Solvent Minimization i&A €tf£Atfdm£ritftSus Liquid/Liquid Extraction
of Aqueous Samples for Semivolatile Organics
Joseph Slayton, Susan Warner,
Philip Shreiner, Carole Tulip, and Edward Messer
U.S. Environmental Protection Agency
Central Regional Laboratory, Region III
839 Bestgate Road, Annapolis, Md. 21401
410-266-9180
Introduction
Continuous extraction (CE) of aqueous samples is quickly replacing
separatory funnel extraction for semivgiatile organics. The
advantages of continuous liquid/liquid extfdi&ion over separatory
funnel extractions include the following:
1) improved extraction efficiencies and accuracy due to the
increased number of theoretical plates associated with the re-
distilled solvent being continously exposed to the sample;
2) savings in manpower due to the reduction of both time and
physical labor;
3) the effectiveness of the CE technique in highly contaminated
matrices containing suspended solids (a problem with Solid Phase
Extractions);
4) the effective elimination of emulsions common with separatory
funnel extractions of environmental samples; and the
5) improved precision using CE.
One disadvantage of the traditional CE procedure is the
considerable volumes of solvent that is required to perform the
analysis versus the separatory funnel method. A commonly used
"macro-sized" extractor is illustrated in Figure 1. The continuous
extraction technique frequently requires 600 to 1000 mLs of
methylene chloride solvent to perform a single extraction. Compare
this to the 180 to 360 mLs to perform a routine separatory funnel
extraction. Given the overall expense of using methylene chloride,
both the initial purchase cost and the extremely costly disposal
fee ($200+ per 55 gallon drum), it would be desirable to
miniaturize the procedure in order to minimize the volume of
solvent. Miniaturization was considered more desirable than Solid
Phase Extraction (SPE) or other technologies, which involve
different chemistries than liquid/liquid extraction, since the use
of these techniques for EPA's programs would require obtaining
analytical "variances". Such variances may take many years to
obtain.
This work was funded by the USEPA Office of Research and
Development. The authors recognize the contribution of Angela
Cogswell, NNEMS Fellowship student, on the preliminary studies
associated with this work.
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A design for a miniaturized continuous extractor (Figure 2) was
developed so as to maintain the sensitivity of the procedure, yet
minimize the solvent necessary to perform the analysis. A full
liter of sample was extracted, as per the current Agency protocols
(SW-846, EPA NPDES Methods 625 and 608, SDWA Method 508, Superfund
CLP Statement of Work) to assure sensitivity and to help assure a
sample aliquot of sufficient size to be accurately representative.
This sample volume also avoids the necessity for concentration of
the extract obtained to a smaller final volume to maintain
sensitivity, e.g., less than 0.5 mL. It was decided to avoid
attempts to reduce the final extract volume to less than 1 mL,
since the extract could easily go to dryness. Going to dryness
would result in the loss of the more volatile compounds.
'(
A series of extraction recovery experiments were performed using
the prototype extractor design to determine the:
* Necessity for design modifications and/or extraction
protocols necessary to maximize target compound recoveries with the
goal being to obtain the performance specifications (% recovery and
standard deviation), required by current Agency protocols (EPA
Methods 625 and 608).
* Effect upon the analytical results (accuracy and precision) .
Recovery of semivolatile organics, pesticides and PCBs listed as
target compounds under the Superfund Contract Laboratory Program ,
EPA methods 608 and 625 (NPDES) and 508 (SDWA) were determined.
This work followed the "initial demonstration of capability"
procedures specified per the 600 series methods. These procedures
test the performance of the method (all steps of the method)
against specified accuracy and precision criteria specified for
each target compound. In addition, the performance of the
miniature extractors (employing 200 mLs of solvent—Figure 2) were
compared to "macro" size extractors (employing 700-1000 mLs of
solvent—Figure 1). These larger "macro" CEs have been routinely
used by our laboratory for the analysis of semivolatile organic
compounds since 1986.
* Ease and practicality of use.
* Consistency with the Agency's mandatory analytical
procedures. As part of this work, it was determined whether
special variances by the Agency are necessary for use of these
protocols in the NPDES, SDWA, Superfund and RCRA programs.
* Effectiveness of the extractor in recovering compounds from
wastewater samples.
.Disclaimer
Although the research described in this document has been supported
by the U.S. Environmental Protection Agency and is awaiting Agency
wide review, it does not necessarily reflect the views of the
Agency, and no official endorsement should be inferred. The
mention of trade names or commercial products in this report is for
illustrational purposes and does not constitute endorsement or
recommendation by the U.S. Environmental Protection Agency.
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I. Experimental
A. Reagents & Equipment
Note: Brand names and catalog numbers are included for
illustrational purposes only.
1 Methylene chloride, B&J high purity solvent,product #300,
contains cyclohexene preservative to inhibit HC1 formation.
2. Sulfuric acid, Baker, Instra-Analyzed, #9673-03,
6N H2S04 prepared by slowly adding 167 mLs of
concentrated H2SO4 to 833 mLs of reagent water.
3. Multi-range pH paper strips, EM-Reagents ColorpHast,
pH indicator strips, pH 0-14.
4. Boiling Stones, Hengar Co., carborundum #12 granules,
#133-B. Conditioned by muffling at 450°C for 3-4 hrs.
5. Sodium sulfate, anhydrous, granular, Mallinckrodt, product
#8024 . Muffled for 3-4 hours at 450°C. Stored in glass.
6. Glass wool, Pyrex brand, fiber glass, sliver 8 micron,
Corning Glass Works. Muffled for 3-4 hours at 450°C.
7. Muffle furnace, Blue M Power-0-Matic 80.
8. Muffle furnace, Blue M Touch Master, Model #CFD-20F-6.
9. Heating mantle, Glas-Col Apparatus Co.,Terre Haulte, In 47802
Cat. No. TM98, (80 Watt, 115 V).
10. Variable transformer, Staco Energy Products Co., type 3PN1010.
11. 125 mL boiling flask.
12. 1000 mL graduated cylinder.
13. Allihn condenser, 45/50 joint, 4 ball, with special drip ring
to catch condensation from room humidity.
14. 3-ball Snyder columns, (macro- and micro-).
15. 500 mL Kuderna-Danish evaporative flask.
16. 10 mL graduated Kuderna-Danish concentrator tube.
17. Continuous extractor, one piece, glass, obtained from LAB
Glass, Inc., Vineland, Pa. (Figure #2—"Micro-" and Figure #1
—"Macro-"). The "macro-" size extractors are routinely
employed in environmental laboratories. The miniature
("micro-") extractors cost about $100/each.
18. Drummond pipet, 100 uL dispensing pipettor, Model #375, used
for pipetting spikes.
19. Volumetric pipet, 1 mL.
20. Volumetric flasks, 1 mL, 2 mL and 10 mL.
21. Milli-R015 Millipore (10 megaohm-cm, deionized water) System.
22. Carbon filter system (made internally, 5 Ibs. activated
charcoal) for final polishing of lab pure water.
23. Screw cap vials with teflon-faced silicone septa, 1.8 mL,
Cat. Nos. 3-3286 (vials) and 3-3210 (caps and septa),
Supelco, Beliefonte, Pa.
24. Pyrex funnels (for sample addition), 60°, 145 mm stem length.
25. Pyrex stirring rods (for sample pH adjustment), 370 mm length,
and 15 mm diameter.
26. Finnigan MAT 4500 GC/MS. The system equipped with: a
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N21344
Figure I
IOOMM _
O.D.
350MM
I35MM
22MM
O.D,
524/40
'INNER Ji
THESE DRAWINGS AND SPECIFICATIONS
ARE THE PROPERTY OF LABGLASS. INC AND
SHALL NOT BE REPRODUCED OR COPIED
OR USED AS THE BASIS FOR THE MANU
FACTURE OR SALE OF APPARATUS OR
DEVICES WITHOUT WRITTEN PERMISSION
OF LABGLASS. INC. VINELAND. N 1.
CUSTOMER
CATALOGUE
DESCRIPTION
RAW MATERIAL COMPONENTS
QTY.
PART NO
QTY I PART NO
DATE -
SCALE
APR.
PRINTS
LABGLASS INC.
NORTHWEST BLVD & OAK
VINELAND. N.J.
-------
Figure 2
S 45/50
80MM
O.D,
irw /
G"0/A
-80MM—H
22MM
"O.D.
4MM TEFLON
STOPCOCK
\ S 24/40
INNER JT.
DRAWINGS AND SPECIFICATIONS
(U THE PROPERTY OF LA8CLASS. INC AND
HALL NOT BE REPRODUCED OR COPIED
OR USED AS THE BASIS FOR THE MANU
FACTURE OR SALE OF APPARATUS OR
DEVICES WITHOUT WRITTEN PERMISSION
OF LABGLASS. INC VtNELANO. N J.
CUSTOMER
CATALOGUE
DESCRIPTION
RAW. MATERIAL COMPONENTS
QTY.|PART NO
QTY I PART NO
DATE
-- 9?
SCALE
APR.
PRINTS
LABGLASS INC.
NORTHWEST BLVO & OAK
VINELAND. N J.
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quadrupole analyzer and El source; an HP 7673 automatic
sampler and an Incos data system. The Fused Silica Capillary
Column (FSCC) was a DB-5, J&W Scientific, 30M x 0.32mm
ID with a film thickness of 1 urn. The GC temperature program
was: 30°C for 2 minutes, ramped to 300°C at 10°C/minute.
27. HP 5890 Series II Gas Chromatograph/BCD/FID system, with an HP
7673 automatic sampler and HP 3365 Chemstation data system.
The ECD was equipped with a Supelco SPB-608, FSCC, 30M x 0.53
mm ID, with a film thickness of 0.50 urn. The GC program for
the pesticides, (ECD) was from 150°C to 280°C at 10°C/minute,
with a final hold of 10 minutes.
The FID was equipped with a Supelco #2-4050, SPB-5 FSCC, 60M,
0.32 mm ID, with a 0.25 um film thickness. For FID analyses,
the GC was programmed from 50°C to a 280°C at 5°C/minute, with
a final hold of 10-25 minutes (compound dependent).
28. S-EVAP, solvent recovery system (during K-D process),
Organomation, Inc., South Berlin, MA.
29. Re-circulating water bath (condenser cooling), FTS Inc., model
RC-25.
30. Methanol, B&J, purity suitable for Purge & Trap analysis.
B. Calibration standards and Spiking Solutions/Procedures
The calibration and spiking solutions used were all from EPA's QA
Materials Bank in RTP, NC or from certified CRADA vendors. A
detailed listing of the sources and preparation procedures for the
following solutions is included in the Appendix: spiking solutions
(general); calibration standards and multiple point curve
preparation; internal standards; Superfund CLP "Matrix Spikes"
(MS); Superfund CLP "Surrogate Compound" spikes; BNA spiking QC
solutions (CRADA); benzidine/s and aniline/s spiking solutions;
Pesticide spikes (single component analytes, toxaphene,
chlordane,and PCBs).
