-------
gas chromatography-mass spectrometry (GC/MS) at full scan, while for better
sensitivity GC/MS Selective Ion Monitoring (SIM) mode was used for residue
and off-gas samples.
-------
5.0 TEST RESULTS
5.1 SUMMARY
Initially, 25 test burns were conducted on overburden and surrogate samples.
Six test burns were aborted due to equipment malfunction. Three of the test
burns were conducted on surrogate compounds to demonstrate the efficiency of
the sampling trains. The remaining test burns were successfully completed;
Table 5.1-1 presents the test matrix for these 16 successful runs.
Analyses for the 10 selected POHCs indicated complete (more that 99.99
percent) destruction of organics associated with Basin F overburden material
at most of the test conditions. Further evaluation of selected runs for
PICs resulted in the selection of preliminary optimum combustion conditions
for the complete destruction of organics. Two additional test burns of
overburden sample were conducted at these optimum conditions and upon
evaluation of identified PICs in off-gases from these two optimization test
runs, the optimum combustion conditions were selected for a full-scale
incineration system concept design.
5.2 FEED SAMPLE ANALYSES
The feed sample (overburden from Basin F) for each test burn was analyzed
for 22 semi-volatile organic compounds (target compounds) by GC/MS full scan
analytical method as certified by USATHAMA. Appendix A contains the
analytical results as reported by the laboratory (Hittman-Ebasco), while
Appendix B contains the chemical structure of each of the 22 compounds.
A summary of results of the feed sample analyses is presented in Table 5.2-1.
The table identifies parameters that were reported to have concentrations
higher than their respective analytical detection limit. The parameters
identified in Table 5.2-1 are Aldrin, Dieldrin, Endrin, Isodrin, DCPD, DBCP,
CPMSO, CPMSO- and Supona.
5-1
2306E
-------
TABLE 5.1-1
TEST MATRIX
Test
Run
2
3
5
6
7
8
9
10
11
12
13
14
17
18
19
20
Temp «C
in
Primary
Burner
900
900
900
650
900
650
900
900
650
900
900
650
650
650
800
800
Tenp *C
in
Secondary
Burner
1200
900
1200
650
900
1200
900
1200
650
900
1200
650
650
900
900
900
Detention
Time (min)
in Primary
Burner
At Operating
Temo.
60
60
60
60
60
60
60
60
60
60
60
60
30
60
30
15
Detention
Time (sec)
in Secondary
Burner
2
2
5
5
5
5
5
2
2
2
2
2
2
2
5
2
0? Level
in
Secondary
Burner
7X
7X
7X
7X
7X
5.4X
5.4X
5.4X
7X
5.4X
5.4X
5.4X
5.4X
5.4X
7X
7X
Type of
Feed in
Primary
Burner
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Remarks
Good
Good
Good
Good
Repeat of Run 4; Good
Good
Good
Good
Good
Good
Good
Good
Good
Good
Test conditions for a
fluidized bed
Test conditions for a
fluidized bed
-------
TABLE 5.2-1
FEED SAHPLE (ug/gm)
Ttst Run
1
2
3
5
6
7
8
9
10
11
12
13
14
17
18
19
20
Aldrin
AborUd
2200
2100
1700
2400
2300
1900
2300
1700
3600
3700
2300
3600
3100
3500
3900
3700
Dltldrln
1800
1600
1200
1600
1800
1400
1800
1000
1800
1800
1100
1600
1500
1600
1800
2800
Endrin
310
350
240
310
330
260
340
170
300
320
200
390
370
400
500
610
Isodrin
240
300
200
110
130
100
130
89
190
180
110
220
180
190
210
180
DCPD
160
170
120
150
110
110
110
59
100
93
70
88
85
140
160
240
DBCP
41
47
33
36
31
28
29
13
23
22
15
20
12
42
48
49
CPUS
2000
1900
1500
2300
2100
2100
2100
1400
2100
2000
1600
1700
2100
2600
2700
2600
CPNSO
120
140
95
51
57
47
47
31
53
53
46
84
100
99
110
91
CPMS02
490
460
360
200
200
170
160
150
270
250
190
310
330
330
360
280
Supona
13
14
13
19
19
15
22
7.8
17
16
11
20
21
22
26
34
-------
As can be seen from this table, the samples used for test burns were not
homogeneous. The concentration of Aldrin ranged from 1700 to 3900 ppm while
Oleldrin ranged from 1000 to 2800 ppm. Among Endrin, Isodrin, and DCPD, the
concentrations ranged from 170 to 610 ppm, 89 to 300 ppm, and 59 to 240 ppm,
respectively. Among the chlorophenylmethyl sulfur compounds, CPMS had the
highest concentration for each test burn from 1400 to 2700 ppm. Concentra-
tions of OBCP and Supona were found in the range of 7.8 to 49 ppm,
respectively.
5.3 RESIDUE ANALYSES
Residue remaining after each test burn was analyzed for all target organic
compounds to determine the completeness of organic volatilization from the
feed samples. The GC/MS-SIM mode was employed for analyses of organic
compounds. Results of analyses of residue samples, as reported by the
laboratory, are presented in Appendix A.
A summary of results of these analyses is presented in Table 5.3-1. Table
5.3-1 shows those 10 parameters that were detected in feed samples, i.e.,
Aldrin, Dieldrin, Endrin, Isodrin, DCPO, DBCP, CPMS, CPMSO, CPMS02 and
Supona. As can be seen from this table, almost all organics associated with
the overburden samples were volatilized under test conditions (650°C -
900°C).
5.4 OFF-GAS ANALYSES
Off-gases from the combustion process was collected in the sampling train.
Off-gas samples comprised condensates, accumulated materials on the filter,
and materials absorbed on carbon and XAD-2 resins. The analytical method
employed for off-gas samples was GC/MS-SIM. Results of these analyses as
reported by the laboratory, are shown in Appendix A. A summary of results
of analyses of off-gas samples, identifying ten principal organic compounds
(i.e., Aldrin, Dieldrin, Endrin, Isodrin, DCPO, DBCP, CPMSO, CPMS02, and
Supona) is presented in Table 5.4-1 and Appendix A.
5-2
-------
TABLE 5.3-1
RESIDUE ANALYSES (ug/gm)
est Run
2
3
5
6
7
8
9
10
11
12
13
14
17
18
19
20
Aldrin
<.05
<.05
<.03
<.03
0.03
0.18
0.05
0.23
3.0
0.05
<0.03
0.07
0.25
0.81
<0.03
<0.03
Dieldrin
0.15
<0.02
0.20
<0.01
<0.01
0.10
<0.01
0.10
2.8
0.03
<0.02
0.04
0.06
0.93
<0.02
<0.02
Endrin
<0.08
<0.08
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
Isodrin
<0.08
<0.08
<0.01
<0.05
<0.05
<0.01
<0.01
<0.01
0.04
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
DCPD
<0.008
<0.008
33
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
DBCP
<0.008
<0.02
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
CPUS
<0.08
<0.08
<0.05
<0.05
<0.05
<0.05
<0.05
0.08
<0.05
<0.05
<0.05
1.1
<0.05
<0.05
<0.05
0.06
CPHSO
<0.08
<0.08
<0.05
<0.05
<0.05
0.06
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
CPHS02
0.25
<0.08
<0.05
<0.05
<0.05
<0.05
<0.05
0.05
4.0
0.87
<0.05
0.10
<0.05
<0.05
<0.05
<0.05
Supona
<0.08
<0.08
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
-------
TABLE 5.4-1
CONTAMINANTS REMAINING IN OFF-GASES (ug)
Test Run
2
3
5
6
7
8
9
10
11
12
13
14
17
18
19
20
Aldrin
21
480
<0.03
<0.03
0.14
<0.03
<0.03
<0.03
<0.03
<0.03
<0.03
0.07
2.0
0.49
0.30
<0.03
DitldHn
23
190
<0.01
<0.01
0.11
<0.01
25
0.36
3.5
<0.01
<0.01
1.2
<0.01
0.25
0.94
0.55
Endrin
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
0.20
3.7
4.6
Isodrin
0.50
8.8
<0.01
<0.01
<0.01
<0.01
0.85
<0.01
<0.01
<0.01
<0.01
0.39
0.39
<0.01
<0.01
<0.01
DCPD
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
08CP
1.1
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
1.8
<0.005
<0.005
CPMS
27
57
<0.05
<0.05
0.13
<0.05
6.44
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
3.8
<0.05
2.0
CPMSO
<0.05
290
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
CPMS02
3.2
<0.05
<0.05
<0.05
<0.05
<0.05
1.94
<0.05
<0.05
<0.05
<0.05
1.4
<0.05
<0.05
<0.15
12
Supona
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
37
<0.05
<0.05
18
<0.05
<0.05
<0.05
<0.05
2306E
-------
As can be seen from this table, the organic species remaining in the off -gas
samples were below the analytical detection limits most of the time. It can
be concluded that the original organic compounds present in the feed sample
can be transformed into some other species if not completely oxidized to CO,
CCL, and H_0 in the specified test conditions.
5.5 DETERMINATION OF ORE
The Resource Conservation and Recovery Act regulation designates the
destruction and removal efficiency (ORE) of principal organic hazardous
constituents (POHC) as the requirement for incinerator design (Federal
Register, 1981). The DRE of an incinerator system is defined as:
* "out
win
where DRE = destruction and removal efficiency, %
W. = mass feed rate of the principal organic hazardous
const ituent(s) to the incinerator
W . = mass emission rate of the principal organic hazardous
out
constituent (s) to the atmosphere (as measured in the
stack prior to discharge).
Thus, destruction and removal efficiency calculations are based on the
combined efficiencies of destruction in the incinerator and removal from the
gas stream in the air pollution control system. The potential presence of
principal organic hazardous constituents in incinerator bottom ash or
solid/ liquid discharges from air pollution control devices is not accounted
for in the destruction and removal efficiency calculation as currently
defined by regulations.
The regulations require a DRE of 99.99 percent for all principal organic
hazardous constituents of a waste, unless it can be demonstrated that a
higher or lower destruction and removal efficiency is more appropriate based
on human health criteria.
5-3
-------
Based on the concept described above, the ORE of each of the 10 organic
compounds found in the feed sample was determined. The mass feed rate of
each organic compound was determined by multiplying concentration times the
mass of feed sample used in each test burn. • The total weight in micrograms
of each organic species present in each feed sample, as reported by the
laboratory, is included in Appendix A.
Table 5.5-1 presents the ORE of 10 principal hazardous organic constituents
at all test conditions. As can be seen from this table, a ORE of more than
99.99 percent was achieved for each POHC at most of the test conditions.
5.6 ANALYSIS OF COMBUSTION RESULTS
To understand the observed thermal decomposition or stability of organic
species detected in feed samples, a discussion on the expected thermal
stability of detected organic species is presented below.
Aldrin
Aldrin is a bridged chlorinated hydrocarbon. This molecule can undergo a
very low energy concerted four-center elimination of hydrogen chloride (HC1)
(see rxn 1).
(rxn 1)
The resulting olefin will have strained bonds at the site of HC1 elimination
and be expected to undergo further decomposition. Four center concerted
eliminations of HC1 have activation energies (Efl) on the order of 45-50 kcal/
mole and frequency factors (A) of 1013'5 - 1014 s"1 (Benson, 1976).
This means that >99.99 percent destruction efficiency is expected for
temperatures around 600-650°C at 2.0 seconds gas phase residence time
(tp). Since the reaction is unimolecular, the rate will not depend on the
oxygen concentration or the concentration of any other component of the
waste feed.
5-4
2306E
-------
TABLE 5.5-1
DESTRUCTION AND REMOVAL EFFICIENCY OF TEN PRINCIPAL HAZARDOUS
ORGANIC CONSTITUENTS IN OVERBURDEN SAMPLE
Temp Degrees C in
Secondary Burner 650
Temp Degrees C in
Primary Burner 650
Gas Residence Tine in
Second Burner 2
(In Seconds)
Oxygen Level in
Off-Gas (X) 5.4
Run Number 14
17
ALDRIN 100.00
100.00
CPMS 100.00
100.00
CPHSO 100.00
mono
CPMSOo 100.00
100.00
OBCP 100.00
100.00
DCPO 99.99
100.00
OIELDRIN 100.00
100.00
ENDRIN 100.00
100.00
ISODRIN 100.00
100.00
SUPONA 99.74
100. DQ
7
11
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
99.38
5
7
6
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
900
650
2
5.4
18
100.00
100.00
100.00
100.00
99.99
100.00
100.00
100.00
100.00
100.00
800
2
7
20
100.00
100.00
100.00
99.99
100.00
100.00
100.00
100.00
100.00
100.00
5
7
19
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
900
2
5.4
12
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
7
3
99.94
99.99
99.41
100.00
100.00
100.00
99.97
100.00
99.99
100.00
5
5.4
9
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
7
7
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
1200
650
5
5.4
8
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
900
2
5.4
10
13
100.00
IQQ.OO
100.00
IQQ.OO |
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
7
2
100.00
100.00
100.00
100.00
99.99
100.00
100.00
100.00
100.00
100.00
5
7
5
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
-------
Dieldrin
This molecule can also undergo a low energy elimination of HC1 (rxn 2). In
addition, the epoxide linking is weak and will undergo homo lysis at low
-------
kcal/mole (Benson & O'Neal, 1970). CPMS02 could undergo the same bond
homolysis although the carbon-sulfur bond would be much stronger in CPMSO-.
Attack by radical species (hydroxyl [OH] in an oxidative environment or
hydrogen [H] in a pyrolytic environment) may be the primary mode of
destruction through abstraction of a H on the methyl substituent. The
authors are not aware of kinetic or mechanistic studies of attack on the
sulfone group itself. Destruction at temperature below 800°C and 2.0 s
residence time seem reasonable.
CPMSO (Chlorophenylmethylsulfoxide)
The authors are not aware of directly relevant studies in the literature.
The same general comments made for CPMSO. would apply to CPMSO.
DBCP CDibromochloropropane)
This molecule may undergo a four center elimination of HC1 and hydrogen
bromide (HBr). Eliminations of HBr are an even lower energy pathway than
HC1 (E = 40-45 kcal/mole (Benson, 1976). Consequently, this molecule is
expected to be very unstable forming several possible inhalogenated olefins
at temperatures below 600°C.
CPMS (p-Chlorophenylmethylsulfone)
The sulfur linkage in this molecule is isoelectronic with oxygen;
consequently, its behavior under thermal stressing is expected to be similar
to that of an ether linkage. There are no low energy concerted pathways or
weak bonds which would readily break upon heating. Electrophilic addition
of OH to the ring or abstraction of H from the methyl group are the most
likely pathways of destruction. This compound may be moderately stable
although it should not be particularly difficult to destroy by controlled
incineration.
5-6
-------
Supona
Supona Is a relatively complex molecule with a number of functional groups
that can decompose by various mechanisms. The dichlorophenyl group would be
expected to be quite stable. The phosphate ester may undergo a 6 center
elimination in analogy to those observed for normal esters (Benson & O'Neal,
1970). The latter type of reaction can be quite rapid (E. = 47 kcal/mole
17-1
and A « 10 s ), resulting in the formation of the carboxylic acid
and an olefin. Bond homo lysis may also occur at the carbon-oxygen linkage
in Supona. As a result Supona may not be very stable, decomposing below
750°C and 2.0 seconds residence time.
Other Low Level Chlorinated Pesticides (Chlordane. DDT. DOE. HCCPD)
Chlordane and DOT can undergo low energy elimination of HC1. DOE is the
elimination product of DOT and should be considerably more stable (rxn 3).
(rxn 3)
DOE will be degraded by radical attack and probably require temperatures in
excess of 750°C at 2.0 s residence time.
HCCPD is a perchlorinated molecule and consequently cannot undergo HC1
elimination. However, the five membered ring is strained and would be
expected to break at relatively low temperatures. It should be noted that
this molecule may react to form the very stable molecule, hexachlorobenzene,
in significant yields.
Other Low Level Phosohonated Pesticides (Malathion and Parathion)
Parathion may decompose by loss of the nitro group at temperatures of around
700°C and residence time of 2.0 s. Malathion will likely undergo a 6 center
5-7
-------
elimination at the ester functional group to form the corresponding acid and
ethylene. The Malathion decomposition may occur at less than 700°C.
Other Low Level Contaminants CDIMP. DMMP. Vapona. Atrazine. Oxathiane.
Dithiane)
With the exception of Atrazine, each of these molecules is a phosphonate.
DIMP may undergo a 6 center elimination at low temperatures; however, the
pathway is not possible in DMMP and Vapona. Consequently, the latter two
compounds may be more stable, although still not extremely stable.
In Atrazine, the amine groups may be susceptible to radical attack at
intermediate temperatures through hydrogen abstraction or radical addition
followed by elimination of the amine. Atrazine may be expected to decompose
between 700 and 800°C at 2.0 seconds residence time.
Oxathiane and Dithiane are isoelectronic. Neither molecule contains any
weak bonds which would readily break under thermal stressing. Abstraction
of H by OH is the most likely mode of destruction. Both species are
expected to be fairly stable, although they should represent no special
problems for the incineration of Basin F wastes.
5.7 ANALYSIS OF PRODUCTS OF INCOMPLETE COMBUSTION
Evaluation of initial results of test burns indicated that the ORE of 99.99
percent for organic compounds could be achieved at all test conditions.
Since the objective of multiple test burns is to determine the optimum
combustion conditions for complete destruction of organics present in the
feed sample, the following assumptions were postulated for further
evaluation.
o Organic compounds present in the feed sample can be destroyed to
99.99 percent at test conditions;
o Test burns performed with a 2-second residence time in the secondary
burner would most likely fail to destroy organics at 99.99 percent
level; and
5-8
-------
o The most complete destruction of organics shouid produce minimum
numbers and quantities of toxic PICs. Therefore, the test burn that
produced the ieast number and quantities of toxic PICs in the
off-gas sample should be selected as the run with the optimum
combustion conditions.
Based on these postulations, the off-gas samples from Runs 12, 13, and 14
were selected for the analyses of PICs. GC/MS-SIM mode was used for PICs
analyses (see Figures 5.7-1 to 5.7-3). The results of these analyses are
presented in Tables 5.7-1 to 5.7-3. The chemical structures of the
identified PICs are provided in Appendix C. The compounds (PICs) identified
were screened for toxicity characteristics. Some compounds were identified
as toxic compounds (irrespective of dose or concentration) in accordance
with the Registry of Toxic Effects of Chemical Substances. The greatest
number and yield were observed from Run No. 14 with the primary and
secondary burners at only 650°C, while the least number and yield were
observed for Run No. 13 with the primary and secondary burners at 900°C and
1200°C, respectively. The resulting toxic PICs for all three runs are
summarized in Table 5.7-4. To understand pathways of PICs, a general
discussion of the mechanism of formation of each class of compound is
presented. Specific compounds are discussed when they are of particular
interest. Non-toxic products are not addressed.
Aliphatics and Substituted AliDhatics
Although not typically reported in combustion studies, simple straight chain
and cyclic aliphatics (e.g., hexane and methylcyclopentane) may be formed by
a variety of radical molecule interactions involving smaller hydrocarbons.
