-------
10.3.5
standard (Section 6.14) to 2.0 mL with
acetone. Spike 1.0 mL of the diluted
precision and recovery standard into .the
remaining reagent' water aliquot. This
aliquot will serve as the PAR (Section
14.5).' ' '
Assemble a Buchner funnel on top of a
clean 1 L filtration flask. Apply a
vacuum to the flask, and pour the entire
contents of the sample bottle through a
glass fiber filter (Section 5.5.4) in the
Buchner funnel, swirling the sample
remaining in the bottle to suspend any
particulates.
Rinse the sample bottle twice with 5 mL of
reagent water to transfer any remaining
particulates onto the filter.
Rinse the any particulates off the sides
of the Buchner funnel with small quanti-
ties of reagent water.
Weigh the empty sample bottle on a top-
loading balance to ±1 g. Determine the
weight of the sample by difference. Oo
riot discard the bottle at this point.
10.3.9 Extract the filtrates using the procedures
in Section 11.1.1.
10.3.10 Extract the particulates using the proce-
dures in Section 11.1.2.
10.4 Preparation of samples containing greater
than one percent solids
10.4.1 Weigh a well-mixed aliquot of each sample
(of the same matrix type) sufficient to
provide 10 g of dry solids (based on the
solids determination in 10.1.3) into a
clean beaker or glass jar.
10.4.2 Spike 1.0 mL of the diluted labeled
compound spiking solution (Section 10.3.2)
into the sample aliquot(s).
10.3.6
10.3.7
10.3.8
10.4.3
10.4.4
i
For each sample or sample set (to a
maximum of 20 samples) ' to be extracted
during the same 12-hour shift, weigh two
10 g aliquots of the appropriate reference
matrix (Section 6.6) into clean beakers or
glass jars.
Spike 1.0 mL of the diluted labeled
compound spiking solution into one
reference matrix aliquot. This aliquot
will serve as the blank. Spike 1.0 mL-of
the diluted precision and recovery
standard (Section 10.3.4) into the
remaining reference matrix aliquot. This
aliquot will serve as the PAR (Section
14.5).
10.4.5 Stir or tumble and equilibrate the
aliquots for 1-2 hours.
10.4.6 Extract the aliquots using the procedures
in Section 11.
10.5 Multiphase samples
10.5.1 Pressure filter the sample, blank, and PAR
aliquots through Whatman GF/0 glass fiber,
filter paper. If necessary, centrifuge
these aliquots for 30 minutes at greater
than 5000 rpm prior to filtration.
10.5.2 Discard any aqueous phase (if present).
Remove any non-aqueous liquid (if present)
and reserve for recombination with the
extract of the solid phase (Section
11.1.2.5'). Prepare the filter papers of
the sample and QC aliquots for, particle
size reduction and blending (Section
10.6).
10.6 Sample grinding, homogenization, or blend-
ing .. samples with particle sizes greater
than 1 mm (as determined by Section
10.2.2) are subjected to grinding, homo-
genization, " or blending. The method of
reducing particle size to less than .1 mm
is matrix dependent. In general, .hard
particles can be reduced by grinding with
a mortar and pestle. Softer particles can
be reduced by grinding in a Wiley mill or
meat .grinder, by homogenization, or by
blending.
10.6.1 Each size reducing preparation procedure
on each matrix shall be verified by run-
ning the tests in Section 8.2 before the
procedure is employed routinely.
V
10.6.2 The grinding, homogenization, or blending
procedures shall be carried out in a glove
box or fume hood to prevent particles from
contaminating the work environment.
10.6.3 Grinding -- Tissue samples, certain papers
and pulps, slurries, and amorphous solids
can be ground in a Wiley mill or heavy
duty meat grinder. In some cases, reduc-
ing the temperature of the sample to
freezing or to dry ice or liquid nitrogen
temperatures can aid in the grinding
process. Grind the sample aliquots from
Section 10.4.5 or 10.5.2 in a clean
21
-------
grinder. Do not allow the sample tempera-
ture to exceed 50 "C. Grind the blank and
reference matrix aliquots using a clean
grinder.
10.6.4 Homogeniza'tion or blending -- Particles
=. that are not ground effectively, or
particles greater than 1 mm in size after
grinding, can ften be reduced in size by
•high speed himogenization or blending.
Homogenize and/or blend the sample, blank,
and PAR aliqMots from Section 10.4.5,
10.5.2, or 10.£.3.
10.6.5 Extract the aliquots using the procedures
in Section 11.
11 EXTRACTION AND CONCENTRATION
11.1 . Extraction of filtrates -- extract the
" -aqueous samples, blanks, and PAR aliquots
according to the following procedures.
11.1.1 Pour the filtered aqueous sample from the
filtration flask into a 2-L separatory
funnel. Rinse, the flask twice with 5 mL
of reagent water and add these rinses to
the separatory funnel. Add 60 mL methy-
lene chloride to the sample bottle
(Section 10.3.8), seal,and shake 60
seconds to rinse the inner surface.
11.1.2 Transfer the solvent to the separatory
funnel and extract the sample by shaking
the funnel for 2 minutes with periodic
venting. Allow the organic layer to
separate from the water phase for a
minimum of 10 minutes. If the emulsion
interface between layers is more than one-
third the volume of the solvent layer,
employ mechanical techniques to complete
the phase separation (e.g., a glass stir-
ring rod). Drain the methylene chloride
extract into a solvent-rinsed glass funnel
approximately one-half full ' of clean
sodium sulfate. Set up the glass funnel
so that it will drain directly into a
solvent-rinsed StlO-mL K-D concentrator
fitted with a 10 mL concentrator tube.
NOTE: Experience with aqueous samples
high in dissolved organic materials (e.g.,
paper mill effluents) has shown that acid-
ification of the sample prior to
extraction may reduce the formation of
emulsions. Paper industry methods suggest
that the addition of up to 400 mL of
ethanol to a 1 L effluent sample may also
reduce emulsion formation. However,
studies by the Agency to date suggest that
the effect may be a result of the dilution"
11.1.4
of the sample, and that the addition of
reagent water may serve the same function.
Mechanical techniques may still be neces-
sary to complete the phase separation. If
either of these techniques is utilized,
the laboratory must perform the startup
tests described in Section 8.2 using the
same techniques.
11.1.3 Extract the water sample two more times
using 60 mL of fresh methylene chloride
each time. Drain each extract through the
funnel containing the sodium sulfate into
the <-D concentrator. After the third
extraction, rinse the separatory funnel
with at least 20 mL of fresh methylene
chloride, and drain this rinse through the
sodium eulfate into the concentrator.
Repeat this rinse at least twice.
The extract of the filtrate must be
concentrated before it is combined with
the extract of the particulates for
further cleanup. Add one or two clean
boiling chips to the receiver and attach a
three-ball macro Snyder column. Prerwet
the column by adding approximately 1 mL of
hexane through the top,. Place the K-D
apparatus in a hot water bath so that the
entire lower rounded surface of the flask
is bathed with steam.
11.1.5 Adjust the vertical' position of the
apparatus and the water temperature as,
required to complete th« concentration in
15-20 .minutes. At the proper rate of
distillation, the balls of the|column will
actively chatter but the chambers will not
flood.
11.1.6 When the liquid has reached ;an apparent
volume of 1 mL, remove the K-D apparatus
from the bath and allow the solvent to
drain and cool for at least 10 minutes.
Remove the Snyder column and rinse the
flask and its lower joint into the concen-
trator tube with 1-2 mL of hexane. A 5 mL
syringe is recommended for this operation.
11.1.7 The concentrated extracts of the filtrate
and the particulates are combined using
the procedures in Section 11.2.13.
11.2 Soxhlet/Dean-Stark extraction lof solids --
Extract the solid samples, particulates,
blanks, and PAR aliquots using the follow-
ing procedure.
11.2.1 Charge a clean extraction thimble with 5.0
g of 100/200 mesh silic
-------
and 100 g of quartz sand (Section 6.3.2).
NOTE: Do not disturb the silica layer
throughout the extraction process.
11.2.2 Place the thimble in a clean extractor.
Place' 30-40 ml of toluene in the receiver
and 200-250 mL of toluene in the flask.
11.2.3 Pre-extract the glassware by heating the
flask until the toluene is boiling. When
properly adjusted, 1-2 drops of toluene
per second will fall from the condenser
tip into the receiver. Extract the
apparatus for three hours minimum.
11.2.4 After pre-extraction, cool and disassemble
the apparatus. Rinse the thimble with
toluene and allow to air dry.
11.2.5 Load the wet sample from Sections 10.4.6,
10.5.2, 10.6.3, or 10.6.4, and any non-
aqueous liquid from Section 10.5.2 into
the thimble and manually mix into the sand
layer with a clean metal spatula carefully
breaking up any large lumps of sample. If
the material to be extracted is the
particulate matter from the filtration of
an aqueous sample, add the filter paper to
• the thimble also.
11.2.6 Reassemble the pre-extracted SOS apparatus
and add a fresh charge of toluene to the
receiver and reflux flask.
11.2.7 Apply power to the heating mantle to begin
ref lu'xing. Adjust the reflux rate to
match the rate of percolation through the
sand and silica beds until water removal
lessens the restriction to toluene flow.
Check the apparatus for foaming frequently
during the first 2 hours of extraction.
If foaming occurs, reduce the reflux rate
until foaming subsides.
11.2.8 Drain the water from the receiver at 1-2
hours and 8-9 hours, or sooner if the
'receiver fills with water. Reflux the
sample for a total of 16-«24 hours. Cool
and disassemble the apparatus. Record the
total volume of water collected.
