United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
Las Vegas, NV 89193-3478
Research and Development
EPA/600/S4-89/039 June 1990
Project Summary
Single-Laboratory Evaluation of
Method 8060-Phthalate Esters
Viorica Lopez-Avila, Franklin Constantine, June Milanes, Robert Gale, and
Werner F. Beckert
SW-846 Method 8060 for the
determination of phthalate esters in
aqueous and solid matrices was
modified and evaluated in a single
laboratory. The range of compounds
of interest was expanded to 16
phthalate esters. A study to
determine the sources of phthalate
esters contamination in the
laboratory, its extent, and ways to
minimize background contamination
was conducted as part of the
evaluation. The packed columns
specified for gas chromatographic
analysis were replaced with two
fused-silica open tubular columns of
dissimilar stationary phases. The two
fused-silica open tubular columns
are connected to an inlet splitter and
two electron capture detectors; this
setup allows the primary and
confirmatory analyses to be
conducted simultaneously. Extract
cleanup was performed on alumina
or on Florisil, however, three of the
target compounds were not
recovered from the 10-g Florisil
column (Method 3620). The use of
commercially available Florisil
cartridges was evaluated. Our results
indicate that this approach is feasible
for all 16 compounds. The
interferences represented by
organochlorine pesticides were
evaluated, and possible internal
standards and surrogate compounds
were identified. The revised method
was tested with an estuarine water, a
leachate, a groundwater, an estuarine
sediment, a municipal sludge, and a
sandy loam soil. The results obtained
indicated acceptable accuracy and
precision for most of the target
analytes.
This Project Summary was
developed by EPA's Environmental
Monitoring Systems Laboratory, Las
Vegas, NV, to announce key findings
of. the research project that is fully
documented in a separate report of
the same title (see Project Report
ordering information at back).
Introduction
Regulations for hazardous waste
activities under the Resource
Conservation and Recovery Act (RCRA)
of 1976 and its elements require
analytical methodologies that provide
reliable data. The document "Test
Methods for Evaluating Solid Waste,
Physical/Chemical Methods," Office of
Solid Waste Manual SW-846 (1),
provides a compilation of methods for
evaluating RCRA solid wastes for
environmental and human health hazards.
One of the methods in this document.
Method 8060, addresses the
determination of phthalate esters. This
method provides conditions for sample
extraction (Methods 3510, 3520, 3540,
3550), sample extract cleanup (Methods
3610, 3620, 3640) and gas
chromatographic (GC) determination of
six phthalates in environmental matrices
including groundwater, liquids, and
solids. Analyses are performed by gas
chromatography (GC) using two packed
columns at various temperatures, and the
compounds are determined with a flame-
lonization (FID) or an electron-capture
detector (ECD).
Problems with the current Method
8060 include.
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The primary column specified, a 1.8-m
x 4-mm ID glass column packed with
1.5 percent SP-2250/1.95 percent SP-
2401 on Supelcoport (100/120 mesh),
needs to be operated at two
temperatures (180°C and 220°C) in
order to chromatograph the six
compounds.
The confirmatory column specified, a
1.8-m x 4-mm ID glass column packed
with 3 percent OV-I on Supelcoport
(100/120 mesh), also needs to be
operated at two temperatures (200°C
and 220 °C) in order to chromatograph
the six compounds.
Only six phthalate esters are currently
listed, but other phthalates have been
found in environmental samples.
Surrogate compounds are required to
be spiked into the sample matrix prior
to extraction, yet no compounds are
specified or recommended for this
purpose. Likewise, internal standards
are required whenever internal
standard calibration is used for
quantification purposes, yet no internal
standards are specified or
recommended.
Extract cleanup is performed
according to Method 3610 or 3620, yet
no data are included on the recovery
of the six compounds from the extract
cleanup step.
Many phthalate esters are present as
contaminants in or on laboratory
equipment and in solvents and
reagents (2). Procedures on how to
clean glassware and how to remove
phthalate esters from solvents and
materials should be tested and
incorporated in the protocol. Also,
examples of typical background
contamination of some common
laboratory items should be given to
make the analyst aware of such
problems.
Acurex, under contract to the
Environmental Monitoring Systems
Laboratory in Las Vegas (EMSL-LV),
conducted an evaluation and
improvement study of Method 8060.
