United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
Las Vegas, NV 89193-3478
Research and Development
EPA/600/S4-89/022 Nov. 1989
Project Summary
Performance Testing of Method
1312-QA Support for RCRA
Testing
T. C. Chiang, C. A. Valkenburg, D. A. Miller, and G. W. Sovocool
The question of how to access the
risks associated with ground water
contamination from soils containing
toxic substances or wastes disposed
of in a monofill environment is a crit-
ical issue for the U.S. Environmental
Protection Agency (EPA). A major
limitation of using Methods 1310 and
1311 for this purpose is the fact that
the sanitary landfill co-disposal scen-
ario does not apply to contaminated
soils or wastes disposed of In a
monofill environment If these meth-
ods are used to assess sites for
cleanup purposes, the acetic acid
leaching fluid could selectively solu-
billze toxicants (specifically lead) and
incorrectly classify the soil or waste
as hazardous when, In fact, no
mobilization (leaching) would be ex-
pected to occur In the environment
The EPA is considering the use of a
newly-created synthetic acid precip-
itation leach test for soils and wastes
(Method 1312) to provide information
about the mobility (teachability) of
both organic and Inorganic contam-
inants present in these materlals.Thls
new test method is similar to the
TCLP (Method 1311) except that the
acetic acid buffer extraction fluid has
been replaced by a dilute nitric
acld/sulfurlc acid mixture. This acid
mixture simulates the nature of the
precipitation occurring in the region
where the soil sample originated. A
pH 4.2 acid precipitation solution is
used for extraction of wastes.
The purpose of the full report Is to
present results obtained from a pre-
cision evaluation of and ruggedness
test for Method 1312 for soils only.
Several different soils were fortified
with semi-volatile organlcs, metal
salts and volatile organics, and then
leached in replicates of 3 or 6 to
determine method precision. A rug-
gedness evaluation was performed
by making minor changes In speci-
fied method values to Identify pro-
cedural variations requiring careful
control.
This Project Summary was devel-
oped by EPA's Environmental Monitor-
Ing Systems Laboratory, Las Vegas,
NV, to announce key findings of the
research project that Is fully docu-
mented In a separate report of the
same title (see Project Report order-
Ing Information at back).
Introduction
The full report summarizes the quality
assurance support provided to the Office
of Solid Waste in FY-88 and FY-89 by the
Quality Assurance and Methods Devel-
opment Division, Environmental Monitor-
ing Systems Laboratory-Las Vegas,
Office of Research and Development,
under D109 QO1, "QA Support for
RCRA." The major activity conducted by
the EMSL-LV under D109 Q01 was the
evaluation of EPA Method 1312, a pro-
posed synthetic acid precipitation leach
test for soils and wastes.
The question of how to assess the risks
associated with ground water contam-
ination from soils containing toxic sub-
stances or wastes disposed of in a
monofill environment is a critical issue for
the EPA. The large number of samples
needing analysis under legislative man-
date requires that a leaching procedure
be rapid, accurate, reproducible, rugged,
-------
and suitable for a variety of matrices. A
major limitation of using Methods 1310
and 1311 for this purpose is the fact that
the sanitary landfill co-disposal scenario
does not apply to contaminated soils or
wastes disposed of in a monofill environ-
ment. If these methods are used to
assess sites for cleanup purposes, the
acetic acid leaching fluid could
selectively solubilize toxicants (specifi-
cally lead) and incorrectly classify the soil
or waste as hazardous when, in fact, no
mobilization (leaching) would be ex-
pected to occur in the environment. The
EPA is considering the use of a newly
created synthetic acid precipitation leach
test for soils and wastes (Method 1312)
to provide information about the mobility
(teachability) of both organic and inor-
ganic contaminants present in these
materials. This new test method is similar
to the TCLP (Method 1311) except that
the acetic acid buffer extraction fluid has
been replaced by a dilute nitric acid/
sulfuric acid mixture. This acid mixture is
either pH 4.2 or 5.0, which simulates the
nature of the precipitation occurring
where the soil sample originated. A pH
4.2 acid precipitation solution is used for
extraction of wastes.
The full report summarizes results ob-
tained from a precision evaluation of and
ruggedness test for Method 1312 for soils
only. Several different soils were fortified
with semi-volatile organic compounds,
metal salts and volatile organic com-
pounds, and then leached in replicates of
3 or 6 analyses to determine method pre-
cision. Minor changes were made in
specified method values, and a rug-
gedness evaluation was performed to
identify procedural variations requiring
careful control.