11.2.9 Remove the distilling flask. Drain the
water from the Dean Stark receiver and add
'any toluene in the receiver to the extract
in the flask.
11.2.10 For solid samples, the extract must be
concentrated to approximately 10 mL prior
to back extraction. - For the particulates
filtered from an aqueous sample, the
extract must be concentrated prior to
combining with the extract of the
filtrate. Therefore, add one or two clean
boiling chips to the round bottom flask
and attach a three-ball macro Snyder
column. Pre-wet the column by adding
approximately 1 mL of toluene through the
top. Place the round bottom flask in a
heating mantle and apply heat as required
to complete the concentration in 15-20
minutes. At the proper rate of distilla-
tion, the balls of the column will
actively chatter but the chambers will not
flood. ''
11.2.11 When the liquid has reached an apparent
volume of 10 mL, remove the round bottom
flask from the heating mantle and allow
the solvent to drain and cool for at least
10 minutes. Remove the Snyder column.
11.2.12 If the ex'tract is from a solid sample, not
the particulates from an aqueous sample,
transfer the concentrated extract to a 250
mL separatory funnel. Rinse the flask
with toluene and add the rinse to the
separatory funnel. Proceed with back
extraction per Section 11.3.
11.2.13 If the extract is from the particulates
from an aqueous sample, it must be com-
bined with the concentrated extract of the
filtrate (Section 11.1.7) prior to back
extraction. Assemble the glass funnel
filled approximately one-half full with
sodium sulfate from Section 11.1.2 such
that the funnel will .drain into the K-0
concentrator from Section 11.1.7 contain-
ing the concentrated methylene chloride
extract of the filtrate. Pour the concen-
trated toluene extract of the particulates
through the sodium sulfate into the K-D
concentrator. Rinse the round-bottom
flask with three 15-20 mL volumes of
hexane, and pour each rinse through the
sodium sulfate into the <-D concentrator.
Add one or two fresh boiling chips to the
receiver and attach the three-ball macro
Snyder column to the K-D concentrator.
Pre-wet the column by adding approximately
1 mL of hexane to the top of the column.
Concentrate the cjpmbined extract to
approximately 10 ml
-------
and lower joint with three 5 ml volumes of
hexane, and add each rinse to the separa-
tory funnel. Proceed with back extraction
pep Section 11.3.
11.3 Back extraction with base and acid
14.3.1
11.3.2
Spike 1.0 mL of the cleanup standard
(Section 6.11) into the separatory funnels
containing the sample and QC extracts
(Section 11.2.12 or 11.2.13).
Partition the extract against 50 mL of
potassium hydroxide solution (Section
6.1.1). Shake for 2 minutes with periodic
venting into a hood. Remove and discard
the aqueous layer. Repeat the base wash-
ing until no color is visible in the
aqueous layer, to a maximum of four wash-
, ings. Minimize contact time between the
^extract and the base to prevent degrada-
tion of the PCOOs and PCDFs. Stronger
potassium hydroxide solutions may be
employed for back extraction, provided
that the laboratory meets the specifica-
tions for labeled compound recovery and
demonstrates acceptable performance using
the procedures in Section 8.2.
11.3.3 Partition the extract against 50 mL of
sodi.um chloride solution (Section 6.1.3)
in the same way as with base. Discard the
aqueous layer.
11.3.4 Partition the extract against 50 mL of
sulfuric acid (Section 6.1.2) in the same
way as with base. Repeat the acid washing
until no color is visible in the aqueous
layer, to a maximum of four washings.
11.3.5 Repeat the partitioning against sodium
chloride solution and discard the aqueous
layer.
11.3.6 Pour each extract through a drying column
containing 7 to 10 cm of anhydrous sodium
sulfate. Rinse the separatory funnel with
30-50 mL of toluene and pour through the
drying column. Collect each extract in a
500 mL round bottom flask. Concentrate
and clean up the samples and QC aliquots
per Sections 11.4 and 12.
11.4 Macro-concentration -- Concentrate the
extracts in separate 100-mL round bottom
flasks on a rotary evaporator.
11.4.1 Assemole the rotary evaporator according
to manufacturer's instructions, and warm
the water bath to 45 °C. On a daily
basis, preclean the rotary evaporator by
concentrating 100 mL of clean extraction
solvent through the system. Archive both
the concentrated solvent and the solvent
in the catch flask for contamination check
if necessary. Between samples, three 2-3
mL aliquots of toluene should be rinsed
down the feed tube into a waste beaker.
11.4.2 Attach the round bottom flask containing
the sample extract to the rotary evapora-
tor. Slowly apply vacuum to the system,
and begin rotating the sample flask.
11.4.3 Lower the flask into the water bath and
adjust the speed of rotation and the
temperature as required to complete the
concentration in 15-20 minutes. At the
proper rate of concentration, the flow of
• solvent into the receiving flask will be
steady, but no bumping or visible boiling
of the extract will occur. NdTE: If the
rate of concentration is> too fast, analyte
loss may r-ccur.
11.4.4 When the liquid in the concentration flask
has reached an apparent volume of 2 mL,
remove the flask from the water bath and
stop the rotation. Slowly and carefully,
admit air into the system. Be sure not to
open the valve so quickly that the sample
is blown out of the flask. Rinse the feed
' tube with approximately 2 mL of hexane.
11.4.5 Transfer the extract to a vial using three
2-3 mL rinses of hexane. Proceed with
micro-concentration and solvent exchange.
11.5 Micro-conc°ntration and solvent exchange
11.5.1 Toluene extracts to be subjected to GPC or
HPLC cleanup are exchanged into methylene
chloride. Extracts that are to be cleaned
up using silica gel, alumina!, and/or AX-
21/Celite are exchanged into hexane.
11.5.2 Transfer the vial containing the sample
extract to a nitrogen evaporation device.
Adjust the flow of nitrogen so that the
surface of the solvent is just visibly
disturbed. MOTE: A large vortex in the
solvent may cause analyte loss.
11.5.3 Lower the vial into a 45 °C water bath and
continue concentrating.
11.5.4 When the volume of the liquid is approxi-
mately 100 uL, add Z-3 mL of the desired
solvent (methylene chloride or hexane) and
r
c
r
r
24
-------
continue concentration to approximately
100 uL. Repeat the addition of solvent
and concentrate once more.
11.5.5 If the extract is to be cleaned up by GPC
or HPLC, adjust the volume of the extract
to 5.0 ml with methylene chloride.
Proceed with GPC cleanup (Section 12.2).
11.5.6 If the extract is to be cleaned up by
column chromatography (alumina, silica
gel, AX-21/Celite), bring the final volume
to 1.0 mL with hexane. Proceed with
column cleanups (Sections 12.3-12.5).
11.5.7 For extracts to be concentrated for
injection into the GCHS -- add 10 uL of
nonane to the vial. Evaporate the solvent
to the level of the nonane. Evaporate the
hexane in the vial to the level of the
nonane.
11.5.8: Seal the vial and label with the sample
number. Store in the dark at room temper-
ature until ready for GCHS analysis.
12 EXTRACT CLEANUP
12.1 Cleanup may not be necessary for
relatively clean samples (e.g., treated
effluents, groundwater, drinking water).
If particular circumstances require the
use of a cleanup procedure, the analyst
may use any or all of the procedures below.
I or any other appropriate procedure.
Before using a cleanup procedure, the
analyst must demonstrate that the require-
ments of Section 8.2 can be met using the
cleanup procedure.
12.1.1
Gel permeation chromatography (Section
12.2) removes many high molecular weight
interferences that cause GC column
performance to degrade. It may be used
for all soil and sediment extracts and may
be used for water extracts that are
expected to contain high molecular weight
organic compounds (e.g., polymeric
materials, humic acids).
12.1.2 . Acid, neutral, and basic silica gel, and
alumina (Sections 12.3 and 12.4) are used
to remove nonpolar and polar
interferences.
12.1.3 AX-21/Celite (Section 12.5) is used to
remove nonpolar interferences.
12.1.4 HPLC (Section 12.6) is used to provide
specificity for the 2,3,7,8-substituted
and other PCDO and PCDF isomers.
12.2 Gel permeation chromatography (GPC)
12.2.1 Column packing
12.2.1.1
Place 70-75 g of SX-3 Bio-beads in a 400-
500 mL beaker.
Cover the beads with methylene chloride
and allow to swell overnight (12 hours
minimum).
Transfer the swelled beads to the column
and pump solvent through the column, from
bottom to top, at 4.5-5.5 mL/min prior to
connecting the column to the detector.
•
After purging the column with solvent for
1-2 hours, adjust the column head pressure
to 7-10 psig and purge for 4-5 hours to
remove air. Maintain a head pressure of
7-10 psig. Connect the column to the
detector.
12.2.2 Column calibration
12.2.2.1
12.2.1.2
12.2.1.3
12.2.1.4
12.2.2.2
12.2.2.3
Load 5 mL of the calibration solution
(Section 6.4) into the sample loop.
Inject the calibration solution and record
the signal from the detector. The elution
pattern will be corn oil, tjis(2-ethyl
hexyl) phthalate, pentachlorophenol,
perylene, and sulfur.
Set the "dump time" to allow >85 percent
removal of the corn oil and >85 percent
collection of the phthalate.
12.2.2.4 ' Set the "collect time" to the peak minimum
between perylene and sulfur.
12.2.2.5 Verify the 'calibration with thevcalibra-
tion solution after every 20 extracts.