Since the current protocol was
inadequate in certain areas (e.g., in
addressing background contamination)
and was lacking information in other
areas such as the sample cleanup and
the GC analysis, the method evaluation
and improvement study was approached
in two phases.
Phase I, the developmental phase,
addressed the following:
Literature review to gather the relevant
information
Assessment of background
contamination of solvents, materials
used in sample cleanup, and
apparatus used for sample extraction
Selection and evaluation of capillary
columns for use in the analysis of 16
phthalate esters (Table 1)
Evaluation of sample extraction
procedures
Evaluation of GC/ECD and GC/FID for
the analysis of samples containing the
test compounds
Evaluation of alumina (Method 3610)
and Florisil chromatography (Method
3620)
Selection of surrogate and internal
standards for use in Method 8060
Sample preservation studies
Upon completion of the experimental
work in Phase I, the protocol was tested
in Phase II on three aqueous matrices
and three solid matrices. Performance
data generated during the evaluation of
the revised Method 8060 include:
Measures of precision and accuracy
Evidence of analyte identification
Evidence of resolution of analyte from
interfering substances
Ruggedness study
Method detection limits
Experimental
Apparatus
(a) Glassware-Essentially as specified
in Methods 3510, 3520, 3540,
3550, 3610, and 3620.
(b) Mixxor-Lidex Technologies, Inc.
(c) Sonicator-Heat Systems
Ultrasonics, Inc., Model W- 375.
(d) Gas chromatographs-Varian 6000
with constant-current/pulsed fre-
quency ECP, interfaced with a
Varian Vista 402 data system;
Varian 6500 with FID, interfaced
with either a Spectra Physics
4290 integrator or a Varian Vista
402 data system. For the
simultaneous injection on the DB-
5 and DB-1701 columns, the
Varian 6000 was equipped with a
J&W Scientific press-fit, Y-shape,
glass-splitter, and with dual ECDs.
(e) Autosampler-Varian Model 8000.
(f) GC Columns-(1) DB-5, (2)
Supelcowax-10, (3) DB-210, (4)
DB-608, (5) DB-1701, (6) RTx-5,
30 m x 0.25 mm ID or 30 m x 0.53
mm ID and different film
thickness.
Materials
(a) Solvents and other reagents-As
specified in Methods 3510, 3520,
3540, 3550, 3610, and 3620.
(b) Florisil-J. T. Baker, Lot N
442707, 60/80 mesh, activated
400"C for 16 hours, th<
deactivated with water (3 perce
by weight).
(c) Alumina-Alumina Woelm N Sup
I, activated/deactivated ,
described for Florisil.
(d) C18 membrane disks-Analytiche
International.
(e) Florisil disposable cartridge
Supelclean SPE tubes consistii
of serological-grade 6-n
polypropylene tubes, packed eai
with 1 g LC-Flonsil (40-p
particles, 60-A pores) he
between polyethylene frits.
(f) Standards-DEP was obtained fro
Scientific Polymer Products,
other phthalates, as well as benz
benzoate and diphen
terephthalate, were obtained frc
Chem Service (distributed I
Bryant Laboratories, Inc.). Puriti'
were stated to be greater than !
percent. Stock solutions of eai
compound at 1 mg/mL we
prepared in isooctane (Bak
Resi-Analyzed, J. T. Bakei
working calibration standan
were prepared initially
isooctane and later in hexane I
serial dilutions of a composi
stock solution prepared from tl
individual stock solutions.
(g) Materials used in contaminate
evaluation (solvents and oth
materials used in samp
preparation)-Various grad<
purchased from a variety
suppliers.
(h) Environmental materials-
Sandy loam soil, obtained fro
Soils Incorporated, Puyallu
Washington, with the followir
characteristics: pH 5.9 to 6.0; I
percent sand, 7 percent silt,
percent clay; cation exchant:
capacity 7 meq/100 g; tot
organic carbon content 1,290
185mg/kg.
A sediment sample of unknov
origin. Analysis of the extract t
GC/MS indicated the presence
petroleum hydrocarbons.
NBS SRM-1572, Citrus leaves.
NBS SRM-1632a, Coal.
NBS SRM-1633a, Coal flyash.