Experimental Design
Extractabfe Compounds
Procedure
Two different types of soil were used in
the single laboratory (EMSL-LV, LESC)
precision and ruggedness evaluation of
the Method 1312 protocol: an eastern
soil with high organic content and a
western soil with low organic content
(sandy type). These soils were first
screened for background level and then
fortified with selected TCLP target
compounds at levels suitable for regu-
latory purposes. Refer to Table 2 for the
amount of each extractable compound
typically spiked into 100 grams of soil.
The spiked soil samples were leached
according to the procedure described in
Method 1312. Triplicate aliquots of the
eastern soil were" leached using four
different extraction fluids (pH 3.2, 4.0, 5.0,
6.1) to determine if the pH of the leaching
fluid has a significant effect on either
method precision or recovery. Triplicate
aliquots of the western soil were spiked
at two different analyte concentration
levels, leached, and analyzed to obtain
data on the matrix sensitivity of the
method as well as its dynamic range.
A ruggedness evaluation was designed
to determine the sensitivity of Method
1312 to modest departures from the
leaching protocol which can be expected
during routine application of the protocol.
The ruggedness evaluation of Method
1312 for both volatile and non-volatile
species was performed by following the
test procedure of Youden and Steiner
(Statistical Manual of the AOAC, 1975)
which is designed to determine the level
of significance for n variables using just
n +1 different measurements (in this case
seven variables were chosen with eight
experiments). For the semi-volatile com-
pounds and the metals, the western soil
was used for the ruggedness evaluation.
Volatile Compounds Procedure
The single laboratory precision and
ruggedness evaluation of Method 1312
for volatile organic compounds was per-
formed by Acurex and Midwest Research
Institute (MRI) as a single parallel labora-
tory study. Two contaminated soils orig-
inating in the western (Soil 1) and eastern
(Soil 2) U.S. from Superfund sites and
two soils prepared by combining a clean
soil from Hayward, California with two
different municipal sludges in the labora-
tory (identified as California Urban Soils 3
and 4) were used for the precision evalu-
ation of Method 1312. These soil samples
were analyzed to measure organic and
inorganic contaminants in order to estab-
lish appropriate spiking levels for the
fortification mixture containing 27 Method
1312 volatile target analytes. The fortified
soils were leached in the ZHE and
analyzed according to the procedure in
Method 1312.
The California Model Urban Soils (Soils
3 and 4) were prepared by separately
mixing clean Hayward, California soil
(dried overnight at 120°C) with two
municipal sludges from San Francisco
Bay area sites. They were prepared to
simulate a worst case soil that might be
tested by Method 1312. Aliquots of 25
grams of Soils 3 and 4 were placed into a
ZHE, then spiked directly with the ZHE
piston up using 240 pL of fortification
solution containing 200 pg/mL of 27 vola-
tile analytes (Table 3). The ZHE was
assembled as quickly as possible ar
then was placed in a refrigerator at 4"
for 1 hour prior to the addition of leachir
fluid. Following this equilibration perio
the sample was leached. The soil lead
ate was transferred to an evacuate
Tedtar bag. Each bag was used to t
several VOA vials. These vials wei
capped and then immediately stored
4°C until they were analyzed. The leac
ate was analyzed for volatile compoum
by GC/MS (Method 8260). Soils 3 and
were leached in replicates of 6 analyst
to obtain additional data to evalua
precision. For the Method 1312 rugge
ness test for volatile compounds usir
the ZHE, the clean Hayward, Californ
soil was used. Refer to Tables 6 and 7 f
the variables and fortification levels.
Results and Discussion
Extractable Compounds
Precision
The precision of Method 1312 w;
evaluated by measuring the repeatabili
of recovery of 14 semi-volatile organ
compounds, lead and cadmium. Table
presents the data for an eastern soil, ar
Table 2 that for a western soil. Tt
recovery determinations were made t
fortifying soil samples prior to using ti
leaching procedure. The reported vai
ability is a combination of that from ti
leaching test (Method 1312) and th
from the analytical methods (Metho<
3250/8270 for organics and Method 60;
for inorganics). The variability of tl
organic analytical methods can be es
mated from the RSDs (relative standa
deviations) of the organic surrogate
thus, they are reported with the samp
data. The organic surrogates added
the eastern soil leachate had recover!)
greater than 60 percent and RSDs lei
than 9 percent while the recoveries f
the semi-volatile analytes varied from G
to 75 percent and the RSOs for analyti
with reasonable recoveries ranged from
to 12 percent. The RSDs of the recovc
ies of most compounds reported in Tab
1 are less than 10 percent. The precis!)