Calibration is verified if the recovery of
the pentachlorophenol is greater than 85
percent. If calibration is not verified,
the system shall be recalibrated using the
calibration solution, and the previous 20
samples shall be re-extracted and cleaned
up using the calibrated GPC system.
12.2.3 Extract cleanup -- GPC requires that the
column not be overloaded. The column
specified in this method is designed to
handle a maximum of 0.5 g of high
molecular weight material in a 5 mL •
25
-------
extract. If the extract is known or
expected to contain more than 0.5 g, the
extract is split into aliquots for GPC and
the aliquots are combined after elution
from the column. The residue content of
the extract may be obtained
gravirnetrically by evaporating the solvent
from a 50 uL aliquot:
12.2.3.1 Filter the extract
filter holder to
Load the 5.0 mL extract onto the column.
or load through the
remove particulates.
12.2.3.2 Elute the extract using the calibration
data determined in Section 12.2.2.
Collect the eluate in a clean 400-500 mL
beaker.
12.2.3.3
12.2.3.4
12.2.3.5
Rinse the sample loading tube thoroughly
with methylene chloride between extracts
%to prepare for the next sample.
If a particularly dirty extract is
encountered, a 5.0 mL methylene chloride
blank shall be run through the system to
check for carry-over.
Concentrate the eluate per Section 11.2.1,
11.2.2, and 11.3.1 or 11.3.2 for further
cleanup or for injection into the GCHS.
12.3 Silica gel cleanup
12.3.1 Place a glass wool plug in a 15 mm i.d.
ehromatography column. Pack the column in
the following order (bottom to top): 1 g
silica gel (Section 6.5.1.1), four g basic
silica gel (Section 6.5.1.3), 1 g silica
gel, 8 g acid silica gel (Section
6.5.1.2), 2 g silica gel. Tap the column
to settle the adsorbents.
12.3.2 Pre-rinse the column with 50-100 mL of
hexane. Close the stopcock when the
hexane is within 1 mm of 'the sodium
sulfate. Discard the eluate. Check the
column for channeling. If channeling is
present, discard the column and prepare
another.
12.3.3 Apply the concentrated extract to the
column. Open the stopcock until the
extract is within 1 mm of the sodium
sulfate.
12.3.4 Rinse the receiver twice with 1 mL
portions of hexane and apply separately to
the column. Elute the PCDDs/PCDFs with
100 mL hexane and collect the eluate.
12.3.5 Concentrate the eluate per Section 11.4 or
11.5 for further cleanup or for injection
into the HPLC or GCHS. i
12.3.6 For extracts of samples known to contain
large quantities of other organic
compounds (such as paper mill effluents)
it may be advisable to increase the
capacity of the silica gel column. This
may be accomplished by increasing the
strengths of the acid and basic silica
gels. The acid silica gel (Section
6.5.1.2) may be increased in .strength to
as much as 44% w/w (7.9 g sulfuric acid
added to 10 g silica gel). The basic
silica gel (Section 6.5.1.3) may be
increased in strength to as much as 33%
w/w (50.mL 1H HaOH added to 100 g silica
gel). NOTE: The use of stronger acid
silica gel (44% w/w) may lead to charring
of organic compounds in some extracts.
The charred material may retain some of
the analytes and lead to lower recoveries
of PCDDs/PCOFs. Increasing the strengths
of the acid and basic silica gel may also
require different volumes of hexane than
those specified above, to elute the
analytes off the column. Therefore, the
performance of the method after such
modifications must be verified by the
procedures in Section' 8.2.
12.4 Alumina cleanup
12.4.1 Place a glass wool plug in a 15 mm i.d.
ehromatography column.
12.4.2 If using acid alumina, pack the column by
adding 6 g acid alumina (Section 6.5.2.1).
If using basic alumina, substitute 6 g
basic alumina (Section 6.5.2.2). Tap the
column to settle the adsorbents.
12.4.3 Pre-rinse the column with 50-100 mL of
hexane. Close the stopcock when the
hexane is within 1 mm of the alumina.
12.4.4 Discard the eluate. Check the column for
channeling. If channeling is present,
discard the column and prepare another.
12.4.5 Apply the concentrated extract- to the
column. Open the stopcock until the
extract is within 1 mm of the ^alumina.
r
12.4.6
Rinse the receiver twice .with 1 mL
portions of hexane and apply separately to
the column. Elute the interfering
compounds with 100 mL hexane and discard
the eluate.
i
t
i
r
E
C
r
26
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12.4.7 The choice of eluting solvents will depend
', on the choice of alumina (acid or basic)
made in Section 12.4.2.
12.4.7.1 If using acid alumina, elute the PCODs and
PCOFs from the column with 20 mL methylene
chlorideihexane (20:80 v/v). Collect the
eluate.
12.4.7.2 If using basic alumina, elute the PCOOs
and PCOFs from the column uith 20 mL
methylene chloride:hexane (50:50 v/v).
Collect the eluate.
12.4.8 Concentrate the eluate per Section 11.4 or
11.5 for further cleanup or for injection
into the HPLC or GCMS.
12.5 AX-21/Celite
12.5.1 Cut both ends from a 10 ml disposable
serological pi pet to produce a 10 cm
column. Fire polish both ends and flare
both ends if desired. Insert a glass wool
plug at one end, then pack the column uith
1 g of the! activated AX-21/Celite to form
a 2 cm long adsorbent bed. Insert a glass
; wool plug on top of the bed to hold the
adsorbent in place.
12.5.2 Pre-rinse the column with five mL of
toluene followed by 2 mL methylene
chloride:methanol:toluene (15:4:1 v/v), 1
mL methylene chloride:cyclohexane (1:1
v/v), and five mL hexane. If the flow
rate of eluate exceeds 0.5 mL per min,
discard the-column.
12.5.3 When the solvent is within 1 rim of the
column packing, apply the sample ex.tract
, to the column. Rinse the sample container
twice with 1 roL portions of hexane and
apply separately to the column. Apply 2
mL of hexane to complete the transfer.
12.5.4 Elute the interfering compounds with 2 mL
of hexane, 2 mL of methylene
chloride:cyclohexane (1:1 v/v), and 2 mL
of methylene chloride:methanol:toluene
(15:4:1 v/v). Discard the eluate.
12.5.5 Invert the column and elute the PCOOs and
PCOFs with 20 mL of toluene. If carbon
particles t.are present in the eluate,
filter through glass fiber filter paper.
12.5.6 Concentrate the eluate per Section 11.4 or
11.5 for further cleanup or for injection
into the HPLC or GCHS.
12.6 HPLC (Reference 6)
12i6.1 Column calibration
12.6.1.1 Prepare a calibration standard containing
the 2,3,7,8- isomers and/or other isomers
of interest at a concentration of approxi-
mately 500 pg/uL in methylene chloride.
12.6.1.2 Inject 30 uL of the calibration solution
into the HPLC and record the signal from
the detector. Collect the eluant for re^
•use. The elution order will be the tetra-
through octa-isomers.
12.6.1.3 Establish the collect time for the tetra-
isomers and for the other isomers of
interest. Following calibration, flush
the injection system with copious
quantities of methylene' chloride, includ-
ing a minimum of five 50-uL injections
while the detector is monitored, to ensure
that residual PCDOs and PCOFs are removed
from the system.
12.6.1.4 Verify the calibration with the calibra-
tion solution after every 20 extracts.
Calibration is verified if the recovery of
the PCDOs and PCOFs from the calibration
standard (Section 12.6.1.1) is 75-125
percent compared to the calibration
(Section 12.6.1.2). If calibration is not
verified, the system shall be recalibrated
using the calibration solution^ and the
previous 20 samples shall be re-extracted
and cleaned up using the calibrated
system.
12.6.2 Extract cleanup -- HPLC requires that the
coluwi not be overloaded. The column
specified in this method is designed to
handle a maximum of 30 uL of extract. If
the extract cannot be concentrated to less
than 30 uL, it is split into fractions and
the fractions are combined after elution
from the column. ••
12.6.2.1 Rinse the sides of the vial twice with 30
uL of methylene chloride and reduce to 30
uL with the blowdown apparatus.
12.6.2.2 Inject the 30 uL extract into the HPLC.
12.6.2.3 Elute the extract using the calibration
data determined in 12.6.1. Collect the
fraction(s) in a clean 20 mL concentrator
tube containing 5 rnL of hexaneracetone
(1:1 v/v).
27
-------
12.6.2.4 If an extract containing greater than 100
ng/rnL of total PCDO or PCDF is encoun-
tered, a 30 uL methylene chloride blank
shall be run through the system to check
for carry-over.
12.6.2.5 Concentrate the eluate per Section 11.5
for injection into the GCHS.
13 HRGC/HRHS ANALYSIS
13.1 Establish the operating conditions given
in Section 7.1.
13.2 Add 10 uL of the internal standard solu-
tion (Section 6.12) to the sample extract
immediately prior to injection to minimize
the possibility of loss by evaporation,
adsorption, or reaction. If an extract is
to be reanalyzed and evaporation has
% % occurred, do not add more instrument
internal standard solution. Rather, bring
the extract back to its previous volume
(e.g., 19 uL> with pure nonane only.
13.3 Inject 1.0 uU of the concentrated extract-
containing the internal standard solution,
using on-colutn or splitless injection.
Start the GC column initial isothermal
hold upon injection. Start HS data
collection after the solvent peak elutes.
Stop data collection after the octachloro-
dioxin and furan have eluted.. Return the
column to the' initial temperature for
analysis of the next extract or standard.