Estuarine water and sedime
collected form San Francisco Ba
South San Francisco, California.
Leachate prepared by Methc
1310 from a soil contaminate
with lead.
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Table 1. Phthalate Esters Included in the Evaluation
Compound CAS No.
Dimethyl phthalate (DMP)
Diethyl phthalate (DEP)
Diisobutyl phthalate (DIBP)
Di-n-butyl phthalate (DBP)
Bis(4-methyl-2-pentyl) phthalate (BMPP)
Bis(2-methoxyethyl) phthalate (BMEP)
Diamyl phthalate (DAP)
Bis(2-ethoxyethyl) phthalate (BEEP)
Hexyl 2-ethylhexyl phthalate (HEHP)
Dihexyl phthalate (DHP)
Benzyl butyl phthalate (BBP)
Bis(2-n-butoxyethyl) phthalate (BBEP)
Bis(2-ethylhexyl) phthalate (DEHP)
Dicyclohexyl phthalate (DCP)
Pi-n-octyl phthalate (OOP)
Dinonyl phthalate (DNP)
131-11-3
84-66-2
84-69-5
84-74-2
146-50-9
117-82-8
131-18-0
605-54-9
75673-16-4
84-75-3
85-68-7
117-83-9
117-81-7
84-61-7
117-84-0
84-76-4
Ground water collected at a
semiconductor plant in Sunnyvale,
California.
Municipal sludge collected from
Santa Clara Valley Water District,
San Jose, California.
Sandy loam soil obtained by
mixing 20 percent organic soil
with 80 percent sand.
Contamination Study
Solvent samples (acetone 150 mL,
hexane 150 mL, diethyl ether 30 mL,
methylene chloride 180 mL) were
individually concentrated by K-D
evaporation to 10 mL and further reduced
to 1 mL with high-purity nitrogen; only
isooctane was not concentrated. At least
two replicate samples of each solvent
were prepared and analyzed.
Samples of Florisil (20 g), silica gel
(20 g), anhydrous sodium sulfate (50 g)
and glass wool (5 g) were immersed
overnight in solvent which was then
separated and concentrated to 1 mL for
GC analysis. Two washings were
performed in each case and the
concentrates analyzed separately. The
effect of baking at 400 °C for 4 hours was
evaluated for anhydrous sodium sulfate
and glass wool.
Samples of filter paper (10 g), paper
thimbles (10 g) and aluminum foil (5 g)
were cut into 0.5-in x 0.5-in pieces and
immersed overnight in solvent which was
then separated and concentrated to 1 mL
for GC analysis. Two washings were
performed in each case and the
concentrates analyzed separately.
Gas Chromatography
Operating conditions: DB-5--120°C to
160°C (hold 16 min) at 15°C/min, injector
temp. 275°C, detector temp. 320"C;
Supelcowax-10--150°C (hold 2 min) to
220°C at 15°C/min, then 260°C (hold 16
min) at 4°C/min, injector temp. 270 °C,
detector temp. 270°C; DB-210-125°C
(hold 1 min) to 240°C (hold 16 min) at
5°C/min, injector temp. 250°C, detector
temp. 250°C; DB-5/DB-608; DB-608/DB-
1701; DB-608/RTx-5; DB-5/DB-1701-
150°C (hold 0.5 min) to 220°C at
3°C/min, then to 275°C (hold 15 min) at
5°C/min, injector temp. 250°C, detector
temp. 320°C.
Sample Extraction
The extraction efficiencies of Methods
3510 (separatory funnel) and 3520
(continuous liquid-liquid extraction) for
the target compounds were determined
with reagent water. Microextraction of 50
mL samples using a Mixxor device and
hexane (10 mL) was also tested.
Preconcentration of phthalate esters onto
C18-membrane disks (Analytichem
International) followed by elution with
acetonitrile resulted in quantitative
recoveries for all 16 phthalate esters.
Solid samples were extracted either in
a Soxhlet extractor with hexane/acetone
(1:1) (Method 3540) or by sonication with
methylene chloride/acetone (1:1) (Method
3550).
