.6
10 min

50.4
139
69.8
48.9
73.1
44.1
78.6
70.5
57.7
69.0
| 92.1
46.1
59.4
134
68.0

71.6
88.8
71.5
20 min

66.0
133
68.7
43.2
67.1
43.0
73.1
67.8
55.3
67.6
| 85.7
44.9
57.0
122
64.4

72.8
90.0
89.3
 a Single determination.  The sample size was 5 g; the solvent volume was 30 mL.  The
  extract was concentrated sixfold prior to GC/MS analysis.
 b The extract was concentrated 30-fold prior to GC/MS analysis.
                                     46

-------
TABLE A-3.  PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
            THE HS-3 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) USING
            MAE (TEMPERATURE 115°C; PRESSURE 72 PSD*
Compound name
"Native" compounds
Naphthalene
Acenaphthyleneb
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(lc)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-dig
Fluoranthene-djQ
Benzo(a)anthracene-d12
Certified value
(mg/kg)

9.0 ± 0.7
0.3 ± 0.1
4.5 ± 1.5
13.6 ± 3.1
85 ± 2.0
13.4 ± 0.5
60 ± 9.0
39 ± 9.0
14.6 ± 2.0
14.1 ± 2.0
7.7 ± 1.2
2.8 ± 2.0
7.4 ± 3.6
5.4 ± 1.3
1.3 ± 0.5
5.0 ± 2.0

25
25
25
Percent recovery
5 min

50.4
118
66.9
40.5
65.6
45.9
68.0
63.1
57.0
59.1
| 80.7
41.2
55.4
122
61.8

72.2
85.2
80.5
10 min

85.2
125
75.6
49.3
86.3
52.0
88.4
83.8
74.2
76.7
| 108
55.0
70.2
152
78.4

83.7
106
105
20 min

61.1
158
72.4
50.9
33.2
49.0
73.5
67.7
54.7
66.2
1 86.9
44.1
57.8
126
66.4

70.0
88.4
86.3
 a Single determination. The sample size was 5 g; the solvent volume was 30 mL. The
  extract was concentrated sixfold prior to GC/MS analysis.
 b The extract was concentrated 30-fold prior to GC/MS analysis.
                                    47

-------
TABLE A-4.  PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
            THE HS-3 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1)  USING
            MAE (TEMPERATURE 145°C; PRESSURE ISO PSI)a
Compound name
"Native" compounds
Naphthalene
Acenaphthyleneb
Acenaphthene
Fluorene
Phenanthrene .
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
D ibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d10
FIuoranthene-d10
Benzo(a)anthracene-d 12
Certified value
(mg/kg)

9.0 ± 0.7
0.3 ± 0.1
4.5 ± 1.5
13.6 ± 3.1
85 ± 2.0
13.4 ± 0.5
60 ± 9.0
39 ± 9.0
14.6 ± 2.0
14.1 ± 2.0
7.7 ± 1.2
2.8 ± 2.0
7.4 ± 3.6
5.4 ± 1.3
1.3 ± 0.5
5.0 ± 2.0

25
25
25

5 min

61.1
118
64.7
48.5
70.0
45.1
77.2
68.5
56.8
62.3
1 83.6
43.4
54.6
124
63.0

70.8
94.0
83.2
Percent recovery
10 min

123
163
53.1
36.7
55.8
43.0
56.4
50.1
40.5
48.7
} 60.8 1
33.8
40.4
86.9
47.0

57.2
66.1
54.1

20 min

73.8
188
66.4
51.0
68.5
50.0
81.4
60.8
52.5
58.5
73. 8
44.2
50.2
111
57.4

68.9
95.6
71.8
a Single determination. The sample size was 5 g; the solvent volume was 30 mL.  The
  extract was concentrated sixfold prior to GC/MS analysis.
b The extract was concentrated 30-fold prior to GC/MS analysis.
                                    48

-------
TABLE A-S.  PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
             THE HS-4 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) AT ROOM
             TEMPERATURE8
                         Certified value
                                                   Percent recovery
Compound name
"Native" compounds
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d10
Fluoranthene-d10
Benzo(a)anthracene-d j 2
(mg/kg)

0.15b
0.15b
0.15b
0.15b
0.68 ± 0.08
0.14 ± 0.07
1.25 ± 0.10
0.94 ± 0.12
0.53 ± 0.05
0.65 ± 0.08
0.70 ± 0.15
0.36 ± 0.05
0.65 ± 0.08
0.51 ± 0.15
0.12 ± 0.05
0.58 ± 0.22