14 SYSTEM AND LABORATORY PERFORMANCE
14.1 -At the beginning of each 12-hour shift
during which analyses are performed, GCHS
system performance and calibration are
verified for all unlabeled and labeled
compounds. For these tests, analysis of
the CS3 calibration verification (VER1
standard (Section 6.13 and Table 4) and
the isomer specificity test standards
(Sections 6.16 and Table 5) shall be used
to verify all performance criteria.
Adjustment and/or recalibration (per
Section 7) shall be performed until all
performance criteria are met. Only after
. all performance criteria are met may
samples, blanks, and precision and
recovery standards be analyzed.
14.2
HS resolution -- A static resolving power
of at least 10,000 (10 percent valley
definition) must be demonstrated at appro-
priate masses before any analysis is
performed. Static resolving power checks
14.3.1
14.3.2
14.3.3
14.3.4
14.3.5
must be performed at the beginning and at
the end of each 12-hour shift according to
procedures in Section 7.1.2. Corrective
actions must be implemented whenever the
resolving power does not meet the
requirement.
r
14.3 Calibration verification
Inject the VER standard
procedure in Section 13,.
using the
The m/z abundance ratios for all PCODs and
PCDFs shall be within t:he limits in Table
3A; otherwise, the mass spectrometer shall
be adjusted until the m/z abundance ratios
fall within the limits specified, and the
verification test (Section 14.3.1)
repeated. If the adjustment alters the
resolution of the mass spectrometeri reso-
lution shall be verified (Section 7.1.2)
prior to repeat of the verification test.
The peaks representing each unlabeled and
labeled compound in the VER standard must
be present with a S/M of at least 10;
otherwise, the mass spectrometer shall be
adjusted and the verification test
(Section 14.3.1) repeated.
Compute the concentration of each
unlabeled compound by isotope dilution
(Section 7.5) for those compounds that
have labeled analogs (Table 1). Compute
the concentration of the labeled compounds
by the .internal standard method. These
concentrations are computed based on the
averaged relative resjxsnse 'and averaged
response factor from the calibration data
in Section 7.
For each compound, compare the concentra-
tion with the calibration ; verification
limit in Table 7. If all compounds meet
the acceptance criteria, calibration has
been verified. If, however, any compound
fails, the measurement system is not
performing properly for that compound. In
this event, prepare a fresh calibration
standard or correct the problem causing
the failure and repeat the resolution
(Section 14.2) ?nd verification (Section
14.3.1) tests, or recalibrate (Section 7).
14.4 Retention times and GC resolution
14.4.1 Retention times
r
r
r
28
r
r
r
r
r
r
-------
14.4.1.1 Absolute -- The absolute retention times
of the 13C12-1,2,3,4-TCDO and C,,,-
1,2,3,7,8.9-HxCBD GCHS internal standards
shall be within ±15 seconds of the
retention times obtained during calibra-
tion (Section 7.2.4).
14.4.1.2 Relative -- The relative retention times
of unlabeled and labeled PCOOs and PCDFs
shall be within the limits given in Table
2- ..e
14.4.2 i GC resolution ^
14.4.2.1 \ Inject the isomer specificity standards
(Section 6.16) on their respective
' columns.
14.4.2.2 The valley height between 2,3,7,8-TCDD and
the other tetra- dioxin isomers at m/z
319.8965, and between 2,3,7,8-TCOF and the
other tetra- furan isowers at m/z 303.9016
shall not exceed 25 percent on their
respective columns (Figure 3).
14.4.3 If the absolute retention time of any
compound is not within the limits
specified or the 2,3,7,8- isomers are not
resolved, the GC is not performing
properly. In this event, adjust the GC
, and repeat the verification test (Section
14.3.1) or recalibrate (Section 7).
14.5 Ongoing precision and accuracy
14.5.1 Analyze the extract 'of the diluted
precision and recovery standard (PAR)
(Section 10.3.4 or 10.4.4) prior to
analysis of samples from the same set.
14.5.2 Compute the concentration of each PCDO and
PCDF by isotope dilution for those
compounds that have labeled analogs
(Section 7.5). Compute the concentration
: of each labeled compound by the internal
standard method.
14.5.3 For each unlabeled and labeled compound,
compare the concentration with the limits
for ongoing accuracy in Table 7. If all
compounds meet the acceptance criteria,
system performance is acceptable and
analysis of blanks and samples may
proceed. ,, If, however, any individual
concentration falls outside of the range
given, the extraction/concentration
processes are not being performed properly
• for that compound. In this event, correct
the problem, re-extract the sample set
(Section 10) and repeat the ongoing
precision and recovery test (Section
14.5). The concentration limits in Table
7 for labeled compounds are based on the
requirement that the recovery of each
labeled compound be in the range of 25-
150X.
14.5.4 Add results which pass the specifications
in Section 14.5.3 to initial and previous
ongoing data for each compound in each
matrix. Update QC charts to form a ,
graphic representation of continued
laboratory performance. Develop a state-
ment of laboratory accuracy for each PCDO
and PCOF in each matrix type by calculat-
ing the average percent recovery (R) and
the standard deviation of percent recovery
(SR). Express the accuracy as a recovery
interval from R - 2S. to R + 2S-. For
example, if R = 95X and SR * 5X, the
accuracy is 85-105X.
15 QUALITATIVE DETERMINATION
For a gas chromatographic peak to. be
identified as a PCDO or PCDF (either a
unlabeled or a labeled compound), it oust
meet all of the criteria in Sections 15.1-
15.4.
15.1 The signals for the two exact m/z's being
monitored (Table 3) must be present, and
must maximize within * 2 seconds of one
another.
15.2 The signal-to-noise ratio (S/N) of each of
the two exact m/z's must be greater than
or equal to 2.5 for a sample extract, and
greater than or equal to 10 for a calibra-
tion standard (see Sections 7.2.3 and
14.3.3).
15.3 The ratio of the integrated ion currents
of both the exact m/z's monitored must be
within the limits in Table 3A.
15.4 The relative retention time of the peaks
representing a unlabeled 2,3,7,8-
substiiuted PCDO or PCDF must be within
the limits given in Table 2. The
retention time of peaks representing non-
2,3, 7,8-substituted PCOOs or PCDFs must be
within the retention time windows
established in Section 7.3.
15.5 Confirmatory analysis -- Isomer
specificity for all of the 2,3.7,8-substi-
tuted analytes cannot be attained by
analysis on the D8-5 (or equivalent) GC
column alone. .The lack of specificity is'
29
-------
of greatest concern for the unlabeled
2,3,7,8-TCDF. Therefore, any sample in
which 2,3,7,8-TCDF is identified by
analysis on a DB-5 (or equivalent) GC
colum must have a confirmatory analysis
performed on a 08-225, SP-2330, or equiva-
lent GC colum. The operating conditions
in Section 7.1.1 way be adjusted for
analyses on the second GC colum, but the
GCHS must meet the mass resolution and
> calibration specifications in Section 7.
15.6 If any gas ehromatographic peak meets the
identification criteria in Sections 15.1,
15.2, and 15.4, but does not meet the ion
abundance ratio criterion (Section 15.3),
and is not a labeled analog, that sample
must be analyzed on a second GC colum, as
in Section 15.5 above. Interferences co-
, eluting in either of the two m/z's may
•cause the ion abundance ratio to fall out-
side of the limits in Table 3A. If the
ion abundance ratio of the peak fails to
meet the criteria on the second GC colum,
then the peak does not represent a POD or
PCOF. If the 'peak does meet all of the
criteria in Sections 15.1-15.4 on the
second GC colum, then calculate the
concentration of that peak from the
analysis on the second GC colum, accord-
ing to the procedures in Section 16.
15.7 If any gas ehromatographic peak that
represents a labeled analog does not meet
all of the identification criteria in
Sections 15.1-15.4 on the second GC
colum, then the results may not be
reported for regulatory compliance
purposes and a new aliquot of the sample
must be extracted and analyzed.
16 QUAHTITATIVE DETERMINATION
16.1 Isotope dilution -- By adding a known
amount of a labeled compound to every
sample prior to extraction, correction for
recovery of the unlabeled compound can be
made because the unlabeled compound and
its labeled analog exhibit similar effects
upon extraction, concentration, and gas
chronatography. Relative response
-------
16.3
16.4
The concentration of the unlabeled
compound in the solid phase of the sample
is computed using the concentration of the
compound in the extract and the weight of
the solids (Section 10), as follows:
Concentration
in solid (ng/Kg)"
where,
V is the extract volume in mL.
W is the sample weight in Kg.
The concentration of the unlabeled
compound in the aqueous phase of the
sanple is computed using the concentration
of the compound in the extract and the
volune of water extracted (Section 10.3),
as follows:
ex
Vex>
Concentration _ (C
in aqueous phase ~-
(pg/L) Vs
where,
V is the extract volune in mL.
• V is the sample volune in liters.
16.5 If the SICP areas at the quantitation
m/z's for any compound exceed the calibra-
, tion range of the system; a smaller sample
aliquot is extracted.
16.5.1 .For aqueous samples containing one percent
solids or less, dilute 100 mL, 10 mL,
etc., of sample to 1 liter with reagent
water and extract per Section 11.
16.5.2 For samples containing greater than one
percent solids, extract an amount of
sample equal to 1/10, 1/100, etc., of the
amount determined in Section 10.1.3.
Extract per Section 10.4.
