United States
Environmental Protection
Agency
Environmental Monitoring and Suppi
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S4-82-041 August 1982
Project Summary
Application of EPA
Method 610 to the Analysis of
Polynuclear Aromatic
Hydrocarbons in Leachate
Samples
Denis L Foerst, Beth A. Froning and Thomas A. Bellar
EPA Method 610, Determination of
Polynuclear Aromatic Hydrocarbons
in Industrial and Municipal Waste-
waters, was designed for the analysis
of 16 PNA compounds in municipal
and industrial discharges. Samples of
a leachate from a sanitary landfill were
obtained and analyzed using method
610 to determine if this method is
applicable for the analysis of PNA
compounds in a leachate matrix.
Leachate samples were also spiked
and analyzed to determine the precision
and accuracy of method 610 for a
leachate matrix.
This Project Summary was developed
by EPA's Environmental Monitoring
and Support Laboratory, Cincinnati,
OH, to announce key findings of the
research project that is fully docu-
mented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
This report summarizes the results of
a spiking study performed on a sanitary
landfill leachate matrix. Fifteen polynu-
clear aromatic hydrocarbons (PNAs)
were dosed into the landfill leachate
and analyzed using EPA method 610.
The results showthatthe PNAs contain-
. ing two, three, or four fused rings gave
U.S. Environmental Protection Agency recoveries greater than 50% (see Table
Region V, Library 1)- Those PNAs containin9 five or six
230 South Dearborn Street
r(-~-7o. Illinois 60604
fused rings gave recoveries less than
50%. All PNAs were spiked at the low
/ug/L to the mid ng/L range.
The leachate matrix was also analyzed
by gas chromatography/mass spectro-
metry (GS/MS) to identify the compounds
present in this complex matrix. Forty-
three compounds were given a tentative
or confirmed identification after packed
column and capillary column GC/MS
analysis. There were an additional 65
compounds present in the leachate
extract that could not be identified.
Further research needs to be performed
to improve the accuracy for the analysis
of high molecular weight PNAs in
leachate samples.
In order to more fully understand the
complexity of this leachate matrix, final
extracts were subsequently analyzed by
GC/MS. The extracts obtained corre-
spond to both the neutral extraction
procedure as specified in method 610
and to the basic and acidic extraction
procedure specified in method 625. The
complex extracts obtained after neutral
extraction showed little difference from
the extract obtained using the basic
extraction. The neutral extraction
procedure gave lesser emulsion prob-
lems than did the basic extraction
procedure. Since the matrix was quite
complex, phenols werealmostquantita-
tively extracted during the basic extrac-
tion. The only phenol found in the
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Table 1.
Recovery and Precision of PNAs Spiked into Landfill Leachate Analysis by Method
610
A
B
C
D
E
F
G
H
1
J
K
L
M
N
0
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo (a) Anthracene
Benzo (b) Fluoranthene
Benzo (k) Fluoranthene
Benzo fa) Pyrene
Dibenzo (ah) Anthracene
Benzo (ghi) Perylene
Indeno f 1,2,3-cd) Pyrene
Spike
Level
10.4
13.7
17.7
1.15
6.31
8.57
0.26
2.35
0.21
0.20
0.09
0.20
0.50
0.51
0.14
Recovery*
From Leachate
%±RSD
115 ±5
85 ±6
94 ±7
117 ±6
81 ±11
71 ± 15
119 ±8
62 ±8
59 ± 10
32 ± 14
29 ±14
26 ± 12
15 ±22
16 ±21
10 ±27
Background*
In Leachate
35.3d
-
1.9 d
3.41"
5.05a
-
0.816
0.52"
0.19
0.03
0.01
0.06"
-
-
-
Recovery0
Reagent Water
%±RSD
79 ±4
80 ±4
81 ±3
84 ±2
85 ±2
71 ±2
92 ±7
85 ±7
82 ±5
90 ±3
94 ±2
67 ±2
86 ±2
86 ±4
94 ±2
'six aliquots
*one aliquot
cthree aliquots
^confirmed by GC/MS
acidic fraction was 2-fluorophenol, the
surrogate standard, and it also carried
over into the.basic fraction.
A summary of the confirmed and
tentative identifications of 43 compounds
found in the leachate sample using both
packed column and capillary column
chromatography is given in Table 2.
Fourteen additional compounds were
identified after using capillary column
chromatography; however, there are
still 65 additional peaks in the capillary
run that defy interpretation and identi-
fication. Packed column chromatography
of the post cleanup leachate extract gave
identifications for some PNA compounds
that were not resolved when the
precleanup extract was analyzed using
capillary column chromatography.
Results
The leachate spiking study revealed a
serious matrix effect for PNA compounds
containing five or six fused rings. The
results are summarized in Table 1 and
demonstrate a trend for much lower
recovery with an increasing number of
fused rings.