1.0
1.0
1.0
5 mm

b
b
b
b
26.8
32.9
27.4
38.7
49.4
39.4
1 21.9
5.5
22.4
c
3.8

53.2
29.2
40.0
10 mm

b
b
b
b
40.6
48.6
44.0
58.7
74.0
51.1
1 34.5
23.7
36.5
c
26.9

80.4
50.0
71.2
20 mm

b
b
b
b
40.6
41.4
43.8
56.2
90.2
43.4
1 32.3
28.6
52.5
c
29.0

66.6
57.2
99.2
   Single determination.  The sample size was 5 g; the solvent volume was 30 mL. The
   extract was concentrated 30-fold prior to GC/MS analysis.
   Upper limit; the amount present is not greater than 0.15 mg/kg.  Therefore the percent
   recovery could not be calculated.
   Not detected; the approximate detection limit was 0.1 mg/kg.
                                       49

-------
TABLE A-6.  PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
             THE HS-4 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) USING
             MAE (TEMPERATURE 80°C; PRESSURE 22 PSI)a
                        Certified value
                                                   Percent recovery
Compound name
"Native" compounds
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d10
Fluoranthene^d10
Benzo(a)anthracene-d 12
(mg/kg)

0.15b
0.15b
0.15b
0.15b
0.68 ± 0.08
0.14 ± 0.07
1.25 ± 0.10
0.94 ± 0.12
0.53 ± 0.05
0.65 ± 0.08
0.70 ± 0.15
0.36 ± 0.05
0.65 ± 0.08
0.51 ± 0.15
0.12 ± 0.05
0.58 ± 0.22

1.0
1.0
1.0
5 mm

b
b
b
b
51.2
50.0
53.8
68.9
105
45.5
1 46.6
35.4
87.5
c
56.2

67.8
64.4
107
10 mm

b
b
b
b
57.6
57.1
62.9
76.4
123
52.3
1 49.4
52.0
76.1
c
54.5

67.4
74.4
128
20 mm

b
b
b
b
62.1
62.9
72.2
80.0
136
52.9
1 53.0
23.7
94.5
c
57.2

73.2
86.0
141
 8 Single determination. The sample size was 5 g; the solvent volume was 30 mL.  The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b Upper limit; the amount present is not greater than 0.15 mg/kg. Therefore the percent
   recovery could not be calculated.
 c Not detected; the approximate detection limit was 0.1 mg/kg.
                                       50

-------
TABLE A-7.   PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
              THE HS-4 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1)  USING
              MAE (TEMPERATURE 115°C; PRESSURE 72 PSI)a
    Compound name
Certified value
   (mg/kg)
                                                      Percent recovery
                                             5 min
10 min
20 min
 "Native" compounds

 Naphthalene                   0.15b              b
 Acenaphthylene                0.15b              b
 Acenaphthene                 0.15b              b
 Fluorene                      0.15b              b
 Phenanthrene               0.68 ±  0.08         62.1
 Anthracene                0.14 ±  0.07         65.7
 Fluoranthene               1.25 ±  0.10         65.9
 Pyrene                    0.94 ±  0.12         75.7
 Benzo(a)anthracene          0.53 ±  0.05         128
 Chrysene                  0.65 ±  0.08         52.9
 Benzo(b)fluoranthene        0.70 ±  0.15    \     52 3
 Benzo(k)fluoranthene        0.36 ±  0.05    /
 Benzo(a)pyrene             0.65 ±  0.08         42.2
 Indeno(l,2,3-cd)pyrene      0.51 ±  0.15         83.9
 Dibenzo(ah)anthracene       0.12 ±  0.05          c
 Benzo(ghi)perylene          0.58 ±  0.22         52.8
 Spikes
 Anthracene-d|0                 1.0              75.2
 Fluoranthene-d,0                1.0              77.4
 Benzo(a)anthracene-d|2          1.0              140
                                    b
                                    b
                                    b
                                    b
                                   62.6
                                   72.9
                                   73.6
                                   86.8
                                  141
                                   63.4
                                   54.5

                                   44.6
                                  111
                                    c
                                   82.4
                                   72.4
                                   87.0
                                  158
                 b
                 b
                 b
                 b
                57.6
                65.7
                66.7
                77.9
               133
                52.6
                51.5

                46.8
               100
                 c
                55.9
                60.6
                80.2
               145
 a Single determination. The sample size was 5 g; the solvent volume was 30 mL.  The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b Upper limit; the amount present is not greater than 0.15 mg/kg.  Therefore the percent
   recovery could not be calculated.
 c Not detected; the approximate detection limit was 0.1 mg/kg.
                                         51

-------
TABLE A-8.  PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
             THE HS-4 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1)  USING
             MAE (TEMPERATURE 145°C; PRESSURE 150 PSI)a
                        Certified value
                                                  Percent recovery
Compound name
"Native" compounds
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
D ibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d,0
Fluoranthene-d,0
Benzo(a)anthracene-d 12
(mg/kg)