Extract Cleanup
Florisil and alumina Chromatography:
glass columns were packed each with 10
g deactivated Florisil or alumina and
topped with 1 cm of precleaned
anhydrous sodium sulfate. The charged
columns were first eluted with 40 mL
hexane which was discarded; the
phthalate esters were eluted with 4:1
hexane/diethyl ether (100 mL for the
Florisil column, 140 mL for the alumina
column).
Florisil disposable cartridges: the
cartridges were washed with 4 mL
pesticide-grade hexane prior to use. The
eluting solvents used were hexane,
mixtures of hexane and diethyl ether, and
mixtures of hexane and acetone.
Removal of organochlorine pesticides in
the presence of phthalates was attempted
with mixtures of 5-percent, 20-percent,
25-percent, and 30-percent methylene
chloride and hexane.
Surrogate Compound and
Internal Standard Evaluation
Ten compounds were evaluated as
possible internal standards and
surrogates for Method 8060.
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Results and Discussion
Phthalate Ester Contamination
Study
Only a brief summary of the results is
presented here. Detailed results of the
study will be published elsewhere (3).
Solvents
Five organic solvents from up to six
different commercial suppliers were
analyzed for 11 phthalate esters. As can
be seen from the summary results listed
in Table 2, six phthalate esters were
detected in some or all of these solvents.
The only phthalate ester detected in any
of the methylene chloride samples above
6 ng/mL was OOP at 8.8 ng/mL in one
sample.
Since typical volumes of hexane and
acetone used in sample preparation are
200 to 300 mL, the amounts of phthalate
esters that can be introduced as
contaminants with solvents could be
considerable.
Materials
The phthalate contamination summary
values (averaged across brands) for the
materials listed in Table 3 represent
averages of second washings. Florisil,
alumina and silica gel showed significant
levels of phthalates even in the second
washing. Florisil disposable cartridges
(not listed in Table 3) in the first washing
showed levels from 10 to 460 iig per
cartridge for 8 of the 11 phthalate esters
listed in Table 3. However, washing of the
cartridges just prior to use with 4 mL
hexane resulted in acceptable method
blanks. Washing alone is not sufficient for
sodium sulfate and glass wool, but baking
these materials at 40°C for 4 hours
followed by solvent washing gave
acceptable blanks. High levels were
found in filter paper, paper thimbles, and
aluminum foil.
Precleaning of these materials is a
must when phthalate esters at low
nanogram levels are to be quantified.
GC Column Evaluation
Of the six fused-silica capillary
columns evaluated, the DB-210 column
was found to be the least desirable
because of a significant baseline drift
during column programming and was
therefore eliminated from further
consideration.
The retention times of the 16
phthalates of interest on the DB-5 fused-
silica capillary column and the
Supelcowax-10 fused-silica open tubular
column and the DB-5 and DB-1701
fused-silica open tubular columns are
presented in Table 4. The GC conditions
were chosen such that all compounds are
resolved and the total analysis time is
approximately 35 min. All phthalate
esters including surrogates were resolved
on the DB-5 and DB-1701 columns; these
columns were proposed for incorporation
in the revised method 8060 since they
can be used in the dual-column/dual-
detector approach for the determination
of Method 8060 phthalate esters.
Sample Extraction
The extraction of reagent water spiked
with each of the 16 phthalate esters at 50
ng/L per component for separatory funnel
and continuous liquid-liquid extraction
and 1 mg/L for the Mixxor extraction gave
the following results:
The continuous liquid-liquid extraction
technique had unacceptable
reproducibilities for all compounds; for
five of the phthalate esters the average
recoveries were only 20 to 45 percent.
Extraction with hexane in the Mixxor
device gave unacceptable recoveries
and reproducibilities.
The separatory funnel extraction
produced recoveries >70 percent for
most compounds, and reproducibilities
were better than 10 percent for two-
thirds of the compounds.
Further evaluation of the separatory
funnel extraction technique at lower
spiking levels (25, 10, and 1 ng/L)
confirmed its usefulness. At 25 ng/L, the
recoveries ranged from 90 to 130
percent, with 11 recoveries between 90
and 110 percent, and at 10 vig/L, the
range was 73 to 117 percent, with 10
recoveries between 90 and 110 percent.
At 1 ng/L, the recoveries ranged from 53
to 152 percent; only four values were
between 90 and 110 percent.