C. General Procedures;
GC Screening;
The initial phases of this work involved numerous re-designs of the
dimensions of the miniaturized CE. As a consequence, a simple
spiking mixture was used (matrix spike and/or surrogate spike
delineated above). This reduced the expense of using more costly
spiking cocktails and provided relatively simple mixtures which
could be analyzed via GC/FID. Once the design was optimized, the
more complex mixtures were tested using a GC/MS system. This
tiered approach saved much expense (reference materials and costly
GC/MS use), and helped speed the progress.
Loading the Continuous Extractors;
Miniature or "Micro-" CE Extractors;
In a fume hood the stopcock on the CE solvent return line was
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closed (see figure 2), a 125 mL flat bottom boiling flask was
attached (containing several boiling stones). 200 mLs of methylene
chloride were placed into the continuous extractor. A 500 mL
volume of the 1 liter sample was added using a glass funnel with
145 mm glass stem. This procedure helped assure that the aqueous
sample would not displace the solvent (avoid water break-through of
the solvent layer). The remaining volume of sample was then poured
into the extractor. The dense solvent was thus layered below one
liter of aqueous sample and therefore exposure of the analyst to
solvent vapor was minimized. The extractors were secured in a
ringstand with the solvent flask placed in a heating mantle. Each
one liter aliquot was adjusted to a pH <2 using 6N H2S04, (5mL auto-
dispenser) , except for spikes of anilines and benzidines, which
were extracted at pH >11 (6N NaOH pH adjustment). Also the
pesticides/PCB extractions were performed at pH 5.5-6.5 (no pH
adjustment necessary). The samples were stirred using a 370 mm
glass rod and a drop of the solution was tested with pH test
strips. The samples were then spiked with 100 uL-1 mL aliquots of
the appropriate stock solutions.
An Allihn condenser was attached. An FTS refrigerated water
recirculator was used to cool the condensers. The temperature of
each condenser was 5°C. The stopcock was opened and approximately
50 mL of methylene chloride siphoned over into the boiling flask.
The heating mantles were turned on after the condensers were cold
to the touch and extraction continued for 24+ 2 hours. All
extractions were generally carried out in the dark (no sunlight and
a minimum of exposure to fluorescent lighting) to avoid photo-
decomposition of light-sensitive compounds.
The extracts obtained were concentrated via the Kuderna-Danish
procedure specified by EPA NPDES method 625 (macro followed by
micro K-D/Snyder columns). However, a condenser device was
employed during the macro K-D step to assure prevention of
emissions (S-EVAP from Organomation Assoc.,Inc., South Berlin,
MA) . Also, less Na2S04 was employed for extract drying (20-30
grams was used).
J'Macro-" CE Extractors (figure /I);
The operation of the these larger extractors was very similar.
However, 600-1000 mL of solvent was used and loading of the
methylene chloride was without the benefit of a stopcock in the
solvent return-line. The flow rate through the extractors was
approximately 6 mLs/minute (rheostat set at 60% full scale).
Instrumental Analysis:
A tiered approach of analysis was employed when working with the
design configuration of the CE. To help resolve and correct CE
design problems, simple spiking solutions were used to verify
performance and analyses were performed on the GC/FID.
Once the design was finalized all analyses were performed by GC/MS,
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except for toxaphene and PCBs, which were via GC/ECD.
GC/MS analysis was performed (GC/MS via 70 eV electron impact as
per EPA method 625 for the reported recoveries of the target
compounds, except for Toxaphene and PCBs, for which GC/ECD was
employed.
Calculations; (The details of calibration solution preparation are
included in the Appendix).
A reference solution (same volume of material that was added as the
spike), was prepared in a volumetric flask (same volume as the
final volume for the K-D process).
The reference solution was analyzed and concentration was verified
versus a 100, 50, 20 and 10 ng calibration standard curve prepared
from AccuStandard stock solutions. The guantitation was based on
internal standard (response factor) calculations as per method 625.
The percent recovery of spiked material was determined as follows:
% Recovery = ng measured in extract X 100
ng measured in reference
This technigue took advantage of the improved precision associated
with the internal standard technigue.
The exception to this reference solution approach was the analyses
of the "BNA Spiking Solution," (48 priority pollutants).
Quantitation was performed as based on the AccuStandard
"Calibration Standards (GC/MS)". This guantitation procedure for
the BNAs was the same for the "macro-" and "micro-" continuous
extractors. As resultant extracts were ideally 100 ng/uL, %
recovery was the same as the ng/uL measured from the calibration
curve.
D.General Quality Control:
a. All glassware including CEs were solvent rinsed, soap and
tap water cleaned, deionized water rinsed and heated in a
high temperature oven (400-450°C) for 6-8 hours prior to
use.
b. All surrogate, matrix spike and priority pollutant
standards, and spiking materials were certified materials
(CRADA) or were obtained directly from the USEPA Quality
Assurance Materials Bank in RTF, NC.
c. The GC/MS mass assignments were calibrated with FC43 prior
to analyses.
d. The GC/MS relative mass abundances were tuned by obtaining
the spectrum of DFTPP. This was stressed for the
identification of non-target compounds in the analyses of
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wastewater.
e. Immediately before GC/MS analysis, each sample was spiked
with an internal standard mixture. GC/FID/ECD used the
external standard quantitation technique. Each batch of
samples analyzed by GC/MS and GC/FID/ECD included
calibration check standards, analyzed throughout each
analytical run.
f. The sensitivity of the GC/MS instrument to 40 ng of
dlO-phenanthrene was at least 50,000 area counts. The
sensitivity of the GC/FID/ECD was confirmed by GC/MS
analyses.
g. All surrogate and matrix spike recovery limits
referenced in this study were from the Super£und
Contract Laboratory Program (CLP) protocols
The recovery limits for the BNAs and pesticides were
as per EPA Methods 625 and 608.
h. Compound spike recoveries were computed against a
the response to a reference standard prepared the same day
the samples were extracted. Reference standards and
samples were analyzed on the same day and on the same
GC/MS or GC/ECD. The exception to this procedure was for
the analyses of BNA spikes (48 compounds), in which a
freshly prepared multiple point calibration curve was
employed to determine the concentration of the analytes
and % recovery was calculated vs. the certified values
for the spiked QC materials.
i. Data quantitation was performed by automated
procedures using Incos software (GC/MS Finnigan MAT, San
Jose, California) and HP Chemstation software (GC/FID,
GC/ECD Hewlett Packard, Palo Alto, California).
j. All compound identifications via GC/MS were made by
comparing known reference spectra to those of the
unknowns. GC/FID identifications were based on retention
time matches to reference material, with GC/MS
confirmation. GC/ECD identifications were based on
retention time matches to reference materials.
k. All spikes into aqueous matrices were prepared in a
hydrophilic solvent.
1. Precision and accuracy were routinely based on four (or
more) replicate spikes carried through the entire
analytical process.
II. Results and Discussion
A major initial challenge of this work was to eliminate the
carry-over of water into the solvent reservoir (boiling flask). A
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combination of design changes and procedural changes (loading
technique) has eliminated this problem and the associated poor
recoveries of hydrophilic compounds (erratic and low recoveries).
Miniature Continuous Extractor Design (Height of the S-shaped
Solvent Return Line):
Initial trials were performed on continuous extractors (.prototype
that used approximately 100 mLs of methylene chloride) by analyzing
laboratory pure water fortified with the CLP matrix spike and
surrogate compounds. This afforded a relatively inexpensive
mixture which resulted in simple chromatographic runs which could
employ GC/FID analyses. A number of difficulties with these
preliminary designs were encountered. One critical parameter was
the height of the "S" shaped solvent return-line. The distance
from the base of the extractor to the top of the return-line
directly determined the depth of the solvent below the aqueous
sample. At the initial height of 175 mm, water routinely "broke
through" the solvent reservoir during the extraction. In addition,
this, design included a return glass tubing line with an inside
diameter of 4 mm and a 2 mm Teflon stopcock. It was found that any
water droplets in the solvent return-line stopped the flow of
solvent (surface tension). The height of the "S" tube was adjusted
to 185 mm and the inside diameter of the tubing was adjusted to 10
mm. A 4 mm Teflon stopcock was bored out to interface with the 10
mm tubing. These adjustments largely avoided water carryover.
Matrix spike and surrogate results were much improved, but water
(aqueous sample) would periodically break through the solvent
reservoir (base of the continuous extractor). As indicated in
Table #1, the recovery of surrogates were acceptable but were more
erratic and lower when water was observed in the extract. The
greatest reduction in recovery was associated with the phenolic
compounds (2-fluorophenol and d5-phenol) , which have great affinity
for water and could be easily lost during the drying step with
sodium sulfate (significant quantities of water causes the Na2S04
to form lumps that could entrap the associated hydrophilic
compounds). Matrix spike recoveries were similarly acceptable.
Only trace amounts (a few drops) of water were observable in the
extracts associated with Table 2. With a height of 185 mm for the
"S" line. 150 mL of solvent was necessary for continuous
extraction.
In previous work with the "macro" CEs (used routinely by our
laboratory since 1986), little concern had been given to losses of
methylene chloride during the extraction period. However, re-
circulating chillers were routinely employed (Neslab-Coolflow 75) .
During the work with miniature or "micro" CEs, slight but
repetitive losses of solvent were visually apparent. For this
reason, volumes of methylene chloride were measured before and
after the extraction period (24 hours + 2 hours) . An FTS model RC-
25 recirculation chiller was employed and set at 5°C. The chiller
was charged with laboratory pure water mixed with 1:1 (v/v)
ethylene glycol. Two hundred mLs of methylene chloride and l L of
water were loaded and the routine extraction procedures were
10
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followed.
measured:
After the extractions the distribution of solvent was
LOSSES OF METHYLENE CHLORIDE DURING CE EXTRACTION
("MICRO" CE, WITH CHILLER AT 5°Cf 24 HOUR EXTRACTION)
CEs were initially charged with 200 mL of CH2CL2
DISTRIBUTION OP METHYLENE CHLORIDE (mL) FOLLOWING EXTRACTION
EXTRACTOR
**
1
2
3
4
AVE.
CE
RESERVOIR
135
105
135.
140
128
SIDE
FLASK
43
75
48
41
52
TOTAL
178
180
183
181
181
LOSS
VS 200 mL
21
20
17
19
19
% LOSS
10.5
10
8.5
9.5
9.6
** Four separate extractor units were tested
Essentially 10% of the solvent was lost during the extraction.
Since methylene chloride is about 2% soluble in water and the
extractors were charged with 1000 mL of water, 20 mL of methylene
chloride could be dissolved in the aqueous sample and could account
for the loss in solvent.