0.15b
0.15b
0.15"
0.15b
0.68 ± 0.08
0.14 ± 0.07
1.25 ± 0.10
0.94 ± 0.12
0.53 ± 0.05
0.65 ± 0.08
0.70 ±0.15 1
0.36 ± 0.05 J
0.65 ± 0.08
0.51 ± 0.15
0.12 ± 0.05
0.58 ± 0.22

1.0
1.0
1.0
5 mm

b
b
b
b
74.7
85.7
66.1
82.3
134
55.7
50.4
44.3
80.4
c
52.4

71.2
79.2
141
10 mm

b
b
b
b
50.0
55.7
52.6
63.6
109
40.9
1 42.8
46.2
83.9
c
38.6

56.4
65.4
113
20 mm

b
b
b
b
50.0
55.7
52.6
63.6
109
40.9
1 42.8
65.8
72.9
c
50.0

72.0
69.4
130
 a Single determination.  The sample size was 5 g; the solvent volume was 30 mL. The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b Upper limit; the amount present is not greater than 0.15 mg/kg. Therefore the percent
   recovery could not be calculated.
 c Not detected; the approximate detection limit was 0.1 mg/kg.
                                       52

-------
TABLE A-9.  PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
             THE HS-5 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) AT ROOM
             TEMPERATURE"
                        Certified value
                                                   Percent recovery
Compound name
"Native" compounds
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l ,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d,0
Fluoranthene-d10
Benzo(a)anthracene-d 12
(mg/kg)

0.25 ± 0.07
0.15b
0.23 ± 0.10
0.4 ± 0.10
5.2 ± 1.0
0.38 ± 0.15
8.4 ± 2.6
5.8 ± 1.8
2.9 ± 1.2
2.8 ± 0.9
2.0 ± 1.0 \
1.0 ± 0.4 }
1.7 ± 0.8
1.3 ± 0.3
0.2 ± 0.1
1.3 ± 0.7

5.0
5.0
5.0
5 mm

28.8
b
13.0
19.5
39.4
48.4
40.2
39.4
41.2
32.3
21.8

22.9
28.9
c
24.8

50.2
54.2
94.6
10 mm

33.6
b
16.5
22.5
46.1
46.8
47.8
44.7
47.9
41.3
) 22.3
1
22.4
48.6
c
32.3

55.6
67.1
112
20 min

31.2
b
13.0
21.5
46.0
45.8
48.4
45.7
52.9
38.0
1 31 7
1
28.8
36.2
c
39.2

53.4
63.7
109
 a Single determination. The sample size was 5 g; the solvent volume was 30 mL. The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b Upper limit; the amount present is not greater than 0.15 mg/kg. Therefore the percent
   recovery could not be calculated.
 c Not detected; the approximate detection limit was 0.1 mg/kg.
                                       53

-------
TABLE A-10. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
             THE HS-5 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) USING
             MAE (TEMPERATURE 80°C; PRESSURE 22 PSI)a
                        Certified value
                                                  Percent recovery
Compound name
"Native" compounds
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l ,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d,0
Fluoranthene-d10
Benzo(a)anthracene-d 12
(mg/kg)
0.25 ± 0.07
0.15°
0.23 ± 0.10
0.4 ± 0.10
5.2 ± 1.0
0.38 ± 0.15
8.4 + 2.6
5.8 ± 1.8
2.9 ± 1.2
2.8 ± 0.9
2.0 ± 1.0 1
1.0 ± 0.4 /
1.7 ± 0.8
1.3 ± 0.3
0.2 ± 0.1
1.3 ± 0.7

5.0
5.0
5.0
5 mm
53.6
c
13.9
29.5
56.4
46.3
61.5
56.8
71.4
36.9
43.1
27.3
51.2
d
37.4

55.3
68.1
130
10 mm
45.6
c
16.5
29.5
60.6
60.0
68.5
59.4
64.1
46.9
1 39.5
28.9
40.6
d
43.8

58.0
71.3
126
20 mm
419b
c
14.8
32.0
58.5
50.0
70.5
61.6
69.9
37.3
1 41.3
29.5
46.0
d
38.3

57.7
73.3
134
 a Single determination.  The sample size was 5 g; the solvent volume was 30 mL. The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b Cannot explain high recovery.
 c Upper limit; the amount is not greater than 0:15 mg/kg.  Therefore the percent recovery
   could not be calculated.
 d Not detected; the approximate detection limit was 0.1 mg/kg.
                                       54