of the Method 1312 recoveries for me
compounds at all four pH values
similar to those of the GC/MS surrogat
and is better than the precision obtain*
using Method 1311. Large (greater th,
15 percent) RSDs were observed for fo
compounds. Three of these, 1,
dichlorobenzene, 2,4-dimethylphenol, ai
2,4-dinitrophenol, present analytical diffi
ulties due to their volatility or reactivi
The fourth compound, hexachlorobe
zene, had very low recovery and its ve
-------
Table 1. Method 7372 Precision Results from Eastern Soil'
Extraction Fluid pH
3.2
FORTIFIED ANALYTES
bis(2-chloroethyl)-ether
2-Chlorophenol
1 -4,Dichlorobenzene
1 -2,Dichlorobemene
2-Methylphenol
Nitrobenzene
2,4-Dimeftylphenol
Hexachlorobutadiene
Acenaphthene
2, 4-Dinitrophenol
2,4-Dinitrotoluene
Hexachlorobenzene
y-BHC
P-BHC
METALS
Lead
Cadmium
SURROGATES (in
Leachate)
2-Fluorophenol
ds-Phenol
ds-Nitrobenzene
2-Fluorobiphenyl
2,4,5-Tribromophenol
d14-p-Terphenyl
Avg.
% flee.
75.6
61.4
15.8
11.5
47.6
72.9
12.3
1.2
4.9
60.4
57.5
0.1
3.46
5.3
3.2*>
55.7
62.0
77.0
64.5
62.0
68.8
89.3
%flSO
9.5
8.8
5.3
20.2
9.9
2.3
9.7
3.5
1.0
16.3
3.9
42.5
9.4
8.5
3.6
7.5
5.3
6.2
3.2
3.7
7.6
8.6
4.0
Avg.
% flee.
80.2
62.5
77.2
11.3
47.3
80.4
13.7
1.5
5.7
68.9"
60.4
0.2
3.1
5.4
1.4
38.7
65.8
83.3
71.8
70.1
71.6
97.9
%RSD
12.5
6.8
12.3
8.0
7.7
10.0
18.4
12.9
8.1
6.1
5.4
12.0
16.3
13.3
4.3
2.3
6.5
5.4
8.3
8.4
5.1
6.7
5.0
Avg.
% flee.
69.4
52. 1
16.0
9.9
40.4
66.9
8.4b
1.2
5.2
56.7
52.7
0.1
3.6
5.5
1.3
33.5
58.2
77.7
65.5
59.7
58.7
80.5
%flSD
5.7
9.7
70.7
72.7
7.6
4.3
0.4
5.8
6.6
70.4
5.6
43.3
77.7
2.9
37.4
78.8
2.5
7.5
4.4
4.0
6.6
2.8
6.0
Avg.
% flee.
77.7
57.2
75.3
77.0
43.5
65.5
7.8
7.2
4.7
46.8
49.8
0.7
2.8"
4.8
7.5
30.3
59.3
70.7
62.5
60.5
56.4
77.7
% flSD
6.0
9.5
72.3
27.5
72.6
4.3
3.8
73.4
70.5
73.7
3.3
0.0
72.7
2.4
76.7
76.8
4.7
2.9
7.5
6.9
3.2
6.8
Method 1311
Avg.
% flee.
56.6
42.5
7.9
8.2
40.8
45.2
3.8
0.3
7.7
20.8
27.7
0.0
5.0
4.0
6.3"
37.4
% flSD
74.7
75.5
77.7
5.8
74.4
72.8
27.5
22.4
70.9
70.9
70.8
22.3
78.2
0.0
7.5
'Triplicate analyses.
bDuplicate analyses: one value was rejected as an outlier at the 90% confidence level using the Dixon Q test.
large RSD, in part, is the result of
measurements made near the quanti-
tation limit of Method 8270.
In general, semi-volatile analyte recov-
eries were lower and the RSDs were
higher for the western soil than for the
eastern soil. This appears to be related to
the extraction and measurements steps
since the RSDs of the organic surrogates
added to the soil leachate were also
higher for the western soil. The eastern
(high organic content clay) and western
(low organic content sand) soils are
considerably different and thus the matrix
sensitivity suggested is reasonable and is
consistent with previous TCLP work. In
Table 2, the surrogate RSOs vary from 7
to 63 percent and the semi-volatile ana-
lyte RSDs range from 6 to 55 percent for
the western soil. Thus, the analytical vari-
ability of Methods 3520/8270 is compa-
rable to the total variability of the leaching
procedure. The precision data reported
for the western soil is in general agree-
ment with that of a prior precision
valuation of the TCLP (Method 1311) for
extractable components. In the TCLP
precision study, RSDs for replicate leach-
ings were usually less than 30 percent.
The precision results for the eastern soil
are much better than those of the
previous TCLP study.
The recovery of lead from both the
eastern and the western soils was very
low and the precision was poor. The large
RSDs are, in part, the result of the fact
that analytical measurements were made
near the quantitation limit of Method 6020
(ICP/MS). Cadmium had reasonable re-
covery (30 to 56 percent) from the
eastern soil and its replicate leaching had
recovery RSDs less than 20 percent.