It was determined that a number of variables associated with the
miniature extractors could affect water breakthrough. These
included: how vertical the extractors were placed in the ring-
stand; the height of the "S" return line; and the possible losses
of solvent during the extraction (10% on average). To allow for
such variables and to reliably avoid water breakthrough, it was
decided to extend the height of the "S" line to 195rom. The
miniature CEs with the 195 mm return line required 200 mL of
methylene chloride.
Continuous Extractor Design (Overall Length) ;
An additional variable that proved important was the length of the
CE extractor above the aqueous sample. During the extraction,
solvent collected at the drip tip of the Allihn condenser and
dropped to the aqueous sample surface. In the "Macro" extractors,
this "drop distance" was sufficient to have the solvent droplets
easily break the water surface tension and pass through the sample
as small droplets. Such solvent droplets with large surface to
volume ratios were thought to provide the best extracting exposure
as they "fall" through the sample. However, the miniature or.
"micro" extractor droplets were accumulating on the sample surface
until large pooled droplets of solvent would "fall" through the
sample. The micro extractor design was altered by extending the
length of the CE extractor 30 mm to 400 mm (figure 2) .
11
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Final Miniature ("micro") CE design:
The final dimensions of the one piece, all glass extractor (with
Teflon stopcock in the solvent return line) were as follows [Figure
2]: overall height 400 mm; height of solvent return line 195 mm;
overall diameter 80 mm; inside diameter of the return line tubing
10 mm; and 4 mm Teflon stopcock bored to interface with the 10 mm
tubing. The simple one piece units were easy to charge with both
solvent and sample and to mount in the ring stands. since they
were all glass (except for the stopcock), they were easy to clean
and the entire extractor could be placed in a high temperature oven
(425-450°C) as the final step in the cleaning procedure.
Loading the Extractor:
A combination of closing the stopcock, followed by adding all 200
mLs of the extracting solvent to the CE unit, plus the slow
addition of the aqueous sample (a funnel used for about the first
half of the sample volume) has minimized water carryover into the
boiling flask (described in detail in Section c (General
Procedures) . This loading technique also minimized the exposure of
the analyst to the organic solvent.
Determination of solvent flow rate;
The flow rate of solvent was set at 7.5 mLs per minute. This was
adjusted by varying the rheostat settings (80% of full scale). The
flow rate was measured by marking the level of the solvent in the
reservoir at equilibrium (at a given rheostat setting) and then
closing the stopcock for a measured time interval and marking the
level of the solvent. The volume of solvent distilled over during
the measured interval was determined by filling the emptied
extractor with solvent (between the two marked levels). Without a
stopcock it would be difficult to determine the solvent flow rate.
Sodium Sulfate and possible alternatives;
The final design of the miniature continuous extractors had
minimized solvent use (about a five fold reduction). However, once
the extraction was completed, the extract was dried (water removed)
by passing it through sodium sulfate. The drying columns specified
by EPA Method 625 are 19 mm ID and long enough to allow 100 mm of
sodium sulfate. The method specifies that 20-30 mL of methylene
chloride be used for rinsing the flask and the drying column after
passing the extract through the column. Large volumes of rinse
solvent (greater than 20-30 mLs) will negate the effort at
minimizing the solvent used during the extraction. Very
preliminary results are listed in the Appendix for one possible
alternative to the use of sodium sulfate dryirig columns, namely
hydrophobia filters. A sample of prototype filters was provided by
Varian Corporation (Sample Preparation Division). 100 ng of the
BNA target compounds were placed in 60 mLs of methylene chloride
(about the volume of the extract resulting for miniature CE
extractions). The filters were rinsed with 5 mLs of solvent and
12
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the extracts were KD concentrated to 1 mL. The recoveries for the
target compounds are listed in the Appendix. The use of these type
of filters for drying extracts with small amounts of water (2-4 %)
would avoid the necessity for sodium sulfate columns and should
require far less solvent volume for rinsing. Similarly, syringe
"micro- sodium sulfate columns" are now available, which may prove
effective.
"Demonstration of Capability" (miniature CEs):
Since the final CE design (figure #2), an extensive series of
spiking experiments were performed into laboratory pure water. The
experimental design (four replicates, at specified concentrations,
and performing all aspects of the analytical method) is that listed
in EPA's organic protocols, e.g., 625, 608, 508. This is referred
to in these methods as the "initial demonstration of capability".
The corresponding analytical methods list specifications for the
accuracy (% recovery) and precision (standard deviation) , which are
to be obtained.
The spiking solutions and procedures for CE as well as quantitation
have been described previously.
CLP Surrogate Compounds
The results for the replicate spikes of the CLP surrogates (n=5),
were excellent (Table #3) . All six compounds were well within the
specified recovery criteria.
Priority Pollutant ("BNA Spiking Solution")
Forty-eight BNA compounds (included in the Supelco CRADA mixes)
were spiked into laboratory pure water in four separate miniature
and macro CEs. Figure #3 is a chromatogram (Reconstructed Ion
Current Profile) resulting from the GC/MS analysis of a "BNA" spike
extract. The resulting recoveries for both the miniature and macro
extractors were all within the acceptance limits as specified by
EPA method 625 (Table 4 and 5) . All but ten compounds were
recovered by the miniature extractor in excess of 90% (average
recovery). The troublesome compounds included:
Average Recovery (Std. Dev.)
with n=4
Compound
Phenol
1 , 3-dichlorobenzene
1 , 2-dichlorobenzene
1 , 4-dichlorobenzene
N-Nitroso-di-n-propylamine
hexachloroethane
1,2, 4-trichlorobenzene
1,1,2,3,4, 4-hexachloro-l , 3-
butadiene
"Miniature"
CE
89.
79.
82.
83.
85.
75.
85.
74.
4
3
9
8
3
7
7
2
(1.
(1.
(2.
(2.
(0.
(1.
(1.
(1.
3)
6)
2)
6)
5)
6)
6)
8)
"Macro"
CE
90.
71.
75.
71.
86.
67.
78.
67.
2
4
7
6
9
5
7
2
(4
(6
(6
(3
(6
(2
(3
(2
•9)
.5)
.4)
•1)
.1)
•7)
•3)
.6)
13
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Average Recovery (Std. Dev.)
with n=4
Compound
2 , 4-dinitrophenol
2-methyl-4 , 6-dinitrophenol
"Miniature"
CE
73.6 (2.0)
80.3 (2.3)
"Macro"
CE
66.1 (4.5)
80.8 (3.2)
The recoveries obtained for these difficult compounds
were in close agreement between the macro and micro extractors,
indicating that the recoveries of these compounds were not related
to the volume of solvent used for extraction.
Figure #4 depicts the BNA spike recoveries (Tables #4 and #5) . As
indicated, the agreement in recoveries was good with the most
notable exceptions occurring when the "macro-" CE recoveries
exceeded 100%. In these cases, the miniature extractors gave
recoveries closer to 100%. The five fold reduction in solvent had
no adverse affect on the recoveries of these target compounds.
NOTE: These extractions were performed at pH<2. It was found that
extraction under acidic conditions greatly improved recovery of
short-chain phthalate esters . Also, floe and emulsion formation
were minimized, even for the continuous extractor method, which is
far less prone to these difficulties than separatory funnel
methods. All compounds, except the most basic ones such as aniline
or benzidine, were effectively extracted at a pH <2.
Spikes of Benzidines and Anilines
Basic semivolatile compounds (substituted benzidines and anilines)
extracted effectively under basic conditions (pH >11), giving spike
recoveries near 100% using the miniature extractors (Table 6) . One
problem encountered involved the recovery of aniline. Though this
compound is not a Priority Pollutant (not an NPDES analyte) and has
been dropped from the Superfund CLP target list, it was in the
spiking mixture and the difficulties encountered were of interest.
The recoveries obtained for aniline were routinely in excess of
150% and were thought related to a adverse "solvent effect"
(presence of methanol in the reference material suppressing the
response of this polar compound. This topic is discussed in more
detail in a later section on recoveries of phenolic compounds in
the.CLP "Matrix Spikes".
Single Component (Priority Pollutant) Pesticides
Single component pesticides (EPA Method 625, 608 and 508) gave
average spike recoveries over 90%, with the exception of endrin
(80%). As indicated in Table 7, all of the accuracy and precision
requirements specified for EPA Method 608 were met (these criteria
were used since they are more demanding) , though GC/MS was used as
the detector for these analyses).
14
-------
Chlordane
The analyses of 50 ug/L spikes (50 ng/uL in the extracts) proved
challenging, but not beyond the quantitation range of the GC/MS.
The chromatographic peaks selected for analysis are presented in
Figure 5 and the mass spectra associated with the heptachlor
component of technical chlordane is presented in Figure 6. The
recoveries averaged 108% with a standard deviation of 2.7 (Table
8) . The range of recoveries specified by EPA Method 608 were 55.2-
109% (limits more restrictive than those in 625).
Toxaphene
The analyses of 50 ug/L spikes (50 ng/uL in the extracts) was
performed by GC/ECD. The recovery data ranged from 100-112% for.
the replicate spikes (n=5) and are presented in Table 9. The
accuracy and precision requirements specified for EPA 608 were met.
PCB-1242 and 1260
The average recoveries for spikes of Aroclor 1242 and 1260 (Tables
10 and 11) were 100 and 97.6 % respectively. The accuracy (average
% recovery) specified for these PCBs in EPA 608 are (24.8-69.6%)
and (18.7-54.9%), respectively.
Figure #7 is the chromatogram associated with one of the spiked
extracts (PCB-1260).
WasteWater Sample
Four liters of waste from a secondary effluent at a local
wastewater treatment plant was extracted in replicate employing
both the "mini-" and "macro" extractors. These analyses included
Superfund Surrogate Spikes (Table 12) . All the recoveries for the
surrogates were within CLP specified limits. The compounds
recovered from this sample are presented in Table 13. The sample
was selected because it contained significant suspended solids.
The resultant CE extracts ("mini-11 and "macro") were orange/brown.
The results indicate that the environmental matrix was successfully
extracted using the miniature extractors, as no apparent bias is
indicated.
S-EVAP
This work was conducted without solvent emissions. A device (the
S-EVAP) was used during the K-D concentration procedure to assure
that methylene chloride was not emitted. The S-EVAP employed
special Hopkins condensers during the KD (macro) solvent
concentration step prior to GC/MS or GC/FID analyses. The use of
this condensing instrumentation for the recovery of methylene
chloride and hexane had been reported as effective and of no
significant effect upon the recovery of semi-volatile compounds .
This current work, "validation" of the miniature continuous
extractors, has provided additional data supporting the use of this
15
-------
pollution prevention device.
Methanol Solvent Effect;
The "solvent effect" of methanol upon acidic semi-volatile
compounds became an inadvertent area of study when spikes of acidic
compounds (prepared in methanol) into deionized water were compared
to spikes made directly into methylene chloride. The spiking
solution contained methanol. The adverse affects were compound
specific with the greatest effect associated with compounds with an
affinity for methanol. The methanol apparently suppressed the
response of H-bonding compounds (acidic compounds such as
pentachlorophenol) in the analysis of the reference standard.