Method Performance
Method performance, as used here,
includes method accuracy (percent
recovery), method precision (percent
relative standard deviation), and method
detection limits. In the case of aqueous
samples, the method accuracy given as
percent recovery of the 16 phthalate
esters spiked into an estuarine water, a
leachate, and a groundwater at 20 ug/L
and 60 jig/L ranged from 59.5 to 117
percent (Figure 1). In the case of solid
samples (an estuarine sediment, a
municipal sludge, and a sandy loam soil)
the recoveries were distributed over a
much wider range (Figure 2) indicating
that method accuracy is a function of
matrix and concentration. Method
precision for aqueous samples (Figure
was better than 27.5 percent. Methc
precision for solid samples (Figure
varied from matrix to matrix (Figure 4).
The method detection limits (MD
were determined for HPLC-grade wat
from the standard deviations (SD)
seven replicate measurements. The
represent the minimum concentratior
that can be measured and reported wi
99 percent confidence. They ranged fro
22 to 640 ng/L for water sample
subjected to Florisil cleanup and 26
320 ng/L for water samples not subjecte
to Florisil cleanup; in both cases a DB
capillary column (single-colum
approach) was used.
Phthalate recoveries from so
samples, spiked at 1 ppm with the 1
phthalates, using Method 3540 (Soxhli
extraction), ranged from 54 percent fi
BEEP to 135 percent for DHP with 1
recoveries >70 percent. When sonicatic
was used, the recoveries ranged from 2
percent for BMPP to 112 percent f<
DMP, with 13 recoveries >70 percent.
Extract Cleanup
Alumina and Florisil chromatograph
were performed with standards in hexar
according to Methods 3610 and 362'
respectively (Table 5). For the Floris
cartridge cleanup, various solvents ar
solvent combinations were tried c
standards in hexane and on standards
the presence of organochlorin
pesticides. It was found that th
organochlorine pesticides can b
removed efficiently from the cartridge
with hexane/methylene chloride (4:1
under these conditions, the phthalal
esters are retained on the Floris
cartridge and can be recovered wil
hexane/acetone (9:1). The recoveries ai
presented in Tables 5 and 6. Addition
details on the Florisil cartridge cleanu
method can be found in Reference 4.
Surrogate Compound and
Internal Standard
Of 10 compounds evaluated, benz'
benzoate was selected as interm
standard and diphenyl phthalat*
diphenyl isophthalate, and dibenz;
phthalate were considered as surrogai
compounds. The selection was base
primarily on the observation that bol
compounds are resolved from the oth<
phthalate esters under the conditions <
the GC analysis.
Conclusions
Contamination from solvents, reagei
materials, and glassware used in th
-------
Table 2. Phthalate Ester Contamination
Phthalate
Dimethyl
Diethyl
Diisobutyl
Di-n-butyl
Diamyl
Dihexyl
Benzyl butyl
Bis(2-ethylhexyl)
Dicyclohexyl
Di-n-octyl
Dinonyl
No. of diff. brands
Below det. limit
Concentr. factor
Acetone
<0.70
< 0.10 -0.40
<0.10 - 0.35
< 0.1 0-0.50
<0.10
< 0.1 0-0.45
< 0.10 - 0.46
<0.10 - 0.45
<0.10
<0.10
<0.10
8
7
750
Ranges
in Common Solvents8
Diethyl
Hexane ether
<0.fO
<0.ro
40 g anhydrous sodium sulfate, second immersion with 300 mL hexane/acetone (1:1).
95 g glass wool, second immersion with 300 mL hexanel acetone (1:1).
'10 g filter paper, second immersion with 100 mL hexanelacetone (1:1).
910 g paper Oiimbles, second immersion with 100 mL hexaneiacetone.
h5 g aluminum foil, second immersion with 200 ml hexaneiacetone (1:1).
'Not able to quantify because of interference.
analysis limit the detection of phthalate
esters at trace levels (ppt-ppb range).
Consequently, their determinations in
environmental samples at ppt-ppb range
require pesticide-grade solvents,
thorough cleaning of the glassware
followed by heat-treatment (for those
items that can withstand 400°C
temperatures), and the minimum number
of steps in sample workup.
Extraction of water samples in a
separatory funnel was desired over the
continuous liquid-liquid extraction since it
gave good recoveries and
reproducibilities for most target analytes,
greatly reduced the extraction time, and
also minimizes contamination.