They may also result from the thermal decomposition of higher molecular
weight hydrocarbons. The observed alcohols, carbonyls, and esters are
typical partial oxidation products for hydrocarbons for temperatures below
450°C. It is suspected that the observed oxidation products may be forming
in cool regions of the transfer line in the laboratory combustor. However,
the authors cannot absolutely rule out the possibility that these products
are formed in the "cool" soil and escape destruction in the gas phase.
5-9
-------
>C017835.8-500.8 *»u. HEfll »4755
400000-
368888-
328888-
288888-
240000-
200900-
160000-
120089-
600R8-
40000-
8-
400
680
1208
1688
Jl
12 16 28 24 28 32
1 I- "I
36
48
067
data file header from : iC0170
Operator: CHUCK
MS
10/19/86 20:49
BTL* 2
nple: HEAI #4755
be :
s. #: 2 MS model: 96 SU/HUi rev.: IA ALS # : 0
lethod file: HE9501 Tuning file: MT9501 No. of extra records: 1
)urce temp.: 190 Analyzer temp.: 200 Transfer line temp. : 250
Chromatographic temperatures : 45. 300. 0.
Chromat ograph ic times, mm. : 4.0 10.0 0.0
Chromatographic rate, deg/min: 10.0 0.0 0.0
0. 0.
0.0 0.0
0.0 0.0
Figure 5.7-1
RECONSTRUCTED ION CHROMATOGRAPH FOR
PRODUCTS OF INCOMPLETE COMBUSTION IN
OFF-GASES OF RUN NO. 12
-------
ll« >C ii. . - . »">u. T1C
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>C0223
Operator: CHUCK
MS
10x27x86
BTL* 2
•nple: HEAI #4765
ic : Compo; i t e
s. #: 2 MS model: 96 SLJxHU rev. : I A ALS * : 0
Method file: HE9501 Tuning file: MT9501 No. of extra records:
surce temp.: 190 Analyzer temp.: 200 Transfer line temp. :
1
250
Chromatcgraph ic temperatures : 45. 300. 0. 0. 0.
Chroma tograph ic times, min. : 4.0 10.0 0.0 0.0 0.0
Chromatograph ic rate, deg
-------
Fii« >coi?i 3s.e-see.e
see
izee
1606
data file header from : >C0171
Operator: CHUCK
MS
rople: HEAI #4787
sc :
5. *: 2 MS model: 96 SU/HU rev.: IA ALS * : 0
Method file: HE9501 Tuning file: MT9501 No. of extra records:
Durce temp.: 190 Analyzer temp.: 200 Transfer line temp. :
10/19/86 21:39
BTL* 3
1
250
Chromatographic temperatures :
Chroma tograph ic times, mm. :
Chromatographic rate, deg/min:
45.
4.0
10.0
300.
10.0
0.0
0.
0.0
0.0
0.
0.0
0.0
0.
0.0
0.0
Figure 5.7-3
RECONSTRUCTED ION CHROMATOGRAPH FOR
PRODUCTS OF INCOMPLETE COMBUSTION IN
OFF-GASES OF RUN NO. 14
-------
TABLE 5.7-1
LIBRARY SEARCH RESULTS OF PRODUCTS OF INCOMPLETE COMBUSTION
IN OFF-GAS SAMPLE FROM RUN NO. 12
Estimated
Total Amount
Compound (ug)
Cyclohexane 1500
Methyl Cyclopentane 620
3-Methyl-2-Butanone 160
Benzene 1200
Hexane 3800
2,2-Dimethyl Hexane 420
Chlorobenzene 250
Hexamethyl Cyclotrisiloxane 4700
Octamethyl-Cyclotetrasiloxane 5000
Decamethyl-Cyclopentasiloxane 4500
Unknown (scan #306 voa) Primary m/z 285 330
Naphthalene 170
Dodecamethyl-Cyclohexasiloxane 1800
Unknown (scan #430 voa) Primary m/z 73 280
2-Pentadecyl-l, 3-Dioxolane 720
Unknown (scan #632 voa) Primary m/z 73 190
o,o,o-Tris-Trimethyl epinephrine 160
Unknown (scan #717 voa) Primary m/z 73 210
Unknown (scan #795 voa) Primary m/z 73 180
Sulfur, mol. (S8) 430
Hexanedioic acid, dioctyl ester 240
2306E
-------
TABLE 5.7-2
LIBRARY SEARCH RESULTS OF PRODUCTS OF INCOMPLETE COMBUSTION
IN OFF-GAS SAMPLE FROM RUN NO. 13
Estimated
Total Amount
Compound (ug)
2-Methyl Benzofuran 470
Octamethyl Cyclotetrasiloxane 13000
Unknown (scan #301) Primary m/z 73 160
Oecamethyl Cyclopentasiloxane 12000
Unknown (scan #339) Primary m/z 285 2200
Unknown (scan #355) Primary m/z 293 160
Unknown (scan #388) Primary m/z 73 170
Unknown (scan #401) Primary m/z 73 130
Unknown (scan #412) Primary m/z 327 170
Unknown (scan #423) Primary m/z 73 240
Dodecamethyl-Cyclohexasiloxane 6500
12-methyl Tetradecanol 1200
Unknown (scan #496) Primary m/z 73 260
12-methyl-l-Tetradecanol 1900
Unknown (scan #569) Primary m/z 64 230
N-methyl-5-nitro-2-Pyridinamine 260
12-methyl-l-Tetradecanol 700
0,0,0-Tris Trimethylsilyl Epinephrine 360
Unknown (scan #742 voa) Primary m/z 73 540
3,4-bis[(Trimethylsilyl) oxyl]-Estratrienone 210
Unknown (scan #820) Primary m/z 73 480
Sulfur, mol. (S8) 510
Unknown (scan #891) Primary m/z 73 400
Unknown (scan #957) Primary m/z 73 360
Silicate anion tetramer 330
Silicate anion tetramer 260
Unknown (scan #1131) Primary m/z 73 220
Unknown (scan #1182) Primary m/z 73 180
3,5-bis (l,l-dimethylethyl)-l,2-Benzenediol 140
2306E
-------
TABUE 5.7-3
LIBRARY SEARCH RESULTS OF PRODUCTS OF INCOMPLETE COMBUSTION
IN OFF-GAS SAMPLE FROM RUN NO. 14
Estimated
Total Amount
Compound (ug)
Cyclohexane 1000
3-Chloro-2-Propenenitrile 780
Benzene 1600
Hexane 2800
Unknown (scan #158 voa) Primary m/z 93 700
Unknown (scan #168 voa) Primary m/z 86 2200
Tetrachloroethene 5000
Methylbenzene 940
Chlorobenzene 4300
N-ethyl-Cyclohexanamine 900
Bromobenzene 570
Hexachloro-1, 3-Butadiene 1700
1,4-Dichlorobenzene 6600
1,2-Dichlorobenzene 3 500
Octamethyl Cyclotetrasiloxane 850
l-Bromo-2-Chlorobenzene 2400
4-Chloro-Benzonitrile 6500
1,3,5-Trichlorobenzene 8100
1,2,3-Trichlorobenzene 3300
2,6-Dichloro Benzonitrile 940
1,2,4,5-Tetrachlorobenzene 6000
2,4,6-Trichloro Benzenamine 240
5-Bromo-6-methyl-3-(l-methylpropyl)-Pyrimidinedione 250
2,5-Dichloro-Thiazolopyrimidine 790
5,7-Dichloro-Thiazolopyrimidine 560
Pentachlorobenzene 1500
4,7-Dichloro-benzo-2,1,3-Thiadiazole 220
3-Chloro-l,lt-Biphenyl-4-01 370
Unknown (scan #611 semi-vol) Primary m/z 241 300
Hexachlorobenzene 220
Hexachlorodifluoro-Pentadiene 270
2306E
-------
TABLE 5.7-4
SUMMARY OF OBSERVED TOXIC PRODUCTS
OF INCOMPLETE COMBUSTION
Compound
T Primary (°C)
T Secondary (°C)
Run No.
Aliphatics and Substituted Aliphatics
Hexane
Cyciohexane
Methyl cyclopentane
2,2 Dimethyl hexane
Hexanedioc acid, dioctyl ester
12-Methyl-l-tetradecanol
3 Methyl-2-butanone
Olefins
Tetrachloroethene
Hexachloro-1 , 3-butadiene
Aroma tics and Substituted Aromatics
Benzene
Toluene
Benzonitrile
3,5-bis (1,1-dimethyl ethyl) -
1,2 benzenediol
2-Methyl benzofuran
Total Amount
650
650
14
2800
1000
NO
ND
ND
ND
ND
5000
1700
1600
2200
1700
ND
ND
900
900
12
3800
1500
620
420
240
ND
160
ND
ND
1200
NO
ND
ND
ND
fUQ)
900
1200
13
ND
ND
ND
ND
ND
700
ND
ND
ND
ND
ND
ND
140
470
2306E
-------
TABLE 5
.7-4
(Continued)
Compound
T Primary (°C)
T Secondary (°C)
Run No.
Halogenated Aroma tics
Chlorobenzene
1,2 Dichlorobenzene
1,4 Dichlorobenzene
1,3,5 Trichlorobenzene
1,2,4,5 Tetrachlorobenzene
Pentachlorobenzene
Hexachlorobenzene
3-chloro-l,!1 biphenyl-4-ol
4-chlorobenzonitrile
2,6-Dichlorobenzonitrile
Heterocyclics
N-Methyl-5 nitro-2-Pyridinamine
5-Bromo-6-methyl-3-(l-methylpropyl)
pyrimidinedione
Polvnuclear Aromatics
Naphthalene
Other
Sulfur, Mol. (S0)
o
650
650
14
4300
3500
6600
8100
6000
1500
220
370
6500
940
NO
250
NO
NO
Total Amount
900
900
12
420
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
170
430
fua)
900
1200
13
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
260
NO
NO
510
2306E
-------
In either case, none of these compounds are on the EPA's Appendix VIII list
and represent little cause for practical concern.
Olefins
Tetrachloroethene (PERC) and hexachloro-l,3-butadiene (HCB) were observed in
the 640°C run (Run No. 14). These results are not surprising, as these
compounds have been observed in a number of other laboratory studies (Taylor
it Oellinger; Graham, et al., 1986) Both PICs are expected to be quite
stable, especially PERC. HCB can easily be formed from the fragmentation of
Aldrin, Endrin, Dieldrin, Isodrin, or Supona. PERC could be formed from the
fragmentation of essentially any of the chlorinated pesticides in the feed.
Both compounds have also been observed to be formed from radical molecule
reactions involving chlorinated C^ and C2 species (see rxn for example)
(Taylor & Dellinger; Frenklack et al., 1983).
•CC13 (or -CHC12) + CHC13 (or CC14) -» C^Cls + -Cl (rxn 4a)
* HCI
C2C13 + C2C1^ -» C^C16 + Cl (rxn Ac)
The suspected stability of PERC suggests it could be one of the more
significant emissions of chlorinated compound from the incineration of Basin
F wastes.
Aromatics and Substituted Aromatics
Benzene and toluene (as well as other substituted benzenes such as ethyl-
benzene and styrene) are frequently observed major PICs, resulting from the
combustion or pyrolysis of most organics. They may be formed from the
dechlorination and loss of other functional groups from the ring structures
of most of the chlorinated pesticides in the Basin F waste. However, it is
more likely that they are formed by radical molecule addition and dispro-
portions! ion reactions similar to those shown in rxn 4 (without the chlorine
c._ -i n
-------
substituents) with an additional reaction involving acetylene or
methylacetylene (see rxn 5).
•C H + C H -» C H + H (rxn 5a)
A 5 22 6 6
•CH + CH -» C H + -H (rxn 5b)
45 34 7 8
Benzonitrile can be formed by addition of the nitrile radical to benzene,
the nitrile radical resulting from any number of fragmentation reactions of
nitrogen containing material in the waste feed. Atmospheric nitrogen is not
expected to play a role as temperatures are not high enough to result in
degradation of N^.
The benzedediol would seem to be the result of a low temperature reaction
either in a transfer line (or the soil). 2-Methyl benzofuran, on the other
hand, may result from either high temperature gas phase reactions or, at
lower temperatures, via pathways similar to that proposed for alcohols and
carboxylic acid. Benzofuran and methyl benzofuran have been observed in
significant yields from other high temperature flow reactor oxidations of
organic waste materials (Graham et al., 1986).
Halogenated Aromatics
A variety of halogenated benzenes were observed for the low temperature run
(Run No. 14). This is not surprising since chlorinated aromatics have been
observed from pyrolysis and oxidation of a number of chlorinated organics
(Frenklack, et al., 1986; Graham, et al., 1986). In fact, the presence of
chlorine has been shown to effectively increase the yield of aromatic
products and chlorinated aromatics (Taylor & Del linger).
The lower chlorinated aromatics may be a result of bond homolysis of more
complex chlorinated species (e.g., CPMSO monochlorobenzene); however, it is
more likely that they form by a complex series of radical molecule
reactions similar to that already illustrated for the formation of benzene.
Chlorine atom addition reactions to already chlorinated aromatic structures
may also contribute to the formation of the higher chlorinated aromatics.
5-11
-------
The formation of chlorinated benzonitriles may proceed through nitrile
radical attack on chlorobenzenes or chlorine atom attack on benzonitrile.
The observation of a chlorobiphenyl-ol is puzzling since the chlorinated
biphenyl is expected to be very resistant to radical attack and partial
oxidation (to form the phenol) without further fragmentation to smaller
species.
The formation of chlorobenzenes is important because they have been shown to
be very stable, especially under pyrolytic conditions, and may be one of the
most difficult PICs (or POHCs) to destroy (Graham et al., 1986; Dellinger
et al., 1984).
Heterocyclics
Two nitrogen containing heterocyclics were observed, a substituted pyridlne
and an pyrimidinedione. The formation of the latter species is puzzling for
two reasons. First of all, it would not appear to be very stable and is a
very complex species to be formed requiring a very complex series of
reactions. The observed pyrimidinedione also has a nitro substituent which
is expected to be easily fragmented. This molecule may have been formed in
the transfer line after the secondary chamber. In any case, it should be
readily destroyed in a full-scale incinerator.
Pyridine is a relatively stable aromatic, expected to be slightly more
stable than benzene (Dellinger et al., 1984). No possible direct precursors
were identified in the waste feed. Consequently, it is felt that this
molecule was formed through a radical molecule addition reaction involving
possibly HCN and butadienyl radical in a manner analogous to that shown for
the formation of benzene (rxn 6).
•C H + HCN -» C H N + -H (rxn 6)
Polynuclear Aromatics
A polynuclear aromatic hydrocarbon such as naphthalene may be formed as an
extension of mechanism responsible for benzene. A possible mechanism would
5-12
-------
be through a styrene intermediate formed from the reaction of butadienyl
radical and vinyl acetylene radical (see rxn 7).
CH,- CH - CH - CH. + CH - C - CH - CH
U
&
CH . CH.
4 CH . CH
(rxn 7b)
It is not difficult to envision a continuation of this process (involving
another vinyl acetylene instead of acetylene) to form higher molecular
weight PNAs.
In fact, it is surprising that other PNAs were not reported. Other
laboratory studies have shown that PNAs can be the major PIC at higher
temperatures even under oxidative conditions (Graham, et al., 1986) The
observation of chlorinated benzenes without the observation of chlorinated
PNAs is also quite puzzling. In fact, as already discussed, chlorine atoms
are implicated in catalyzing the formation of aromatics, PNAs, and soot due
to their ability to abstract hydrogen atoms and initiate the reaction
sequences shown in reactions 3, 4, 5, and 6 (Taylor & Dellinger; Frenklack,
et al., 1983).
Other Emissions
Elemental sulfur (S_) was observed under all of the conditions tested.
o
These species have also been observed from the thermal degradation of sulfur-
containing materials (Taylor & Dellinger). Elemental sulfur is apparently
stable enough to resist oxidation at the temperatures and oxygen levels
studied. The authors are not aware of any concern by EPA over its emission.
5-13
-------
5.8 OPTIMUM COMBUSTION CONDITIONS
Conditions at which Run No. 13 was conducted have been chosen as the optimum
combustion conditions for achieving ORE of 99.99 percent for Basin F
contaminated soils. Run No. 13 was conducted at the following conditions:
Temperature in the Primary Burner 900°C
Temperature in the Secondary Burner 1200°C
Gas Residence Time in the Secondary Burner 2 seconds
Oxygen Level in Off-Gases 5.4 percent
Reasons for selecting the above conditions as the optimum combustion
conditions are discussed in previous subsections. Primarily, these operating
conditions are chosen because in Run No. 13 ORE of 99.99 percent for all
detected organic compounds and least numbers and quantities of toxic PICs
were observed amongst the test runs that were considered to represent the
failure (i.e., not achieving appropriate ORE) conditions.
Furthermore, the measurements of the carbon monoxide (CO) concentration
levels in the off-gases indicated the most complete combustion of organic
contaminants. The concentration of CO in the incinerator off-gases is an
indicator for PIC and POHC emissions (Lee & Huffman, 1984). That is, if
significant CO emissions are not present, the presence of other carbon-based
pollutants would be highly unlikely. Conversely, the presence of significant
levels of CO in the combustion products would indicate that the conditions
in the incinerator are improper and may result in POHC and other PIC
emissions.
Figures 5.8-1, 5.8-2 and 5.8-3 represent the CO levels observed in off-gases
for Run Nos. 12, 13, and 14. The graphs were plotted CO levels in off-gases
versus temperatures in the primary burner. The least amount of CO was
observed during Run No. 13 test burn period.
5-14
-------
RUN # 12 TASK 17
CSI 1001 - 017
coo -
soo -
30O -
200 -
100 -
o -
«.
1
1
I
^
"L^ ^ - -
-------
C
1
0.9 -
o.e -
0.7 -
0.6 -
0.5 -
0.4 -
0.3 -
0.2 -
0.1 -
o
RUN # 13 TASK #17
ESI 1001-107
0.2
I
0.4 % 0,6
(7he»w sends.'
P.*. k'ART TtM^fctTURE (C)
0.6
Figure 5.8-2
CONCENTRATION OF CO IN
OFF-GASES OF RUN NO. 13
-------
0.5 -
RUN # 14 TASK #17
1001-1O7
200
i
400
II
(I
600
HtVAHT 7EK«*E«:iTUK£ (C)
Figure 5.8-3
CONCENTRATION OF CO IN
OFF-GASES OF RUN NO. 14
-------
5.9 OPTIMIZATION RUNS
Two additional test burns were conducted at these optimum conditions, with
the exception of Run No. 2 which utilized 50 percent excess air (7 percent
0- in the off-gases) for the purpose of determining the effect of excess
oxygen on the formation of products of incomplete combustion. It was found
in the literature that the yield and stability of PICs increase with
decreased oxygen concentration (Graham, et al., 1986). Figures 5.9-1 and
5.9-2 depict reconstructed ion chromatograms of observed PICs in off-gases
of the optimization test runs. Table 5.9-1 presents the comparative
evaluation of these two PIC analyses. It can be seen from this table that
the test run with 7 percent oxygen level produced the least numbers and
quantities of products of incomplete combustion. Off-gas samples were not
analyzed for the target organic compounds.