Since methanol does not extract from water using the CE procedures,
the test CE extracts were free of methanol and the associated
suppression. This effect was related to several different
capillary columns and chromatographic conditions (Appendix). The
higher the initial GC temperature, the less pronounced the solvent
effect. Similarly the thinner the stationary phase, the less
"effect" was measured. A tight narrow band of methanol condensed
after injection would be associated with the lower initial
temperatures (30C) and the thicker column phase. As the initial
temperature increased, the methanol would be expected to occupy a
wider band, and the "effect" would be reduced.
III. Conclusions
The miniature continuous extractors:
* Effectively extracted the target semivolatile organics (EPA
Method 625, Superfund Contract Laboratory SOW) with recoveries
(accuracy) and precision within the performance specifications
specified in EPA Methods 625 and 608 (in laboratory pure water and
the tested wastewater).
* Required less methylene chloride per sample extracted, which
should result in significant savings in solvent costs. A 3- to 5-
fold reduction of methylene chloride required for continuous
liquid/liquid extraction was obtained. The use of this device
represents a laboratory pollution prevention measure.
* Required significantly less time to K-D concentrate the
resulting extracts, since less volume- of extract was involved (50-
75 mLs for the miniature extractors versus 200-300 raLs for the
macro CE extractors).
* Significantly reduced the volume of waste solvent to be
recycled. This will save on the expense of recycling this
halogenated solvent (externally) and/or reduce the number of
distillation runs to recover the solvent for direct reuse by the
laboratory.
16
-------
* The extractors were relatively inexpensive ($100 from Lab Glass,
Vineland, New Jersey). The manufacturer has indicated that they
are less expensive to produce than the "macro" extractors because
of the smaller diameter of the CE extractor (smaller stock tubing
is needed for construction).
* Were applicable to most of the Agency's methods for the analyses
of semivolatile compounds. The use of "miniaturized techniques"
(reduction in scale, which preserve the basic chemistries) do not
require the application for a "variance" for use under SDWA and
NPDES. This is an extensive confirmation that the analytical
results are consistent with the mandated EPA methods. The
semivolatile techniques for the RCRA and Superfund programs have
few specifications for the extractors. Therefore the use of this
device should be applicable to most environmental laboratories for
use in the determination of semivolatile organics for the Agency's
programs. One notable exception is EPA's Method 608. This
pesticide method for wastewater does not include the use of a
continuous extractor. However, EPA Method 625 (which uses a
different detector, namely MS) includes the extraction of some of
the method 608 pesticides using CE. The reality is that the 608
analytes extract well by CE and this extraction technique has been
used for years by the Superfund and RCRA programs. However, the
analysis via 608 must be followed for compliance under the NPDES
program (an issue of program compliance as opposed to an analytical
problem).
With this exception, employing this apparatus for the NPDES,
Superfund and RCRA programs would require only a demonstration by
the laboratory of analytical capability ("initial demonstration of
capability" procedure as specified in EPA Methods SDWA, NPDES and
RCRA). Though this "demonstration" is not mandated under the
Superfund program, such a procedure should be part of the
laboratory's routine QC procedure.
In addition, as many of these programs are now operated by State
Authorities, prior to use of this device, the State Authority
should be consulted . (since under delegated programs, States are
able to be more restrictive than the Agency).
* Were easy to setup (ring stands, etc.) and load with sample and
solvent.
* Retained the necessary analytical sensitivity, since the initial
1 L sample volume was retained as specified by the Agency's organic
protocols and the final extract' volumes were as mandated. The
miniature extractors resulted in no loss of analytical sensitivity.
If the sample volume had been reduced, the final extract volume
would have to be correspondingly reduced. This is generally
undesirable for environmental samples, since these extracts
generally have significant suspended/dissolved solids and/or foam.
* Were safer to load, because they use less solvent and because
the stopcock allowed the solvent to be loaded and the sample placed
17
-------
on top. The sample served as a barrier to escaping solvent fumes.
* Unlike extracting devices which employ hydrophobia membranes to
help reduce the volume of solvent for extraction (as low as 100
mLs), the miniature extractors do not suffer reduced recoveries for
hydrophilic compounds, e.g., phenolics.
Additional Observations;
Several of the BNAs (1,4-, 1,3-, 1-2-dichlorobenzenes and 1,2,4-
trichlorobenzene), which are poorly recovered by CE actually should
be dropped from the Agency's semivolatile protocols. These
compounds are too volatile and too hydrophobia to be sampled in 1
L amber containers (too easily lost to the headspace of these
containers) . These compounds are already redundantly listed in the
Agency's volatile organics methods and their measurement should be
restricted to these protocols (required zero head-space septa vial
sample containers are mandatory for these methods).
Though the time for extraction in this study was routinely 24
hours, because of the reduction in the solvent reservoir volume
with this design, the time required to complete extraction should
be reduced (less time for the extracted compounds to be washed from
the solvent reservoir below the sample).
"Drip Lips" placed on the condensers used during CE extraction have
helped avoid contamination at the condenser/CE joint (45/50) when
room humidity condenses. Also this has helped avoid water
(condensation) near electrical equipment (mantles, rheostats),
which would be an obvious hazard for the analyst.
The use of condensers during the K-D concentration step (S-EVAP)
allowed the recovery of solvent, which would otherwise be vented up
the fume hood.
IV. References
1. U.S. EPA Contract Laboratory Program, "Statement of Work for
Organic Analysis, Multi-media, Multi-Concentration", OLM01.0,
12/1990.
2. "Guidelines Establishing Test Procedures for the Analysis of
Pollutants Under the Clean Water Act; 40 CFR Part 136, Federal
Register, October 8, 1991.
3. Slayton, J., Molnar, J. and Alvero, M., "Recovery of Solvents
Utilized in EPA Methods for Extractable Organics", Pittsburgh
Conference, March 1992.
4. Slayton, J. and Trovato, R., "Acid-Neutral Continuous Liquid-
Liquid Extraction of EPA Priority Pollutants and Hazardous
Substances List Compounds", 28th Rocky Mountain Conf., Aug., 1986.
5. Slayton, J., "EPA Case Study", International Conference and
Exhibition on Pollution Prevention in the Laboratory, June 1993.
18
-------
Data Tables and Additional
Figures:
19
-------
TABLE 1
MINIATURE CONTINOUS EXTRACTORS
185mm RETURN LINE
SURROGATE AQC X RECOVERY MICRO
SAMPLE • 2-FLUORO- 05- D5-NITRO-
PHENOL PHENOL BENZENE
2-FLUORO-
l.l'-BI-
PHENYL
2,4.6-TRI- D14-TER-
BROMO- PHENYL
PHENOL
CLP TARGET LIMITS
(21-100) (10-94) (35-114) (43-116) (10-123) (33-141)
NO WATER IN EXTRACT:
T2062403
T2062404
T2062405
T2062406
T629-01
T629-03
T629-04
T629-05
T629-06
AVERAGE
STO.DEV.
67.80
70.60
79.60
83.75
66.45
75.55
65.00
70.17
74.75
72.63
6.28
71.06
72.80
80.26
84.70
71.19
79.65
69.64
74.30
79.50
75.90
5.25
77.13
79.86
85.34
90.36
78.36
85.50
77.36
79.79
85.80
82.17
4.68
84.36
88.70
85.50
81.05
72.72
78.70
74.00
74.39
81.01
80.05
5.58
87.54
89.27
96.07
99.00
86.40
91.00
82.15
. 84.28
89.46
89.46
5.37
91.80
90.30
90.70
89.54
93.07
99.86
92.68
91.79
97.70
93.05
3.48
*************************************************************************
**********************************************************************
WATER OBSERVED IN EXTRACT:
T2062401
T2062402
T629-02
AVERAGE
STD.DEV.
56.46
41.80
49.70
49.32
7.34
57.46
40.90
53.15
50.50
8.59
67.30
48.47
57.77
57.85
9.42
85.40
51.06
50.50
62.32
19.99
71.18
57.37
62.30
-63.62
7.00
90.40
89.50
69.32
83.07
11.92
20
-------
TABLE 2
MINIATURE CONTINOUS EXTRACTORS
185nro RETURN LINE
GCXFID
EXPERIMENT: -MATRIX SPIKE RECOVERY
GC RUN DATE: 19 Aug 92
REFERENCE: T2081701
REF. FILE #: A081992\001F0101.D
COMPOUND NAME
Phenol
2-Chlorophenol
1 , 4-Di chl orobenzene
N-Ni troso-Di -n-Propyl ami ne
1,2, 4-Tr 1 chl orobenzene
4-Chl oro-3-Methyl phenol
Acenaphthene
4-Nitrophenol
2.4-Dinitrotoluene
Pentachl orophenol
Oi-N-Butylphthalate
Pyrene
SJ
T2081702
83.954
85.746
80.058
78.046
79.523
87.769
84.490
92.677
88.453
94.340
86.253
88.283
\MPLE NUMBER
T2081703
85.569
85.447
61.947
72.118
62.032
87.201
76.035
92.966
81.652
93.709
77.747
82.337
T2081704
82.658
82.834
72.310
80.156
72.652
88.104
83.893
95.578
91.285
93.473
87.073
90.322
T2081705
74.619
71.044
62.896
70.276
63.317
78.788
73.806
85.881
78.054
87.736
76.754
78.493
AVE
X REC
81.700
81.268
69.303
75.149
69.381
85.466
79.556
91.776
84.861
92.315
81.957
84.859
STO.OEV
4.024
5.464
4.338
3.738
4.352
3.648
3.814
3.550
4.865
2.410
4.073
4.295
21
-------
180.0-1
.00
0)
p
00
•1-1
RIC
DATA: Al
CALI: CALi
RIC
11/12/92 14:14:00
SAMPLE: FC43
CONDS.: UPGRADE 30C 2 MIN TO 300 AT 10C/MIN
RANGE: G 1/3675 LABEL: N 0, 4.0 QUAN: A
#3
SCANS 600 TO 3400
0, 1.0 J 0 BASE: U 20, 3
225536.
1000
13:20
1500
20:00
2000
26:40
2500
33:20
i
3000
40:00
SCAN
TIME
-------
TABLE 3
Surrogate Recovery (Miniature Continuous Liquid/Liquid Extraction) CESUR.WK1
195mm RETURN LINE
50 ug/L Spike into Lab Pure Water (100 uL of 500 ug/mL of USEPA RTF Repository Standard).