-------
TABLE A-ll. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
             THE HS-5 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) USING
             MAE (TEMPERATURE 115°C; PRESSURE 72 PSI)a
                        Certified value
                                                   Percent recovery
Compound name
"Native" compounds
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d,0
Fluoranthene-d10
Benzo(a)anthracene-d 12
(mg/kg)
0.25 ± 0.07
0.15C
0.23 ± 0.10
0.4 ± 0.10
5.2 ± 1.0
0.38 ± 0.15
8.4 ± 2.6
5.8 ± 1.8
2.9 ± 1.2
2.8 ± 0.9
2.0 ± 1.0 1
1.0 ± 0.4 I
1.7 ± 0.8
1.3 ± 0.3
0.2 ± 0.1
1.3 ± 0.7

5.0
5.0
5.0
5 mm
416b
c
20.0
30.0
63.7
52.6
74.3
63.5
72.7
40.2
42.8
30.1
55.1
d
38.2

57.5
76.2
134
10 mm
61.6
c
18.3
32.5
61.3
65.8
69.8
65.1
77.3
48.4
1 41.8
22.4
50.8
d
35.8

56.9
73.2
141
20 mm
67.2
c
20.0
31.0
65.0
70.0
78.3
68.2
76.6
45.1
j 43.6
31.6
49.2
d
34.9

58.8
81.7
143
 a  Single determination.  The sample size was 5 g; the solvent volume was 30 mL. The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b  Cannot explain high recovery.
 c  Upper limit; the amount present is not greater than 0.15 mg/kg. Therefore the percent
   recovery could not be calculated.
 d  Not detected; the approximate detection limit was 0.1 mg/kg.
                                       55

-------
TABLE A-12. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
             THE HS-5 MARINE SEDIMENT WITH HEXANE-ACETONE (1:1) USING
             MAE (TEMPERATURE 14S°C; PRESSURE 150 PSI)a
                        Certified value
                                                  Percent recovery
Compound name
"Native" compounds
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
Spikes
Anthracene-d10
Fluoranthene-d10
Benzo(a)anthracene-d j2
(mg/kg)

0.25 ± 0.07
0.15°
0.23 ± 0.10
0.4 ± 0.10
5.2 ± 1.0
0.38 ± 0.15
8.4 ± 2.6
5.8 ± 1.8
2.9 ± 1.2
2.8 ± 0.9
2.0 ± 1.0
1.0 ± 0.4
1.7 ± 0.8
1.3 ± 0.3
0.2 ± 0.1
1.3 ± 0.7

5.0
5.0
5.0
5 min

76.8
c
19.1
32.0
59.8
66.8
69.3
62.5
71.2
38.5
1 40.9
33.6
50.8
d
29.7

53.6
69.3
130
10 min

522b
c
15.7
31.0
64.0
62.1
70.5
65.4
83.7
38.1
1 45.9
37.4
59.2
d
45.1

56.4
70.6
133
20 min

73.6
c
22.6
33.0
67.8
63.2
73.0
69.6
85.2
42.6
1 43.6
22.2
63.1
d
39.1

60.0
74.0
154
 8 Single determination.  The sample size was 5 g; the solvent volume was 30 mL.  The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b Cannot explain high recovery.
 c Upper limit; the amount present is not greater than 0.15 mg/kg.  Therefore the percent
   recovery could not be calculated.
 d Not detected; the approximate detection limit was 0.1 mg/kg.
                                       56

-------
  TABLE A-13. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS
              FROM THE NIST SRM1941 MARINE SEDIMENT WITH HEXANE-
              ACETONE (1:1) AT ROOM TEMPERATURE"
Compound name
"Native" compounds
NaphthaJeneb
2 -Methyl naphthal eneb
Acenaphthyleneb
Acenaphtheneb
FIuoreneb
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chryseneb
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno( 1 ,2 ,3-cd)pyrene
Benzo(ghi)perylene
Spikes
Anthracene-d10
Fluoranthene-d10
Benzo(a)anthracene-d , 2

Certified value
(mg/kg)

1.322 ± 0.014
0.406 ± 0.036
0.115 ± 0.010
0.052 ± 0.002
0.104 ± 0.005
0.577 ± 0.059
0.202 ± 0.042
1.22 ± 0.24
1.08 ± 0.20
0.55 ± 0.079
0.702 ± 0.016
0.78 ± 0.19 1
0.444 ± 0.040 /
0.67 ± 0.13
0.569 ± 0.040
0.516 ± 0.083