Cadmium recovery was only 4 to 9 per-
cent from the western soil. The precision
(variability) of the triplicate teachings of
cadmium was much greater for the
western soil (63 percent RSD versus 2.3
percent RSD at pH 4.0). Thus, cadmium
showed a greater sensitivity to soil type
in these experiments than did lead.
Both cadmium and lead recoveries are
sensitive to the pH of the leaching fluid.
Lead recovery is significantly greater
when the pH 3.0 leaching fluid is used.
although all of the lead recovery values
are low (1.3 to 3.2 percent). Cadmium
recovery is also greater when low pH
leaching fluid is used, but it varies over a
greater range than lead (30 to 56
percent). The method precision for both
metals is worst when the recoveries are
lowest. Interestingly, lead recovery was
low and only moderately higher when
Method 1311 was used to leach the
fortified eastern soil; this is in contrast to
the results obtained in a recent inter-
laboratory study that showed dramatically
higher lead recoveries with Method 1311.
The reason for this difference is not
known, but points out the need for further
study on the sensitivity of leaching
methods to soil type as well as to the
metal species presented in the sample.
In contrast to results for the metals, the
pH of the leaching fluid has little effect on
either the recovery or the precision (vari-
ability) of replicate teachings for semi-
volatile organic compounds. Periodic
monitoring of the pH of the fluid during
the leaching showed that the pH of the
fluid changed negligibly after the first
-------
Method 1312 Precision Results from Western Soil
Amount
Spiked
(VQ)
pH = 4.2
High Spiking Level
pH *5.0
Low Spiking Level6
Avg.
% flee."
%flSD
Avg.
flec.«
FORTIFIED ANALYTES
bis(2-chloroe1hyl)-ether 1040 45.1 13.7 59.2 14.2
2-Chlorophenol 1620 58.9 28.6 32.4 54.9
1,4-Dichlorobenzene 2000 12.8 11.8 13.6 34.6
1,2-Dichlorobenzene 8920 15.0 6.0 17.0 28.4
2-Methytphenol 3940 40.5 12.2 28.6 32.6
Nitrobenzene 1010 36.1 14.6 45.2 21.3
2,4-Dimethylphenol 1460 3.6 23.3 1.2 87.6
Hexachlorobutadiene 6300 2.5 17.0 4.5 22.8
Acenaphthene 3640 22.2 20.6 8.4* 7.7
2,4-Dinitrophenol 1300 20.5 - 1.8" 15.7
2,4-Dinitrotoluene 1900 61.6 30.1 30.8 54.4
Hexachlorobenzene 1840 0.2 41.8 0.8 173.2
y-BHC 7440 2J.2 23.8<> 76.6 55.2
0-BHC 640 t3.2 33.7 T0.2 5f.7
METALS
Lead
Cadmium
SURROGATES (In Leachate)
2-Fluorophenol
ds-Phenol
d5-Nitrobenzene
2-Fluorobiphenyl
2.4.5-Tribromophenol
d,4-p-Terphenyl
5000
1000
200
200
100
100
200
100
0.3
4.4
65.1
93.5
41.4
44.0
68.0
100.1
27.0
63.0
7.5
10.4
52.4
42.1
10.3
8.1
0.2
9.1
34.4
51.7
46.4
36.8
50.7
87.7
51.7
71.3
60.6
62.7
10.6
15.6
57.1
13.6
•Triplicate analyses.
^Duplicate analyses; one value was rejected as an outlier at the 90% confidence level using
the Dixon 0 test.
cThe low spiking level was 0.20 times the high spiking level.
hour of the 18-hour leaching period. The
final leachate pH of all the eastern soil
samples was nearly the same (pH 4.57 to
pH 4.64) for the pH 4, 5 and 6 fluids and
was thus unaffected by the initial pH of
the leaching fluid. The final leachate pH
was low (pH 4.14) when pH 3.2 fluid was
used. This might be partly responsible for
the 'higher recovery observed for the
metals with low pH leaching fluid.
Volatile Compounds Precision
The precision of Method 1312 was
evaluated by measuring the repeatability
of recovery of 27 volatile organic com-
pounds using four different types of soil.
A summary of the precision data for
these compounds is presented in Table
3. Soil 1 was collected at a Superfund
site west of the Mississippi River and Soil
2 came from a Superfund site in the
eastern United States. Excluding isobu-
tanol, a polar water soluble compound
with known purging difficulties, the
average recoveries for the target analytes
ranged from 10 percent to 85 percent for
Soil 1 and ranged from 7 percent to 89
percent for Soil 2. Twenty-two of the 26
(85 percent) analytes for Soil 1 and 17 of
26 (65 percent) analytes for Soil 2 had
RSDs less than 20 percent. Only four
analytes had RSDs greater than 50 per-
cent; these analytes present significant
analytical difficulties during the purge-
and-trap GC/MS analysis (Method 8260).