% Recovery
Average Std. CLP
Compound Run 1 Run 2 Run 3 Run 4 Run 5 Recovery Dev. Limits
(n-1)
2-Fluorophenol 87 84.7 91 86.3 88.5 87.5 2.39 21-100
D5-Phenol 92.7 90.6 94.3 90.7 93.9 92.4 1.74 10-94
05-Nitrobenzene 95.6 93 94.4 93.6 96.4 94.6 1.40 35-114
2-Fluoro-l.r-biphenyl 95.8 93.7 99.7 97 99.5 97.1 2.54 43-116
2,4.6-Tribromophenol 101.6 96.6 96.7 92.2 97 96.8 3.33 10-123
014-p-Terphenyl 96 95 93.2 89.6 93.6 93.5 . 2.44 33-141
23
-------
TABLE 4
Validation of Miniature Continuous Extractors BNA TARGETS(195 im S-tube)
Calibration Standard (ACCU Standard 100 ng Z014A.B.O.E.GR.H) With Ultra Sc. Int.
Supelco CRADA QC SAMPLES
NO. COMPOUND
2 PHENOL *CCC*
3 ETHANE, 1.1'-OXYBIS\2-CHLORO-
4 2-CHLOROPHENOL
5 1.3-DICHLOROBENZENE (COELUTES)
7 1.4-DICHLOROBENZENE (COELUTES) *CCC*
8 1,2-DICHLOROBENZENE (COELUTES)
13 1-PROPANAMINE. N-NITROSO-N-PROPYL-
14 ETHANE. HEXACHLORO-
15 BENZENE, NITRO-
16 2-CYCLOHEXEN-l-ONE, 3,5,5-TRIMETHYL- *CCC*
17 2-NITRO-PHENOL
18 PHENOL, 2,4-DIMETHYL-
20 ETHANE, 1,1'-[METHYLENEBIS(OXY)]BIS[2-CHLOR
21 2,4-DICHLORO-PHENOL
22 BENZENE, 1,2.4-TRICHLORO-
24 NAPHTHALENE
25 1,3-BUTAOIENE, l.l^.S^^-HEXACHLORO- *CCC
26 PHENOL, 4-CHLORO-3-METHYL-
29 2,4,6-TRlCHLOROPHENOL HSL
31 2-CHLORONAPHTHALENE
32 1.2-BENZENEDICARBOXYLIC ACID, OIMETHYLESTER
33 2.6-DINITRO-TOLUENE
36 ACENAPHTHYLENE, 1,2-DIHYDRO- *CCC*
37 2,4-DINITROPHENOL *SPCC*
40 4-NITROPHENOL (SEC ION)
41 2,4-DINITRO-TOLUENE
42 1,2-BENZENEOICARBOXYLIC ACID, DIETHYLESTER
43 l-CHLORO-4-PHENOXY-BENZENE
44 9H-FLUORENE
45 2-METHYL-4.6-DINITROPHENOL
47 BROMOPHENOXYBENZENE
48 BENZENE, HEXACHLORO- *CCC*
49 PENTACHLOROPHENOL
51 PHENANTHRENE
52 ANTHRACENE
53 1.2-BENZENEDICARBOXYLIC ACID, DIBUTYLESTER
54 FLUORANTHENE CCC*
55 PYRENE
56 N-BUTYL BENZYL PHTHALATE
57 BIS(2-ETHYLHEXYL)PHTHALATE
59 BENZO/A/ANTHRACENE
60 CHRYSENE
61 DIOCTYLPHTHALATE *CCC*
62 BENZO\B\FLUORANTHENE
63 BENZO\K\FLUORANTHENE
64 BENZO/A/PYRENE
67 DIBENZO(A,H) ANTHRACENE
68 BENZO\GHI\PERYLENE
Al
90.5
91.5
95.7
78.3
84.1
84.3
85.1
76.9
91.6
96.0
95.2
111.8
112.7
95.8
85.3
96.2
71.0
98.3
96.8
95.1
93.8
95.8
95.4
76.1
91.2
97.8
95.8
114.1
99.9
83.8
92.9
98.6
95.1
101.4
96.1
94.7
92.8
93.0
96.0
94.3
95.4
96.1
95.2
106.5
101.3
90.2
94.4
103.7
A2
89.7
91.0
94.1
79.6
79.8
79.5
85.7
73.4
93.7
96.1
98.0
99.7
113.5
96.7
84.5
92.3
74.8
101.7
94.9
90.6
90.0
95.3
93.3
76.0
103.4
97.4
92.0
104.8
92.9
76.9
89.0
91.6
101.7
94.1
88.6
88.6
93.3
91.7
96.5
87.5
95.5
92.5
93.6 .
92.8
112.6
83.0
85.0
92.0
A3
90.4
91.3
94.9
81.1
85.4
86.2
84.4
77.8
91.5
95.6
94.2
104.9
112.9
96.1
87.7
96.0
76.2
98.0
94.2
93.2
91.0
93.0
95.9
72.3
91.2
94.8
92.8
108.0
96.3
81.6
90.7
93.2
90.3
101.1
95.9
96.9
94.1
92.6
99.5
96.0
95.3
95.5
97.9
92.7
102.3
86.6
94.4
105.6
A4
89.6
90.2
94.6
80.8
84.4
86.6
86.0
76.0
90.9
94.6
94.0
113.0
111.8
94.2
87.5
94.9
75.5
95.3
93.2
91.3
90.7
93.0
96.1
72.1
85.8
94.3
93.0
111.7
97.3
79.6
92.8
94.8
88.9
100.3
95.9
95.5
100.8
97.0
103.0
101.5
94.0
98.4
97.0
98.1
95.9
84.0
93.8
10.7.7
REQUIRED 625
AVE STD. RANGE FOR
A5 % REC DEV. AVERAGE
86.9
88.5
91.5
76.8
81.0
82.6
85.3
74.5
88.0
92.7
91.4
111.3
108.5
92.5
83.7
92.8
73.7
94.7
92.1
89.5
89.2
92.6
92.1
71.4
85.2
86.8
92.6
109.6
95.6
79.8
91.4
96.2
91.1
99.5
94.9
94.2
98.6
96.9
98.1
98.0
93.7
95.8
92.2
95.6
96.1
83.3
97.0
100.1
89.4
90.5
94.2
79.3
82.9
83.8
85.3
75.7
91.1
95.0
94.6
108.1
111.9
95.1
85.7
94.4
74.2
97.6
94.2
91.9
90.9
93.9
94.6
73.6
91.4
94.2
93.2
109.6
96.4
80.3
91.4
94.9
93.4
99.3
94.3
94.0
95.9
94.2
98.6
95.5
94.8
95.7
95.2
97.1
101.6
85.4
92.9
101.8
1.3
1.1
1.4
1.6
2.2
2.6
0.5
1.6
1.8
1.3
2.1
5.1
1.8
1.5
1.6
1.6
1.8
2.5
1.6
2.0
1.6
1.3
1.6
2.0
6.5
4.0
1.3
3.2
2.3
2.3
1.4
2.4
4.6
2.7
2.9
2.8
3.2
2.3
2.5
4.6
0.8
1.9
2.1
5.1
6.1
2.7
4.1
5.5
16.6—100
42.9--126
36.2--120.4
16.7—153.9
37.3—105.7
48.6—112.0
13.6—197.9
55.2—100.0
54.3—157.6
46.6—180.2
45.0—166.7
41.8-109.0
49.2-164.7
52.5-121.7
57.3-129.2
35.6-119.6
37.8-102.2
40.8—127.9
64.5-113.5
0—100^
68.1— 13|fl
60.1-132H
D— 172.9
13.0—106.5
47.5—126.9
D-100
38.4—144.7
71.6-108.4
53.0-100.0
64.9—114.4
7.8—141.5
38.1-151.8
65.2—108.7
43.4-118.0
8.4-111.0
42.9-121.3
69.6-100.0
D--139.9
28.9—136.8
41.8-133
44.1—139.9
18.6-131.8
42.0—140.4
25.2-145.7
31.7-148.0
D-199.7
D— 195.0
24
-------
TABLE 5
GC/MS Method Validation Study (October 30, 1992)
Performed by Ed Messer. EPA Central Regional (III) Laboratory
TARGET COMPOUNDS
2 Phenol
3 Bis(2-Chloroethyl)Ether
4 2-Chlorophenol
5 1,3-Oichlorobenzene
7 l.4-D1chlorobenzene
8 1,2-Dichlorobenzene
13 Nitrosodi-n-propylamine
14 Hexachloroethane
15 Nitrobenzene
16 Isophorone
17 2-Nitrophenol
18 2.4-Dimethyl Phenol
20 Bis(2-Chloroethoxy)Methane
21 2-4-Oichlorophenol
22 1.2,4-Tri-chlorobenzene
24 Naphthalene
25 Hexachlorobutadiene
26 4-Chloro-3-Methyl Phenol
29 2,4,6-Trichlorophenol
31 2-Chloronaphthalene
32 Dimethyl Phthalate
33 2,6-Dinitrotoluene
36 Acenaphthene
37 2,4-Dinitrophenol
40 4-Nitrophenol
41 2,4-Dinitrotoluene
42 Diethyl' Phthalate
43 4-Chlorophenyl Phenyl Ether
44 Fluorene
45 2-Methyl-4.6-Dinitrophenol
47 4-Bromophenyl Phenyl Ether
48 Hexachlorobenzene
49 Pentachlorophenol
51 Phenanthrene
52 Anthracene
53 Di-n-Butyl Phthalate
54 Fluoranthene
55 Pyrene
56 Benzyl Butyl Phthalate
57 Bis(2-Ethylhexyl)Phthalate
59 Benzo(a)Anthracene
60 Chrysene
61. Di-n-Octyl Phthalate
62 Benzo(b)Fluoranthene
63 Benzo(k)Fluoranthene
64 Benzo(a)Pyrene
67 Dibenzo(a,h)Anthracene
68 Benzo(g,h,i)Perylene
TRUE
MV1
MV2
MV3
MV4
AVERAGE
VALUE
100
100
100
100
100
100
100
100
100
100
100
100
100
100
.100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
. 100
100
100
100
100
100
100
100
100
100
100
82.9
84.1
85.6
61.1
66.7
65.8
76.6
63.0
98.9
97.9
96.1
84.7
112.0
92.1
73.8
85.7
62.9
105.0
95.1
87.9
98.1
87.0
94.2
68.6
109.0
94.7
90.9
103.0
91.1
80.5
87.8
87.0
94.9
86.9
85.7
85.6
90.9
84.5
102.0
83.2
91.5
86.9
85.6
97.5
87.6
78.0
71.6
66.4
88.3
94.5
92.1
71.3
72.0
75.0
88.2
68.1
91.6
102.0
87.3
104.0
119.0
92.9
77.5
88.7
67.2
108.0
97.8
91.6
97.6
92.3
92.4
61.0
114.0
100.0
96.2
105.0
92.2
85.9
91.1
95.1
102.0
94.1
89.3
87.0
' 95.3
94.3
104.0
86.7
99.2
87.8
94.9
96.0
93.2
79.9
71.9
65.5
95.2
102.0
99.9
78.6
75.5
83.3
92.2
70.1
93.6
104.0
92.3
102.0
124.0
94.8
82.1
88.6
69.6
108.0
98.2
95.3
99.3
96.1
94.3
62.5
111.0
104.0
101.0
107.0
93.8
77.1
90.4
95.3
95.5
97.9
89.5
91.0
103.0
104.0
108.0
94.9
103.0
92.1
98.4
83.0
98.3
73.2
70.4
80.6
94.2
98.6
96.0
74.6
72.0
78.