16.5.3 If a smaller sample size will not be
representative of the entire sample,
dilute the sample extract by a factor of
10, adjust the concentration of the
instrument internal standard to 100 pg/uL
in the extract, and analyze an aliquot of
this diluted extract by the internal
standard method.
16.6 Results are reported to three significant
figures for the unlabeled and labeled
isomers found in all standards, blanks,
and samples. For aqueous samples, the.
units are pg/L; for samples containing
greater than one' percent solids (soils.
sediments, filter cake, compost), the
units are ng/Kg based on the dry weight of
the sample.
16.6.1 Results for samples which have been
diluted are reported at the least dilute
level at which the areas at the quantita-
tion m/z's are within the calibration
range (Section 16.5).
16.6.2 For unlabeled compounds having a labeled
analog, results are reported at the least
dilute level at which the area at the
quantitation m/z is within the calibration
range (Section 16.5) and the labeled
compound recovery is within the normal
range for the method (Section 17.4).
16.6.3 Additionally, the total concentrations of
all isomers in an individual level of
chlorination (i.e., total TCOD, total
PeCDD, etc.) are reported to three signi-
ficant figures in units of pg/L, for both
dioxins and furans. The total or ng/Kg
concentration in each level of chlorina-
tion is the sun of the concentrations of
all isomers identified in that level,
including any non-2,3,7,8-substituted
isomers.
17 ANALYSIS OF COMPLEX SAMPLES
17.1 Some samples may contain high levels (>10
ng/L; >1000 ng/Kg) of the compounds of
interest, interfering compounds, and/or
polymeric materials. Some extracts will
not concentrate to 10 uL (Section 11);
others may overload the GC column and/or
mass spectrometer.
17.2 Analyze a smaller aliquot of the sample
(Section 16.4) when the extract will not
concentrate to 20 uL after all cleanup
procedures have been exhausted.
17.3 Recovery of labeled compound, spiking
standards -- In most samples, recoveries
of the labeled compound spiking standards
will be similar to those .from reagent
water or from the alternate matrix
(Section 6.6). If recovery is outside of
the 25-150% range, a diluted sample
(Section 16.4) shall be analyzed. If the
recoveries of the labeled compound spiking
standards in the diluted sample are
outside of the limits (per the criteria
above), then the verification standard
(Section 14.3) shall be analyzed and
calibration verified (Section 14.3.4). If
ithe calibration cannot be verified, a new
31
-------
L
calibration oust be performed and the
original sample extract reanalyzed. If
the calibration is verified and the
diluted sample does not meet the limits
for labeled compound recovery, then the
method does not apply to the sample being
analyzed and the result may not be
reported f r regulatory compliance
purposes.
18 METHOD PERFOHANCE
The performance specifications in this
method are based on the analyses of more
than 400 samples, representing matrices
from at least five industrial categories.
These specifications will be updated
periodically as more data are received,
and each time the procedures in the method
" tare revised.
REFERENCES
1 Tondeur, Yves, "Method 8290: Analytical
Procedures and Quality Assurance for
Multimedia Analysis of Polychlorinated
Dibenzo-p-dioxins and Oibenzofurans by
High-Resolution Gas Chromatography/High-
Resolution Hass Spectrometry", USEPA EMSL,
Las Vegas, Nevada, June 1987.
2 "Measurement of 2,3.7,8-Tetrachlorinated
Dibenzo-p-dioxin (TCOO) and 2,3,7,8-Tetra-
chlorinated Dibenzofuran (TCOF) in Pulp,
Sludges, Process Samples and Waste-waters
froa Pulp and Paper Mills", Wright State
University, Dayton, OH 45435, June 1988.
3 "NCASt Procedures for the Preparation and
Isomer Specific Analysis of Pulp and Paper
Industry Samples for 2,3,7,8-TCDO and
2,3,7,8- TCOF", National Council of the
Paper Industry for Air and Stream Improve-
ment, 260 Madison Avenue, Hew York, NY
10016, Technical Bulletin No. 551. Pre-
release Copy, Julv 1988.
4 "Analytical Procedures and Quality
Assurance Plan for the Determination of
PCDD/PCOF in Fir.h«, USEPA, Environmental
Research Laboratory, 6201 Congdon
Boulevard, Ouluth, HN 55804, April 1988.
5 Tondeur, Yves, "Proposed GC/MS Methodology
for the Analysis of PCDDs and PCDFs in
Special Analytical Services Samples",
Triangle Laboratories, Inc., 801-10
Capitola Or, Research Triangle Park, NC
27713, January 1988; updated by personal
communication September 1988.
6 Lamparski, L.L., and Hestrick, T.J.,
"Determination of Tetra-, Hexa-, Hepta-,
and Octachlorodibenzo-p«dioxin Isomers in
Particulate Samples at Parts per Trillion
Levels", Analytical Chemistry. 52: 2045-
2054, 1980.
7 Lamparski, L.L., and Nestrick, T.J.,
"Novel Extraction Device . for the
Determination of Chlorinated Dibenzo-p-
dioxins (PCDDs) and Dibenzofurans (PCDFs)
in Matrices Containing Water",
Chemosphere. 19:27-31, 1989. !
8 Patterson, D.G., et. al. "Control of
Interferences in the Analysis of Human
Adipose Tissue for 2,3,7,8-Tetra-
chlorodibenzo-p-dioxin". Environmental
Toxicological Chemistry. 5: 355-360, 1986.
9 Stanley, John S., and Sack, Thomas M.,
"Protocol for the Analysis ;of 2,3,7,8-
Tetrachlorodibenzo-p-dioxin by High-
Resolution Cas Chromatography/High-
Resolution Mass Spectrometry", USEPA EMSL,
Las Vegas, Nevada 89114, EPA 600/4-86-004,
January 1986.
10 "Working with Carcinogens", OHEW, PHS,
CDC, NIOSH, Publication 77-206, August
1977.
11 "OSHA Safety and Health Standards, General
Industry" OSHA 2206, 29 CFR 1910, January
1976.
12 "Safety in Academic Chemistry
Laboratories", ACS Committee on Chemical
Safety, 1979.
13 "Standard Methods for the Examination of
Water and Wastewater", 16th edition and
later revisions, American Public Health
Association, 1015 15th St, N.U.,
Washington, DC 20005, 46: Section 108
(Safety), 1985.
14 "Method 613 -- 2,3,7,8-Tetrachlorodibenzo-
p-dioxin", 40 CFR 136 (49 FR 43234),
October 26, 1984, Section 4.1.
15 Provost, L.P., and Elder, R.S.,
"Interpretation of Percent Recovery Data",
American Laboratory. 15: 56-83, 1983.
16 "Handbook of Analytical Quality Control in
Water and Wastewater Laboratories", USEPA
EMSL, Cincinnati, OH 45268, EPA-600/4-79-
019, March 1979.
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32
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17 "Standard Practice for Sampling Water",
ASTM Annual Book of Standards, ASTM, 1916
Race Street, Philadelphia, PA 19103-1187,
1980.
18 "Methods 330.4 and 330.5 for Total
', Residual Chlorine", USEPA, EMSl, Cincin-
nati, OH 45268, EPA 600/4-70-020, March
1979.
19 Barnes, Donald G., Kutz. Frederick U., and
Baltimore, David P., "Update of Toxicity
Equivalency Factors CTEFs) for Estimating
Risks Associated with Exposures to
Mixtures of Chlorinated Dibenzo-p-Oioxins
and Dibenzofurans (CDDs/CDFs)", Risk
Assessment Forua, USEPA, Washington, DC
20460, February 1989.
33
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Table 1
POLYCHLORINATED DIBENZOOIOXINS AND FURANS DETERMINED BY ISOTOPE DILUTION AND INTERNAL STANDARD
HIGH RESOLUTION GAS CHROMATOGRAPHY (HRGO/HIGH RESOLUTION MASS SPECTROMETRY (HRMS)
PCODs/PCOFs (1)
Isomer/Congener
2,3,7,8-TCOD
*
Total-TCDO
2,3 7,8-TCDF
Totul-TCOF
1,2,3,7,8-PeCDD
Total-PeCOO
1,2,3,7,8-PeCOF
2,3,4,7,8-PeCOF
Total-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCOD
1,2,3/7,8,9-HxCOD
Total-Hx'COD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9- HxCDF
2,3,4,6,7,8-HxCOF
Total -HxCDF
1,2,3,4,6,7,8-HpCOD
Total-HpCOD
1 ? ^ L ft 7 8-HnCDF
I ,£,.?, *»,Q,/ ,o n|A»ur
1 ? ^ L 7 8 9-rioCOF
•i&t^t^t ' t°i* npuur
. Total-HpCDF
OCOD
OCOF
(1) Polychlorinated dioxins
CAS Registry
1746-01-6
*
41903-57-5
51207-31-9
55722-27-5
40321-76-4
36088-22-9
57117-41-6
57117-31-4
30402-15-4
39227-28-6
57653-85-7
19408-74-3
34465-4608
70648-26-9
57117-44-9
72918-21-9
60851-34-5
55684-94:1
35822-46-9
37871-00-4
67562-39-4
55673-89-7
38998r75-3
3268-87-9
39001-02-0
and furans
TCDD " Tetrachlorodibenzo-p-dioxin
PeCOD 3 Pentachlorodibenzo-p-dioxin
HxCDD * Hexachlorodibenzo-p-dioxin
HpCOD => Heptachlorodibenzo-p-dioxin
OCDD a Octachlorodibenzo-p-dioxin
Labeled Analog
"c12-2,3,7.8-TCDD
37Cl4-2,3,7,8-TCOD
13C12-2,3,7,8-TCOF
13C12-1,2,3,7,8-PeCOD
13C12-1,2,3,7,8-PeCDF
13Cl2-2,3,4,7,8-PeCDF
.