5.10 EP TOXICITY OF RESIDUE
EP toxicity tests were performed on the feed and residue samples of the
optimization Run No. 1. The results of the toxicity tests are indicated on
Table 5.10-1. No organic parameters in EP leachate were analyzed because
the residue samples from all test burns consistently showed target organic
compounds below the analytical detection limits. Moreover, for organic
analyses, residue samples were extracted using methylene chloride solution.
Therefore, it is assumed that no organics can be detected in the EP extract.
The EP toxicity test on the feed sample was performed to determine the
mobility of toxic metals present in Basin F soils and any effects the
incineration process would have on the behavior of these toxic metals.
It can be seen from Table 5.10-1 that the toxic metal concentration in
neither extract exceeded the EP Limit concentrations. Moreover, it was
observed that arsenic was not reported to be present in the feed extract
while small amount of arsenic leached out from the residue sample.
5.11 LIQUID TEST BURN RESULTS
(Later)
5-15
-------
Fil« >VN119 46.0-460.0 *»u.
100000*
90000*
•0000*
70000*
60000*
60000*
40000*
30000*
20000*
10000*
Full
1200
1680
32
36
12 ' 16 ' 20 ' 24 ' 20 ' 32 ' 3* ' 40
data file header from : >UN119
Operator: CHUCK
MS
11/19/66 2:42
BTL*12
pie: HEAI $6866
c : Fu 11
. *: 2 MS model: 96 SU/HU rev.: IA ALS * : 0
ethod file: HE9503 Tuning file: MT9501 No. of extra records: 1
jrce temp.: 190 Analyzer temp.: 200 Transfer line temp. :
Chroma tographic temperatures : 49. 300. 0.
Chrometographic times, min. : 4.0 10.0 0.0
Chromatogrephic rate, deg/min: 10.0 0.0 0.0
0. 0.
0.0 0.0
0.0 0.0
Figure 5.9-1
RECONSTRUCTED ION CHROMATOGRAPH FOR
PRODUCTS OF INCOMPLETE COMBUSTION IN
OFF-GASES OF THE OPTIMIZATION RUN NO. 1
-------
>VN126 46.0-460.0 A»u. MEHI •6876
«f«
Full
1266
1«66
866666-
766666-
66666
666666-
486086-
36eeee-
zeeooo-
160666-
lata file header from : >UN120
11x19/86 3:32
BTL*13
ile: HEAI *687f Operator: CHUCK MS
: : Fu 1 1
*: 2 MS model: 96 SU/HU rev.: IA ALS * : 0
thod file: HE9503 Tuning file: MT9501 No. of extra records: 1
irce temp.: 190 Analyzer temp.: 200 Transfer line temp. : 250
•
Chromatographic temperatures : 45. 300. 0. 0. 0.
Chromatographic times, min. : 4.0 10.0 0.0 0.0 0.0
Chromatographic rate, deg/min: 10.0 0.0 0.0 0.0 0.0
Figure 5.9-2
RECONSTRUCTED ION CHROMATOGRAPH FOR
PRODUCTS OF INCOMPLETE COMBUSTION IN
OFF-GASES OF THE OPTIMIZATION RUN NO. 2
-------
TABLE 5.9-1
SUMMARY OF IDENTIFIED PRODUCTS OF INCOMPLETE COMBUSTION
IN OFF-GAS SAMPLES OF TWO OPTIMIZATION RUNS
Compound
T Primary (°C)
T Secondary (°C)
02 (X)
Optimization Run No.
Octamethyi Cyclotetrasiloxane
1 , 2-Dichlorobenzene
Tetramethyl Pentane
1, 2, 3-Trich lorobenzene
Chloro-4-(methylthio)-Benzene
Dodicamethyl Cyclohexasiloxane
Tetrachlorobenzene
Pent ach lorobenzene
12-Methyl-l-Tetradecanol
4-Methoxy-Benzoic acid Trimethylsilyl ester
Tetrachloro-5-dichloromethylene-Cyclopentadiene
Isocyano-Naphthalene
Pentadecyl-1, 3-Dioxolane
Ethyi-Indolecaiboxylic acid ethyl ester
Ethyl-methyl-Pyridinethione
Benzeneacetic acid
Sulfur, mol (S8)
Total Amount
900
1200
5.4
1
25,000
1700
540
1900
12,000
8800
3000
3700
4000
670
770
640
710
NO
NO
NO
1600
Estimated fuo")
900
1200
7
2
ND
NO
NO
ND
ND
8700
ND
ND
1000
760
ND
NO
640
6200
2200
2200
5000
2306E
-------
TABLE 5.10-1
EP TOXICITY TEST RESULTS
EP Limit
Concentration (mg/L) Feed Samples (mg/1) Residue Sample (mg/1)
As
Ba
Cd
Cr
Pb
Hg
Ag
Se
5.0
100.0
1.0
5.0
5.0
0.2
5.0
1.0
0
0.212
0
0.017
0.098
0.020
0.043
0.273
0.081
0.200
0
0.037
0.033
0.020
0.040
0.268
2306E
-------
6.0 SUMMARY AND CONCLUSIONS
The data generated in the laboratory tests thus far conducted indicate that
the toxic organics identified in the Basin F soil samples are amenable to
incineration. The data suggests that a ORE of >99.99 percent can be
achieved at relatively low reactor temperatures (650°C), a total gas phase
residence time of approximately 7.0 seconds, and flue gas oxygen
concentrations of 5-7 percent. Examination of the available literature and
consideration of chemical kinetic principals suggest that most of the
identified toxic organics are thermally fragile and easily decomposed.
The sulfone and sulfoxide compounds (CPMS02, CPMSO, and CPUS) appear, from
a theoretical standpoint, to be the most stable toxic compounds in the
waste. Oxathiane and Dithiane, which are basically hydrocarbons with
thioether and ether linkages, are also expected to be moderately stable.
However, it is felt that none of these materials represent a special
challenge to available incineration technologies.
Analysis for products of incomplete combustion indicated that a number of
chlorinated and nonchlorinated products were formed during the low tempera-
ture test runs. At higher temperatures, these compounds appeared to be
destroyed and only a few products were observed. The majority of these high
temperature PICs were siloxanes and partially oxidized hydrocarbons (alcohols
and esters). Siloxanes may result from the thermal degradation of the
stationary phase GC columns or sealing materials containing silicone rubber
(such as GC septa). In light of this, one must consider the possibility
that their observation is due to experimental artifact; although, their
precursor may also be in the original Basin F sample. The alcohols and
esters may have been formed in "cool" regions (300-500°C) of the transfer
lines of the laboratory system.
The observation of chlorinated olefins and aromatics in addition to benzene,
toluene, and naphthalene is as expected. These compounds have been
previously shown, both experimentally and theoretically, to be thermally
stable. It is surprising that such compounds as benzene, toluene,
-------
naphthalene, and hexachlorobenzene were not observed in the high temperature
runs. They were expected due to the extreme stability of hexachlorobenzene
and the expected yields of the other three species. It is also surprising
that some chlorinated and nonchlorinated PNAs were not observed, as previous
laboratory studies have shown that they can be major products at higher
temperatures.
One reason for the lack of observation of these compounds may have been that
most of the off-gas GC-MS analyses were run in the selected ion monitoring
(SIM) mode. This means that only a limited number of species (similar in
structure to the POHCs analyzed for in the waste feed) would be observed.
Still, these higher molecular weight species were not observed in the full
scan PIC runs. The high molecular weight materials in question (naphthalene
and hexachlorobenzene) are difficult to transport, requiring a temperature
of 200-250°C to maintain them in the gas phase. If any cold spot exists in
the transfer lines these species may be condensed out and not be observed in
the off-gas analysis.
Consequently, it is felt that the PIC issue for Basin F wastes deserves
further study. Special attention should be paid to being sure that quantita-
tive transport of combustion products is assured. Gas chromatographic
analysis using a flame ionization detector (FID) should be employed because
this technique responds to a broad spectrum of organics, more completely
identifying the full range of possible products. Mass spectral analysis may
then be employed to analyze for specific compounds observed in the GC/FID
trace as well as other suspected products of special interest such as
chlorinated aromatics, PNAs, benzene, toluene, and naphthalene.
In summary, however, it is concluded that Basin F wastes are incinerable and
that combustion of these wastes at the following conditions would result in
the most complete oxidation.
Primary Kiln Temperature 900°C
Afterburner Temperature 1200°C
Gas Residence Time in Afterburner 2 seconds
Oxygen Level in Off-Gases 7 percent
6-2
-------
APPENDIX A
ANALYTICAL RESULTS OF FEED, RESIDUE AND OFF-GAS SAMPLES
2306E
-------
FEED ANALYSES
2306E
-------
H1TTHAM EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DMMP
5) Dithiane
6) DBCP
7 ) Vapona
8) CPMS
9) HCCPD
10) CPMSO
11) CPMSO2
12) Atrazine
13) Malathion
14) Aldrin
15) Parathion
16) Isodrin
17) Supona
18) DDE
19) Dieldrin
20) Endrin
21) DDT
22) Chlordane
SURROGATE Recoveries
31) 1,3-Dichlorobenzene-d4
32) Diethylphthalate-d4
33) Dloctylphthalatc-d4
54) Chlorophenol-d4
HEAI*
4338
<0.9
160
<0.8
<0.8
<0.3
41
<0.6
2000
<0.3
120
490
<3.0
<0.4
2200
<0.6
240
13
<0.9
1800
310
<0.3
<2.0
90
114
126
86
HEAI*
4339
ug/g
<0.9
170
<0.8
<0.8
<0.3
47
<0.6
1900
<0.3
140
460
<3.0
<0.4
2100
<0.6
300
14
<0.9
1600
350
<0.3
<2.0
76
96
81
72
HEAI*
4340
<0.9
130
<0.8
<0.8
<0.3
35
<0.6
1800
<0.3
110
460
<3.0
<0.4
2100
<0.6
250
15
<0.9
1500
270
<0.3
<2.0
75
119
100
67
HEAI*
4341
<0.9
120
<0.8
<0.8
<0.3
33
<0.6
1500
<0.3
95
360
<3.0
<0.4
1700
<0.6
200
13
<0.9
1200
240
<0.3
<2.0
72
102
78
63
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIHP
4) DNMP
5) Dithiane
6) DBCP
7) Vapona
8) CPMS
9) HCCPD
10) CPMSO
11) CPHSO2
12) Atrazine
13) Malathion
14) Aldrin
15) Parathion
L6) Isodrin
17) Supona
L8) DDE
L9) Dieldrin
20) Endrin
21) DDT
22) Chlordane
SURROGATE Recoveries
51) 1,3-Dichlorobenzene-d4
52) Diethylphthalate-d4
53) Dioctylphthalate-d4
54) Chlorophenol-d4
HEAI*
4342
run 6
HEAI*
4343
run 7
ug/g
HEAI*
4344
run 8
HEAI*
4345
run 9
<0.9
150
<0.8
<0.8
<0.3
36
<0.6
2300
<0.3
51
200
<3.0
<0.4
2400
<0.6
110
19
<0.9
1600
310
<0.3
<2.0
<0.9
110
<0.8
<0.8
<0.3
31
<0.6
2100
<0.3
57
200
<3.0
<0.4
2300
<0.6
130
19
<0.9
1800
330
<0.3
<2.0
<0.9
110
<0.8
<0.8
<0.3
28
<0.6
2100
<0.3
47
170
<3.0
<0.4
1900
<0.6
100
15
<0.9
1400
260
<0.3
<2.0
<0.9
110
<0.8
<0.8
<0.3
29
<0.6
2100
<0.3
47
160
<3.0
<0.4
2300
<0.6
130
22
<0.9
1800
340
<0.3
<2.0
140
68
136
124
121
74
158
106
125
70
130
111
102
64
158
97
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
.) Oxathiane
!) DCPD
I) DIMP
-) DMMP
0 Dithiane
) DBCP
) Vapona
) CPMS
) HCCPD
) CPMSO
) CPMS02
) Atrazine
) Malathion
) Aldrin
) Parathion
) . Isodrin
) Supona
) DDE
) Dieldrin
) Endrin
) DDT
) Chlordane
RROGATE Recoveries
) 1,3-Dichlorobenzene-d4
) Diethylphthalate-d4
) Dioctylphthalate-d4
) Chlorophenol-d4
HEAI*
4346
runftlO
92
64
95
102
HEAI*
4347
runail
ug/g
88
62
85
105
HEAI*
4348
run«12
<0.9
59
<0.8
<0.8
<0.3
13
<0.6
1400
<0.3
31
150
<3.0
<0.4
1700
<0.6
89
7.8
<0.9
1000
170
<0.3
<2.0
<0.9
100
<0.fr
<0.8
<0.3
23
<0.6
2100
<0.3
53
270
<3.0
<0.4
3600
<0.6
190
17
<0.9
1800
300
<0.3
<2.0
<0.9
93
<0.8
<0.8
<0.3
22
<0.6
2000
<0.3
53
250
<3.0
<0.4
3700
<0.6
180
16
<0.9
1800
320
<0.3
<2.0
84
68
101
100
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
L) Oxathiane
>) DCPD
J) DIMP
I) DMMP
>) Dithiane
,) DBCP
') Vapona
:) CPMS
') HCCPD
) CPMSO
) CPMS02
) Atrazine
) Malathion
) Aldrin
) Parathion
) Isodrin
) Supona
) DDE
) Dieldrin
) Endrin
) DDT
) Chlordane
RROGATE Recoveries
) 1,3-Dichlorobenzene-d4
) Diethylphthalate-d4
) Dioctylphthalate-d4
) Chlorophenol-d4
HEAI*
4349
run*13
<0.9
70
<0.8
<0.8
<0.3
IS
<0.6
1600
<0.3
46
190
<3.0
<0.4
2300
<0.6
110
11
<0.9
1100
200
<0.3
<2.0
107
107
94
95
HEAI*
4350
run*14
ug/g
<0.9
88
<0.8
<0.8
<0.3
20
<0.6
1700
<0.3
84
310
<3.0
<0.4
3600
<0.6
220
20
<0.9
1600
390
<0.3
<2.0
68
101
88
73
HEAI*
4351
run*15
<0.9
95
<0.8
<0.8
<0.3
24
<0.6
2000
<0.3
87
300
<3.0
<0.4
3300
<0.6
200
18
<0.9
1700
390
<0.3
<2.0
90
110
135
78
-------
HITTHAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
L) Oxathiane
!) DCPD
I) DIMP
,) DMMP
.) Dithiane
) DBCP
) Vapona
) CPMS
) HCCPD
) CPMSO
) CPMS02
) Atrazine
) Malathion
) Aldrin
) Parathion
) Isodrin
) Supona
) DDE
) Dieldrin
) Endrin
) DDT
) Chlordane
RROGATE Recoveries
) 1,3-Dichlorobenzene-d4
) Diethylphthalate-d4
) Dioctylphthalate-d4
) Chlorophenol-d4
HEAI*
4352
run#16
33
81
145
HEAI*
4353
run#17
ug/g
24
87
154
HEAI*
4354
run*18
<0.9
100
<0.8
<0.8
<0.3
17
<0.6
2200
<0.3
100
350
<3.0
<0.4
3300
<0.6
180
17
<0.9
1500
390
<0.3
<2.0
<0.9
85
<0.8
<0.8
<0.3
12
<0.6
2100
<0.3
100
330
<3.0
<0.4
3100
<0.6
180
21
<0.9
1500
370
<0.3
<2.0
<0.9
140
<0.8
<0.8
<0.3
42
<0.6
2600
<0.3
99
330
<3.0
<0.4
3500
<0.6
190
22
<0.9
1600
400
<0.3
<2.0
15
79
142
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
I) Oxathiane
>) DCPD
5) DIMP
I) DMMP
i) Dithiane
.) DBCP
') Vapona
i) CPMS
i) HCCPD
>) CPMSO
) CPMS02
) Atrazine
) Malathion
) Aldrin
) Parathion
) Isodrin
) Supona
) DDE
) Dieldrin
) Endrin
) DDT
) Chlordane
RROGATE Recoveries
) 1,3-Dichlorobenzene-d4
) Diethylphthalate-d4
) Dioctylphthalate-d4
) Chlorophenol-d4
HEAI*
4355
run#19
ug/g
<0.9
160
<0.8
<0.8
<0.3
48
<0.6
2700
<0.3
110
360
<3.0
<0.4
3900
<0.6
210
26
<0.9
1800
500
<0.3
<2.0
28
76
152
HEAI*
4356
run*20
<0.9
240
-------
HITTHAM EBASCO Associate*
COMPOUND
1)
2)
3)
4)
5)
6)
7)
6)
9)
10)
11)
12)
13)
14)
15)
Oxathiane
DCPD
DIMP
DMMP
Dithiane
DBCP
Vapona
CPMS
HCCPD
CPM5O
CPMS02
Atrazine
Malathion
Aldri-n.
Parathion
Supona
DDE
17)
18)
eoj— Endrin
Zl) DDT
22) Chlordane
Results of Feed Soil Analysis
HEAI*
4338
?UN* 2
<320
56000
<280
<280
<100
14000
<210
700000
<100
42000
170000
<1000
<140
770000
<210
4600
<320
0-30OOO
1-000OO'
<100
<700
HEAXft
4339
B?l IAJ *t ^
&vn " »
Total
<320
60000
<280
<280
<100
16000
<210
660000
<100
49000
160000
<1000
<140
•740000
<210
VOOOOO
4900
<320
$€0000.