90.
68.
96.
105.
97.
102.
125.
95.
81.
89.
69.
109.
95.
92.
94.
94.
91.
72.
110.
102.
97.
103.
90.
79.
87.
95.
101.
94.
86.
87.
93.
93.
100.
86.
98.
86.
92.
91.
94.
75.
70.
70.
,7
.5
,9
,2
0
2
0
0
4
2
6
0
0
8
8
6
8
2
1
0
0
6
0
7
7
8
8
0
6
2
0
3
5
0
2
4
5
7
3
1
2
7
6
90.2
94.8
93.4
71.4
71.6
75.7
86.9
67.5
95.1
102.2
93.2
98.2
120.0
93.8
78.7
88.2
67.2
107.5
96.7
91.9
97.4
92.6
. 93.0
66.1
111.0
100.2
96.4
104.5
92.0
80.8
89.3
93.3
98.4
93.4
87.7
87.7
95.6
94.1
103.5
87.8
98.0
88.3
92.9
92.0
93.3
76.6
71.2
70.8
RANGE
REQUIRED
STD
FOR AVG
16
42
36
16
37
48
13
55
54
46
45
41
49
52
57
35
37
40
52
64
68
60
13
47
38
71
53
64
7
.6-100
.9-126
.2-120
.7-153
.3-105
.6-112
.6-197
.2-100
.3-157
.6-180
.0-166
.8-109
.2-164
.5-121
.3-129
.6-119
.8-102
.8-127
.4-129
.5-113
D-100
.1-136
.2-132
D-172
.0-160
.5-126
D-100
.4-144
.6-108
.0-100
.9-114
.8-141
38.1-151,
65.2-108,
43.4-118,
.0
.0
.4
.7
.7
.0
.9
.0
.6
.2
.7
.0
.7
.7
.2
.6
.2
.9
.2
.5
.0
.7
.3
.9
.5
.9
.0
.7
.4
.0
.4
.5
.8
.7
.0
8.4-111.0
42.9-121,
69.6-100,
D-139,
28.9-136.
41
.8-133.
44.1-139.
.3
.0
.9
.8
,0
,9
18.6-131.8
42.0-140.4
25.2-145.7
31.
.7-148.0
D-199.7
D-195.0
DEV
4.9
6.7
5.3
6.5
3.1
6.4
6.1
2.7
2.7
2.7
3.9
7.8
5.1
1.3
3.3
1.5
2.6
1.5
1.3
2.7
1.7
3.5
1.3
4.5
1.9
3.5
3.6
1.7
1.2
3.2
1.5
3.6
3.2
4.0
1.7
2.0
4.5
6.9
3.0
4.3
4.1
2.2
4.7
5.7
3.8
2.6
0.6
6.0
625
LIMIT
STD DEV
22.6
55.0
28.7
41.7
32.1
30.9
55.4
24.5
39.3
63.3
. 35.2
26.1
34.5
26.4
28.1
30.1
26.3
37.2
31.7
13.0
23.2
29.6
27.6
49.8
47.2
21.8
26.5
33.4
20.7
93.2
23.0
24.9
48.9
20.6
32.0
16.7
32.8
25.2
23.4
41.1
27.6
48.3
31.4
38.8
32.3
39.0
70.0
58.9
25
-------
Figure
MINI vs MACRO EXTRACTION
K.
U
>
O
O
U
a:
i-
u
O
a:
u
a.
u
130
120 -
110 -
100 -
vO
64
COMPOUND NUMBERS
D MACRO -h MINI
-------
TABLE 6
Recovery of Anilines and Benzidines ("Basic Compounds"):
Min. Cont. Liq/Liq. Extractors ( 195 mm )
Spikes: 100 ug/L (1.0 mL of 100 ug/mL Working Stock)
Stocks: 5000 mg/L from EPA RTP Repository (MEOH);
Working Stock: diluted 200 uL of each RTP Stock to 10 ML MEOH.
Extraction: 24 hrs; pH >11 (6N NaOH); Chiller 3C;
200 mL Fisher "Optima" CH2C12; 1L Lab Pure Water.
Recovery: Determined Relative to Direct Analysis of Spike.
Compound ***
2-Nitroaniline
3-Nitroaniline
izidine
3,3'-Di chlorobenzi di ne
*** Aniline was tested as well, but the MEOHMeoH in the-reference solution
resulted in multiple peaks (6-8 peaks) in the reference resulting
in exaggerated recoveries (»150% in the extracts (MeOH does not CE extract).
This chromatographic problem was not observed for the substituted anilines or benzidines.
Run 1
96
101
92.
.2
,9
.7
100
Run 2
101
107
98
101
.3
.8
.7
.5
ng or %
Run 3
103.9
114
113.5
116.7
Recovery
Run 4
100.8
107.6
101.4
103.8
Run 5
99,
108,
109,
110.
.4
.3
.9
,5
Average
Recovery
100.3
107.9
103.2
106.5
EPA
625
RECOVERY
-
-
-
8.2-212
Std.
Dev.
(N-l)
2.8
4.3
8.4
7.0
EPA
625
Std.Oev
-
-
-
71.4
27
-------
TABLE 7
Pesticide Validation (Miniature Continuous Liquid/Liquid Extraction) [ FILE : PESTCE.VK1 ]
100 ug/L Spike into Lab Pure Water (1.0 mL of 500 uL of AccuStandard Z-014C diluted to 10.0 ML with
MEOH).
6C/MS ANALYSIS
Compound
Alpha-BHC
Oelta-BHC
Gamma-BHC
Beta-BHC
Heptachlor
Aldrln (HHDN)
Heptachlor Epoxide
Endosulfan I
4,4'-DDE
Dieldrin
'Endrln
4.4'-DDD
Endrin Aldehyde
4.4'-DDT
Endosulfan Cyclic Sulfate
Endosulfan II
Run 1
96.1
98.8
95.9
99.1
93.5
90.9
89.8
99.2
96
90.9
86.6
95.6
94.5
95.9
91.2
98.9
Run
103
% Recovery
2 Run 3 Run
.6
104
103
106
103
101
100
. 107
99
.5
.3
.8
.2
.4
.5
.5
101
91
100
98
102
98
103
.2
.7
.3
.4
.2
.1
92.2
91.8
98.8
105.3
109
101.9
94.2
108.3
96.6
95.6
99
94.2
92.9
86
87.7
102.7
101
91
• 101
98
96
99
4
.1
92
91
.7
,9
.2
.7
.9
95.3
95
81
94
93
95
.1
.3
.2
.3
.6
97
98
.4
Run
98
101
98
103
100
98
97
103
99
98
80
101
108
105
107
Average
5 Recovery
.4
.2
.9
.3
.3
.4
.7
.7
.3
.9
.3
.5
.4
.9
.2
108
98.
97.
97.
101.
101.
98.
95.
103.
97.
96.
87.
97.
97.
97.
96.
102.
,3
.6
6
1
7
1
8
7
3
3
7
2
5
2
3
2
40 CFR
Requi red
Recovery
37-134
19-140
32-127
17-147
34-111
42-122
37-132
45-153
30-145
36-146
30-147
31-141
-
25-160
726-144
D-202
Std.
Dev.
(n-1)
4.42
5.49
4.59
5.96
5.63
4.36
4.00
4.19
1.94
3.87
7.70
3.58
6.47
7.62
7.46
3.87
28
-------
Figure 5
100.0-1
100
482.1-
DATA: CHLOR02 #1
CALI: CAL0715 #3
RIC+MASS CHRGMATOGRAM ' DATA: CHLOR02 #1 SCANS 1700 TO I860
82/17/93 14:17:00
SAMPLE: FC43
CONDS.: UPGRADE 38C 2 MIN TO 300 AT 10C/MIN
RANGE: G 1,3675 LABEL: N 1, 4.0 QUAN: A -1.. 4.0 J 8 BASE: U 20, 3
1799
1136. 3253!
3001.
1729
15.
29.
T
1799
5769.
13547.
1198.
100.030
± 0.509
1841
12.
RIC
.176
392
946
6
9.
1.
J
1
L k
• ' ' ' ' ^L ' ' 1 ' 1 ' ^ I
m 1720 1740 1760 •l0 1800 1820 1843 •360
T40 22:56 23:12 23:28 T3:44 24:00 24:16 24:32 ~4:48
SCAN
TIME
-------
Figure 6
SAMPLE
LIBRARY SEARCH
82/17/93 14:17:68 + 23:59
SAMPLE: FC43
CQNDS.! UPGRADE 30C 2 HIM'TO 380 AT 10C/MIN
ENHANCED 3,4-METHENO-2H-CYCLOBUTACCD3PEHTALEN-2-OHE, 1,1A,3,3ft,4,5,5,5A,5B-N!
M/Z
100
150
280
256
308
358
480
-------
TABLE 8
Miniature Continuous L/L Extraction: Chlordane
50 ug/L spike (Methanol. EPA-RTP). GCMS (100 m/z)
% RECOVERY: STO.
OEV.
Replicate Replicate Replicate Replicate AVE. ug/L
#1 #2 #3 #4 % (n-1)
100 112.1 108 112 108 2.7
608 REQ. (55.2 - 109) 10.0
31
-------
TABLE 9
PERCENT RECOVERY OF TOXAPHENE via MINIATURE CONTINUOUS EXTRACTION
=====================:====:===:================================================
TARGET| PERCENT RECOVERY
CPD I
t j REP-1 REP-2 REP-3 REP-4 REP-5 AVERAGE std (n-1)
====== I =================s======:============:========s:=============:==========
1 | 100 112 108 112 108 108 4.9
TABLE 10
RECOVERY OF PCB-1260 VIA MINIATURE CONTINUOUS EXTRACTION
============
TARGET) PERCENT RECOVERY
CPO | LIMIT
# I PCB1242-2 PCB1242-3 PCB1242-4 PCB1242-5 AVE std (n-l)STO DEV
==== = = I ============
1 | 94 100 101 105 100 4.6 12
TABLE 11
RECOVERY OF PCB-1242 VIA MINIATURE CONTINUOUS EXTRACTION
TARGET| ' PERCENT RECOVERY .
CPD j
« j 1260CE1 1260CE2 1260CE3 1260CE4 1260CE5 AVERAGE std (n-1)
====== I == ================================ ========= === ======================
1 I 91 100 101 95 101 97.6 4.6
32
-------
Figure 7 PCB 1260
0
1 .