0.6
0.6
0.6
Percent recovery
5 min

15.7
16.3
76.5
57.7
65.4
54.1
85.1
68.4
50.0
62.5
61.0
85.7

51.6
59.8
73.6

117
90.3
73.3
10 min

22.2
11.8
64.3
42.3
46.2
42.6
51.5
52.1
38.7
46.2
55.6
1 67 4 1
/ ' J
36.7
54.5
48.8

101
51.7
42.3
20 min

34.0
12.3
69.6
42.3
44.2
40.2
92.1
47.0
31.1
36.7
55.3
i 68.0

37.0
51.0
53.9

98.0
74.0
56.3
a Single determination. The sample size was 5 g; the solvent volume was
  extract was concentrated 30-fold prior to GC/MS analysis.
b The concentration reported for this compound is not certified by NIST.
mL. The
                                    57

-------
TABLE A-14.
                PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS
                FROM THE NIST SRM1941 MARINE SEDIMENT  WITH HEXANE-
                ACETONE  (1:1) USING MAE  (TEMPERATURE 80°C;  PRESSURE
                22 PSI)a
Compound name
"Native" compounds
Naphthalene1*
2-Methylnaphthaleneb
Acenaphthyleneb
Acenaphtheneb
Fluoreneb
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chryseneb
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l ,2,3-cd)pyrene
Benzo(ghi)perylene
Spikes
Anthracene-d10
FluorantheneHdl0
Benzo(a)anthracene-d j 2

Certified value
(mg/kg)

1.322 ± 0.014
0.406 ± 0.036
0.115 ± 0.010
0.052 ± 0.002
0.104 ± 0.005
0.577 ± 0.059
0.202 ± 0.042
1.22 ± 0.24
1.08 ± 0.20
0.55 ± 0.079
0.702 ± 0.016
0.78 ±0.19 1
0.444 ± 0.049 J
0.67 ± 0.13
0.569 ± 0.040
0.516 ± 0.083

0.6
0.6
0.6
Percent recovery
5 min

23.9
22.2
83.5
53.8
73.1
70.7
90.1
76.7
51.3
68.7
82.1
82.7

50.4
65.4
74.4

103
95.7
98.7
10 min

24.1
25.1
76.5
76.9
78.8
76.9
92.1
71.0
45.7
74.5
63.8
1 78 1
J
49.9
63.3
75.2

102
70.7
77.7
20 min

162C
36.5
67.8
69.2
63.5
76.6
98.0
80.2
50.0
85.1
85.5
1 89.3

52.8
68.5
85.7

105
101
99.3
a Single determination. The sample size was 5 g; the solvent volume was 30 mL.
  extract was concentrated 30-fold prior to GC/MS analysis.
b The concentration reported for this compound is not certified by NIST.
c Cannot explain high recovery.
                                                                 The
                                    58

-------
TABLE A-15.
PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS
FROM  THE  N1ST SRM1941  MARINE SEDIMENT WITH HEXANE-
ACETONE (1:1) USING MAE (TEMPERATURE  115°C; PRESSURE
72PSI)a
Compound name
"Native" compounds
Naphthalene6
2-Methylnaphthaleneb
Acenaphthyleneb
Acenaphtheneb
Fluoreneb
Phenanthrene
Anthracene
Fluoramhene
Pyrene
Benzo(a)anthracene
Chryseneb
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Benzo(ghi)perylene
Spikes
Anthracene-d|0
Fluoranthene-d10
Benzo(a)anthracene-d 12

Certified value
(mg/kg)

1.322 ± 0.014
0.406 ± 0.036
0.115 ± 0.010
0.052 ± 0.002
0.104 ± 0.005
0.577 ± 0.059
0.202 ± 0.042
1.22 ± 0.24
1.08 ± 0.20
0.55 ± 0.079
0.702 ± 0.016
0.78 ±0.19 \
0.444 ± 0.049 j
0.67 ± 0.13
0.569 ± 0.040
0.516 ± 0.083

0.6
0.6
0.6
Percent recovery
5 min

38.0
39.9
88.7
80.8
69.2
91.9
109
76.9
52.4
82.9
71.5
80.0
54.3
69.2
93.0

112
79.0
64.0
10 min

345b
62.6
85.2
80.8
53.8
85.6
92.1
84.6
55.9
68.4
64.7
1 80.9
59.1
69.9
88.0

100
85.0
61.3
20 min

488b
78.3
85.2
88.5
57.7
95.7
120
93.0
62.4
76.7
66.4
1 91.1
62.7
74.2
93.0

103
95.3
64.0
 a Single determination. The sample size was 5 g; the solvent volume was 30 mL. The
   extract was concentrated 30-fold prior to GC/MS analysis.
 b The concentration reported for this compound is not certified by NIST.
 c Cannot explain high recovery.
                                      59