T20DOO
<100
<700
HEAI«
4340
ug
<320
46000
<280
<280
<100
12000
<210
630000
<100
38000
160000
<1000
<140
740000
<210
6604)0-
5200
<320
•520000
94000
<100
<700
HEAI«
4341
Eo«^*r
<320
42000
<280
<280
<100
12000
<210
520000
<100
33000
130000
<1000
<140
600000
<210
•7 OX) 00
4600
<320
420000
64000
<100
<700
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DHMP
5) Dithiane
6) DBCP
7) Vapona
8) CPMS
9) HCCPD
LO) CPMSO
11) CPMSO2
.2) Atrazine
.3) Malathion
.4) Aldrin
.5) Parathion
.6) Isodrin
.7) Supona
8) DDE
.9) Dieldrin
:0) Endrin
11) DDT
:2) Chlordane
020
52000
<290
<290
<110
13000
<220
800000
<180
18000
70000
<1100
<140
840000
<220
38000
6600
<320
560000
110000
<110
<720
HEAI*
4343
run 7
Total ug
<320
38000
<290
<290
11000
<220
740000
<180
20000
70000
<1100
<140
800000
<220
46000
6600
<320
630000
120000
HEAI*
4344
run 8
<320
38000
<290
<290
9800
<220
740000
<180
16000
60000
<1100
<140
660000
<220
35000
. 5200
<320
490000
91000
<720
<720
<320
38000
<290
<290
<110
10000
<220
740000
<180
16000
56000
<1100
<140
800000
<220
46000
7700
<320
630000
120000
<110
<720
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
I) DUMP
5) Dithiane
>) DBCP
') Vapona
5) CPMS
») HCCPD
)) CPMSO
. ) CPMS02
!) Atrazine
I) Malathion
,) Aldrin
>) Parathion
) Isodrin
') Supona
.) DDE
1) Dieldrin
) Endrin
) DDT
) Chlordane
HEAI*
4346
runtflO
HEAI*
4347
run*ll
Total ug
HEAI*
4348
run*12
<320
21000
<290
<290
4600
<220
490000
<180
11000
52000
<1100
<140
600000
<220
31000
2700
<320
350000
60000
<320
35000
<290
<290
8000
<220
740000
<180
19000
94000
<1100
<140
1300000
<220
66000
6000
<320
630000
100000
<320
33000
<290
<290
7700
<220
700000
<180
19000
88000
<1100
<140
1300000
<220
63000
5600
<320
630000
110000
<720
<720
<720
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
:OMPOUND
) Oxathiane
) DCPD
) DIMP
I DUMP
) Dithianc
I DBCP
I Vapona
i CPUS
I HCCPD
CPMSO
i CPMSO2
Atrazine
Malathion
Aldrin
Parathi on
Isodrin
Supona
DDE
Dieldrin
Endrin
DDT
Chlordane
HEAI*
4349
run«13
HEAI*
4350
run«14
Total ug
HEAI*
4351
run«15
<320
24000
<290
<290
5200
<220
560000
<180
16000
66000
<1100
<140
800000
<220
38000
3800
<320
380000
70000
<320
31000
<290
<290
7000
<220
600000
<180
29000
110000
<1100
<140
1300000
<220
77000
7000
<320
560000
14000
<320
33000
<290
<290
8400
<220
700000
<180
30000
100000
<1100
<140
1200000
<220
70000
6300
<320
600000
14000
<720
<720
<720
-------
HITTHAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
) Oxathiane
) DCPD
) DIMP
) DUMP
) Dithiane
) DBCP
) Vapona
) CPUS
) HCCPD
) CPMSO
) CPMSO2
Atrazine
Malathion
Aldrin
Parathion
Isodrin
Supona
DOE
Dieldrin
Endrin
DDT
Chlordane
HEAI*
4352
run*16
HEAI*
4353
run#17
Total ug
HEAI*
4354
run*lB
<320
35000
<290
<290
6000
<220
770000
<180
35000
120000
<1100
<140
1200000
<220
63000
6000
<320
520000
140000
<320
30000
<290
<290
4200
<220
740000
<180
35000
120000
<1100
<140
1100000
<220
63000
7400
<320
520000
130000
<320
49000
<290
<290
15000
<220
910000
<180
35000
120000
<1100
<140
1200000
<220
66000
7700
<320
560000
140000
<720
<720
<720
-------
HITTMAN EBASCO Associates
Results of Feed Soil Analysis
COMPOUND
) Oxathiane
) DCPD
) DIMP
) DUMP
) Dithiane
) DBCP
) Vapona
I CPMS
I HCCPD
I CPMSO
I CPMS02
i Atrazine
! Malathion
i Aldrin
i Parathion
Isodrin
Supona
DDE
Dieldrin
Endrin
DDT
Chlordane
HEAI*
4355
run#19
HEAI#
4356
run#20
Total ug
<320
56000
<290
<290
17000
<220
940000
<180
38000
130000
<1100
<140
1400000
<220
74000
9100
<320
630000
180000
<320
84000
<290
<290
17000
<220
910000
<180
32000
98000
<1100
<140
1300000
<220
63000
12000
<32X)
980000
210000
<720
<720
-------
RESIDUE ANALYSES
2306E
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) CIMP
4) DHHP
5) Dithiane
6) DBCP
7) Vapona
8) CPUS
9) HCCPD
10) CPMSO
11) CPMSO2
12) Atrazine
13) Malathion
14) Aldrin
15) Parathion
16) Isodrin
17) Supona
18) DDE
L9) Dieldrin
10) Endrin
21) DDT
22) Chlordane
SURROGATE Recoveries
51) 1,3-Dichlorobenzene-d4
52) Diethylphthalate-d4
53) Dioctylphthalate-d4
54) Chlorophenol-d4
HEAI*
4595
run 2
61
120
86
59
HEAI*
4602
run 3
HEAI*
4633
run 4
ug/g
45
112
135
44
46
113
93
41
HEAI*
4647
run 5
<0.008
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DHMP
5). Dithiane
6) DBCP
7) Vapona
8) CPMS
9) HCCPD
0) CPMSO
1) CPMSO2
2) Atrazine
3) Malathion
4) Aldrin
5) Parathion
6) Isodrin
7 ) Supona
8) DDE
9) Dieldrin
0) Endrin
1 ) DDT
2) Chlordane
URROGATE Recoveries
1) 1,3-Dichlorobenzene-d4
2) Diethylphthalate-d4
3) Dioctylphthalate-d4
4) Chlorophenol-d4
HEAI*
4656
run 6
HEAI*
4667
run 7
HEAI*
4686
run 8
HEAI*
4697
run 9
<0.05
ug/g
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
<0.03
<0.05
<0.05
<0.05
<0.03
<0.01
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
0.03
<0.05
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
31 DIMP
4) DUMP
5) Dithiane
6) DBCP
7) Vapona
3) CPUS
9) HCCPD
D) CPMSO
L) CPMS02
>) Atrazine
1) Malathion
l) Aldrin
i) Parathion
i) Isodrin
') Supona
I) DDE
» Dieldrin
») Endrin
. } DDT
'.) Chlordane
IRROGATE Recoveries
) 1,3-Dichlorobenzene-d4
!) Diethylphthalate-d4
l) Dioctylphthalate-d4
t) Chlorophenol-d4
HEAI*
4715
run 10
64
51
50
98
HEAI#
4725
run 11
ug/g
101
53
99
138
HEAI*
4753
run 12
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
0.08
<0.02
<0.05
0.05
<0.05
<0.05
0.23
<0.05
<0.01
<0.05
<0.03
0. 10
<0.05
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
4.0
<0.05
<0.05
3.0
<0.05
0.04
<0.05
<0.03
2.8
<0.05
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
0.87
<0.05
<0.05
0.05
<0.05
<0.01
<0.05
<0.03
0.03
<0.05
<0.05
<0.05
60
55
45
99
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
I) DMMP
5) Dithiane
5) DBCP
7) Vapona
3) CPMS
?) HCCPD
)) CPMSO
L) CPMS02
>) Atrazine
3) Malathion
I) Aldrin
j) Parathion
>) Isodrin
') Supona
!) DDE
)) Dieldrin
)) Endrin
: ) DDT
!) Chlordane
JRROGATE Recoveries
.) 1,3-Dichlorobenzene-d4
>) Diethylphthalate-d4
J) Dioctylphthalate-d4
I) Chlorophenol-d4
HEAIft
4763
run 13
51
96
80
79
HEAI*
4785
run 14
ug/g
54
97
82
80
HEAI*
4799
run 15
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
<0.03
<0.05
<0.01
<0.05
<0.03
<0.02
<0.05
<0.05
<0.05
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
) Oxathiane
) DCPD
) DIMP
) DMMP
) Dithiane
) DBCP
) Vapona
) CPMS
) HCCPD
) CPMSO
) CPMSO2
) Atrazine
) Malathion
) Aldrin
) Parathion
) Isodrin
) Supona
) DDE
) Dieldrin
) Endrin
) DDT
) Chlordane
UROGATE Recoveries
) 1,3-Dichlorobenzene-d4
) Diethylphthalate-d4
) Dioctylphthalate-d4
) Chlorophenol-d4
HEAI*
4961
runtflfi
83
60
155
34
HEAI*
5155
runtfl?
ug/g
45
65
83
48
HEAI*
5190
run*18
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.005
.005
.05
.05
.005
.005
.05
17
.02
.05
2.7
.05
.05
16
.05
.27
.10
.03
9.2
.38
.05
.05
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
<0
<0
<0
<0
0
<0
<0
<0
.005
.005
.05
.05
.005
.005
.05
.05
.02
.05
.05
.05
.05
.25
.05
.01
.05
.03
.06
.05
.05
.05
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
<0
<0
<0
<0
0
<0
<0
<0
.005
.005
.05
.05
.005
.005
.05
.05
.02
.05
.05
.05
.05
.81
.05
.01
.05
.03
.93
.05
.05
.05
40
53
149
39
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DMMP
5) Dithiane
6) DBCP
7) Vapona
8) CPMS
9) HCCPD
0) CPMSO
1) CPMS02
2) Atrazine
3) Malathion
4) Aldrin
5) Parathion
6) Isodrin
7) Supona
8) DDE
9) Dieldrin
0) Endrin
1 ) DDT
2) Chlordane
URROGATE Recover
1) 1 ,3-Dichlorob
ies
enz
2) Diethylphthalate
3) Dioctylphthal
ate
4) Chlorophenol-d4
HEAI*
5247
run#19
60
62
92
66
HEAI*
5275
run*20
ug/g
97
78
105
119
HEAI*
5297
run#21
<0.005
<0.005
<0.05
<0.05
<0.005
(0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
<0.03
<0.05
<0.01
<0.05
<0.03
<0.02
<0.05
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
0.06
<0.02
<0.05
<0.05
<0.05
<0.05
<0.03
<0.05
<0.01
<0.05
<0.03
<0.02
<0.05
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
0.09
<0.05
<0. 01
<0.05
<0.03
0.03
<0.05
<0.05
<0.05
85
70
85
88
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DHMP
5) Dithiane
6) DBCP
7) Vapona
8) CPMS
9) HCCPD
10) CPMSO
ll) CPMSO2
12) Atrazine
13) Malathion
i4) Aldrin
L5) Parathion
16) Isodrin
i7 ) Supona
18) DDE
L9) Dleldrin
JO) Endrin
51) DDT
12) Chlordane
HEAI*
4595
run 2
HEAI*
4602
run 3
HEAI*
4633
run 4
Total ug
HEAI*
4647
run 5
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
1.5
1.5
15
15
1 . 5
1 . 5
15
15
5.5
15
46
IS
IS
9.2
15
15
15
9.2
27
15
15
15
<1
<1
<
<
<1
3
<
<
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DUMP
5) Dithiane
6) DBCP
7) Vapona
8) CPUS
9) HCCPD
10) CPMSO
LI) CPMSO2
L2) Atrazine
.3) Malathion
.4) Aldrin
.5) Parathion
.6) Isodrin
.7) Supona
.8) DDE
.9) Dieldrin
10) Endrin
!1) DDT
!2) Chlordane
HEAI*
4656
run 6
HEAI*
4667
run 7
Total ug
HEAI*
4686
run 8
HEAI*
4697
run 9
<0.78
<0.78
< 7.8
< 7.8
<0.78
<0.78
< 7.8
< 7.8
< 3.1
< 7.8
< 7.8
< 7.8
< 7.8
< 3.1
< 7.8
< 1.6
< 7.8
< 3.1
< 1 ,6
< 7.8
< 7.8
< 7.8
<0.92
<0.92
< 9.2
< 9.2
<0.92
<0.92
< 9.2
< 9.2
< 3.7
< 9.2
< 9.2
< 9.2
< 9.2
5.6
< 9.2
< 1 .8
< 9.2
< 3.7
< 1 .8
< 9.2
< 9.2
< 9.2
<0.90
<0.90
< 9.0
< 9.0
<0.90
<0.90
< 9.0
< 9.0
< 3.6
11
< 9.0
< 9.0
< 9.0
33
< 9.0
< 1 .8
< 9.0
< 3.6
18
< 9.0
< 9.0
< 9.0
<0.83
<0.83
< 8.3
< 8.3
<0.83
<0.83
< 8.3
< 8.3
< 3.3
< 8.3
< 8.3
< 8.3
< 8.3
8.3
< 8.3
< 1.7
< 8.3
< 3.3
< 1.7
< 8.3
< 8.3
< 8.3
-------
HITTHAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
I) DUMP
5) Dithiane
s) DBCP
7) Vapona
i) CPMS
n HCCPD
)) CPMSO
L) CPMSO2
!) Atrazine
)) Malathion
L) Aldrin
i) Parathion
i) Isodrin
') Supona
I) DDE
i) Dicldrin
i) Endrin
.) DDT
:) Chlordane
HEAI*
4715
run 10
<0.7
<0.7
<7.5
<7.5
<0.7
<0.7
<7.5
12
<2.6
<7.5
7.5
<7.5
<7.5
34
<7.5
<7.5
<3.6
15
<7.5
<7.5
<7.5
HEAI*
4725
run 11
HEAI*
4753
run 12
Total ug
<0.7
<0.7
<7.5
<7.5
<0.7
<0.7
<7.5
<7.5
<2.6
<7.5
600
<7.5
<7.5
450
<7.5
6.0
<7.5
<3.6
420
<7.5
<7.5
<7.5
<0.7
<0.7
<7.5
<7.5
<0.7
<0.7
<7.5
<7.5
<2.6
<7.5
130
<7.5
<7.5
7.5
<7.5
<1 . 5
<7.5
<3.6
4.5
<7.5
<7.5
<7.5
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DMMP
5) Dithiane
&) DBCP
7) Vapona
3) CPUS
9) HCCPD
)) CPMSO
I) CPMSO2
2) Atrazine
3) Malathion
I) Aldrin
j) Parathion
>) Isodrin
') Supona
)) DDE
M Dieldrin
)) Endrin
. J DDT
!) Chlordane
HEAI#
4763
run 13
<0
.7
7
,5
5
.7
7
.5
5
,6
5
,5
5
5
6
5
<7.5
<7.5
<3.6
<1 .8
<7.5
<7.5
<7. 5
<7
<0
<7
<2
<7
<7
<7
HEAI#
4785
run 14
HEAI*
4799
run 15
Total ug
<0.7
<0.7
<7.5
<7.5
<0.7
<0.7
<7.5
160
<2.6
<7.5
15.
<7.5
<7.5
10
<7.5
<7.5
<7.5
<3.6
6.0
<7.5
<7.5
<7.5
<0.7
450
<7.5
<7.5
<0.7
140
<7.5
380000
<2.6
800000
130000
<7.5
<7.5
260000
<7.5
24000
2100
<3.6
330000
12000
<7.5
<7.5
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
) Oxathiane
) DCPD
) DIMP
) DMMP
I Dithiane
I DBCP
I Vapona
I CPUS
i HCCPD
i CFMSO
CPMSO2
Atrazine
Halathion
Aldrin
Parathion
Isodrin
Supona
DDE
Dieldrin
Endrin
DDT
Chlordane
HEAI*
4961
run*16
190 gm
HEAI*
5155
run*17
184 gm
HEAI*
5190
run*18
183 gm
Total ug
<0.95
<0.95
<9.5
<9.5
<0.95
<0.95
<9.5
3230
<3.8
<9.5
510
<9.5
<9.5
3000
<9.5
51
19
<5.7
1700
72
<9.5
<9.5
<0
<0
<9
<9
<0
<0
<9
<9
<3
<9
<9
<9
<9
<9
<1
<9
<5
<9
<9
<9
.92
.92
.2
.2
.92
.92
.2
.2
.8
.2
.2
.2
.2
46
.2
.8
.2
.5
11
.2
.2
.2
<0
<0
<9
<9
<0
<0
<9
<9
<3
<9
<9
<9
<9
1
<9
<1
<9
<5
1
<9
<9
<9
.92
.92
.2
.2
.92
.92
.2
.2
.8
.2
.2
.2
.2
50
.2
.8
.2
.5
.7
.2
.2
.2
-------
HITTMAN EBASCO Associates
Results of Residue Analysis
COMPOUND
) Oxathiane
) DCPD
) DIMP
} DMMP
) Dithiane
) DBCP
) Vapona
) CPUS
HCCPD
CPMSO
CPMS02
Atrazine
Maiathion
Aldrin
Parathion
Isodrin
Supona
DDE
Di eldrin
Endr i n
DDT
Chlordane
HEAI*
5247
run*19
187 gm
HEAI*
5275
run*20
186 gm
HEAI*
5297
run#21
136 gm
Total ug
<0.93
<0.93
<9.3
<9.3
<0.93
<0.93
<9.3
<9.3
<3.7
<9.3
<9.3
<9.3
<9.3
<5.6
<9.3
<1 .9
<9.3
-------
OFF-GASES ANALYSES
2306E
-------
HITTMAN EBASCO Associates
Composite of Charcoal, XAD-2, and filter
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DUMP
5) Dithiane
6) DBCP
7) Vapona
6) CPMS
9) HCCPD
.0) CPMSO
.1) CPMSO2
2) Atrazine
3) Malathion
4) Aldrin
5) Parathion
6) Isodrin
7) Supona
8) DDE
9) Dieldrin
0) Endrin
1) DDT
2) Chlordane
URROGATE Recoveries
1) 1,3-Dichlorobenzene-d4
2) Diethylphthalate-d4
3) Dioctylphthalate-d4
4) Chlorophenol-d4
HEAI*
4599
run 2
<0.005
<0.005
<0.05
<0.05
<0.005
1.1
<0.05
27
<0.02
<0.05
3.2
<0.05
05
21
05
50
05
03
23
05
05
<0
<0
0.
<0
<0
<0.05
79
89
92
75
HEAI*
4603
run 3
Total
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
57
<0.02
290
<0.05
<0.05
<0.05
480
<0.05
8.8
<0.05
<0.03
190
<0.05
<0.05
<0.05
%
54
65
106
56
HEAI*
4638
run 4
ug
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
.35
<0.05
<0.05
<0.03
<0.05
<0.01
-------
HITTMAN EBASCO Associates
Composite of Charcoal, XAD-2, and filter
COMPOUND
1
2
3
4
5
6)
7)
8)
9)
0)
1)
2)
3)
4)
51
6)
7)
8)
9)
0)
1 )
2)
Oxathiane
DCPD
DIMP
DMMP
Dithiane
DBCP
Vapona
CPUS
HCCPD
CPMSO
CPMS02
Atrazine
Malathion
Aldrin
Parathion
Isodrin
Supona
DOE
Dieldrin
Endrin
DDT
Chlordane
URROGATE Recoveries
1) 1,3-Dichlorobenzene-d4
2) Diethylphthalate-d4
3) Dioctylphthalate-d4
I) Chloroph«nol-d4
HEAI*
4658
run 6
005
.005
.05
.05
.005
,005
.05
05
.02
05
,05
.05
.05
,03
.05
01
.05
03
.01
<0.05
<0.05
-------
HITTHAN EBASCO Associates
Composite of Charcoal, XAD-2, and filter
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DMMP
5) Dithiane
6) DBCP
7) Vapona
8) CPUS
9) HCCPD
D) CPMSO
1) CPMS02
2) Atrazine
3) Malathion
1) Aldrin
5) Parathion
5) Isodrin
7) Supona
n DDE
I) Dieldrin
)) Endrin
L) DDT
I) Chlordane
JRROGATE Recoveries
.) 1,3-Dichlorobenzene-d4
n Diethylphthalate-d4
n Dioctylphthalate-d4
I) Chlorophenol-d4
HEAI*
4717
run 10
130
72
80
106
HEAI*
4727
run 11
Total ug
107
52
101
4
HEAI*
4755
run 12
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
<0.03
<0.05
<0.01
<0.05
<0.03
0.36
<0.05
<0.05
<0.05
< 0.00 5
<0.005
<0.05
-------
HITTMAN EBASCO Associates
Composite of Charcoal, XAD-2, and filter
COMPOUND
) Oxathiane
) DCPD
) DIMP
) DMMP
) Dithiane
) DBCP
) Vapona
) CPUS
) HCCPD
) CPMSO
) CPMSO2
) Atrazine
) Malathion
) Aldrin
) Parathion
) Isodrin
) Supona
) DDE
) Dieldrin
) Endrin
) DDT
) Chlordanc
RROGATE Recoveries
) 1,3-Dichlorobenzene-d4
) Diethylphthalate-d4
) Dioctylphthalate-d4
) Chlorophenol-d4
HEAI*
4765
run 13
59
68
49
58
HEAI*
4787
run 14
Total ug
107
26
48
56
HEAI*
4801
run 15
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
<0.03
<0.05
<0.01
<0.05
<0.03
<0.01
<0.05
<0.05
<0.05
<0.005
2.9
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
1.4
<0.05
<0.05
0.7
<0.05
<0.01
18
<0.03
-1.2
<0.05.