Vinyl chloride and the Freons are
extremely volatile and are not trapped
efficiently; acrylonitrito Is water soluble
and does not purge well. In general, re-
coveries were lower and RSDs were
higher from the eastern soil than from the
western soil. This matrix sensitivity ap-
pears most pronounced for carbon tetra-
chloride, ethylbenzene. tetrachloroethene,
Freon 13 (trichlorofluoromethane) and
Freon 113 (1,1.2-trichloro-trifluoroethane).
In general, replicate teachings of the
sludge-contaminated soils (Soils 3 and 4
in Table 3) exhibited greater variability
(larger RSD) than those of the Superfund
soils (Soils 1 and 2). For Soil 3, 20 of the
27 volatile analytes had RSD values be-
tween 28 percent and 42 percent and 5
of the target analytes had RSDs great
than 50 percent. Ethyl acetate displa)
highly variable recoveries ranging from
to 50 percent, its lack of precisic
probably reflects the known difficult!*
associated with purging polar con
pounds from water. The sludge samp
used to prepare Soil 3 contained aceton
(120 ppm) which resulted in an apparei
high recovery (116 percent) for aceton
For Soil 4, 19 of 27 volatile analytes he
RSDs between 24 and 41 percent ar
only two compounds, both polar, eth
acetate and acetone, had RSD value
greater than 50 percent.
Three volatile surrogate compounc
were spiked into the leachates of Soils
4 just prior to analysis by Method 826
Surrogate recoveries were consistent
high (greater than 90 percent with RSC
less than 6 percent) and indicated th
the purge-and-trap and GC/MS systerr
used in the volatile analyses were pe
forming satisfactorily. The Method 131
precision data reported for Soils 1 and
is in general agreement with that ri
ported in a previous precision evaluatic
of the TCLP (Method 1311). The RSC
reported in the TCLP study general
ranged from 3 percent to 20 percent fi
three different types of waste; volati
compound recoveries were found to t
matrix and compound dependent.
Ruggedness
The minor procedural variations use
in the AOAC type ruggedness evaluatic
of Method 1312 for semi-volatile cor
pounds and metals are listed in Table
Two levels of each experimental corn
tion are assigned capital and lower ca
letters and are varied in the mann
shown in the matrix given in Table 4. Tl
group differences calculated from tl
recovery results are shown in Table 5.
columns Va, Vc, and Vd, nearly all groi
difference values have the same sig
generally this indicates possible signi
cance of the column variable. Usually ai
difference which is more than twice tJ
standard deviation of the analytical met
ods is significant and should be furth
studied. Most values in Column Va a
negative, which implies that the extra
table compounds had greater recove
with pH 5.0 leaching fluid than with f
4.2 fluid. However, since all the d
ferences in Column V, pf Table 6 a
less than twice the analyte standa
deviations calculated from the RSDs ai
recoveries given for the western soil
Table 2, the Va group differences a
insignificant and careful control
leaching fluid pH does not appear to I
-------
~«ftte 3. Method 1312 Precision Results on Volatile Compounds
Soil No. 1
Soil No. 2
Soil No. 3
•Triplicate analyses.
hSix replicate analyses.
«Rve replicate analyses.
Soil No. 4
Compound Name
Acetone
Acrylonitrile
Benzene
n-Butyl alcohol (1-Butanol)
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1.2-Dichtoroethane
1,1-Dichloroethene
Ethyl acetate
Ethylbenzene
Ethyl ether
Isobutanol (4-Methyl-i -propanol)
Methylene chloride
Methyl ethyl ketone (2-Butanone)
Methyl isobutyl ketone
1, 1,1,2-Tetrachloroethane
1, 1,2,2-Tetrachloroethane
TetracHoroethene
Toluene
1,1,1-Trichloroethane
1, 1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,1,2-Trichlorotrifluoroethane
Vinyl chloride
Avg.
% Rec.»
44.0
52.5
47.8
55.5
27.4
40.6
64.4
67.3
73.4
37.4
76.4
56.2
48.0
0.0
47.5
56.7
87.7
69.0
85.3
45.7
59.2
47.2
76.2
54.5
20.7
78.7
70.7
%RSD
12.4
68.4
8.29
2.91
16.4
18.6
6.76
8.04
4.59
14.5
9.65
9.22
16.4
NA
30.3
5.94
10.3
6.73
7.04
12.7
8.06
16.0
5.72
77.7
24.5
26.7
20.3
Avg.