0
E
H
D
>
H
>
(D
U
0
CO
M
M
td
/
0
0
p
fl
0
p
0
M
b
i o
so
C3O
-------
TABLE 12
Surrogate Recovery (Miniature & Macro- Continuous Liquid/Liquid Extraction)
50 ug/L Spike into Secondary Effluent (100 uL of 500 ug/mL of USEPA RTP Repository Standard).
% Recovery
Compound
2-Fluorophenol
05-Phenol
05-Nitrobenzene
2-Fluoro-1,1'-biphenyl
2,4,6-Tribromophenol
D14-p-Terphenyl
Min. CE 1
Run 1
85.3
89.5
91.8
88.6
96.8
92.6
-------
TABLE 13
Continuous Extraction of Secondary Effluent
Miniature (HIN.) vs. Macro- CEs
Quantitat ion Based on Assumed Response Factor = 1.
Qualitative Identifications Based Upon EPA-NIH Mass Spectral Library Match.
Scan
413
680
794
815
948
'1012
1103
1106
1125
1393
1404
1583
1743
1755
1911
Compound
Name
dimethyl disulfide
sulfonylbismethane
1-(2-methoxy-1 -methyl ethoxy)-2-propanol
1-(2-methoxypropoxy)-2-propanol
2-(methylthio)pyridine
4,4,5-trimethyl-2-hexene
2-(2-hydroxypropoxy)-1-propanol
3-Ethyl-4-Methyl-1H-pyrrole-2,5-dione
2-methyl-2-(,1-methylethoxy)propane
N,N-diethyl-1,2-ethanediamine
2,6-bis(1,1-dimethylethyl)-4-methylphenol
4-(dimethylamino)-3-methyl-2-butanone
Caffeine
4-(dimethylamino)-3-methyl-2-butanone
methoxycylobutane
MIN. CE
4.5
4
3.3
4.6
0.7
0.6
8.4
0.7
0.7
2.6
1.9
7.6
2.9
2.9
0.7
Estimated
Concentration
(ug/L)
Max. CE
3.7
4.2
2.9
4.2
0.6
1.3
7.5
0.6
0.7
2.5
1.7
8
2.5
4.2
1.5
35
-------
Appendix:
** Calibration standards and Spiking Solutions/Procedures.
** Hydrophobic Membranes—possible mode of extract drying with
minimum use of rinsing solvents.
** Possible "Solvent Effect" associated with methanol.
36
-------
Calibration Standards and
Spiking Solutions/Procedures:
Spiking Solutions (General);
The spiking cocktails were methanol or acetone (miscible with
water) . Additions were made using volumetric pipets, or calibrated
uL pipets. A "reference standard" was prepared using the same
volume as was the spike into a volumetric flask of the same volume
as the final K-D volume (final extract volume) .
Calibration Standards fGC/MS);
Calibration standards (10, 20, 50, 100 ng/uL in MeCL2) for all of
the tested semivolatile compounds (excluding pesticides and PCBs)
were prepared volumetrically from AccuStandard (New Haven, CT)
stock solutions (ampules at 2 mg/mL in MeCl2). The procedure was
as follows:
AccuStd .
(Stock ID)
Z-014A
Z-014B
Z-014D
Z-014E
Z-014G-R
Z-014P
Z-014A
Content
(in MeCl,)
Base Neutral Mix 1
Base Neutral Mix 2
Tox. Sub. Mix 1
Tox. Sub. Mix 2
PNA Mix
Phenols Mix
Int. Std. Mix
Cone.
(ng/uL
2000
2000
2000
2000
2000
2000
4000
Vol. (uL)
AccuStd.
Stock a
Vol. (uL)
AccuStd .
Int. Std.
Final
Vol. (mL) c
Final Cone.
(ng/uL)
10.0
20.0
2.0
10.0
20.0
20.0
2.0
20.0
50.0
20.0
2.0
50.0
50.0
10.0
1.0
100.0
50 uL syringe. 20 uL syringe. Volumetric flask (Class "A")
37
-------
The compound names are delineated in Table #4. The final
concentrations of the internal standards were 40 ng/uL.
Internal Standards;
AccuStandard Internal Standard Mix (Z-014J) was employed, which
consisted of 4000 ng/uL (in methylene chloride) of each of the
following: dlO-acenaphthene; d!2-chrysene; d4-l,4-dichlorobenzene;
d8-naphthalene; d!2-perylene; and dlO-phenanthrene. Because of
concern for the stability of dlO-perylene in solution, it was not
employed as an internal standard (quantitation).
All extracts were spiked with the internal standards mix just prior
to GC/MS analysis.
Superfund CLP "Matrix Spikes" (MS):
Stock solutions (ampules) at 5000 ng/uL were in methanol were
obtained from the EPA Quality Assurance Materials Bank in RTF,
North Carolina. These were diluted 10 fold with methanol to give
500 ng/uL spiking solutions. One hundred uL spikes were performed
directly into 1 L of the aqueous samples (deionized water) prior to
continuous extraction (50 ug/L spike). The compounds included:
1,2-dichlorobenzene; N-nitroso-n-propylamine; 2,4-dinitrotoluene;
di-n-butylphthalate; acenaphthene; 1,2,4-trichlorobenzene; pyrene;
4-nitrophenol; pentachlorophenol; 4-chloro-3-methylphenol; phenol;
and 2-chlorophenol.
This spiking cocktail was used during the design/re-design phases
of this work, in which a relatively simple mixture, with a wide
range of chemical qualities could be accurately measured via GC/FlD
(a means of quickly screening different CE designs, without costly
GC/MS analyses).
Superfund CLP "Surrogate Compound" Spikes:
Stock solutions (ampules at 5000 ng/uL in methanol) were obtained
from the EPA Quality Assurance Materials Bank in RTF, North
Carolina. These were diluted 5 fold to give 1000 ng/uL spiking
solutions. One hundred uL spikes were placed directly into 1 L of
the aqueous samples prior to continuous extraction (100 ug/L
spike). The compounds included: 2-fluorophenol; d5-phenol; d5-
nitrobenzene; 2-fluoro-l,l-'biphenyl; 2,4,6-tribromophenol; and
d!4-p-terphenyl.
BNA QC Spiking Solution:
Quality Control solutions (CRADA ampules) were obtained from
Supelco Inc., Bellefonte, PA. Base/Neutral #1, Base/Neutral #2
ampules were in acetone and contained 37 target semivolatile target
priority pollutant (base/neutral) compounds. Acid #1 ampules
contained 11 priority pollutant (acid) compounds in methanol. All
compounds were at a concentration of 100 ng/uL. These were added
as 1.0 mL (class A volumetric pipets) into 1000 mL of aqueous
38
-------
sample (deionized water) to result in a 100 ug/L spike for each
compound. The compound names are delineated in Table # 4.
Benzidine/s and Aniline/s Spikes;
Stock solutions (ampules) were obtained from the EPA Quality
Assurance Materials Bank, RTF/ North Carolina. C-075 and 62-53-3
(aniline) at 5000 ng/uL in benzene were diluted 50 fold (200 UL to
10 mil in methanol) to result in a working stock of 100 ng/uL. The
excessive dilution was performed to maximize the quantity of
methanol (hydrophilic solvent). This mixed stock solution was
added as 1.0 mL (class "A" volumetric pipet) into 1000 mL of
aqueous sample (deionized water) to result in a 100 ug/L spike for
each compound. The compounds are delineated in Table # 6.
Pesticide Spikes;
Single Component Analvtes;
Stock solutions (ampules) were obtained from Accustandard Z-014C at
2000 ng/uL in 1:1 toluene/hexane. These were diluted 500 uL to 10
mL in methanol (to maximize the hydrophilic solvent). This stock
solution was added as 1.0 mL (class "A" volumetric pipet) into 1000
mL of aqueous sample (deionized water) to result in a 100 ug/L
spike for each compound. The compound names are delineated in
Table # 7.
Toxaphene;
Stock solutions (ampules) were obtained from the EPA Quality
Assurance Materials Bank, RTF, North Carolina. These were as 1000
ng/uL solutions in methanol. Spikes were prepared by the addition
of 50 uL of the stock solutions to 1000 mL of aqueous sample
(deionized water) to result in a 50 ug/L spike for this compound.
The resulting CE extracts were exchanged to hexane (as per method
608/508).
Chlordane;
Stock solutions (ampules) were obtained from the EPA Quality
Assurance Materials Bank, RTP, North Carolina. These were as 1000
ng/uL solutions in methanol. Spikes were prepared by the addition
of 50 uL of the stock solutions to 1000 mL of aqueous sample
(deionized water) to result in a 50 ug/L spike for this compound.
PCBs;
Stock solutions (ampules) were obtained from Supelco, Inc. (CRADA
QC material) for Aroclor 1260 and 1242. These solutions were in
acetone at 50 ng/uL. Spikes were prepared by the addition of 1 mL
(class "A" volumetric pipet) to 1000 mL of aqueous sample
(deionized water) to result in a 50 ug/L spike for these compounds.
The resulting extracts were exchanged to hexane (as per method
608/508).
39
-------
Hydrophobic Membranes
[filters2.wkl]
EXPERIMENT: Validation of the hydrophobic filters. 60 mL of methylene
chloride spiked with the list below and gravity filtered.
"Extracts were concentrated via K-D (EPA 625) and
GC/MS analysis was performed vs. a "reference spike".
COMPOUND
;_
— •--
1 METHANAMINE. N-METHYL-N-NITROSO-
2 PHENOL *CCC*
3 ETHANE. l.l'-OXYBIS\2-CHLORO-
4 2-CHLOROPHENOL
5 1.3-DICHLOROBENZENE (COELUTES)
6 *** D4-1.4-DICHLOROBENZENE ***INTERNAL STD.***
7 1.4-DJCHLOROBENZENE (COELUTES) *CCC*
8 1.2-DICHLOROBENZENE (COELUTES)
9 BENZENEMETHANOL HSL
10 2-METHYLPHENOL HSL
11 BIS(2-CHLOROISOPROPYL)ETHER
12 4-METHYLPHENOL HSL
13 1-PROPANAMINE. N-NITROSO-N-PROPYL-
14 ETHANE, HEXACHLORO- •
15 BENZENE. NITRO-
16 2-CYCLOHEXEN-l-ONE. 3.5.5-TRIMETHYL- *CCC*
17 2-NITROPHENOL
18 PHENOL. 2,4-DIMETHYL-
19 BENZOIC ACID HSL
20 ETHANE. l.l'-[KETHYLENEBIS(OXY)]BIS[2-CHLORO-
21 2.4-DICHLOROPHENOL
22 BENZENE. 1,2.4-TRICHLORO-
23 *** 08-NAPHTHALENE *** INTERNAL STD.***
24 NAPHTHALENE
25 1,3-BUTADIENE. 1,1,2.3.4.4-HEXACHLORO- *CCC*
26 PHENOL. 4-CHLORO-3-METHYL-
27 NAPHTHALENE, 2-METHYL- HSL
28 1.2.3.4.5,5-HEXACHLORO-1,3-CYCLOPENTADIENE *SPCC*
29 2.4,6-TRICHLOROPHENOL *CCC*
30 2.4.5-TRICHLOROPHENOL HSL
31 2-CHLORONAPHTHALENE
32 1,2-BEHZENEDICARBOXYLIC ACID. DIMETHYLESTER
33 2.6-DINITROTOLUENE
34 ACENAPHTHYLENE
35 *** D10-PHENANTRENE ***INTERNAL STD.***
36 ACENAPHTHYLENE. 1.2-DI HYDRO- *CCC*
37 2.4-DINITROPHENOL *SPCC* . .