<0.05
<0.05
-------
HITTMAN EBASCO Associates
Composite of Charcoal, XAD-2, and filter
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DMMP
5) Dithiane
6) DBCP
7) Vapona
8) CPMS
9) HCCPD
10) CPMSO
11) CPMSO2
12) Atrazine
13) Halathion
14) Aldrin
15) Parathion
16) Isodrin
17) Supona
18) DDE
19) Dieldrin
D) Endrin
**21 ) DDT
22) Chlordane
SURROGATE Recoveries
SI) 1,3-Dichlorobenzene-d4
52) Diethylphthalate-d4
S3) Dioctylphthalate-d4
54) Chlorophenol-d4
HEAI*
4963
run#16
37
63
73
33
HEAI*
5157
run*17
Total ug
37
88
73
29
HEAI*
5192
run*18
<0.005
3.2
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
3.2
<0.05
0.38
0.75
<0.03
<0.01
<0.05
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
2.0
<0.05
0.39
-------
HITTHAN EBASCO Associates
Composite of Charcoal, XAD-2, and filter
COMPOUND
1) Oxathiane
2) DCPD
3) DIMP
4) DUMP
5) Dithiane
6) DBCP
7) Vapona
8} CPMS
9) HCCPD
10) CPMSO
11) CPMS02
12) Atrazine
13) Malathion
14) Aldrin
15) Parathion
16) Isodrin
17) Supona
18) DDE
") Dieldrin
„, ) Endrin
21 ) DDT
22) Chlordane
SURROGATE Recoveries
SI) 1J3-Dichlorobenzene-d4
S2) Diethylphthalate-d4
S3) Dioctylphthalate-d4
S4 ) Chlorophenol-d4
HEAI#
5249
run#19
HEAI#
5277
run*20
HEAI*
5300
run#21
47
39
71
63
Total ug
<0.005
<0.005
<0.05
<0.05
<0.005
0.16
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
0.30
<0.05
<0.01
<0.05
<0.03
0.94
3.7
<0.05
<0.05
<0.005
<0.005
<0.05
<0.05
<0.005
<0.005
<0.05
2.0
<0.02
<0.05
12
<0.05
<0.05
<0.03
<0.05
<0.01
<0.05
<0.03
0.55
4.6
<0.05
<0.05
<0.005
490 "
<0.05
<0.05
<0.005
930 <
<0.05
<0.05
<0.02
<0.05
<0.05
<0.05
<0.05
1500
<0.05
<0.01
<0.05
<0.03
22
<0.05
<0.05
<0.05
61
60
97
91
.3
62
55
127
73
-------
HITTMAN E8ASCO Associates
Blank Sample Results
COMPOUND
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)
16)
17)
18)
19)
0)
i)
22)
Oxathiane
DCPD
DIMP
DUMP
Dithiane
DBCP
Vapona
CPMS
HCCPD
CPMSO
CPMS02
Atrazine
Malathion
Aldrin
Parathion
Isodrin
Supona
DDE
Dieldrin
Endr in
DDT
Chlordane
SURROGATE Recover
SI )
52)
S3)
54)
ies
1 ,3-Dichlorobenzene-d4
Diethylphthalate-d4
Dioctylphthalate-d4
Chlorophenol-d4
HEAI QC#
0828C
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
,005
005
,05
05
,005
005
,05
05
.02
05
.05
05
.05
,03
.05
,01
.05
,03
.01
.05
.05
.05
70
64
88
81
HEAI QC*
0902A
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
005
005
OS
05
005
005
,05
05
.02
,05
.05
.05
.05
.03
.05
.01
.05
.03
.01
.05
.05
.05
59
69
86
62
-------
APPENDIX B
CHEMICAL STRUCTURES OF 22 SEMIVOLATILE ORGANIC
TARGET COMPOUNDS
2306E
-------
CROSS REFERENCE TO STRUCTURES OF COMPOUNDS TESTED FOR
IN THE BENCH SCALE LABORATORY TEST PROGRAM
1. Oxathiane - Thioxane, C^sSO.l.A-Oxathiane
2. DCPD - dicyclopentadlene, C-|QHi2» 3a,4,7,7a-Tetrahydro-
4,7-methanoindene
3. DIMP - diisopropylmethylphosphonate,
4. DMMP - dimethylmethylphosphonate,
5. Dfthlane - Nabam, C4HsN2Na2S4, Ethylenebis(dithiocarbamic
acid)disodium salt
6. DBCP - Nemagon, dibromochloropropane, Cs^BrgCT, 3-Chloro-l,2-
dibromopropane
7. Vapona - dichlorvos, C4H7C12P04 0,0-dimethyl
0-(2,2-dichlorovinyl phosphate)
8. PCPMS - p-chlorophenylmethylsulfide,
9. HCPD - CsCls, hexachlorocyclopentadiene
10. PCPMSO - p-chlorophenylmethylsulf oxide, C7H7C1SO
11. PCPMS02 - p-chlorophenylmethylsulf one,
12. Atrazlne - C8Hi4NsCl, 2-chloro-4-ethylamino-6-isopropylamino-
s-triazine
13. Malathlon - CioHi906PS2, S - (1-2 dicarbethoxyethyDO.O-
dimethyldithiophosphate
14. Aldn'n - Ci2HsCl6, ],2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-
hexahydro-1, 4: 5, 8-dimethano naphthalene
15. Parathlon - CioH^NOsPS, 0,0-dietlyl 0-p-nitrophenyl
phosphorothioate
16. Isodrin - C^HsCle* l,2,3,4,10,10-hexachloro-l,4,4a,8,8a
hexahydro-l,4:5,8-endo-dimethanonaphthalene
17. Supona - Chlorfenvinphos, C^H^ClsOs?, 0,0-diethyl 0-[2-chloro-
l-(2,4-dichlorophenyl)v1nyl J phosphate
18. P.P'-DDE - Ci4HgCl4, l,l-dichloro-2,2-bis-(p-chloropheny1)ethylene
0488D
-1-
-------
CROSS REFERENCE TO STRUCTURES OF COMPOUNDS TESTED FOR
IN THE BENCH SCALE LABORATORY TEST PROGRAM (Continued)
19. Dfeldrin - C^HsCls0* 1, 2,3,4, 10,10-hexachloro-6, 7-epoxy-
l,4,4a,5,6,7,8,8a-octahydro-l,4,5,8-dimethanonaphthalene
20. Endrln - C^gHsCleO, 1,2, 3,4,10, 10-hexachloro-6,7-epoxy,
l,4,4a,5,6,/,8,8a-octahydro-endo-endo-l,4:5,8-dimethanonaphthalene
21. P.P'-DDT - dlchloro diphenyl trichloroethane
l,l,l-trichloro-2,2-bis(p-chlorophenyl)ethane
22. Chlordane - Cio^Cls. 1,2,4,5, 6,7, 8,8-octachloro-4,7, methane-
3a,4,7,7a-tetrahydroindane
0488D
-2-
-------
' 1
0
CHo
HoC-P-0-C-H
'
0
H3C-C-CH3
H
0
0
H-C
IH
C- C-CI
Br (I
-------
0
O=P-O
0
CH3
___ /" —i—
Cl
c
Cl
8
s
xk,
"t
Cl
Cl
Cl
Cl
Cl
10
12
N
V
ty
H-C-CH3
-------
81
II
0
Z.T
H
91
SI
>0
OH
£,.
-------
zz
IZ
61
-------
APPENDIX C
CHEMICAL STRUCTURES OF IDENTIFIED PRODUCTS OF INCOMPLETE
COMBUSTION IN OFF-GASES FROM RUN NOS. 12, 13, AND 14
2306E
-------
' ALPHABETIZED CROSS-REFEREN/
OF PRODUCTS OF INCOMPLETE
1. Benzene
2. Benzeneacetlc acid
3. Benzonltrlle
4. 3,5-bls (l,l-din)ethylethyl)-1,2-Benzenediol
5. 3,4 bis [(Tr1m1ehyl1s11y)oxyl] - Estratrienone
6. Bromobenzene
7. l-Bromo-2-Chlorobenzene
8. 5-Bromo-6-methyl-3-(l-methylpropyl)-Pyrimidinedione
9. Chlorobenzene
10. 4-Chloro-Benzonitrile
11. 3-Chloro-l,r-B1phenyl-4-Ol
12. Chloro-4-(methylthio)-Benzene
13. 3-Chloro-2-Propenenitrile
14. Cyclohexane
15. Decamethyl-Cyclopentasiloxane
16. 1,2-Dichlorobenzene
17. 1,4-Dichlorobenzene
18. 2,6-Dichlorobenzonitrile
19. 4,7-D1chloro-benzo-2,l,3-Thiadiazole
20. 2,5-Dichloro-Thiazolopyrimidine
21. 5,7-Dichloro-Thlazolopyrimidine
22. 2,2-Dimetnyl Hexane
23. Dodecamethyl-Cyclohexasiloxane
24. Ethyl-Indole carboxyllc acid ethyl ester
25. Ethyl-methyl-Pyrldinethione
26. Hexachlorobenzene
27. Hexachloro-l,3-Butadiene
28. Hexachlorodifluoro-Pentadiene
T0 THE STRUCTURES
-JMBUSTION (PICs)
29. Hexamethyl Cyclotrisiloxane
30. Hexane
31. Hexanedioic acid, dioctyl ester
32. Isocyano-Naphthalene
33. 4-Methoxy-Benzoic acid Trimethylsilyl ester
34. Methylbenzene
35. 2-Methyl Benzofuran
36. 3-Methyl-2-Butanone
37. Methyl Cyclopentane
38. 12-methyl Tetradecanol
39. 12-methyl-l-Tetradecanol
40. N-ethyl-Cyclohexylamine
41. N-methyl-5-n1tro-2-Pyridinarnine
42. Naphthalene
43. Octamethyl Cyclotetrasiloxane
44. Pentachlorobenzene
45. Pentadecyl-l,3-Dioxolane
46. 2-Pentadecyl-l,3-Dioxolane
47. Silicate anion tetramer
48. Tetrachlorobenzene
49. 1,2,4,5-Tetrachlorobenzene
50. Tetrachloro-5-dichloromethylene-Cyclopentadiene
51. Tetrachloroethane
52. Tetramethyl Pentane
53. 2,4,6-Trichloro Benzenamine
54. 1,2,3-Trichlorobenzene
55. 1,3,5-Trichlorobenzene
56. 0,0,0-Tris-Trimethyl Epinephrine
57. 0,0,0-Tris-Trimethylisilyl Epinephrine
-------
0
I
H
OH
C(CHi):
POSSIBE STRUCTURE
Cl
N
N
CH3
Cl
-------
D
D
NsO
81
D
D
91
0
!S
H
I I
6 A
H
H
€1
^H?
0-H
D
Zl
II
D
01
-------
19
20
21
22
CH3
CH3
24
25
26
Cl
Cl
27
Cl
xcr
a"" Nci
-------
?
f\>
0=0
II
II
en
o— cn_o
x /•• \
^ o L
\
\
o
oJ
0
oJ
os
U)
X-O-X
I
o-=o
r
vX>
vJj
OJ
O
ro
-------
37
38
H
H CH3 H
39
SAME AS 38
40
41
42
N-C-OH
NH2
CH3
43
44
45
Cl
Cl
Cl
Cl
O
CH3
Cl
-------
r
46
H C-CCHp) -CHp
3 R
*bc — o
0 1
M ^C — C —H
H H
49
SAME AS L*S
52
H Cl Cl H H
1 1 I i I
H-C-C-i-C-C-H
1 1 1 1 1
H Cl Cl H H
47
50
c' ,0
1 1
ci\/ Cl
ChC-CI
53
N-H
0,.
^-'
Cl
48
Cl
P1 ci
..
Cl
51
Cl Cl
1 1
Cl- C- C-CI
1
H H
-
54
Cl
i
aci
v-l
______^_ _^— —
-------
55
Cl
Cl
58
61
56
-C-N
59
62
57
5i(CHi>
/
c-c -
H
I
N
I
60
63
-------
APPENDIX 0
REFERENCES
2306E
-------
REFERENCES
Babcock and Wilcox. 1978. Steam: Its Generation and Use. The Babcock and
Wilcox Company, New York, New York.
Benson, S.W. 1976. Thermochemical Kinetics, John Wiley and Sons, 2nd ed.,
New York, New York.
Benson, S.W. and H.E. O'Neal. 1970. Kinetic Data on Gas Phase Unimolecular
Reactions, NSRDS-NBS21, C13.48:21.
Bonner, T. et al. 1981. Hazardous Waste Incineration Engineering. Noyes
Data Corporation, Park Ridge, New Jersey.
Bunts, R.E., N.R. Francinques and A.J. Green. 1977. "Basin F Investigative
Studies, Chemical Assessment and Survey." Environmental Laboratory, U.S.
Army Engineers Waterways Experiment Station, Vicksburg, Mississippi.
Dellinger, B. 1984. Determination of the Thermal Decomposition Properties
of 20 Selected Hazardous Organic Compounds. EPA-600/2-84-138. August.
Dellinger, B., et al. 1984. Hazardous Waste, Vol. 1, No. 2, pp. 137-157.
Ebasco Services Incorporated. 1986a. Final Technical Plan, Task No. 17.
June.
Ebasco Services Incorporated. 1986b. Final Laboratory Test Plan for
Incineration of Basin F Wastes at Rocky Mountain Arsenal. June.
Environmental Science and Engineering, Inc. 1986. Draft Final
Contamination Assessment Report, Source 26-6: Basin F. October.
Federal Register. 1981. Vol.. 46, No. 15, 40 CFR Parts 122, 264 and 265.
January.
D-l
-------
Frankel, I., N. Sanders, and G. Vogel. 1983. Survey of Incinerator
Manufacturing Industry. Chemical Engineering Process 79(3):44-55.
Frenklack, M., et al. 1986. Combust. Flame, Vol. 64:141-155.
v
Graham, J.L., et al. 1986. Env. Scl. &Tech., Vol. 20, No. 7, pp. 703-710.
Kramllch, J. et al. 1984. Laboratory-Scale Flame-Mode Hazardous Waste
Thermal Destruction Research. EPA-600/2-84-086. April.
Lee, C.C. and G.L. Huffman. 1984. An Overview of "Who is Doing What" in
Laboratory and Bench-Scale Hazardous Waste Incineration Research. EPA-600/
D-84-209. August.
Myers, T.E. and D.W. Thompson. 1982. "Basin F Overburden and Soil Sampling
and Analysis Study, Rocky Mountain Arsenal." Environmental Laboratory, U.S.
. Army Engineer Waterways Experiment Station, Vicksburg, Mississippi.
Registry of Toxic Effects of Chemical Substances. 1979 Edition. Volume One
and Volume Two. NTIS-PB81-154478.
Taylor, P.H., and B. Dellinger, submitted Env. Sci. & Tech.
D-2
-------
DRAFT
LABORATORY TEST PLAN FOR INCINERATION OF
BASIN F WASTES AT
ROCKY MOUNTAIN ARSENAL
APRIL 1986
TASK NO. 17
CONTRACT NO DAAK11-84-D-0017
THE VIEWS, OPINIONS, AND/OR FINDINGS CONTAINED IN THIS REPORT ARE THOSE OF
THE AUTHOR(S) AND SHOULD NOT BE CONSTRUED AS AN OFFICIAL DEPARTMENT OF THE
ARMY POSITION, POLICY, OR DECISION, UNLESS SO DESIGNATED BY OTHER
DOCUMENTATION.
THE USE OF TRADE NAMES IN THIS REPORT DOES NOT CONSITITUTE AN OFFICIAL
ENDORSEMENT OR APPROVAL OF THE USE OF SUCH COMMERCIAL PRODUCTS. THIS REPORT
MAY NOT BE CITED FOR PURPOSES OF ADVERTISEMENT.