•]3C12-1,2.3,4,7,8;HXCDD
13C12- 1,2,3,6,7,8-HxCOD
13C12- 1,2,3, 7,8,9- HXCODC2)
13C12-1,2,3,4,7,8-HxCOF
13Cl2-1,2,3,6,7,8-HxCOF
13C12-1, 2,3, 7,8,9- HxCOF
13C12-2,3,4,6,7,8-HxCDF
13C12-1,2,3,4,6,7,8-HpCDD
12
13C12-OCOD '
none
TCDF = Tetraehlor'odibenzofuran
PeCDF = Pentachlorodibenzofuran
HxCDF = Hexachlorodibenzofuran
HpCDF 3 Heptachlorodibenzofuran
OCDF = Octaehlorodibenzofurari
CAS Registry
76523-40-5
85508-50-5
89059-46-1
109719-79-1
109719-77-9
116843-02-8
109719-80-4
109719-81-5
109719-82-6
114423-98-2
116843-03-9
116843-04-0
116843-05-1
109719-83-7
109719-84-8
109719-94-0
114423-97-1
<2> Labeled analog is used as an internal standard and therefore is not used for quantitation of the native
cotrpound.
r
r
r
r
r
r
r
r
r
r
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•4,
34
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Table 2
RETENTION TIMES AND MINIMUM LEVELS FOR PCDDs AND PCDFs
Minimum Level (1)
Compound .
Compounds using C12* 1,2,3,
Native Compounds
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2;3,4,7,8-PeCDF
1,2,3,7,8-PeCDO
Labeled Compounds
l3C1.-2,3,7,8-TCDF
IT 12
13C12-1,2,3,4-TCDD
13C1,-2,3,7,S-TCDD
T7 12
•i/Cl4-2,3,7,8-TCDD
13C12-1,2,3,7,8-PeCOF
13C12-2,3,4,7,8-PeCDF
13C12-1,2,3,7,8-PeCDD
Compounds using C12~ 1,2,3,
Native Compounds
1,2,3,4,7,8-HxCOF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3, 4,7,8- HXCDD
1,2,3,6,7,8-HxCDD
1,2,3, 7,8, 9- HxCDD
1,2,3,4,6.7,8-HpCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,7,8,9-HpCDF
OCDD.
'. OCDF
Labeled Compounds
13C12-1,2,3,4,7,8-HxCDF
13C12- 1,2,3,6,7,8-HXCDF
13Cl2-1,2,3,7,8,9-HxCDF
13C12-2,3,4,6,7,8-HxCDF
13C12-1,2*3,4,7,8-HxCOD
13C12- 1 ,2, 3,6,7,8-HxCDD
13C,_- 1,2,3, 7,8, 9-HxCOD
1*1 1 £
^C12-1,2,3.4,6,7.8-HpCDF
"c12-1,2,3,4,6,7.8-HpCOO
13C12-1, 2,3,4,7 8,9-HpCDF
13C12.-OCDD
Retention
Time
Reference
4-TCDD as internal standard
13C12-2,3,7,8-TCDF
13C12-2,3,7,8-TCDD
13C12-1,2,3,7,8-PeCDF
13C12-2,3,4,7,8-PeCDF
13C12-1,2,3,7,8-PeCDD
13C12-1,2,3,4-TCDD
3C12-1,2,3,4-TCDD
J3C12-1. 2.3.4- TCOD
J3C12- 1,2.3, 4-TCDD
]3C12-1,2,3,4-TCDO
"C12-1, 2,3,4- TCDD
13C12-1,2,3,4-TCDD
7, 8, 9- HxCDD as internal standard
13C12-1,2,3,4,7,8-HXCDF
13C12-1,2,3,6,7,8-HxCDF
13C12-1,2,3,7,8,9-HxCDF
3C12-2,3,4,6,7,8-HxCOF
13C12-1, 2,3,4, 7,8-HxCDD
13C,,-1,2,3,6,7,8-HxCDD
n ib
•3C12-1,2,3,6,7,8-HxCDD
]3C12-1,2,3,4,6,7,8-HpCDF
]3C12-1,2,3,4.6,7,8-HpCDD
13C12-1,2,3,4,7,8,9-HpCOF
3C12-OCDD
I3c12-ocoo
13C12-1.2,3,7,8,9-HxCOD
13C12- 1,2,3,7,8,9- HxCDD
13C12-1, 2,3,7.8,9- HxCOD
13c'12-1, 2,3,7,8,9- HxCOO
13C12- i2,3,7,8,9-HxCDD
13C,_- ,2,3,7.8,9-HxCOD
C12- ,2,3,7,8,9-HxCDD,
13C12- ,2,3,7,8,9-HxCDD
13C12- ,2,3.7.8,9-HxCDO
13C12- ,2,3,7,8,9-HxCDO
13C12-1, 2,3,7,8,9- HxCDD
Relative
Retention
Time
0.993 -
0.993 -
0.918 -
0.999 •
0.987 -
0.931 -
1.000 •
0.993 -
1.002 -
1.091 -
1.123 -
1.134 -
0.936 -
0.973 -
0.937 -
0.999 -
0.999. -
0-.992 -
0.936 -
0.930 -
0.986 -
0.896 -
0.996 -
0.995 -
0.947 •
0.940 •
0.993 -
0.971 -
0.974 -
0.975 -
1.000 -
0.953 -
1.023 -
1.024 -
1.050 -
1.009
1.009
1.076
1.001
1.016
0.994
1.000
1.036
1.013
1.371
1.408
1.428
1.015
1.025
1.068
1.001
1.001
1.009
1.016
1.022
1.016
1.079
1.005
1.013
0.992
1.006
1.017
1.000
1.002
1.006
1.000
1.172
1.125
1.148
1.275
Water
pg/L
ppq
10
10
so
so
50
50
50
50
50
50
50
50
50
50
50
100
100
Solid
ng/kg
ppt
1
1
5
5
5
5
5
5
5
5
5
5
5
5
5
10
10
Extract
pg/uL
PPO
0.5
. 0.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5.0
5.0
'
(1) Level at which the analytical system will give acceptable SICP and calibration.
35
-------
Table 3
DESCRIPTORS, MASSES, M/Z TYPES, AND ELEMENTAL COMPOSITIONS OF THE CODs AND CDFs (1)
Descriptor Accurate
Number m/z (2)
" 1 292.9825
303.9016
305.8987
315.9419
317.9389
319.8965
321.8936
327.8847
"*• 330.9792
»
331.9368
333.9339
375.8364
2 339.8597
341.8567
351.9000
353.8970
354.9792
355.8546
357.8516
367.8949
369.8919
409.7974
3 373.8208
375.8178
383.8639
385.8610
389.8157
391.8127
392.9760
401.8559
403.8529
430.9729
445.7555
36
m/z
Type Elemental Composition
Lock C7 F11
" C12H435CI4°
M+2 C12 H4 35C1337CI 0
% «4 ^ °
% H, 35d3 37Cl 0
H . C12 H4 35cl4 °2
M+2 C,2 H4 35C13 37Cl 02
H C12H437C1402
QC C7 Fn
"l^^Cl^ClO,
M+2 C12 H4 35C15 37Cl 0
M+2 - C12 H3 35C14 37Cl 0
H+4 C12 H3 35C13 37C12 0
H+2 13C12 H, 35C14 37Cl 0
M+4 " 13C12 H3 35C13 37C12 0
Lock C0 F13 .
H+2 C12 H3 35Ct4 37Cl 02
H+4 C12 H3 35d3 37C12 0,
H+2 13C12 H3 35C14 37Cl 02
H+4 . 13C12 H, 35C13 37C12 O,
"« '12 "3 35'16 37CI °
H+2 C12 H2 3SClg 37Cl 0
H+4 C12 H2 35C14 3 C12 0
H 13C12 H2 35C16 0
:H+2 13c12 H2 35ci5 37ci o
H+2 C,, H2 35C15 37Cl O,
H+4 C12 H2 35C14 37C12 02
.Lock C9 F15
H+2 13C12 H2 35C15 37Cl 02
H+4 13C12 H, 35C14 37C12 O,
QC C, F13
H+4 C12 H2 35C16 37C12 0
Compound
PFK
TCDF
TCDF
TCDF<4)
TCDF<4)
TCDD
TCDD
TCDD (5)
PFK
TCDDC4)
TCDDC4)
HxCDPE
PeCOF
PeCDF
PeCDF(4)
PeCDF<4)
PFK
PeCOD
PeCOD
PeCDOriJ
PeCDD(4)
HpCOPE
HxCDF
HxCDF
HXCDFC4)
HxCOF(4)
HxCBD
HxCDD
PFK
HxCDD<4:>
HXCDOC4)
PFK
OCDPE
H^^BJJH
Primary
: m/z?
! Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
; Yes
Yes
Yes
' |
Yes
••^H
-------
Table 3 (continued)
DESCRIPTORS, MASSES, M/Z TYPES, AND ELEMENTAL COMPOSITIONS OF THE CODs AND CDFs (1)
Descriptor Accurate m/z
Number ' m/z (2) Type
(1)
(2)
(3)
4 " 407.7818 M+2
409.7789 M+4
417.8253 H
419.8220 M+2
423.7766 M+2
425.7737 M+4
430.9729 Lock
. 435.8169 . M+2
437.8140 M+4
479.7165 M+4
5 441.7428 M+2
442.9728 Lock
443.7399 M+4
457.7377 M+2
459.7348 M+4
469.7779 M+2
471.7750 M+4
513.6775 M+4 '
From Reference 5
Nuclidic masses used:
H = 1.007825 C 3 12.00000
0 a 15.994915 35Cl = 34.968853
Compound abbreviations:
Chlorinated dibenzo*p-dioxins
TCDD 3 Tetrachlorodibenzo-p-dioxin
PeCDD = Pentachlorodibenzo-p-dioxin
HxCDD = Hexachlorodibenzo-p-dioxin
HpCDD 3 Heptachlorodibenzo-p-dioxin
OCDD = Octachlorodibenzo-p-dioxin
Elemental Composition
C12 H 35C16 37Cl 0
C12 H 35C15 37C12 0
13C12 H 35C17 0
13C12 H 35C16 37Cl 0
C12 H 35C16 37Cl 02
C12 H 35C15 37C12 02
C9F17
13C,_ H 35Cl, 37Cl 0-
\£. O c.
13. „ 35 . 37 .
C12 H C15 C12 °2
C12 H 35C17 37C12 0
c12 35d7 37ci o
C,n F,_
10 17
C 35Cl 37Cl 0
C12 C16 C12 °
C 35Cl 37Cl 0
C12 C17 Cl °2
C 35Cl 37Cl 0
C12 C16 C12 °2
13C12 35C17 37Cl 02
13 35 37.
C12 C16 C12 °2
C 35Cl '37Cl 0
C12 C18 C12 °
13C = 13.003355
37Cl = 36.965903
Compound
(3)
HpCOF
HpCDF
HpCDF(4)
HpCDF(4)
HpCDO
HpCDD
PFK
HpCDO(4)
HpCDD(4)
NCDPE
OCDF
PFK
OCDF
OCDD
OCDD
OCDD (4)
OCDD(4)
DCOPE
F = 18.9984
Primary
m/z?
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Chlorinated diphenyl ethers
HxCOPE »
HpCDPE =
OCDPE =
NCDPE =
DCOPE =
Hexachlorodiphenyl ether
Heptachlorodiphenyl ether
Octachlorodiphenyl ether
Nonachlorodiphenyl ether
Decachlorodiphenyl ether
*
Chlorinated dibenzofurans
TCDF = Tetrachlorodibenzofuran
PeCDF = Pentachlorodibenzofuran
HxCDF a Hexachlorodibenzofuran
HpCDF = Heptachlorodibenzofuran
Lock mass and QC compound
PFK = Perfluorokerosene
<4) Labeled compound
37
<5) There is only one m/z for Cl,-2,3,7,8-TCDD (cleanup standard).
37
-------
Table 3A
THEORETICAL ION ABUNDANCE RATIOS AND CONTROL LIMITS
No. of m/z's
Chlorine Forming Theoretical Control Limits(l)
Atoms Ratio Ratio Lower Upper
•4 <2> H/H+2 0.77 0.65 0.89
5 M+2/H+4 1.55 1.32 1.78
6 H+2/H+4 1.24 1.05 1.43
6 (3) H/H+2 0.51 0.43 0.59
7 • H+2/H+4 1.05 0.88 1.20
7 (4) H/H+2 0.44 0.37 0.51
8 H+2/H+4 0.89 0.76 1.02
(1) Represent + 15X windows around the theoretical ion
L*
r
r
r
c
abundance ratios. : I"
(2) Does not apply to Cl,-2,3,7,8-TCDD (cleanup
standard).
(3) Used for 13C-HxCDF only.
(4) .Used for 13C-HpCDF only.
38
r
L
C
c
-------
Table 4
CONCENTRATIONS OF SOLUTIONS CONTAINING LABELED AND UNUBELED PCDOS AND PCDFS ••
STOCX AND SPUING SOLUTIONS
Labeled
Compound
Stock
Solution (1)
(ng/iBL)
Labeled
Coinpound
Spiking
Solution <2)
(ng/iK.)
PAR
Stock
Solution (3)
(ng/irt.)
Cleanup
Standard
Spiking
Solution <4)
Internal
Standard
Spiking
Solution (5)
(ng/mt)
Native CDOs and CDFs
2,3,7,8-TCDO
2.3.7.8-TC8F
1,2,3,7.8-PeCOO
1,2.3.7,8-PeCOF
2,3.4,7,8-PeCDF
1,2.3,4,7,8-HxCDD
1.2,3,6,7.8-HxCDD
1.2.3,7,8,9-HxCOO
1,2,3.4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3.7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2.3.4,6,7,8-HpCOO
1,.2,3.4,6,7,8-HpCDF
1,2,3,4.7,8,9-HpCOF
OCDF
Labeled CDOs and CDFs
13C12-2.3,7,8-TCOO
13C12-2,3,7,8-TCDF
13C12-1.2,3.7.S-PeCDO
. 13C12-1,2,3,7,8-PeCOF
- 13C12-2,3,4,7,3-PeCDF
13C12-1,2,3,4.7,8-HXCDO
]3C12-1,2,3,6,7,8-HxCOO
13C12-1,2,3,4.7.8-HxCDF
13C12-1,2,3,6,7,3-HxCOF
13C12-1,2,3,7,8,9-HxCOF
13C12-2,3,4.6,7,8-HxCDF
]3C12-1,2,3,4,6,7,8-HpCDO
]3C12-1,2,3,4,6,7,8-HpCDF
13C12-1,2,3,4,7,8,9-HpCDF
13C12-OCDD
Cleanup Standard
37Cl4-2,3,7.8-TCDD
Internal Standards
13C12-1,2,3,4-TO»
13C,2-1.2,3,7.8,9-HXCDO
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
40
40
200
200
200
200
200
200
200
200
200
200
200
200
200
400
400
0.8
200
200
(1) Section 6.10 - prepared in nonane and diluted to prepare spiking solution.
(2) Section 10.3.2 - prepared fron stock solution daily.
(3) Precision and Recovery (PAR) standard. Section 6.14 - prepared in nonane and diluted to prepare spiking
solution in Section 10.3.4.
(4) Section 6.11 - prepared in nonane.
(S) Section 6.12 - prepared in nonane.
39
-------
Table 4 (continued)
CONCENTRATIONS OF SOLUTIONS CONTAINING LABELED AND UNLABELED PCDDS AND PCDFS
CALIBRATION AND VERIFICATION SOLUTIONS
Compound .
Native CDDs and CDFs
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3, 6,7, 8-HxCDD
1, 2,3,7,8,9- HxCDD
1,2.3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
"1,2,3',7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCOF
1,2,3,4,7,8,9-HpCDF
OCDD
OCOF
Labeled CODs and CDFs
13C12-2,3,7,8-TCDD
13C12-2,3.7,8-TCOF
]3C12-1,2,3,7,S-PeCDD
]3C12-1,2,3,7.8-PeCDF
13C12-2,3,4,7,8-PeCOF
13C12-1,2,3,4,7,8-HxCDD
13C12-1,2,3,6.7,8-HXCOD
13C12-1,2,3,4.7,8-HxCDF
13C12-1,2,3,6,7,8-HXCDF
13C12-1,2,3,7,8,9-HXCOF
13C12-2,3,4,6,7,8-HxCDF
13C12-1,2,3r4,6,7,8-HpCOD
]3C12-1,2,3,4,6,7,a-HpCDF
13C12-1,2,3,4,7.8,9-HpCDF
13C12-OCDD
Cleanup Standard
37Cl4-2,3,7,8-TCOD
Internal Standards
13C12-1,2,3,4-TCDD
13C12-1,2,3,7,8,9-HxCDD
CS1
0.5
0,5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5.0
5.0
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
0.5
100
100
CS2
(ng/mL)
2
2
10
10
10
10
10
10
10
10
10
10
10
10
10
20
20
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
2
100
100
VEIU6)
CS3
(ng/mL)
10
10
50
50
50
50
50
50
50,
50
50
50
50
50
50
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
10
100
100
CS4
(ng/mL)
40
40
200
200
200
200
200
200
200
200
200
200
200
200
200
400
400
100
100
100
100
100
100
100
100
in
100
100
100
100
100
200
40
100
100
CSS
(ng/mL)
200
200
1000
1000
1000
1000
1000
1000
1000
: 1000
1000
1000
1000
: 1000
1000
2000
2000
: 100
100
', 100
100
100
100
100
: 100
100
100
100
100
100
100
200
200
100
; 100
L<
[
r-
(6) Section 14.3 - calibration verification (VER) solution.