-------
TABLE A-l
-------
TABLE A-17.
PERCENT RECOVERIES OF "NATIVE" COMPOUNDS FROM THE
SRS103-100 SOIL  WITH  HEXANE-ACETONE  (1:1) AT  ROOM
TEMPERATURE"
Compound name
Naphthalene6
2-MethylnaphthaJeneb
Acenaphthyleneb
Acenaphthene
Dibenzofuran
Fluorene
Pentachlorophenolb
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b + k)fluoranthene
Benzo(a)pyrene
Certified value
(mg/kg)
23.6
56.7
16.3
591
306
476
884
1,450
425
1,307
961
249
310
156
97.5
± 28.1
± 21.0
± 11.1
± 104
± 74.8
± 101
± 692
± 570
± 67.5
± 396
± 428
± 56.8
± 62.9
± 40.1
± 26.6
Percent recovery
5 min
64.6
54.0
73.6
59.1
67.9
66.2
60.5
91.7
71.2
63.9
81.1
65.7
68.0
48.8
48.0
10 min
64.1
56.3
76.6
54.9
61.1
54.8
59.5
86.1
72.2
62.1
74.7
67.1
57.6
48.8
45.5
20 min
75.8
59.0
86.9
63.8
75.2
71.7
68.7
101
74.0
74.6
94.3
82.5
67.4
59.6
58.5
 a Single determination. The sample size was 5 g; the solvent volume was 30 mL. The
  extract was diluted 10-fold prior to GC/MS.
 b The extract was diluted twofold prior to GC/MS analysis.
                                     61

-------
TABLE A-18.  PERCENT  RECOVERIES  OF  "NATIVE"  COMPOUNDS  FROM  THE
             SRS103-100  SOIL  WITH  HEXANE-ACETONE   (1:1)   USING   MAE
             (TEMPERATURE 80°C; PRESSURE 22 PSI)a
Compound name
Naphthalene1*
2-Methylnaphthalenet>
Acenaphthyleneb
Acenaphthene
Dibenzofuran
Fluorene
Pentachlorophenolb
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b + k)fluoranthene
Benzo(a)pyrene
Certified value
(mg/kg)
23.6
56.7
16.3
591
306
476
884
1,450
425
1,307
961
249
310
156
97.5
± 28.1
± 21.0
± 11.1
± 104
± 74.8
± 101
± 692
± 570
± 67.5
± 396
± 428
± 56.8
± 62.9
± 40.1
± 26.6
Percent recovery
5 min
116
82.3
101
84.0
82.5
83.0
40.3
106
92.1
82.2
85.0
69.8
82.1
82.1
72.6
10 min
133
90.8
107
94.2
91.3
92.7
70.5
118
106
91.0
95.1
76.7
90.4
86.3
75.7
20 min
152
100
123
98.3
96.4
96.5
73.1
125
110
100
103
83.0
92.6
92.1
86.8
 a Single determination.  The sample size was 5 g; the solvent volume was 30 mL.  The
  extract was diluted 10-fold prior to GC/MS analysis.
 b The extract was diluted twofold prior to GC/MS analysis.
                                     62

-------
TABLE A-19. PERCENT  RECOVERIES  OF  "NATIVE"  COMPOUNDS  FROM  THE
            SRS103-100  SOIL   WITH  HEXANE-ACETONE   (1:1)   USING   MAE
            (TEMPERATURE 11S8C; PRESSURE 72 PSI)a
Compound name
Naphthalene6
2-Methyloaphthaleneb
Acenaphthyleneb
Acenaphthene
Oibenzofuran
Fluorene
Pentachlorophenolb
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b + k)fluoranthene
Benzo(a)pyrene
Certified value
(mg/kg)
23.6
56.7
16.3
591
306
476
884
1,450
425
1,307
961
249
310
156
97.5
± 28.1
± 21.0
± 11.1
± 104
± 74.8
± 101
± 692
± 570
± 67.5
± 396
± 428
± 56.8
± 62.9
± 40.1
± 26.6
Percent recovery
5 min
132
89.3
111
94.6
91.5
86.9
76.0
122
104
94.5
95.7
83.7
85.0
88.6
75.1
10 min
136
94.4
119
94.1
91.1
92.9
97.1
124
106
101
102
84.2
89.3
90.9
81.2
20 min
146
91.4
107
93.8
93.8
92.7
95.5
122
101
94.6
97.1
84.9
86.8
89.2
80.0
a Single determination.  The sample size was 5 g; the solvent volume was 30 mL.  The
  extract was diluted 10-fold prior to GC/MS analysis.
b The extract was diluted twofold prior to GC/MS analysis.
                                     63