% flec.«
43.8
50.5
34.8
49.2
72.9
22.3
47.5
54.8
68.7
22.9
75.4
23.2
55.7
0.0
42.2
67.9
68.9
47.7
58.9
75.2
49.3
33.8
67.3
39.4
72.6
6.95
7.77
%RSD
2.25
70.0
76.3
74.6
49.5
29.7
73.7
76.4
77.3
39.3
4.02
77.5
9.72
NA
42.9
3.94
2.99
11.3
4.15
17.4
70.5
22.8
8.43
79.5
60.7
58.0
72.8
Avg.
% flee.*
776.0
49.3
49.8
65.5
36.5
36.2
44.2
67.8
58.3
32.0
23.0
37.5
37.3
67.8
52.0
73.7
58.3
50.8
64.0
26.2
45.7 i
40.7
67.7
38.8
28.5
27.5
25.0
%flSD
77.5
44.9
36.7
37.2
57.5
47.4
32.0
29.7
33.3
54.4
779.8
36.7
37.2
37.7
37.4
37.3
32.6
37.5
25.7
44.0
35.2
40.6
28.0
40.9
34.0
67.8
67.0
Avg.
% flec.c
27.3
57.8
33.4
73.0
27.3
24.0
33.0
45.8
47.2
76.8
77.0
27.2
42.0
76.0
37.3
40.6
39.8
36.8
53.6
78.6
37.4
26.2
46.4
25.6
79.8
75.3
77.8
%RSD
71.4
4.6
41.1
13.9
31.5
34.0
24.9
38.6
37.8
26.4
115.5
28.6
77.6
72.2
76.6
39.0
40.3
23.8
75.8
24.2
37.2
38.8
25.4
34.7
33.9
24.8
25.4
Tattle 4. Variables Selected for Method 1312 Ruggedness Test on Semi-Volatile Compounds
Parameter
Type
Rug 1 Rug 2 Rug 3 Rug 4 Rug 5 Rug 6 Rug 7 Rug 8
pH
Extraction time
Particle size
Extractor
Liquid/Solid
Ratio
Temperature
filter
A *4.2pH
a = S.OpH
A.a
B,b
C.c
D.d
Ee
F,f
G,g
A
B
C
D
E
F
G
B- 18 hr
b = 16 hr
E = ratio = 20 (2000 mL HjOHOOg)
e * ratio = 16 (1600 mL H^/IOOg)
A
B
c
D
e
f
g
F *
f =
A A a
b b B
C c C
d d d
E e e
f F F
g G g
C * not reduced
c * reduced (grinded)
Ambient approx. 77'F (25'C)
60 - 65'F (16-18'C)
a
B
c
d
e
f
G
a
b
C
D
e
f
G
a
b
c
D
f
F
g
D * standard vessel
d =bottle
G *
g "
one filter
two filters
-------
Table 5. Ruggedness Test Results
Fortified Analytes V,
bis (2-Chloroethyl)ether
2-Chlorophenol
1,4-Dichtorobenzene
1,2-Dichlorobemene
2-Methytphenol
Nitrobenzene
2,4-Dimethylphenol
Hexachlorobutadiene
Acenaphthene
2,4-Dlnitrophenol
2,4-Dinitrotoluene
Hexachlorobenzene
y-BHC
0-BHC
Lead
Cadmium
-2.70
-10.92
-2.52
-4.40
-4.20
-1.72
1.00
-2.25
-3.70
-22.35
-4.90
0.00
-4.68
-2.15
0.20
-3.6
- Group Differences
v* vc
1.75
-4.77
1.77
1.90
-0.05
2.87
0.25
-0.60
2.30
-6.15
0.40
0.05
-1.88
-6.35
-0.20
-0.80
-2.20
-8.08
-1.07
-2.70
-7.90
-3.03
-3.55
0.70
-2.05
-24.70
-2.75
0.10
-0.97
6.30
0.0
7.7
for Semi-Volatile Test Compounds
Vd V. V, vg
6.40
0.23
4.88
4.80
2.40
4.22
0.95
1.00
7.05
5.90
1.65
-0.05
2.68
-5.60
-0.55
-1.85
-0.35
-5.88
-0.67
-0.30
2.05
1.03
0.15
0.50
-2.10
-21.95
2.10
-0.00
3.47
8.55
-0.10
-5.42
2.90
-3.93
-1.08
-1.50
0.40
1.23
1.30
2.25
5.50
-0.15
4.00
0.15
3.97
4.05
0.10
-2.08
-1.55
2.27
-2.77
-4.90
0.15
-0.82
0.30
-0.45
-2.25
5.00
-4.75
0.05
-0.97
1.20
-0.10
-3.30
a critical parameter for Method 1312. A
similar comparison of analyte method
precision with the mostly small dif-
ferences given in Columns Vc and Vd
leads to the same conclusion for the
experimental parameters, particle size
reduction and extractor vessel type. The
other four variables, extraction time,
liquid solid ratio, extraction temperature,
and number of filters used, do not
appear to affect the performance of
Method 1312. Since none of the seven
variables tested is a critical parameter,
Method 1312 appears rugged for the
leaching of semi-volatile compounds and
metals. These results concur with a
previous ruggedness evaluation that
demonstrated the TCLP to be "fairly rug-
ged" for the semi-volatile organic ana-
lytes which were unaffected by variables
B, D. and E in Table 4 in addition to the
parameters: (a) headspace amount, (b)
medium acidity, (c) acid washing of filter,
and (d) filter type. It is interesting to note
that the EPA had previously intended to
investigate extraction temperature but
was unable to do so due to a lack of the
laboratory equipment necessary to vary
the temperature. This study addressed
this issue and determined that extraction
temperature is not a critical method
parameter for the leaching of semi-vola-
tile organic compounds and metals.