38 PHENOL. 4-NITRO- *SPCC*
39 DIBENZOFURAN HSL " '
40 4-NITROPHENOL (SEC ION)
41 2.4-DIN1TROTOLUENE
42 1.2-BENZENEDICARBOXYLIC ACID. DIMETHYLESTER
43 l-CHLORO-4-PHENOXYBENZENE
44 9H-FLOURENE
45 2-METHYL-4.6-DINITROPHENOL
Percent R
T073101
85.500
93.354
92.498
90.780
91.007
86.060
85.535
86.503
82.977
69.216
84.193
83.023
97.464
98.508
96.241
104.924
100.037
95.042
90.548
93.348
91.623
93.790
92.721
90.745
64.775
84.823
80.859
83.988
85.173
76.472
81.324
82.432
69.712
67.536
84.284
81.055
77.978
81.574
87.701
87.246
80.430
scoveri es
SAMPLE NU
T073102
90.268
92.885
96.790
95.814
92.881
87.442
89.520
88.717
82.477
97.299
86.212
86.868
91.929
92.175
99.470
107.665
71.771
96.104
97.734
96.470
90.906
98.902
95.399
93.457
66.911
93.313
92.302
86.651
92.398
87.642
88.287
87.826
83.007
75.770
87.618
95.171
84.672
86.406
96.009
92.556
89.049
IB
AVERAGE
87.884
93.120
94.644
93.297
91.944
86.751
87.528
87.610
82.727
93.258
85.203
84.946
94.697
95.342
97.856
106.295
85.904
95.573
94.141
94.909
91.265
96.346
94.060
92.101
65.843
89.068
86.581
85.320
88.786
82.057
84.806
85.129
76.360
71.653
85.951
88.113
81.325
83.990
91.855
89.901
84.740
STD. DEV.
2.4
0.2
2.1
2.5
0.9
0.7
2.0
1.1
0.3
4.0
1.0
1.9
2.8
3.2
1.6
1.4
14.1
0.5
3.6
1.6
0.4
2.6
1.3
1.4
1.1
4.2
5.7
1.3
3.6
5.6
3.5
2.7
6.6
4.1
1.7
7.1
3.3
2.4
4.2
2.7
4.3
40
-------
Hydrophobic Membranes (cont'd)
46 ^»HO STD. AVAILABLE
47 BROMOPHENOXYBENZENE
48 BENZENE, HEXACHLORO- *CCC*
49 PENTACHLOROPHENOL
SO *** D10-PHENANTHRENE ***INTERNAL STD.***
51 FHENANTHRENE
52 ANTHRACENE
53 1,2-BENZENEDICARBOXYLIC ACID. DIBUTYLESTER
54 FLUORANTHENE CCC*
55 PYRENE
56 N-BUTYL BENZYL PHTHALATE
57 B1S(2-ETHYLHEXYL)PHTHALATE
58 *** D12-CHRYSENE***INTERNAL STD.***
59 BENZ/A/ANTHRACENE
60 CHRYSENE
61 DIOCTYLPHTHALATE *CCC*
62 BENZO\B\FLUORANTHENE
63 BENZO\K\FLUORANTHENE
64 BENZO/A/PYRENE
65 *** D12-PERYLENE ***INTERNAL STD.***
66 INDENO(1.2,3-CD)PYRENE
67 DIBENZO(A.H) ANTHRACENE
68 BENZO\GHI\PERYLENE
N-PHENYLBENZENEAMINE DECOMP. OF NNDPA
78.500
79.194
78.996
79.313
82.499
79.466
86.907
91.250
89.885
97.158
103.051
87.408
94.722
74.639
74.949
82.893
83.144
89.225
92.429
88.329
82.387
87.924
89.361
92.561
89.901
87.524
93.386
107.378
103.851
106.327
108.143
91.997
97.892
93.802
86.738
92.354
90.382
90.171
99.621
96.353.
80.444
83.559
84.179
85.937
86.200
83.495
90.147
99.314
96.868
101.743
105.597
89.703
96.307
84.221
80.844
87.624
86.763
89.698
96.025
92.341
1.9
4.4
5.2
6.6
3.7
4.0
3.2
8.1
7.0
4.6
2.5
2.3
1.6
9.6
5.9
4.7
3.6
0.5
3.6
4.0
-------
Possible "Solvent Effect"
(Methanol)
MATRIX SPIKE X RECOVERY MICRO—REFERENCE CONTAINING 200 UL OF METHANOL
(1) PHENOL
(2) 2-CHLOROPHENOL
(3) 1,4-DICHLOROBENZENE
(4) N-NITROSO-N-PROPYL-1-PROPANAMINE
(5) 1,2,4-TRICHLOROBENZENE
(6) PHENOL-4-CHLORO-3-METHYL-
(7) ACENAPHTHENE
(8) 4-NITROPHENOL
(9) 2,4-DINITROTOLUENE
(10) PENTACHLOROPHENOL
(11) 1,2-BENZENEDICARBOXYLICACID,DIBUTYLESTER
(12) PYRENE
SAMPLE
1
(12-89)
30C( initial temp.
921101-01
921101-02
921101-03
921101-04
REF.ffl
REF. #2
REF. #3
AVE. SAMPLES
STD.DEV. SAMPLE
AVE. REF.
) via
83.7
78.3
77.2
84.5
91.9
100.0
97.8
80.9
3-7
96.6
STD.DEV.REF. 4.2
2
(27-123)
GC/MS: 30M
87.7
84.2
82.8
91.0
96.4
100.0
99.0
86.4
3.7
98.5
1.9
50C(initial temp.)GC/MS 30M SPB-5
921101-01
921101-02**
921101-03
921101-04
REF.#1
REF. #2 **
REF. #3
AVE. SAMPLES
STD.DEV. SAMPLE
AVE. REF.
STD.DEV.REF.
79.6
78.7
81.5
91.3
100.0
79.9
1.4
95.7
6.2
81.5
82.8
87.4
92.8
100.0
83.9
3.1
96.4
5.1
3 4
TARGET X
(36-97) (41-116)
SPB-5, 1uM FILM
74.4 82.7
72.7 78.5
69.2 77.1
77.1 84.3
97.3 94.4
100.0 100.0
101.0 99.3
73.4 80.7
3.3 3.4
99.4 97.9
1.9 3.1
5
WATER
(39-98)
, 0.32 mm
77.4
75.2
75.9
80.8
97.9
100.0
102.3
77.3
2.5
100.1
2.2
6
(23-97)
ID
86.6
83.1
82.1
88.1
95.1
100.0
93.7
85.0
2.8
96.3
3.3
7
(46-118)
92.5
91.3
90.1
96.8
98.4
100.0
.101.5
92.7
2.9
100.0
1.6
8
(10-80)
146.0
142.6
142.6
151.7
77.0
100.0
106.1
145.7
4.3
94.4
15.3
9
(24-96)
95.6
93.2
95.3
97.1
97.0
100.0
97.7
95.3
1.6
98.2
1.6
10
(9-103)
212.1
229.9
221.6
216.5
100.1
100.0
90.8
220.0
7.6
97.0
5.3
11
(11-117)
95.3
94.2
94.0
93.6
97.3
100.0
96.8
94.3
0.7
98.0
1.7
12
(26-127)
99.0
95.9
97.7
93.8
101.2
100.0
98.9
96.6
2.3
100.0
1.2
, 1uM FILM, 0.32 mm ID
68.8 80.9
73.5 83.9
77.8 87.0
88.5 95.5
100.0 100.0
73.4 83.9
4.5 3.1
94.3 97.8
8.1 3.2
74.0
76.6
78.1
97.9
100.0
76.2
2.1
99.0
1.5
81.5
84.5
85.6
97,2
100.0
83.9
2.1
98.6
2.0
91.1
93.1
92.3
97.2
100.0
92.2
1.0
98.6
2.0
91.7
92.6
94.3
93.7
100.0
92.9
1.3
96.9
. 4.5
93.4
98.7
97.9
89.4
100.0
96.7
'2.9
94.7
7.5
207.3
241.5
251.4
92.0
100.0
233.4
23.1
96.0
5.7
90.3
92.9
96.0
90.5
100.0
93.1
2.9
95.3
6.7
84.2
91.1
91.1
92.1
100.0
88.8
4.0
96.1
5.6
»****»*******»**«,:***»*********»**********************************************************
42
-------
Possible "Solvent Effect"
(Methanol)
Cont'd
fMb
^Rinitial temp.) GC/FID: 60M SPB-5, 0.25uM FILM,
921101-01
921101-02
921101-03
921101-04
REF.tfl
REF.#2
REF.tt
AVE. SAMPLES
STO.OEV. SAMPLE
AVE. REF.
STD.OEV.REF.
85.5
87.0
81.6
82.6
100.0
94.4
92.8
84.2
2.5
95.7
3.8
84.1
86.1
81.3
82.2
100.0
94.7
93.2
83.4
2.1
96.0
3.6
69.9
75.9
73.5
74.2
100.0
95.8
93.9
73.4
2.5
96.6
3.1
77.1
77.9
73.7
74.7
100.0
94.8
92.3
75.9
2.0
95.7
3.9
0.32imi ID
74.1
78.1
77.4
78.0
100.0
95.0
93.4
76.9
1.9
96.1
3.4
87.4
87.8
81.9
83.3
100.0
95.2
93.3
85.1
2.9
96.2
3.5
88.0
86.1
85.3
86.2
100.0
95.5
93.8
86.4
1.1
96.4
3.2
109.7
111.2
98.4
101.4
100.0
96.4
91.1
105.2
6.2
95.8
4.5
90.4
87.8
86.2
87.4
100.0
95.8
94.6
88.0
1.8
96.8
2.8
130.1
129.7
120.4
127.4
100.0
102.3
91.6
126.9
4.5
98.0
5.6
94.9
90.9
88.7
'••90.. 8
100.0
95.7
93.4
91.3
2.6
96.4
3.4
94.7
92.2
89.8
90.7
ioo.o
96.2
94.0
91.9
2.1
96.7
3.0
A*****************************************************************************************
Solvent minimization in the continuous liquid/liquid
extraction of aqueous samples for semivolatile
organics
OC:35112543
*.,
------- |