2140E
-------
TABLE OF CONTENTS
SECTION PAGE
1.0 TEST PLAN OVERVIEW 1-1
1.1 INTRODUCTION 1-1
1.2 LABORATORY TEST PROGRAM OBJECTIVES 1-3
1.3 TECHNICAL APPROACH OVERVIEW 1-4
1.4 EXPECTED RESULTS 1-5
2.0 BENCH-SCALE INCINERATION 2-1
2.1 BENCH-SCALE TEST SYSTEM 2-1
2.1.1 Rationale for a Bench-Scale System 2-1
2.1.2 Design Philosophy 2-1
2.1.3 Sample Size 2-2
2.1.A Primary Furnace 2-2
2.1.5 Fly Ash Trap 2-2
2.1.6 Secondary Combustion Gas 2-3
2.1.7 Secondary Furnace 2-3
2.1.8 Cooling Section 2-4
2.1.9 Sample Collection 2-4
2.1.10 Range of Test Conditions 2-4
2.2 SAMPLE COLLECTION SYSTEM 2-4
2.2.1 Particulate and Residue Collection 2-5
2.2.2 Gas Collection 2-7
2.3 BENCH-SCALE TEST OPERATIONS 2-8
2.3.1 Soil Tests 2-8
2.3.2 Sludge Tests 2-9
2.3.3 Liquid Tests 2-10
3.0 FEEDSTOCK CONSIDERATIONS 3-1
3.1 INTRODUCTION 3-1
3.2 SAMPLE CONSIDERATIONS 3-1
3.3 SAMPLE TESTING 3-2
3.2.1 Feedstock Characterization 3-3
3.2.2 Analytical Screening for Potential POHCs 3-4
2140E
-------
TABLE OF CONTENTS
(Continued)
SECTION PAGE
4.0 SELECTION OF TEST PARAMETERS 4-1
4.1 INTRODUCTION 4-1
4.2 TEST MATRIX PARAMETERS 4-2
4.2.1 Selection of Time Parameter 4-3
4.2.2 Selection of Temperature Parameter 4-3
4.2.3 Oxygen Concentration 4-5
4.2.4 Test Execution 4-7
4.3 SELECTION OF PRINCIPAL ORGANIC HAZARDOUS
CONSTITUENTS (POHCs) 4-7
4.4 SELECTION OF ANALYTICAL PARAMETERS 4-9
5.0 ANALYTICAL DETAILS 5-1
5.1 SAMPLE HANDLING AND SAMPLE FLOW 5-1
5.2 ANALYTICAL PROTOCOL SUMMARY 5-2
5.2.1 Volatile Organics in Soil and Solid Samples
by Gas Chromatography/Mass
Spectrometry (GC/MS) 5-2
5.2.2 Semivolatile Organics in Soil and
Solid Samples by Gas Chromatography/
Mass Spectrometry (GC/MS) 5-3
5.2.3 Metals in Soil and Solid Samples by
Inductively Coupled Argon Plasma (ICP)
Emission Spectrometry 5-3
5.2.4 Arsenic in Soil and Solid Samples by Graphite
Furnace Atomic Absorption (AA) 5-4
5.2.5 Mercury in Soil and Solid Samples by Cold
Vapor Atomic Absorption (CVAA) Spectroscopy 5-4
5.2.6 Extraction Procedure (EP) Toxicity Protocol
for Soils, Incineration Residues, and Solids 5-5
5.2.7 Ignitability in Soil and Solid Samples 5-5
ii
2140E
-------
TABLE OF CONTENTS
(Continued)
SECTION PAGE
5.2 ANALYTICAL PROTOCOL SUMMARY (Continued)
5.2.8 Corrosivity Toward Steel in Soil and
Solid Samples 5-5
5.2.9 Reactivity in Soils and Solid Samples 5-6
5.2.10 Proximate Analysis of Soil and Solid Samples 5-6
5.2.11 Unknown Identification in Soil, Solid, and
Sludge Samples by Gas Chromotography/
Mass Spectrometry (GC/MS) 5-7
5.2.12 Volatile Halogenated Organics in Liquid Samples 5-8
5.2.13 Volatile Aromatic Organics in Liquid Samples 5-8
5.2.14 Organochlorine Pesticides in Liquid Samples 5-8
5.2.15 Organosulfur Compounds in Liquid Samples 5-9
5.2.16 Organophosphorous Pesticides in Liquid Samples 5-9
5.2.17 Phosphonates in Liquid Samples 5-10
5.2.18 Metals in Liquid Samples 5-10
5.2.19 Ignitability in Liquid Samples 5-11
5.2.20 Corrosivity Toward Steel in Liquid Samples 5-11
5.2.21 Reactivity in Soils and Solid Samples 5-11
5.2.22 Proximate Analysis of Liquid Samples 5-12
5.2.23 Volatile Organics in Incineration Off-Gas
Samples by Gas Chromotography/
Mass Spectrometry (GC/MS) 5-13
5.2.24 Acid Gases in Incineration Off-Gas Samples 5-14
5.2.25 Volatile Metals by Inductively Coupled
Argon Plasma (ICP) Emissions Spectrometry
in Incineration Off-Gas Samples 5-14
5.2.26 Volatile Metals/Arsenic in Incineration Off-Gas
Samples by Graphite Furnace Atomic
Absorption (AA) Gas Spectrometry 5-14
iii
?140E
-------
TABLE OF CONTENTS
(Continued)
SECTION PAGE
5.2 ANALYTICAL PROTOCOL SUMMARY (Continued)
5.2.27 Volatile Metals/Mercury in Incineration
Off-Gas Samples by Cold Vapor Atomic
Absorption (CVAA) Spectrometry 5-15
5.2.28 Moisture Content in Incineration Off-Gas Samples 5-15
5.2.29 Organophosphorous, Organosulfur, and
Organochlorine Compounds in Incineration
Off-Gas Samples by GC/Selective Detectors 5-15
5.3 ANALYTICAL RESULTS 5-16
5.3.1 System Performance Parameters 5-16
5.3.2 Analytical Results 5-16
5.4 CERTIFICATION 5-16
5.5 QA/QC 5-16
6.0 EXPECTED RESULTS 6-1
6.1 INTRODUCTION 6-1
6.2 EXPECTED ORE RESULTS 6-1
6.3 EXPECTED TECHNOLOGY SELECTION CONFIRMATION RESULTS 6-2
6.4 OTHER EXPECTED RESULTS 6-3
Appendix 1 - REFERENCES A-l
iv
2140E
-------
LIST OF TABLES
NUMBER
1.1-1 Chemical Characterization of Basin F Liquid
1.1-2 Hazardous Chemicals Contained in the Soils
1.1-3 Summary of Thermal Decomposition Data
2.2-1 Gas Sample Collection Matrix
3.1-1 Properties of Selected Compounds
4.3-1 Heats of Combustion for Hazardous Wastes
5.1-1 Analytical Methodology
5.1-2 Number of Analyses
FOLLOWING PAGE
1-1
1-1
1-3
2-7
3-1
4-8
5-1
5-1
2140E
-------
LIST OF FIGURES
NUMBER FOLLOWING PAGE
1.1-1 Schematic Diagram of Processes Occurring
During the Destruction of a Solid Waste 1-2
2.1-1 Laboratory-scale Incineration Unit 2-1
2.1-2 Rotating Tube Furnace Arrangement 2-2
2.1-3 Rotating Tube Unit 2-2
2.1-4 Test Condition Range, 7810 cm Furnace Volume 2-4
2.1-5 Test Condition Range, 3124 cm Furnace Volume 2-4
2.2.1 Sample Train 2-5
2.2-2 Solid Residue Collection Flow Chart 2-6
2.2-3 Modified Sampling Train for High Moisture Samples 2-7
3.1-1 Soil Sampling Location 3-2
4.2.1 Exhaust CO and Total Hydrocarbons and Fraction of
Test Compound Remaining in Exhaust as a Function
of Theoretical Air 4-6
5.1-1 Sample Analytical Flow 5-1
vi
2140E
-------
1.0 TEST PLAN OVERVIEW
1.1 INTRODUCTION
Wastes in Basin F at Rocky Mountain Arsenal (RMA), which require treatment,
include liquid and sludge as well as soils associated with the lagoon.
These soils include fill, placed above and below the liner, as well as the
3/8-inch asphalt liner itself. These materials, which contain various
concentrations of hazardous compounds as shown in Tables 1.1-1 and 1.1-2,
are candidates for treatment by incineration. If treated by incineration,
the hazardous organic compounds present in Basin F wastes must be destroyed
at a destruction and removal efficiency (ORE) of 99.99 percent.
A conventional incinerator system, including an afterburner, subjects a
compound to a variety of severe environments which may destroy hazardous
waste at the desired ORE levels. Any organic compound subjected to
hazardous waste incineration may be subjected to at least three, if not all,
of the following environments:
1. Pyrolvsis - Solids are volatilized or sublimed, volatiles and
semivolatiles are evolved in the gas phase, and gaseous products may
be further fragmented into smaller compounds and radicals;
2. Oxidation in the flame - Volatile compounds and radicals are
subjected to a radical-rich environment and converted into C02,
H20, and products of incomplete combustion (PICs);
3. Oxidation in a high temperature, postflame region - Final thermal
reactions leading to complete oxidation of the organic constituents
in the incinerator's combustion zone occur;
4. Oxidation in a second flame - Subsequent destruction (in the
afterburner) of unreacted components of the hazardous wastes; and
1-1
2140E
-------
TABLE 1.1-1
CHEMICAL CHARACTERIZATION OF BASIN F LIQUID
Compound or Parameter
PH
Aldrin
Isodrin
Dieldrin
Endrin
Dithiane
DIMP
DMMP
Sulfoxide
Sulfone
Chloride
Sulfate
Copper
Iron
Nitrogen
Phosphorus (total)
Hardness
Fluoride
Arsenic
Magnesium
Mercury
Cyanide
COD
TOC
Units
-
ppm
PPb
ppb
ppb
ppb
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppb
ppm
ppm
ppm
Concentration Range!/
6.9
50.0
2.0
5.0
5.0
30.0
10.0
500.0
4.0
25.0
A8, 000.0
21,000.0
700.0
5.0
120.0
2,050.0
2,100.0
110.0
1.0
35.0
26.0
1.45
24,500.0
20,500.0
- 7.2
- 400
- 15
- 110
- 40
- 100
- 20
- 2,000
- 10
- 60
- 56,000
- 25,000
- 750
- 6
- 145
- 2,150
- 2,800
- 117
- 1.3
- 40
- 29
- 1.55
- 26,000
- 22,500
I/ Based on analysis of various samples from different locations and
depths in the basin (Bunts et al. 1977).
2140E
-------
TABLE 1.1-2
HAZARDOUS CHEMICALS CONTAINED IN THE SOILS
VOLATILE ORGANICS
1,1-Dichloroethane
Dichloromethane
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Carbon tetrachloride
Chloroform
Tetrachloroethylene
Trichloroethylene
Trans-1,2-Dichloroethylene
Benzene
Toluene
Xylene
Ethylbenzene
Chlorobenzene
Methylisobutyl ketone
Dimethyldisulfide
Bicycloheptadiene
Dicyclopentadiene
SEMIVOLATILE ORGANICS
Aldrin
Endrin
Dieldrin
Isodrin
p,p'-DOT
p,p'-DOE
Chlorophenylmethyl sulfide
Chlorophenylmethyl sulfoxide
Chlorophenylmethyl sulfone
Hexachlorocyclopentadiene
Oxathiane
Dithiane
Malathion
Parathion
Chlordane
Azodrin
Vapona
Supona
DIMP
Atrazine
METALS
Aluminum
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Zinc
2140E
-------
5. Oxidation in a second high temperature, postflame region - Final
thermal oxidation reactions occur before the combustion gases are
exhausted to pollution control devices.
In general, it is believed that 99 percent of the destruction of any
hazardous organic compound occurs in the flame region. The postflame region
destroys 99 percent of the remaining one percent of material to achieve the
99.99 percent destruction removal efficiency (ORE). (For detailed
discussions, see Kramlich et al. 198A, and Dellinger et al. 1984.)
Pyrolysis reactions are shown in Figure 1.1-1. Flame and postflame
reactions are summarized in Figure 1.1-1 as "Thermal Oxidation."
The bench-scale laboratory program, designed and described in the following
pages, recognizes the difficulty in handling the compounds listed in
Tables 1.1-1 and 1.1-2 and the complexity of thermal destruction through
incineration as illustrated in Figure 1.1-1. This program is designed,
therefore, to accomplish the following:
1. Provide sufficient information on the physical, chemical, and
thermodynamic properties of the compounds listed in Table 1.1-1 and
1.1-2 to ensure reasonable success in designing and implementing an
incineration program;
2. Provide a bench-scale apparatus that accurately simulates all or a
major portion of a full-scale incineration system;
3. Demonstrate the achievement or potential to achieve 99.99 percent
ORE for hazardous compounds present in Basin F; and
4. Contribute to the selection of an incineration technology.
Data developed by Dellinger et al. (1984) demonstrate that most organics can
be incinerated to a ORE of 99.99 percent within two seconds at temperatures
of 600°C to 950°C (Table 1.1-3). In addition, Kramlich et al. (1984), have
determined that excess air used in the
1-2
2140E
-------
PYRC
i
•LYSIS
\
PYROLYSI
!^P
PYROLYZED PRODUCT
MIX
ING
SOLID
MEL
TING
LIQUID
/APORI
SUBLIN/
ZATION
VAPOR
S
MIX
IATION
MIXING
IGNITION
\
ING
PARTIALLY OXIDIZED
PRODUCTS AND
INTERMEDIATES
MIX
ING
THERMAL OXIDATION
1
PARTIALLY
OXIDIZED PRODUCT
FIGURE 1.1-1
SCHEMATIC DIAGRAM OF PROCESSES
OCCURRING DURING THE DESTRUCTION
OF A SOLID WASTE
-------
flame mode of destruction is best held within 30 percent to 40 percent
(35 percent excess air corresponds to 5.4 percent 0_ in the dry stack
gas) to produce the lowest levels of CO and hydrocarbon emissions, and
ensure the most complete combustion of any supplementary fuel, as well
as hazardous wastes. Consequently, the bench-scale program has been
designed recognizing the fairly narrow ranges of temperatures, times,
and excess air associated with achieving 99.99 percent ORE of most
organic hazardous wastes.
1.2 LABORATORY TEST PROGRAM OBJECTIVES
The laboratory test program has been designed to accomplish the
following objectives:
o Demonstrate that 99.99 percent ORE is achievable for the hazardous
wastes contained in the liquid, sludge, and contaminated soils
associated with Basin F;
o Determine what temperatures, residence times, and levels of
excess 02 can be used to achieve 99.99 percent ORE within the n
cost-effective incinerator technology framework;
o Provide sufficient data to determine hazardous waste destruction
kinetics based on first order approximations;
o Provide guidance for final incineration technology selection and
optimization for transition from bench-scale to pilot plant or from
bench-scale to a full-scale operation. In this respect, bench-scale
testing is designed to provide guidance for initial conditions and
subsequent conditions to be tested by the next scale of operation.
1-3
2140E
-------
TABLE 1.1-3
SUMMARY OF THERMAL DECOMPOSITION DATA
Empirical
Compound Formula
Acetonitrile C^N
Tetrachloroethylene C2C1A
Acrylonitrile C3H3N
Methane CH^
Hexachlorobenzene C6C16
l,2,3,A-Tetra-
chlorobenzene CgH-Cl^
Pyridine C5H5N
Dichloromethane CH2C12
Carbon Tetrachloride CC1
Hexachlorobutadiene C*C16
l,2,A-Trichloro-
benzene C.hLCl,
1,2-Dichloro-
benzene C6HAC12
Ethane C2»6
Benzene C6^6
Aniline C6H?N
Monochlorobenzene C,H_C1
Nitrobenzene CgHLNO,,
Hexachlorethane C2C16
Chloroform CHClj
1,1, 1-Trichlorethane C_H Cl
Tonsetd)
760
660
650
660
650
660
620
650
600
620
6AO
630
500
630
620
SAO
570
A70
AID
390
T99(2)
900
850
830
830
820
800
770
770
750
750
750
7AO
735
730
730
710
670
600
590
570
T99.99(2)
950
920
860
870
880
850
8AO
780
820
780
790
780
785
760
750
780
700
6AO
620
600
I/ Temperature at which decomposition initiates at 2 seconds reaction time.
21 Temperature where 99 and 99.99% of the compound is destroyed at a 2
second reaction time.
Source: Dellinger et al. 198A.
21AOE
-------
1.3 TECHNICAL APPROACH OVERVIEW
Given the nature of the compounds being destroyed and the objectives of the
program, a technical approach has been developed to ensure success of the
ultimate full-scale incineration effort. This approach recognizes the
inherent limitations of laboratory investigations, along with the lack of
precise data concerning the feedstocks to be incinerated.
The technical approach involves using equipment that will simulate three of
the major incineration mechanisms: 1) pyrolysis; 2) postflame (primary
incinerator); and 3) postflame (afterburner). Basin F samples will be sent
to Hittman/Ebasaco Associates Inc. (HEAI) for preparation. HEAI will
perform the actual bench-scale incineration testing. If necessary, HEAI
will send the feed samples to UBTL and CAL for laboratory analysis. The
tests will be carried out with the largest sample sizes possible given the
constraints of laboratory operations in order to ensure data accuracy in
scale-up. Large-scale (e.g., 250-500 gram) samples are to be used. Because
relatively large samples are being used, testing of the consequences of
flame-mode destruction cannot be directly simulated.
The technical approach is designed largely to focus on and evaluate the
impact of incineration on Basin F contaminated soil. The incineration
regime found to be successful with soil then will be confirmed for the
incineration of liquid and sludge. This approach, initially, does not
designate one or more principal organic hazardous constituents (POHCs), but
evaluates the impact of incineration on all compounds identified in
Tables 1.1-1 and 1.1-2.
The technical approach begins with limited characterization of selected
compounds in terms of physical, chemical, and thermodynamic properties. Of
most significance are the ash fusion temperatures of the principle types of
soil and, consequently, the potential for operating any incineration system
in the slagging mode. The technical approach then tests the impact of
incineration of contaminated soil at two temperatures, two residence times
(in the afterburner), and two levels of excess 0_. Multiple runs will be
used to ensure that the ORE associated with any compound will not be masked,
1-4
-------
regardless of concentration in the incoming material to be incinerated. The
impact of incineration on sludge, liquid, and a proportionate mixture of
liquid, sludge, and soil will be the final test sequence.
The actual matrix of test conditions is summarized below:
Parameter Maximum Value Second Value Minimum Value
Temperature 1,250°C 900°C 650°C
Time 5 sec 2 sec N/A
0 Level 5.4% 7.0% N/A
This rationale, discussed in Chapter 4, is based upon conditions expected to
occur in a full-scale incinerator system. Further, this rationale is based
upon providing sufficient spread in the parameters to permit extrapolation
of results between extreme points.
1.4 EXPECTED RESULTS
Test program results will facilitate scale-up of the bench-scale thermal
destruction system to either pilot plant or full-scale operations. Expected
results include the following specific data:
o Evaluation of hazardous chemicals remaining in the residues of soils
or sludges after incineration;
o Degree of destruction associated with specific pyrolysis and
postflame environments, to determine acceptable regimes for
incineration processes (e.g., temperature in the afterburner,
residence time, and excess 02 in the flue gas); and
o Sufficient time, temperature, and oxygen concentration data to
extrapolate rough optimal conditions between the tested points
identified above, assuming first order kinetics.
1-5
-------
The bench-scale program, designed to test for the destruction of all
hazardous waste compounds identified in Tables 1.1-1 and 1.1-2, will permit
final selection of POHCs to be used for determination of the success of
larger-scale systems. Additionally, pretesting of soil, sludge, liquid, and
selected hazardous materials will provide essential physical, chemical, and
thermodynamic data for design and operation of the primary thermal
destruction (incinerator) unit at either the pilot-scale or full-scale.
These data will include, but not necessarily be limited to:
o Ash fusion temperature of the soil;
o Thermal conductivity, specific heat, and heat capacity of the soil
and sludge;
o Selected calorific values, proximate analyses, and related data for
the compounds to be incinerated; and
o Corrosivity (with particular respect to refractories) of the liquid
with five percent chlorides and two percent sulfides.
These data will assist in the determination of fuel requirements, residence
times of solids, and desired temperatures associated with the pilot plant
and full-scale primary incinerator. They also will be used to determine the
maximum temperature associated with the Linder furnace in the bench-scale
test. The Linder furnace accomplishes the solids' heatup and volatile
evolution. While full-scale operation may occur in the slagging mode, the
bench-scale apparatus will be operated below slagging temperatures.