The variables chosen for evaluation in
the ruggedness test of Method 1312 for
volatile organics are listed in Tables 6
and 7. Variables C and G are not method
parameters, per se; they were chosen to
determine the effect of analyte concen-
tration upon compound recovery and to
determine the effect of buffering the
leaching fluid. The group differences
calculated from the recovery results are
given in Table 8. Since the differences in
columns Va, Vd, and Ve are generally
small (absolute value less than 5) and of
random sign, the variables leaching fluid
pH, leaching fluid liquid/solid ratio, and
extraction time, do not exhibit an ob-
servable effect on analyte recoveries
and, thus, are not critical parameters for
Method 1312. Due to the large magni-
tude of many values and the general
uniformity of value sign, the variables
associated with Columns Vb, Vc. and Vg
may be significant. Particle size reduc-
tion (Column Vf) generally resulted in
increased recoveries for the more highly
volatile compounds. Smaller soil particle
size probably decreases compound vola-
tility loss during the soil spiking step by
facilitating adsorption of the fortified
compounds by increasing the surface
area of the soil particles. As grinding a
soil sample would increase the loss of
environmentally incorporated analytes,
particle size reduction should not be
considered a critical method parameter
in the leaching of real soil samples.
Addition of 0.1 M acetate buffer (Column
Vg) adversely affected recoveries of vir-
tually all the volatile compounds: studied.
This effect is probably the result, in large
part, of chromatographic analysis diffi-
culties caused by the loading of acetic
acid onto the capillary GC column and/or
into the purge and trap system used in
Method 8260. Fortifying the soil at lower
concentration (i.e., 1 ppm versus 4 pprr
yielded better overall recoveries (Columi
Vc) for the more highly volatile con-
pounds. This higher recovery may b
related to limited analyte solubility in th
purge vessel and/or could result fror
less compound loss during the so
spiking step. Interestingly, the onl
experimental parameter of importanc
appears to be the type of ZHE used. Th
Millipore ZHE gave higher recovery tha
the Associated Design ZHE for nearly a
the organic compounds. This result i
surprising given our experience wit
leakage difficulties associated with use c
the Millipore ZHE and is in contrast wit
the results of a previous ruggednes
evaluation of the TCLP for volatil'
compounds. In that study, the onl
critical parameter identified was the typi
of ZHE; the Millipore ZHE producei
lower analyte recoveries than thi
Associated Design ZHE and had notabli
leakage problems. The reason for thi:
major discrepancy is not known but i
may be related to operator experience
with the different ZHE devices in thi
different laboratories.
Recommendations
Method 1312 is suitable for thi
characterization of soil samples. How
ever, additional information on the per
formance of the method as a model fo
the mobility of toxicants in the environ
ment is required. It is recommended tha
studies be conducted to: measure thi
mobility of different lead- and mercury
containing compounds in the soil; comp
are the mobility of toxicants in soi
columns with Method 1312 mobility; am
develop specific performance data fo
SW-846 methods (i.e., Method 8150 ant
Method 8081) when they are used t<
analyze Method 1312 leachates.
Conclusions
Method 1312 is a reasonably ruggec
and precise method that can be used to
address the mobility of pollutants in soi
samples. The performance of Methoc
1312 for leaching organic compound!
was very similar to that of Method 131
(TCLP). Method 1312 was less efficien
at leaching cadmium and lead than was
Method 1311.
-------
Table 9. Variables Selected for Method 1312 Ruggedness T
Upper Lower
Variable case (A) case (a)
Extraction fluid pH
ZHE apparatus
Analyte soil cone.'