Preconcentration of aqueous samples on
C18.membrane disks followed by
extraction of the phthalate esters with
acetonitrile gave quantitative recoveries
and good reproducibilities and was
therefore incorporated in the revised
Method 8060.
Extract cleanup using Florisil
disposable cartridges and elution with
hexane/acetone (9:1) gave quantitative
recoveries for all 16 phthalate esters
proposed for incorporation in Method
8060. Organochlorine pesticides overlap
with the phthalate esters when the GC is
performed on a DB-5 fused-silica capil-
lary column. Use of Florisil disposable
cartridges and elution with 20 percent
methylene chloride in hexane helps to
remove the organochlorine pesticides.
Phthalate esters are then recovered from
the Florisil cartridge with hexane/acetone
(9:1). The use of Florisil disposable
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Table 4. GC Retention Times for the Phthalates*
Retention time (min)
Phthalate
Dimethyl
Diethyl
D/isobutyl
Di-n -butyl
Bis(4-methyl-2-pentyl)
Bis(2-methoxyethyl)
Diamyl
Bis(2-ethoxyethyl)
Hexyl 2-ethy/hexyl
Dihexy/
Benzyl butyl
Bis(2-n-butoxyethyl)
Bis(2-ethythexyl)
Dicyclohexyl
Di-n-octyl
Dinonyl
DB-5"
30 m x
0.25 mm ID
3.42
3.45
6.48
7.14
7.96
740
8.41
8,17
863
9.62
969
70.53
11.13
10.98
13.03
16.00
Supelco-
wax-Wt>
30 m x
0.53 mm ID
5.62
6.11
7.26
8.43
8.14
12.05
10 15
1241
11.13
1221
16.36
16.94
13.31
16.66
17.25
20.73
DB-5<=
30 m x
0.53 mm ID
7.06
9.30
14.44
16.26
1877
1702
2025
19.43
21.07
24.57
24.86
27.56
2923
28.88
3333
38.80
DB-1701C
30 m x
0.53 mm ID
6.37
8.45
72.97
74.66
76.27
76.47
7808
78.27
78.97
27.85
23.08
2524
2567
26.35
2983
33.84
Benzyl benzoate (IS) 5.77
Diphenyl phthalate (SU) d
Diphenyl isophthalate (SU) d
Dibenzyl phthalate (SU) d
7.87
d
d
d
12.71
29.46
32.99
34.40
11 07
2832
31.37
32.65
a The GC conditions have been specified under "Gas Chromatography."
b Single-column approach.
c Dual-columnidual-detector approach. The two columns were connected to a J&W Scientific press-
fit, V'-shape, glass-splitter.
d Not available.
cartridges was included as an option
since it results in quantitative recoveries,
reduces contamination, saves chemicals,
and reduces laboratory waste.
Preservation of aqueous samples at
neutral and acidic pH and 4°C is
adequate for 21 days. Preservation of
water samples at pH 9 and 4°C should
be avoided since most compounds show
significant decrease in concentration after
14 days of storage. Storage of spiked soil
samples at -10°C is preferred over
refrigeration at 4°C, since it minimizes
loss of the lower-molecular-weight esters.
The dual-column/dual-detector ap-
proach for the analysis of phthalate
esters increases sample throughput by
allowing the primary and confirmatory
column analyses to be performed
simultaneously. Excellent reproducibilities
of the retention times and detector
responses were achieved with two 30 m x
0.53-mm ID fused-silica open tubular
columns of dissimilar stationary phases
connected to an injection tee and two
ECDs
References
1. Test Methods for Evaluating Solid
Waste (1986), 3rd Ed., SW-846, U.S.
Environmental Protection Agenc
Washington, DC.
2. Giam, C. S , H. S. Chan, and Q.
Neff. Anal. Chem. 47, 225-229 (1975)
3. Lopez-Avila, V., J. Milanes, and W.
Beckert. "Phthalate Esters <
Contaminants in Gc
Chromatography." In preparation.
4. Lopez-Avila, V., J. Milanes, N.
Dodhiwala, and W. F. Beckei
"Cleanup of Environmental Samp
Extracts Using Florisil Solid-Pha;
Extraction Cartridges." J. Chromatoc
Sci. 27(5), 209-215(1989).