The ultimate value of the bench-scale test program will be to develop data
for operation scale-up. The results described above will assist not only in
determination of a combustion regime that will achieve 99.99 percent ORE,
but also will confirm the most appropriate technology for incineration of
Basin F waste. Specific parameters associated with technology selection
will be temperatures, the evolution of hazardous chemicals from soil and
sludge, residence times, and excess oxygen levels. Specific technologies
1-6
2140E
-------
to which these data can be applied include countercurrent and cocurrent
rotary kilns, fluidized beds, and hearth-type furnaces.
The bench scale test regimes have been designed to achieve 99.99 percent
ORE. The most severe conditions including a temperature of 1250°C and a
residence time of 5 sec exceed those used by other researchers (see, for
example, Dellinger et al. 1984) to achieve 99.99 percent ORE. The margins
of safety to ensure that the desired ORE is obtained exist both in
temperature and time. These margins of safety have been selected based on a
review of the literature associated with hazardous waste destruction, where
the hazardous compounds are in dilute concentrations.
It is recognized, however, that the laboratory program simulates the
post-flame oxidation zone, but does not simulate flame-mode destruction of
hazardous chemicals. The laboratory test program, then, does not simulate
the most severe environments available. Such environments include higher
temperatures, if shorter residence times. Typical flame temperatures may be
about 1725°C (2000 K), and residence times may be 0.1 sec (Perry et al.
1963). Further, the flame environment is characterized by high
concentrations of free radicals; and consequently the mechanisms for
hazardous waste destruction in that environment are most different from
those associated with the post-flame oxidation zone. Radical dominated
mechanisms increase the rate of hazardous waste destruction relative to that
rate associated with oxygen-rich non-flame environments (Kramlich et al.
1984). Consequently, the destruction in an incinerator typically occurs as
follows: 1) 99 percent within the flame region and 2) 99 percent of the
remaining 1 percent of material in the post-flame region.
Given these data, it is reasonable to conclude that the laboratory program,
by itself, will achieve 99.99 percent ORE levels for the wastes in Basin F.
Dilute concentration kinetics as developed by previous research leads to
this conclusion. At the same time, however, the experiment is not
simulating the flame mode destruction. Consequently, it is not simulating
one mechanism for achieving at least 99 percent ORE. Given that
consideration, if the laboratory test achieves in excess of 99 percent ORE,
it is reasonable to conclude that a pilot plant or full-scale incinerator
would achieve 99.99 percent ORE when combining flame mode destruction with a
strong post-flame oxygen-rich environment.
1-7
2140E
-------
2.0 BENCH-SCALE INCINERATION
2.1 BENCH-SCALE TEST SYSTEM
2.1.1 Rationale for a Bench-Scale System
Thermal decomposition laboratory tests have been performed on both pure
compounds and field samples to determine incineration parameters,
including temperature, residence time, and excess oxygen, required to
decompose toxic chemicals. These laboratory tests have been performed,
primarily, using milligram-to-gram size samples. These small sample
sizes have been adequate to characterize incineration parameters for
pure compounds and compounds in high concentrations. For chemicals
which are present in low concentrations, these small sample sizes are
not adequate to demonstrate 99.99% destruction due to the analytical
limits of detection of the off-gases. It is of interest to demonstrate
99.99% destruction for all toxic constituents in a feed sample
regardless of whether or not that constituent is chosen as a principal
organic hazardous constituent (POHC). Although there are substantial
data on the thermal destruction of individual compounds, incineration
tests on field samples are necessary to adequately simulate the
interaction of various constituents at high temperatures and the
production of products of incomplete combustion (PIC). The bench-scale
test unit for Task 17 was designed to measure ORE up to 99.99% for
constituents of concern at Basin F for soil, sludge, and liquid samples.
2.1.2 Design Philosophy
The laboratory bench-scale unit was designed to evaluate thermal
destruction efficiency at temperatures up to 1300°C and residence times
from 2 to 5 seconds. The unit is a batch-load system with two furnaces
and a blended carrier gas to simulate combustion gases (Figure 2.1-1).
The first furnace is used to volatilize the constituents. The carrier
gas moves these constituents into the secondary furnace which is used
2-1
-------
ROTATING
FURNACE
INCINERATION
FURNACE
(AFTERBURNER)
GAS
SUPPLY
CONTROLS
FLY ASH
SEPARATOR
COOLING
SECTION
SAMPLING
TRAIN
EXHAUST
PUMP
SECONDARY
GAS
PREHEATER
FIGURE 2.1-1
LABORATORY SCALE INCINERATION UNIT
-------
to simulate afterburners in a full-scale incineration plant. In the
secondary furnace, additional blended gases with 0_ are added and
temperature is increased to decompose the hazardous constituents. The
combustion products in the off-gas are then collected in various
sorbents in the sampling train.
2.1.3 Sample Size
The first design consideration was that of the overall apparatus size.
The primary concern with respect to this was that of being able to
collect and analyze an off-gas constituent to demonstrate 99.99% ORE of
a chemical present in the feed sample in a few parts per billion. For
the chlorinated compounds which can be analyzed using GC/ECD, a sample
size of several hundred grams is adequate. Task budget and
availability of a rotating tube furnace, capable of handling batch
samples up to five hundred grams, determined the laboratory bench-scale
unit design based on a sample size of 200-500 grams.
2.1.4 Primary Furnace
The primary furnace (Figure 2.1-2) is an electric furnace with a
programmable temperature controller capable of maintaining 1000°C with
gas flows up to 20 liters per minute. A gas supply system is used to
provide blends of N2> C02, and 02 to simulate various combustion
processes in fuels. The primary furnace barrel (Figure 2.1-3) is 130
mm in diameter and 200 mm in length. The maximum temperature rise of
the primary furnace is about 5.5°C per minute. The carrier gas
velocity will be between 6 and 8 cm per second at test conditions.
2.1.5 Fly Ash Trap
Provisions will be made for a fly ash separator between the primary and
secondary furnace. The purpose of this separator is to remove ash
which may be entrained in the carrier gas and to prevent plugging of
the secondary furnace. The ash separator will be a cyclone type design
2-2
•71 A or
-------
(Ins Supply
Filter
On/
101 Off
Temperature
Controllers
Ji
Temperature
Recorder
Programmer
FIGURE 2.1-2
ROTATING TUBE FURNACE ARRANGEMENT
-------
SLIP
SEAL
GAS
OUTLET
RIDING
RING
DRIVE
CHAIN
SPROCKET
130 mm DIA.
RIDING
RING
150 mm DIA.
GAS
INLET
TYPE
THERMOCOUPLE
FIGURE 2.1-3
ROTATING TUBE UNIT
-------
V,
capable of removing particulates down to 100 microns. It will be
constructed of stainless steel and insulated to prevent heat loss
between the primary and secondary furnaces.
2.1.6 Secondary Combustion Gas
Additional gases will be introduced between the primary and secondary
furnaces to simulate secondary combustion gases. The composition of
this gas will be the same as that of the primary carrier gas and will
increase the total gas flow rate by 50 percent. The carrier gas will
be preheated to near (± 50 C°) that of the primary carrier gas
temperature.
2.1.7 Secondary Furnace
The secondary furnace was designed to heat gases from the primary
furnace along with the secondary airflow up to 1250°C and to maintain
the gases at this temperature for between 2 and 5 seconds. To have
fully developed flow while avoiding high pressure losses in the
furnance, a velocity range of 20 cm/sec to 500 cm/sec was established.
For this velocity range and the desired gas flow rate, the furnace tube
diameter would be approximately 2 1/2 cm. For a residence time of 5
seconds, the furnace tube would be approximately 10 meters long. The
secondary furnace tube will be constructed of fused quartz to provide a
nonreactive environment at high temperature. With proper bending of
the quartz tube, the secondary furnace would require a O.lA-cubic meter
volume. This size is consistent with small pottery kilns which are
capable of withstanding a temperature of up to 1300°C. Three
temperature probes will be installed in the secondary furnace to
monitor furnace temperature. The kiln should be able to maintain
temperature within ± 10 C°.
Gas residence time in the secondary furnace can be varied by changing
gas flow rate or length of the furnace tube. Since the desired
residence times range from 2 to 5 seconds, the gas flow rate would have
2-3
-------
to be varied by a factor of 2.5 to cover that range. Since this
variation in the gas flow rate is too large to maintain reasonably
consistent test conditions, two furnace tube lengths will be used.
2.1.8 Cooling Section
The cooling section will consist of a straight 2.5-cm diameter quartz
tube approximately 3 feet long. Exit temperature from the cooling
section will be monitored to insure that temperature will be maintained
between 200°C and 300°C. Insulation will be applied to the tube to
adjust the exit temperature.
2.1.9 Sample Collection
All off-gases from the secondary furnace will enter the sample
collection system. The sample collection system is designed to remove
organic and inorganic constituents of concern. A pump will be used
downstream of the sample collection system to maintain a near
atmospheric pressure in the entire flow train. The sample collection
system is described in detail in Section 2.2.
2.1.10 Range of Test Conditions
Once the design of the bench-scale test apparatus is fixed, variations
in test conditions from the design point are possible; however,
parameters are interdependent for a fixed furnace volume. Residence
time in the furnace is a function of volume flow rate which is a func-
tion of the mass flow rate, pressure, and temperature (Figures 2.1-4
and 2.1-5). Actual operating regimes will be established as the design
is finalized.
2.2 SAMPLE COLLECTION SYSTEM
Collection of the gases generated from all test incineration runs will
require a system for collection of non-particulate and particulate
2-4
2140E
-------
-------
GAS FLOW RATE AT STANDARD CONDITIONS (l/m)
CO
o
o
en
o
H
m
10
Z
0
m
-------
fractions. Sampling of off-gases depends on the nature of POHCs and
other large species. In general, the sampling apparatus for collecting
off-gas effluents includes three major components:
o One or more thermostatically controlled compartments to maintain the
gas at a temperature consistent with the collection medium, usually
hot (200°C) for particulate collection and cool (20°C) for sorbent
collection of the more volatile constituents;
o Sample collectors to collect the samples, such as, filters and
sorbents; and
o Vacuum pump and gas meter
The sampling train used will be similar to the one shown in Figure
2.2-1. Using this sampling train will provide both adequate trapping
of particulate and non-particulate fractions from the off-gas. The
number of impingers and sorbent tubes may vary in number and type
depending upon the test run. This device is physically similar to the
Modified Method 5 (MM5) sampling train.
2.2.1 Particulate and Residue Collection
Bottom residue left in the kiln from the test burn will be removed by
the most efficient means available to the lab which will be consistent
with:
o Complete removal (>99%);
o Prevention of outside contamination; and
o Prevention of damage to the kiln.
Bottom residue removal will be dependent upon the physical
characteristic of the test sample after incineration. The bottom
residue mass may vary from <10% of the starting material weight to >90%
depending upon the sample matrix (liquid, sludge, soil). The
laboratory anticipates some flexibility will be required in attaining
2-5
2140E
-------
HEATED AREA
TEMPERATURE SENSOR
THERMOMETER
Y ^FILTER HOLDER
THERMOMETER
CHECK VALVE
RECIRCULATION PUMP
THERMOMETERS
DRY GAS AIR-TIGHT
METER PUMP
VACUUM LINE
FIGURE 2.2-1
SAMPLE TRAIN
-------
an efficient removal of the bottom residue. Residue removal and
cleaning of the kiln will be adequate to assure subsequent test burns
are not cross-contaminated. Bottom residue will be stored at about 4°C
in glass bottles with Teflon lined caps until combined with the fly ash.
The fly ash separator will retain the larger particulates carried
through the primary furnace tube. As with the bottom residue, the
volume of fly ash produced will vary with respect to sample matrix.
Efficient removal of the fly ash to Teflon-capped glass bottles can be
expected. The fly ash will be stored at about 4°C.
Filter cassettes will be used to trap particulates which are not
separated as fly ash and may vary in size from 1 to 100 microns. The
filter used will be a glass fiber type and will be stored in a glass
bottle with a Teflon-lined cap at 4°C.
Figure 2.2-2 illustrates the flow of the residue sample into the
analytical system. The three solid fractions from the test burns are
weighed and the weight summed to estimate the percentage of sample
volatilized:
WB + WF + WP
% Sample Volatilized = (1 - L ) x 100
WS
Where Wg = Weight of Bottom Residue
Wp = Weight of Fly Ash
Wp = Weight of Filter Particulates
W = Weight of Original Sample
The bottom ash and fly ash will be combined and homogenized. Aliquots
of this residue will be taken for the various chemical and physical
analyses required to determine destruction efficiency of the POHCs and
the EP toxicity of the residue.
The particulate filter is weighed and combined with the XAD-2 resin for
extraction and analysis.
2-6
-------
Physical
Tests
Inorganic
Tests
Organic
Tests
Participates
i
Weighed
Combine with
XAD-2
Extract
1
Analyse
FIGURE 2.2-2
SOLID RESIDUE COLLECTION FLOW CHART
-------
The chemical and physical analyses to be performed on these
incineration residues are described in detail in Section 5.0. Section
4.3 contains details of the analytical test matrix after the
incineration tests.
2.2.2 Gas Collection
The gas collection procedures are dependent upon the POHCs that have
been selected for analysis to determine if they have been destroyed to
99.99% ORE. The PICs are also important in the selection of the types
of impingers and sorbents used. As a result of the initial sample
size, it is necessary to completely extract and concentrate the XAD-2
sorbent, and combine it with the extracted condensate, and the other
impinger solutions to achieve parts per trillion detection limits.
Table 2.2-1 describes the types of sorbent and impinger solutions that
will be used to trap organic and inorganic products from the
incineration. When the waste sample matrix is water or sludge, a
condensate trap will be used to reduce the volume of liquids delivered
to the sorbent traps. Figure 2.2-3 describes this trap. The
condensate collected in the trap must be tested for the various
compound classes. An aliquot of the liquid can be analyzed for
volatile and semivolatile organics and acid and basic inorganics (i.e.,
F~, Cl", phosphorous, and metals). Section 5.2 provides more
details on the analytical protocol for handling the condensate fraction.
After a test run, the sorbents and impinger fractions, as well as the
condensate when applicable, are transferred to glass bottles with
Teflon-lined caps for storage at about 4°C. The analytical protocols
which can be performed on the various fractions are described in
Section 5.0.
2-7
-------
TABLE 2.2-1
GAS SAMPLE COLLECTION MATRIX
Compound
Class
Sorbent
Impinger
Water *
Trap
Volatile Organics
Tenax/Charcoal
Test
Semivolatile Organics XAD-2
Volatile Metals
Acid Compounds
Cyanide
Basic Compounds
Test
Silver Catalyzed Test
Ammonia Persulfate
0.1 NaOH
0.1 NaOH
0.1 HC1
Test
Test
Test
*A water trap will be utilized when the test sample is sludge or liquid.
(See text.)
2140E
-------
GAS FLOW.
FILTER
CONDENSER
CONDENSATE
TRAP
TENAX/CHARCOAL
TRAP
IMPINGERS
XAD-2
FIGURE 2.2-3
MODIFIED SAMPLING TRAIN
FOR HIGH MOISTURE SAMPLES
VACUUM
PUMP
-------
2.3 BENCH-SCALE TEST OPERATIONS
A detailed operating procedure will be developed after the final design of
the bench-scale unit and modified during the course of the system checkout.
The following sections outline some of the operational considerations for
the soil, sludge, and liquid tests.
2.3.1 Soil Tests
Typical operation of the bench-scale test aparatus for soil samples
will involve the following:
1. Weigh out appropriate sample size (200-500 grams + 0.5 grams).
2. Place the sample in the kiln barrel and bolt the barrel halves
together.
3. Place the kiln barrel into the furnace and attach the thermocouple
and gas connections.
4. Set the secondary furnace temperature and allow it to reach test
condition temperature before proceeding.
5. Switch on the evacuation exhaust pump.
6. Establish carrier gas flow at the desired blend and flow rate.
7. Start temperature ramp on primary furnace.
8. After reaching the desired test temperature on the primary furnace,
start barrel rotation and maintain desired test conditions for one
hour before starting shut down procedures.
9. Turn primary furnace off and stop barrel rotation, but continue gas
flow.
2-8
-------
10. After primary furnace has cooled to 400°C, turn off secondary
furnace.
11. Divert gas from sampling train and remove collected samples.
12. After primary furnace has cooled to near room temperature, remove
kiln barrel and disassemble.
13. Remove residual sample from barrel.
14. Disassemble fly ash collection system and remove fly ash.
15. During the course of the system operation, the following
parameters will be monitored and recorded: N_, CO- and 0.
flow rate of primary and secondary gasses, temperature of the
rotating kiln gas, fly ash separation system exit gas, secondary
furnace, and cooling section exit gas, particulate sample
isothermal box and impinger isothermal box. Sample train flow
meter delta pressure also will be monitored.
2.3.2 Sludge Tests
The operation of the bench-scale apparatus during sludge tests would be
the same as that for the soil tests except for those considerations
necessary to deal with the high moisture content of the sample. The
following additions or changes would be made to the operating procedure:
1-6. Identical to soil tests (2.3.1).
7. The primary furnace temperature will be raised to 90°C and held
at this temperature until most of the moisture is removed from
the sample. The carrier gas flow rates will be reduced during
this drying period to compensate for the increased flow rate due
2-9
2140E
-------
to the water vapor. This adjustment is necessary to maintain the
desired residence time of the gases through the secondary furnace.
8-15. Identical to Soil Tests (2.3.1).
(Note: A condensate trap will be placed between the particulate
filter and the sorbant traps in the sampling train to remove
the high load of moisture. The moisture in the trap will be
analyzed for POHCs).
2.3.3 Liquid Tests
Unlike the soils and sludges which would be batch fed, the liquid waste
would be continuously fed through a probe into the primary furnace
barrel. The desired temperatures and carrier gas flows would be
established in both the primary and secondary furnace prior to feeding
the liquid waste. The liquid waste systems would consist of a
reservoir and peristaltic pump. For a 300-gram liquid sample fed into
the primary furnace over a 1-hour period, the sample volume flow rate
in the secondary furnace would be approximately 30% of the total sample
flow rate. This percentage can be reduced by slower feed rates
occuring over longer periods.
2-10
-------
3.0 FEEDSTOCK CONSIDERATIONS
3.1 INTRODUCTION
The success of the bench-scale incineration test program depends upon
obtaining samples containing the chemicals to be incinerated in sufficient
quantity to provide for the detection of very low concentrations (.01
percent not destroyed by incineration). Such samples must be obtained for
liquids, sludges, and soils.
The success of the bench-scale testing program depends on the development of
an adequate database concerning the soils, sludges, and liquids to be
incinerated. Furthermore, the success of incineration depends upon
obtaining sufficient information concerning the feedstocks to ensure safe
and complete destruction. Feedstock characterization must be performed with
respect to physical, chemical, and thermodynamic properties of the soils,
sludges, liquids, and selected major compounds found at Basin F. Of the
materials to be incinerated, information exists concerning most of the
contaminated chemicals themselves (Table 3.1-1). However, this data set is
insufficient to ensure success, and data concerning the soils, sludges, and
liquids as a whole are virtually nonexistent.