Extraction time
Liquid/solid ratio
Particle size reduction
Buffer addition
% Recovery of analytes
4.1
MP
0.8 ppm
20hrs
22:1
with
with
4.3
AD
4 ppm
16hrs
18:1
without
without
esting for Volatile Compounds
Experiment Number
1
A
B
C
D
E
F
G
s
2
A
B
c
D
e
f
9
f
3
A
b
C
d
E
f
9
u
4
A
b
C
d
e
F
G
V
5
a
B
C
d
e
f
9
w
6
a
B
c
d
E
f
G
X
7
a
b
C
D
e
f
G
y
8
a
b
c
D
E
F
g
z
"Fortified soil nominal concentration level. Refer to Table 7 for experiment dependent fortification levels.
Abbreviations: MP: Millipore AD: Associated Design ppm: mg/kg
Table 7. Soil Fortification Levels for Ruggedness Experiments
Variable
Combination
C E
c e
C e
c e
Solid/Liquid
Ratio
1:22
1:22
1.18
1:18
Sample
grams
22
22
22
22
Leachate
mL
484
484
396
396
Spike Level
mg/kg
0.88
4.40
0.72
3.60
Max. Leachate
Cone, yglkg
40
200
40
200
Table 8. Ruggedness Test Results for Method 1312 Group Differences for Volatile Test Compounds
Conditions
Compound Name
Chloromethane
Bromoethane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1 ,1 -Dichloroethene
1 , 1 -Dichloroethane
trans-t ,2-DicWoroetr»ene
Chloroform
1 ,2-Dichloroethane
2-Butanone
1,1,1 -Trichloroethane
Carbon Tetrachloride
Bromodichloromethane
1,1,2,2-Tetrachloroethane
1 ,2-Dichloropropane
cis- 1 , 3 -Dichloropropene
Trichloroethene
Dibromochloromethane
1, 1 ,2-Trichloroethane
Benzene
trans- 1,3-Dichloropropene
Bromoform
4-Methyl-2-pentanone
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl benzene
Styrene
v,
-6
1
-9
-7
-2
7
-5
-6
0
-5
1
5
8
1
-1
7
3
8
8
1
1
3
3
8
-1
31
1
4
2
4
-1
vb
13
11
11
24
34
76
12
11
15
13
17
3
-3
5
4
3
3
7
3
3
2
1
6
4
2
38
2
4
1
3
-1
Vc
16
20
14
23
69
119
19
13
19
18
29
8
11
7
6
9
5
5
6
4
7
7
9
4
3
-27
2
9
7
6
6
va
0
2
0
-8
-7
40
5
4
6
7
4
0
9
-1
-1
3
-2
2
3
1
1
0
1
1
-2
-20
2
1
2
4
3
v*
0
6
-3
-1
8
30
3
1
6
4
6
1
6
0
1
3
4
-1
5
2
4
4
3
4
5
40
2
3
4
3
2
v,
12
8
11
18
26
87
10
13
a
8
6
3
-1
14
13
6
-1
5
5
6
2
5
6
6
-2
28
3
5
0
4
-6
Vg
-18
-12
-11
-38
-45
37
-15
-14
-20
-15
9
-2
20
-6
-6
-1
-2
-10
1
-3
2
-1
-1
-3
-1
58
-1
-3
-1
-5
-4
-------
fabfo 0. (continued)
Conditions
Compound Name
p-Xylene
o-Xylene
1 ,4-Dichlorobenzene
Trichlorofluoromethane
Acrylonttrile
n-Butanol
Ethyl acetate
Ethyl ether
Isobutanol
1, 1,2-Trichlorotrifluoroethane (Freon-1 13)
1, 1. 1.2-Tetrachloroethane
V.
1
0
-1
-7
10
0
11
7
0
-7
2
vb
2
2
-1
10
13
0
-5
5
0
10
4
vc
5
9
4
9
4
0
8
-2
0
9
6
vd
5
2
4
2
2
0
-12
-2
0
1
-1
ve
1
3
1
-1
17
0
16
5
0
-3
4
v,
-1
-1
-6
17
1
0
-20
7
0
15
3
Vg
-2
-2
2
-13
-8
0
29
0
0
-12
-4
NOTE: n-Butanol and isobutanol were not recovered in any of the ruggedness experiments.
T. C Chiang. C . A. Valkenburg, and D. A. Miller are with Lockheed-ESC, Las
Vegas, NV 89119. The EPA author, G. W. Sovocool, (also the EPA Project Officer)
is with the Environmental Monitoring Systems Laboratory, Las Vegas, NV 89193-
3478 (see below).
The complete report, entitled "Performance Testing of Method 1312-QA Support
for RCRA Testing," (Order No. PB 89-224 901 /AS; Cost: $21,95, 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 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
Official Business
Penalty for Private Use $300
EPA/600/S4-89/022
CHICAGO
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