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TABLE A-20. PERCENT  RECOVERIES  OF  "NATIVE"  COMPOUNDS  FROM  THE
            SRS1Q3-100  SOIL   WITH  HEXANE-ACETONE   (1:1)  USING   MAE
            (TEMPERATURE 145°C; PRESSURE 150 PSI)'
Compound name
Naphthalene1"
2-MethyInaphthaleneb
Acenaphthyleneb
Acenaphthene
Dibenzofuran
Fluorene
Pentachlorophenolb
Phenanthrene
Anthracene
Fluoranthene
Pyrene
8enzo(a)anthracene
Chrysene
Benzo(b + k)fluoranthene
Benzo(a)pyrene
Certified value
(mg/kg)
23.6
56.7
16.3
591
306
476
884
1,450
425
1,307
961
249
310
156
97.5
± 28.1
± 21.0
± 11.1
± 104
± 74.8
± 101
± 692
± 570
± 67.5
± 396
± 428
± 56.8
± 62.9
± 40.1
± 26.6
Percent recovery
5 min
118
75.3
95.0
94.7
93.5
93.5
74.4
123
102
92.9
96.4
82.5
84.3
85.9
75.1
10 min
162
92.5
123
88.2
92.5
91.5
81.5 .
122
102
92.9
95.6
79.6
89.3
86.7
75.1
20 min
166
96.5
113
95.2
94.6
90.2
89.7
126
98
95.7
.102
82.0
92.0
92.1
79.4
 a Single determination.  The sample size was 5 g; the solvent volume was 30 mL. The
  extract was diluted 10-fold prior to GC/MS analysis.
 b The extract was diluted twofold prior to GC/MS analysis.
                                     64

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TABLE A-21. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
            THE ERA SOIL (LOT NO. 321) WITH HEXANE-ACETONE (1:1) AT ROOM
            TEMPERATURE*
                          Certified value
                                                  Percent recovery
Compound name
"Native" compounds
Naphthalene
Dibenzofuran
Pentachlorophenol
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo(b)fluoranthene
1 ,2-Dichlorobenzene
2-MethyIphenol
N-Nitroso-di-n-propylamine
Nitrobenzene
2,4-Dichlorophenol
1 ,2,4-TrichIorobenzene
2,4,6-Trichlorophenol
2,4-Dinitrotoluene
Carbazole
Di-n-butyl-phthalate
Bis(2-ethylhexyl)phthaJate
Spikes
Anthracene-djQ
Fluoranthene-djQ
Benzo(a)anthracene-dt2
(mg/kg)

2.96
1.70
6.68
3.52
8.09
3.78
4.47
2.03
10.0
5.46
5.01
7.87
5.52
9.36
2.82
4.86
5.00
3.43
7.62

5.00
5.00
5.00
5 mm

58.6
67.4
36.3
44.0
65.2
48.7
70.7
44.6
33.4
20.3
93.7
90.2
65.0
52.5
59.1
139
79.4
129
53.5

87.6
98.8
99.2
10 mm

50.5
59.9
34.1
41.6
62.7
48.5
65.5
43.4
30.5
19.2
89.2
87.9
64.0
49.4
58.2
123
74.8
121
51.4

86.4
89.0
94.5
20 mm

46.4
53.8
35.3
39.6
61.1
44.6
61.6
47.6
25.5
16.7
79.7
74.7
57.8
43.7
48.6
112
65.6
112
54.9

89.2
105
103
 a Single determination: The sample size was 5 g; the solvent volume was 30 mL. The extract
  was concentrated 30-fold prior to GC/MS analysis.
                                    65

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TABLE A-22. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
            THE ERA SOIL (LOT NO. 321) WITH HEXANE-ACETONE (1:1) USING
            MAE (TEMPERATURE 80°C; PRESSURE 22 PSI)a
Compound name
"Native" compounds
Naphthalene
Dibenzofuran
Pentachlorophenol
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo(b)fluoranthene
1 ,2-Dichlorobenzene
2-Methylphenol
N-Nitroso-di-n-propylamine
Nitrobenzene
2,4-Dichlorophenol
1 ,2,4-Trichlorobenzene
2,4,6-Trichlorophenol
2,4-Dinitrotoluene
Carbazole
Di-n-butyl-phthalate
Bis(2-ethylhexyl)phthaJate
Spikes
Anthracene-d10
Fluor anthene-d,0
Benzo(a)anthracene-d,2
Certified value
(mg/kg)

2.96
1.70
6.68
3.52
8.09
3.78
4.47
2.03
10.0
5.46
5.01
7.87
5.52
9.36
2.82
4.86
5.00
3.43
7.62

5.00
5.00
5.00
Percent recovery
5 min

53.9
71.4
47.6
49.3
70.2
55.6
66.0
50.0
31.3
20.7
78.0
79.4
78.7
53.0
71.1
123
87.6
113
59.7