40
-------
Table 5
GC RETENTION TIME WINDOW DEFINING STANDARD MIXTURES AND
ISOMER SPECIFICITY TEST STANDARD MIXTURES
DB-5 Column GC Retention Time Window Defining Standard
(Section 6.15)
Congener First Eluted Last Eluted
TCDF
TCDD
PeCDF
PeCDO
HxCDF
HXCOD
HpCDF
HpCOD
1,3,6,8-
1,3,6,8-
1,3,4,6,8-
1,2,4,7,9-
1,2,3,4,6,8-
1,2,4,6,7,9-
1,2,3,4,6,7,8-
1,2,3,4,6,7,9-
1.2.8,9-
1.2,8,9-
1,2,3,8,9-
1.2,3,8,9-
1,2,3,4,8,9-
1,2,3,4,6,7-
1,2,3,4.7,8,9-
1,2,3,4,6,7,8-
DB-5 TCDD Isomer Specificity Test Standard
(Section 6.16.1)
1,2,3,4-TCDD 1,2,3,7-TCDD
1,2,7,8-TCDD 1,2,3,8-TCDD
1,4,7,8-TCDD 2,3,7,8-TCDD
DB-225 Column TCDF Isomer Specificity Test Standard
(Section 6.16.2)
2,3,4,7-TCOF
2,3,7,8-TCDF
1,2,3,9-TCDF
41
-------
REFERENCE
2,3,7,8-TCDD
2.3.7,8- TCOF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCOD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCOF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2.3,4,6,7,8-HpCOF
1,2,3,4,7,8,9-HpCDF
OCDD ,
OCDF
Table
COMPOUNDS FOR QUAHTITATION OF
Reference Compound
13C12-2,3,7.8-TCDD
13C12-2.3,7.8-TCDF
13C112-1,2,3.7.S-S*eCDF
13C12-2,3,4,7.8-feCDF
13C12-1. 2.3,4,7,8- 1XCOD
13C12-1,2,3,6,7,8-HXCDD
(1)
13C12-1,2,3f6f7,8-HxCDF
13C12-2,3,4,6,7,S-HXCDF
l3Cl2-1,2.3,4,6,7,8-HpCDD
13Cl2-1,2,3.4,6,7,8-HpCDF
13C12-1,2.3,4,7,8,9-HpCDF
13C,,-OCDD
11 '*
"C^-OCDD
6
NATIVE AND LABELED PCDDS AND
Labeled PCDDs and PCDFs
13C12-2,3,7.8-TCOD
13C12-2,3,7.8-TCOF
13C12-1.2,3.7.8-PeCDD
13Cl2:1.2,3,7,8-PeCDF
13C12-2,3,4,7.8-PeCDF
13Cl2-1.2.3f4.7,8-HxCDD
13C12-1.2.3,6.7.8-HXCOD
13C12-1.2,3,7,8,9-HXCDD
13C12-1,2,3,4,7,8-HXCDF
13C12-1, 2,3,6. 7,8;HXCDF
13C12-1,2,3,7.a,9-HxCDF
13C12'2,3,4,6,7,8-HXCDF
13C12-1.2,3,4,6,7.8-HpCDO
13C12-1f2,3,4,6,7.8-HpCDF
13C12-1,2.3,4,7,8,9-HpCDF
13C12.OCDD
37Cl4-2.3,7.8-TCDD
*„ »k_ ^^r -1 ?_3.4
PCDFS
Reference Compound
13C12-1,2,3,4-TCDD
13C12-1,2,3,4-TCDO
13C12-1,2,3,4-TCDD
13C12-1,2,3,4-TCDD
13C12-1,2,3f4-TCDD
13C12-1,2,3,7,8,9-HXCDD
13C12-1,2,3,7,8,9-HXCDD
13C12-1.2.3.7J,8,9-HXCOD
13C12-1,2,3,7,8,9-HXCDD
13Cl2-l,2.3,7,8f9-HxCDD
13Cl2-1,2,3,7,a,9-HxCDD
13C12-1,2,3,7,8,9-HXCDD
13C12-1,2,3,7,8,9-HxCDD
13C12-1,2,3,7r8,9-HxCOD
13C12-1,2,3,7,a,9-HxCDD
13C12-1,2,3.7,8,9-HxCDD
13C12-1;2,3,4-TCDD
.7.8-HxCDD and C---
(1) 1,2,3,7,8,9-HxCDD is
1,2,3,6,7,8-HxCDD.
quantified using the average responses for the Cl2
r
r
r
c
42
-------
THIFID REVISION
>
TO METHOD
. i :
1613 PERFORMANCE S
Tafate 7 :
; ACCEPTASCE CRnSSZA. FOK PERFORHMiC£ tESTS
: T«t
Cooe. CU G .
Compound Cng/flt) Cng/itJ-
2,3,7.8-rGDD
2.3,7,8-rCDF
1.2r3,7,S-PeCDO
1,2.3.7,8-PeCDF
2,3.4.7,8-PeOJF
1 ,2,3,4,7,8-HxCDO
1, 2,3.6. r,S-Hxa»
1. 2^5,7,8. 9-H*n»
1,2,3,4,7.3-axCOF .
1 ,2^.6.7.8-HXCDF
1,2.3,7,8,9-lfcCJF
1 -2 .? •£ A T X.UrSTTln
; 10 1.1
10 0.9
,50 3.6
=50 3.4
ISO 4.2;
-50 6.7
50 3.9
;SO 7.0
SO S-5 '
ISO 3.0
-50 2.9
SO 4.2
'cn T0 r
IF* C2> :
* OFR{23
8.3 - 11.8 6,9 - 13.
8.4 - 13.2 ' 6.9 - 15.
41.4 - 56.8 35.7 - £S.
43.0 - SS.O 35,7 - 69.
«2-7 - 61.5 34.3 - 72.
40.8 - 67.1 36-S - 70.
42.9 - S7.S 42^ - F 100
^12-l»2,3,7,8-PeCDO 100
^ci2-t.2,3,7.8-PeCOF 100
"Cl2-2.3;4,r,8-Pe£3»F 100
*fCl2-!.2,3;4,7.8-Hxa» 100
ci2-i,2A6/7,a-atfeo 100
'HC12-1,2,3,4,7^-H>S»F 100
Ci2-1,2;3A7,8-aF 100
Ct2"1«2^t^7J8-9*fi3rf!DF 100
13 •• ••
^ Ct2-2A4,6,7.8-HtfOF 100
Ci2rl^^,4,6,7,S-8paiO 100
^2-l,2,3,4,6,7,8^pO»F 100
^2"1'2>3**'7*?'9"HPa)£: 1°°
C12~OCDO 200
L
. 1S.»
20-S
3Z.1 •
as •
25,1
24^-,
31.4
19.9
15.1 .
1&.X
**°
17.3
20.9
23^
22.9
4SJ5
-
CU All specificariaos are sivw as eotKantrsiHons
C23 s = standard devfatfcn of tiJe cofa-~^— «^' ~-
coopountfe in IPR and OPS eliquits.
8.2^ and 14^,3J.
Re^sed 2/28/92
•*a<^% «x^.iu«t~ A
ere based on
t i .
25.0 -
-25JJ -
25.0 -
25.0 •
25-0 -
• 2510 -
' 25.0 -
: 25-0 -
25.0 -
9? it
O.w -
25.0 -
25.0 -
25.0 -
25.0 -
5Q.O -
Z.3 -
in tie f Ire
= av«r»s« <
requTresMnt
150.0:-
: 150.0;
! 150.0;
iso.o:
i 150,0-'
; iso.o.
150-0 ;
150.0 i
1SO.O;
• _
150.0
; iso.o •
; 150.0:
150.0 ;
150.0 i
300.0!
15.0 :
fl extract or :
aocentrarioa,
s far Labeled
i
25,0 -
25.0 -
25.0 -
25.0 -
25.0 -
25.0 -
25JJ -
2S.« -
25.0 -
_^
2SJ3 _ -
25.0 -
2SJJ -
2S.O -
2S.O -
50,0 -
3LS.-
150.6
isp,o
150.0
150.0
• 150.0
: isb-d
iso.o;
150.0:
' 750.0
: " J
. 159.0
150-0
150.01
150.01
150.oi
'30Q.oi
I5_oi
standcfX* SoLut.ioiw
Concentration iis
ecepouad recovery
. i
:
: . :
82.0 -
71.0 -
62.4 -
6&.7 r
SS.O -
. 81,8 -
79JS -
71.4 -
65.3 -:
75.4 -
73^5 -
63.7 -'
S5.1 -
60.O -
94^ -
7.1 -:.
118.0
129.0
137.6
133,3
12S.O
118.2
120.7
IZS^
134.7
124^6
126,6
T45^
113.5
140.0
«2.S
12.9
ifts for labeled
erf 25-150K CSeccfons
, • .*
- 59,2
40^ -
79.7 - 125,«
'71^ - -B9.7
-------
L
Table S
SAMPLE PHASE AND QUANTITY EXTRACTED FOR VARIOUS MATRICES
Sample Matrix (1)
. SINGLE PHASE
Aqueous
Example
Drinking water
Percent
Solids
<1
Phase
(2)
Quantity
Extracted
1000 mL
Solid
Organic
MULTIPHASE
Liquid/Solid
..Aqueous/solid
Organic/solid
Liquid/Liquid
Aqueous/organic
Aqueous/organi c/
solid
Groundwater
Treated wasteuater
Dry soil
Compost
Ash
Waste solvent
Waste oil
Organic polymer
Wet soil
Untreated effluent
Digested municipal sludge
Filter cake
Paper pulp
Tissue
Industrial sludge
Oily waste
In-process effluent
Untreated effluent
Drum waste
Untreated effluent
Drum waste
1-30
1-100
Solid
Organic
Solid
Both
Organic
Organic
& solid
10 g
10 g
10 g
10 g
10 g
10 g
i_
(1)
(2)
The exact matrix may be vague for sons samples. In general, when the CDDft andi CDFs are |"'
multiphasa system in which one of the phases is water, they will be preferentially dispersed in or adsorbed
on the alternate phase, because of their low solubility in water.
Aqueous samples are filtered after spiking with labeled analogs. The filtrate and the material trapped on
the filter are extracted separately, and then the extracts are combined for cleanup and analysis.
44
*U.S. GOVERNMENT PRINTING OFFICE: 1991—517-003/47034
-------