-------
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\7~7~\Mici
M1C2
M2C1
M3C1
M3C2
Figure 1. Method accuracy for aqueous matrices (Mt--estuarme water; M2--leachate; M3--groundwater; C^-concentration at 20
component; C2~concentration at 670 ngiL per component)
per
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Figure 2. Method accuracy for solid matrices (M,-estuarine sedtment; M2municipal sludge; M3--sartdy loam soil; C, concentration at 1
per component; C2--concentration at 3 itg!g per component).
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Figure 3. Method precision for aqueous matrices (M,-estuanne water; M2--leachate; M3--groundwater; C,--concentration at 20 ng/L per component;
C2--concentration at 60 ng/L per component).
-------
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-------
Table 5. Extract Cleanup Recoveries (in Percent)
Phthalate
Florisil Cartridges^
Florisil3
Alumina*
Fraction 1
3 Average of two determinations.
b Averages of three determinations, RSDs given in parenthesis.
Fraction 1 was eluted with 5 ml hexane/methylene chloride (4:1) and
Fraction 2 with 5 mL hexane/acetone (9:1).
Fraction 2
Dimethyl
Diethyl
Diisobutyl
Di-n-butyl
Bis(4-methyl-2-pentyl)
Bis(2-methoxyethyl)
Diamyl
Bis(2-ethoxyethyl)
Hexyl 2-ethylhexyl
Dihexyl
Benzyl butyl
Bis(2-n-butoxyethyl)
Bis(2-ethylhexyl)
Dicyclohexyl
Di-n-octyl
Dmonyl
43
57
80
85
85
0
82
0
105
74
90
0
82
84
115
73
65
62
77
77
89
70
75
67
91
72
37
63
91
84
108
71
0
0
0
12
0
0
3.3
0
0
0
0
0
0
0
0
0
130
88
118
121
123
32
94
82
94
126
62
98
no
106
123
102
(52)
(2.8)
(16)
(13)
(57)
(31)
(8.3)
(19)
(8.3)
(6.4)
(15)
(6.5)
(2.7)
(3.3)
(7.0)
(8.7)
Table 6. Percent Recoveries of Phthalate Esters from Various Matrices by Florisil Cartridge Cleanup with
Hexane/Methylene Chloride (4:1) and Hexane/Acetone (9:1) as Eluants"
Phthalate
Dimethyl
Diethyl
Diisobutyl
Dibutyl
Bis(4-methyl-2-pentyl)
Diamyl
Bis(2-ethoxyethyl)
Hexyl 2-ethylhexyl
Dihexyl
Benzyl butyl
Bis(butoxyethyl)
Bis(2-ethylhexyl)
Dicyclohexyl
Dioctyl
Dmonyl
Sandy
Loam
Soil
78
79
79
74
77
82
37
80
78
82
86
74
91
80
84
Sediment
75
79
82
78
84
86
24
88
88
99
94
85
96
92
96
NBS
SRM-1572
80
89
90
84
102
100
62
95
86
114
98
108
106
104
106
NBS
SRM-1632a
76
79
108
83
91
76
32
93
92
102
106
88
98
95
111
NBS
SRM-1633a
82
84
86
83
86
89
33
81
80
98
98
112
95
88
92
a Spiking level is 50 ng/mL for each compound. Data shown are for Fraction 2 which was eluted with 5 mL
hexane/acetone (9:1).
11
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Viorica Lopez-Avila, Franklin Constantino, June Milanes, and Robert Gale are
with Acurex Corp., Mountain View, CA 94039. The EPA author, Werner F.
Beckert (also the EPA Project Officer, see below) is with the
Environmental Monitoring Systems Laboratory, Las Vegas, NV 89193-3478.
The complete report, entitled "Single-Laboratory Evaluation of Method 8060--
Phthalate Esters," (Order No. PB 90-191 7761 AS; Cost: $39.00, subject to
change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Las Vegas, NV 89193-3478
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
x&N^US-OFrFIC'ALMA'L:
*i> '.J\*a»tt-Tv
Official Business
Penalty for Private Use $300
U.S.POSTA6E i«
EPA/600/S4-89/039
iGE'CI
CHICAGO
------- |