The high recoveries for A-naphthalene,
D-f luorene, and G-fluoranthene are due
to the relative magnitude of the amount
spiked to the amount present in the
background. In each of these three
cases, the leachate was spiked at
approximately one-third the background
level. The remaining PNA compounds
were spiked at a level at least twice the
background level. All recoveries from
reagent water are consistent and show
no trend. The correlation coefficients for
recovery versus number of fused rings
are -0.867 for the Jeachate matrix and
0.414 for reagent water when the
results for compounds A,D, and G are
included and are -0.954 and 0.448
when these three compounds are not
included.
Conclusions
Landfill leachates contain a large
number of polar and nonpolar materials.
Method 610 performs reasonably well
for leachate samples containing jug per
liter levels of PNA compounds containing
two, three or four fused rings. PNA
compounds containing five or six fused
rings exhibit low recoveries from landfill
leachates. Almost all polar interferences
are removed using the silica gel
chromatography cleanup procedure.
Confirmation of identity in the post
cleanup extract is easily performed
by GC/MS using packed column chrom-
atography.
Recommendations
Since these leachate samples exhibit
a serious matrix effect of low recovery
for PNA compounds containing five and
six fused rings, further research must
be performed to improve the accuracy of
the analytical method for measuring the
high molecular weight PNA compounds
in landfill leachates.
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Table 2. Compounds Identified in Leachate Samples
Compound
Retention Times Relative
to 4,4'-Dibromobiphenyf
Packed Capillary
Column Column
Identification
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Tetrachloroethene
Chlorobenzene
Dimethylbenzene
2 -Fluorophenol-Surrogate Standard
Cumene
Camphene
1,2,4- Trimethylbenzene
1 ,3-Dichlorobenzene
2,3-Dihydro- IH-indene
1 ,2-Dichlorobenzene
4-Methylbenzene amine
Camphor
Tetramethylbenzene
Triethylphosphate
Naphthalene
t-Butylphenol
2-Methylnaphthalene
1 -Methylnaphthalene
2, 6-Di-t-Butylbenzoquinone
Dicyclohexylamine
Dimethylnaphthalene
Dimethylnaphthalene
Acenaphthene
Dibenzofuran
Octylphenol
Fluorene
Tributylphosphate
N.N-Dimethyl 4-toluenesulfonamide
2(3H)-Benzothiazolone
Phenanthrene
N- Ethyl -4 -toluenesulfonamide
Methyl phenanthrene
Dibutylphthalate
Phenobarbitol
4. 4 '-Dibromobiphenyl-Surrogate Standard
Unknown mol. wt. 238
Fluoranthene
Pyrene
Tetramethylphenanthrene
N-cyclohexyl 4-toluenesulfonamide
4,4' -(1 -methylethylidene) bisphenol
Tributoxyethyl phosphate
Bis (2-ethyhexyl) phthalate
Dioctyl phthalate
Benzo {a) pyrene
—
—
—
—
—
0.117
0.184
0.199
0.216
—
—
—
—
0.332
0.482
0.482
0.506
—
0.523
0.558
0.570
0.652
0.675
0.705
0.734
0.754
0.830
—
0.854
0.874
0.336
0.353
—
7.000
7.0/5
7.044
7.082
7.088
7.777
7.740
7.787
7.225
7.263
—
0.057
0.037
0.732
0.742
0.272
0.253
0.236
0.376
0.343
0.343
0.388
0.338
0.426
0.432
0.483
0.567
0.577
—
0.630
0.700
0.643
—
0.705
0.725
0.776
0.767
0.807
—
0.824
0.884
0.835
—
0.363
0.383
7.000
7.045
7.058
—
7.702
7.070
7.077
7.773
—
7.230
7.473
T
T
T
—
T
T
C
C
T
C
T
T
T
T
C
T
C
C
T
T
T
T
C
T
T
C
T
T
T
C
T
T
C
T
.
T
C
C
T
T
T
T
C
C
C
"Ret. time of 4,4=-dibromobiphenyl is 35.4 min on packed column, and 20.0 min on capillary column.
^T-tentative by similarity of mass spectra; C - confirmed identification by retention time and similarity of mass spectra.
* UAOOVBINMINTMINnNaOmOIMMt-559-017/0718
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The EPA authors Denis L. Foerst (also the EPA Project Officer, see below), Beth
A. Froning, and Thomas A. Bellarare with the Environmental Monitoring and
Support Laboratory, Cincinnati, OH 45268.
The complete report, entitled "Application of EPA Method 610 to the Analysis of
Polynuclear Aromatic Hydrocarbons in Leachate Samples," (Order No. PB
82-22 J 235; Cost: $6.00, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use $300
PS 0000329
U S ENVIR PROTECTION AGENCY
REGION 5 LIBRARY
330 S DEARBORN STREET
CHICAGO IL 60604
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