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been  replaced by a  dilute nitric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,

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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

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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

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         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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