86.2
95.2
98.2
10 min

56.8
74.1
45.7
48.9
72.3
55.6
69.3
51.0
33.8
21.1
81.9
83.7
80.9
54.6
70.8
122
95.3
117
62.2

82.3
91.3
91.6
20 min

64.9
80.7
56.8
54.5
83.5
66.7
83.7
62.1
32.4
23.2
84.3
84.3
79.6
55.7
82.4
140
107
141
73.2

84.4
97.1
97.7
8 Single determination.  The sample size was 5 g; the solvent volume was 30 mL. The extract
  was concentrated 30-fold prior to GC/MS analysis.
                                   66

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TABLE A-23. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
            THE ERA SOIL (LOT NO. 321) WITH HEXANE-ACETONE (1:1)  USING
            MAE (TEMPERATURE 115°C; PRESSURE 72 PSI)a
                          Certified value
                                                  Percent recovery
Compound name
"Native" compounds
Naphthalene
Dibenzofuran
Pentachlorophenol
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo(b)fluoranthene
1 ,2-Dichlorobenzene
2-Methylphenol
N-Nitroso-di-n-propylamine
Nitrobenzene
2,4-Dichlorophenol
1 ,2,4-Trichlorobenzene
2,4,6-Trichlorophenol
2,4-Dinitrotoluene
Carbazole
Di-n-butyl-phthalate
Bis(2-ethylhexyl)phthalate
Spikes
Anthracene-d10
Fluoranthene^d10
Benzo(a)anthracene-d , 2
(mg/kg)

2.96
1.70
6.68
3.52
8.09
3.78
4.47
2.03
10.0
5.46
5.01
7.87
5.52
9.36
2.82
4.86
5.00
3.43
7.62

5.00
5.00
5.00
5 mm

71.4
91.6
52.5
64.5
102
81.2
106
74.7
37.6
25.4
98.7
104
112
67.0
94.8
143
136
166
92.4

83.9
92.6
98.2
10 mm

105
82.2
67.5
61.3
89.3
78.8
87.2
68.9
32.7
17.9
80.7
82.6
87.1
55.7
90.9
142
113
125
79.1

87.9
98.0
96.8
20 min

113
84.4
76.6
64.8
96.6
79.4
100
73.4
33.4
23.8
85.6
88.6
93.2
59.4
100
144
120
145
88.6

88.4
101
96.6
 a Single determination. The sample size was 5 g; the solvent volume was 30 mL. The extract
  was concentrated 30-fold prior to GC/MS analysis.
                                    67

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TABLE A-24. PERCENT RECOVERIES OF "NATIVE" AND SPIKED COMPOUNDS FROM
            THE ERA SOIL (LOT NO. 321) WITH HEXANE-ACETONE (1:1) USING
            MAE (TEMPERATURE 14S°C; PRESSURE 150 PSI)a
                         Certified value
                                                 Percent recovery
Compound name
"Native" compounds
Naphthalene
Dibenzofuran
Pentachlorophenol
Anthracene
Fluoranthene -
Pyrene
Chrysene
Benzo(b)fluoranthene
1 ,2-Dichlorobenzene
2-Methylphenol
N-Nitroso-di-n-propylamine
Nitrobenzene
2,4-Dichlorophenol
1 ,2,4-Trichlorobenzene
2,4,6-TrichJorophenol
2,4-Dinitrotoluene
Carbazole
Di-n-butyl-phthalate
Bis(2-ethylhexyl)phthalate
Spikes
Anthracene-d10
Fluoranthene-d10
Benzo(a)anthracene-d 12
(mg/kg)

2.96
1.70
6.68
3.52
8.09
3.78
4.47
2.03
10.0
5.46
5.01
7.87
5.52
9.36
2.82
4.86
5.00
3.43
7.62

5.00
5.00
5.00
5 mm

160
83.6
76.8
69.5
91.1
78.3
89.7
74.8
29.6
24.5
85.9
96.3
96.4
54.1
109
140
125
134
85.7

96.0
104
99.6
10 mm

69.3
92.7
83.6
78.9
102
92.1
104
80.9
32.3
28.0
85.7
98.2
103
61.9
129
159
142
146
89.8

93.8
100
101
20 mm

66.8
81.3
76.0
63.6
89.4
79.7
84.3
68.8
27.6
20.6
74.9
83.4
85.7
52.5
91.1
125
118
130
76.7

85.7
93.1
92.2
a Cinrrla Hotorminot inn Th» eomnlo C'ITO u/ac S o- th(> cnlvpnt vnliimp. was ^0 ml. The extract
  was concentrated 30-fold prior to GC/MS analysis.
                                   68

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