3.2 SAMPLE CONSIDERATIONS
The principal material to be incinerated is contaminated soil found at
Basin F. Soils include both the overburden and the soil beneath the 9.5-mm
(3/8-inch) asphalt liner. As a practical matter, the soils to be
incinerated will include the asphalt liner as well. Liquid and sludge
materials exist in significant quantities, but relative to the soils, are of
less consequence.
The hazardous chemicals identified in Table 1.1-1 and 1.1-2 exist in various
concentrations in the soils at Basin F. Basin F liquid, however, is
considered to be homogeneous. Similarly, the sludges are considered to be
relatively homogeneous. The concentrations of chemicals in soils vary as a
3-1
2140E
-------
TABLE 3.1-1
PROPERTIES OF SELECTED COMPOUNDS
Chemical Compound
1 Chloropane
1,1 Dichloroethylene
1,2 Dichloroethylene
2 Chloropane
Acetophenone
Aldrin
Arsenic
Benzaldehyde
Benzene
Benzole Acid
Bromo Dichloromethane
Carbon Disulfide
Carbon Tetrachloride
Chlorobenzene
1-Chlorobutane
Chloroform
Chlorohexane
Copper
Cyclohexane
Dieldrin
Dihydroxybenzoic acid (methyl ester)
Dimethyl Disulfide
D imethy loxyethane
DIMP (diisopropylmethylphophonate)
Empirical
Formula
CH2C12
C1CHCHC1
CHjCHClCHj
CHgCOC6H5
C12H8C16
As
f* LJ pi in
i* Ji |JL*nu
C6H6
C g. Hq COOH
PhRrPl
CS2
cci4
C6H5C1
CH3(CH2)2CH2C1
CHC13
C6H13C1
Cu
C6H12
C12H8C16°
W*
CHj-S-S-CHj
CHjOCH^OCHj
C^K-PO,
Molecular
Weight
97
97
79
120
365
75
106
78
122
164
76
154
113
93
119
121
64
84
381
154
94
90
193
Specific State
Gravity (at 25°C)
Liquid
Liquid
Liquid
Liquid
Solid
Solid
Liquid
0.880 Liquid
Solid
Liquid
Liquid
1.590 Liquid
1.100 Liquid
Liquid
1.490 Liquid
Liquid
Solid
Liquid
Solid
Solid
1.060 Liquid
Liquid
0.980 Liquid
Melting
Point (C)
-50
19.7
104 - 105
814
-26
5.5
121.7
-111
-22.6
-45
-123.1
-63.5
1,083
6.5
150
199-200
Boiling
Point (C)
31.6
48
35.3
202.3
615
179
80.1
249
89.2 - 90.6
46.5
76.8
131.7
78
61.26
134
2,324
80.7
175 - 176
109.7 - 115
83
174
Flash
Point (C)
-17.8
2.2
-32.2
82.2
64.4
-11.1
121.1
-30
None
29.4
-9.4
None
35
-20
40
Auto Ignition
Temp (C)
570
460
599.3
571.1
191.7
562.2
571.1
90
638.3
460
245
-------
TABLE 3.1-1 (Continued)
PROPERTIES OF SELECTED COMPOUNDS
Chemical Compound
Diphenylethane
Dithiane
DMMP (Dimethylmethylphosphonate)
Endrin
Ethoxyethylene
Fluoride
Heptane
He xachlorobenzene
Hexane
Iron
Isodrin
Magnesium
Mercury
Methyl Acetate
Methylacetophenone
Naphthalene
Pentachlorobenzene
Pentachloroethane
Phenol
Phosphorus
Sodium Acetate
Sodium Fluoride
Sodium Hydroxide
Sodium Methyl Phosphonate
Sodium Sulfate
Sodium Sulfate
Empirical
Formula
(C^CHCHj
C4H8S2
W°3
C12H8C16°
F2
CH3(CH2)5CH3
C6C16
Fe
C12H8C16
Mg
Hg
CHjCOgCH,
C10H8
C6HC15
p| y i r*^l
l^rB^irtU'Lii^
C H OH
P
NaC2H^02
NaF
NaOH
Na-SO.
Molecular
Weight
182
120
124
381
38
100
285
86
56
365
24
200
74
128
250
202
94
31
82
Specific State
Gravity (at 25°C)
Liquid
Solid
1.140 Liquid
1.645 Solid
Liquid
Liquid
Liquid
Solid
Solid
Solid
Liquid
Liquid
Solid
Liquid
Solid
Solid
Solid
Melting
Point (C)
-20
108 - 113
235
-218
230
1,535
241 - 242
651
-38.89
-98.7
80.1
-29
40.6
44.1
324
Boiling
Point (C)
272
199 - 200
181
-187
98.5
326
68.7
3,000
1,107
356.9
57.8
217.9
162
181.9
280
Flash Auto Ignition
Point (C) Temp (C)
128.9 440
-3.9 215
242.2
-21.7 225
-10 501.7
78.9 526.1
79.4 715
Spont AI 30
607.2
-------
TABLE 3.1-1 (Continued)
PROPERTIES OF SELECTED COMPOUNDS
Chemical Compound
Sulfur (Flowers of Sulfur)
Tetrachlorobenzene
Tet rachloroethylene
Toluene
Trlchlorobenzene
Xylene (Ortho, Meta, and Para)
Empirical
Formula
S8
CCljCClj
C6H3C13
CfiH (CHj).
Molecular
Weight
256
216
166
92
181
106.2
Specific
Gravity
2.07
1.73
1.63
0.866
0.861-0.88
State
(at 25°C)
Solid
Liquid
Liquid
Liquid
Solid
Liquid
Melting
Point (C)
119
138
-23.4
-95
63.4
-47.9
Boiling
Point (C)
444.6
245
121.2
110.4
208.5
138.8 - 144.4
Flash
Point (C)
207
155
None
4.4
107
27.2 - 32.2
Auto Ignition
Temp (C)
232
480
—
465 - 530
-------
function of borehole location and depth (see Appendix C of the Task 17
Technical Plan). Most concentrations are in the parts per billion (ppb)
range, although some concentrations are in the parts per million (ppm) range.
It is not essential that the samples of soil used in the bench-scale
incineration testing program contain a representative average of waste
concentrations. Average conditions may never be encountered in the actual
program. Rather, it is essential that the severe problems be tested
explicitly. For this reason, soils from the area of Borehole No. 01 will be
used to test the adequacy of the incineration regimes available. The area
of Borehole No. 01 has been chosen because it has not lost its asphalt
liner. The overburden is particularly contaminated, and the soils beneath
the. liner also exhibit significant levels of contamination. Borehole No. 01
is located in the area known as "Little F," the area dyked in 1962 and
apparently containing the most problematical soils and potential sludges as
well as liquids (See Figure 3.1-1).*
3.3 SAMPLE TESTING
Sample testing includes physical, chemical, and thermodynamic properties of
the liquids, potential sludges, and soils as well as screening for potential
POHCs. Sample testing, therefore, will occur in two phases. All samples to
be subjected to the bench-scale incineration system will be homogenized and
then characterized for physical, chemical, and thermodynamic (PCT)
properties and potential POHCs. Samples will be obtained in 15 kg
quantities in order to provide sufficient material for the bench-scale
process plus all characterization studies which must precede it.
*Note: Under Task Order No. 6, Environmental Sciences and Engineering (ESE)
is developing the contamination profile of Basin F and soon will send
Ebasco a copy of the draft report. This report will define the locations
and magnitude of contaminants presently existing in and around Basin F.
Upon evaluation of the report, Ebasco may change the soil sampling
location.
3-2
/,nc
-------
A ALDRIN
B DIELDRIN
C ARSENIC
D ENDRIN
ISODRIN
FLUORIDE
G SULFURS
H DBCP
X ACTION LEVELS NOT EXCEEDED
NO SAMPLE NOT ANALYZED
* INDICATES CONCENTRATION
EXCEEDS 100X THE ACTION LEVEL
NUMBERS IN PARENTHESIS
DENOTE INTERVALS BELOW
LINER AS FOLLOWS:
(1) = 0.0-1.0 FT
(2) = 1.0-2.0 FT
(3) = 2.0 - 3.0 FT
(4) = 3.0 • 4.0 FT
X(2)
NO (3)
NO (4)
*— APPROXIMATED^
A, B, D (2)
31 F(3)
WATER LEVEL
1982
X(2)
B, C(3)
NO (4)
32 X(2)
X(3)
NO (4)
AD(1)
X(2)
NO (3)
NO (4)
C(2)
A,D(3)
X(4)
X(D 22
X(2)
X(3)
NO (4)
A.B.C. D, E(1)
A, C, D, F (2)
A, B, C. D, f (3)
A, B, C, D, F (4)
A*B*C, D*E*F, G,
A, B*C. D, E, F, G (2) 02
A, B, C, D, F, G (3) •
A, C, D, F, G (4)
C(2)
NO (3)
NO (4)
LIQUID
BORING LOCATIONS
Figure 3.1-1
SOIL SAMPLING LOCATION
SOURCE: MYERS AND THOMPSON. 1982
-------
3.3.1 Feedstock Characterization
The feedstock characterization program is designed to define those PCT
properties essential for understanding the bench-scale program and for
contributing to the larger-scale operations. Such characterizations
are not intended to provide a complete listing of properties, but only
such a listing as is essential for safe and cost-effective operation of
the system.
Certain physical and chemical properties have already been partially
determined for the hazardous chemicals to be destroyed and removed by
incineration. Some of these properties include chemical formula,
molecular weight, melting point, boiling point, flash point, and
autoignition temperature. Heats of combustion either have been
determined or calculated, as will be shown in Chapter 4.
Critical parameters are those describing the matrix containing the
hazardous chemicals. Those parameters requiring definition are
identified below:
Material
Parameters to be Determined
Soils (including
overburden and liner)
Specific heat
Heat capacity
Thermal conductivity
Moisture content
Ash fusion temperature
Sludges
Viscosity
Moisture content
Ash fusion temperature
Distillation curve
Liquids
Viscosity
Corrosivity (with respect to refractory)
2140E
3-3
-------
These parameters will be determined, to the greatest extent
possible, in the evaluation of the samples prior to bench-scale
incineration testing.
3.3.2 Analytical Screening for Potential POHCs
Samples collected for test incineration from Basin F will include:
o Soil;
o Sludge; and
o Liquid.
Nonhomogeneity of the collected samples is expected due to the
wide variability in soil type and multi-phase characteristics of
the liquid/sludge in Basin F. As the lagoon evaporates, the
liquid/sludge portion of the basin becomes more concentrated with
organic and inorganic constituents. As a result, the
concentrations of these compounds can be expected to vary widely
across the basin area. Therefore, the samples taken and delivered
to the laboratory will not be homogeneous.
An initial screen of the samples may be performed on aliquots of
each matrix that has been made as homogeneous as possible by
mixing. Enough sample of each matrix type will be collected,
homogenized, and stored at the Hittman/Ebasco laboratory at 4°C or
less to use for all incineration tests. Chemical characterization
of waste samples is critical to evaluating the destruction and
removal efficiency (ORE) of incineration tests. The most effi-
cient and cost effective means of characterizing the waste is to:
1. Combine all samples received by matrix into one bulk sample.
2. Homogenize by mixing or agitating the bulk sample.*
* The effectiveness of this process will be evaluated. If found to be
unsatisfactory, alternate procedures will be investigated.
3-4
-------
3. Prepare aliquots from each bulk matrix for analytical screen.
4. Ship aliquots to appropriate laboratory.
5. Determine the constituent concentration.
Soil, sludge, and liquid samples will be assayed semiquantitatively by gas
chromatography/mass spectrometry (GC/MS) for volatile and semivolatile
organic target analytes. An attempt will be made to identify other major
unknown peaks present in the GC/MS total ion current profiles. Potential
unknown analytes will be tentatively identified, if possible. Collected
samples will also be assayed quantitatively by graphite furnace atomic
absorption spectroscopy for arsenic, by cold vapor atomic absorption
spectroscopy for mercury, and for other target metals by inductively
coupled argon plasma (ICP) emission spectroscopy. Soils, sludges, and
liquids will be characterized in terms of ignitability, corrosivity, and
reactivity.
3-5
2140E
-------
4.0 SELECTION OF TEST PARAMETERS
4.1 INTRODUCTION
The planned bench-scale test consists of 20 test burns, largely on
contaminated soils but also including sludges and liquid from Basin F. The
20 test burns are necessary due to the multiple runs required to adequately
test for all major contaminants regardless of concentration. Such testing
will lead to the ultimate selection of POHCs for pilot-scale and full-scale
operations.
A bench-scale test matrix was developed recognizing the typical operating
parameters for hazardous waste incinerators capable of handling chemically
contaminated solids. These representative parameters are as follows (from
Frankel, Sanders, and Vogel 1983).
Type of Incinerator
Parameter Rotary Kiln Fluid Hearth
Temperature of
Primary Chamber (°C) 280-1,280 750 560-900
Temperature of
Afterburner (°C) 900-1,600 N/A 1,000-1,600
Residence Time
in Primary Chamber 2 hrs 0.75-2.5 sec 10-30 min
Residence Time
in Afterburner 1.3 sec N/A 2 sec
The parameters shown by Frankel et al. are not the only ones utilized in or
reported for incineration. Other authors have shown afterburner residence
times of up to 5 seconds for gases evolved in primary incinerators. For
example, Bonner et al. (1981) report that
-------
afterburner residence time requirements may be 0.2-6.0 seconds depending
upon the waste being destroyed. Bonner also reports varying temperature
regimes depending upon technology. The temperatures reported for a
fluidized bed in Bonner et al. (1981) are 450-980°C. These are consistent
with, but broader than, the temperatures previously mentioned. Dellinger et
al. (1984) gives typical afterburner conditions of 2-4 seconds (out of a
potential range of 1-12 seconds) and bulk gas temperatures of 600-1,100°C.
The basis for the parameters also includes optimal fuel combustion
conditions as discussed in Kramlich et al. (1984), focusing on excess 0_
in the stack gas at 5.4 percent (35 percent excess air), and an upper bound
of approximately 7 percent 0_ in the stack (corresponding to about 50
percent excess air). The basis of the parameters includes the limitations
of the laboratory equipment, identified as follows:
1. Maximum primary chamber temperature, 800-1,000°C
2. Maximum practical afterburner temperature, 1,250°C
The basis of the test matrix also includes the goals of: 1) obtaining
sufficient spread in the parameters to develop first order kinetic
approximations of destructive mechanisms (a problem with the residence times
of the MRI experiments); and 2) obtaining at least one regime where ORE
levels of 99.99 percent are reasonably assured.
4.2 TEST MATRIX PARAMETERS
The test matrix parameters involve varying residence time in the
afterburner, temperature in the afterburner, and 0_ concentration in the
carrier gas. These parameters are summarized as follows:
Value
Parameter
Time (sec)
Temp (°C)
Minimum
2
900
5.4
Maximum
5
1,250
7.0
4-2
2140E
-------
Additional runs will be made at 65Q°C, as discussed below, in order to
\, ensure that some regimes will be tested that will not succeed. These runs
will be at 2 and 5 seconds residence time in the afterburner, but will only
be at 5.4% 0. concentration.
The basis for each parameter is summarized below.
A.2.1 Selection of Time Parameter
The variation in residence time is based upon the values in the
literature. The minimum value of 2 seconds appears in virtually all
scientific and engineering materials concerning hazardous waste
incineration. Dellinger et al. (1984), for example, reports the
temperature to achieve destruction of a compound at a ORE of 99.99
percent in 2 seconds (see Table 1.1-3). The residence time of 2
seconds is also consistent with the data presented by Frankel et al.
(1983) for afterburners being operated commercially, as shown above.
•-. The maximum value of 5 seconds appears to be a practical upper limit
based upon the bench-scale apparatus and the need for firing 300-500
grams of contaminated materials per test to fairly simulate larger-
scale operations. The 5-second value appears near the upper end of the
scale presented by Bonner et al. (1981). Further, the spread between
2 seconds and 5 seconds provides sufficient range to achieve a fair
extrapolation to 6 seconds should such an extrapolation be necessary.
4.2.2 Selection of Temperature Parameter
The laboratory-scale operations will use a primary chamber (Linder
furnace) temperature of 1,000°C, or as close to that as can be
achieved. It is expected that the actual temperature reached will be
between 800 and 1,000°C, rather than the peak value. This temperature
is consistent with the values reported by Frankel et al. (1983) for
rotary kilns and hearth type furnaces and the values reported by Bonner
et al. (1981) for fluidized bed furnaces. The final temperature
selected could well be limited by the feedstock tests concerning ash
fusion temperatures of the soils to be fed.
4-3
21AHF
-------
The first temperature in the afterburner, 900°C, is consistent with the
minimum afterburner temperature reported by Frankel et al. (1984) for
afterburners associated with rotary kilns. Further, it is consistent
with the literature concerning temperatures required to achieve 99.99
percent destruction (see, for example, Dellinger et al. 1984 as shown
in Table 1.1-3). It presents a minimum temperature below which 99.99
percent ORE is probably not achievable.
The maximum temperature in the afterburner, 1,250°C, represents a
practical upper limit of the bench-scale equipment. Further, it is in
the middle of the range for afterburners as reported by Frankel et al.
(1984). Because there is a 350 Centigrade degrees spread between the
minimum and maximum temperatures, there is considerable reason for
confidence in extrapolating the results to higher temperatures (e.g.,
1,500°C) should such extrapolation prove necessary.
A third temperature, 650°C, has been chosen as a minimum value for test
purposes. This temperature is consistent with the low end of values
shown for afterburners. Further, it is at the low end of temperatures
where 99.99 percent ORE for hazardous organics is achieved as shown in
Dellinger et al. (1984). The temperature of 650°C is designed to
provide a failure to achieve 99.99 percent ORE for some (but not all)
compounds in order to provide the most effective data for kinetic
calculations. Tests run at 650°C will be at 2 and 5 seconds, but will
only be at 5.4 percent 0_ in the carrier gas.
The third temperature provides a matrix of six points for the
establishment of time and temperature requirements to incinerate the
soils. The matrix appears as follows:
4-4
-------
Minimum
650°C
650°C
Intermediate
900°C
900°C
Maximum
1,250°C
1,250°C
Temperature
Time
2 seconds
5 seconds
A.2.3 Oxygen Concentration
Oxygen concentration is a parameter chosen to determine the level of
excess air which is optimal in firing of the supplementary fuel.
Oxygen concentration is varied in the carrier gas as a means of making
the bench-scale tests most representative of the postflame oxidation
regions as well as the pyrolysis region. Oxygen concentration
influences not only the temperatures achieved in the flame (see, for
example, Babcock and Wilcox (1978) for a correlation between excess
0 and flame temperature), but also influences the degree of
completeness of combustion and the minimization of PIC formation. The
correlation between excess air and excess 0_ in the dry stack gas is
shown in the following equation (Babcock and Wilcox 1978):
XEA = 100 x (02 - 0.5 CO)/(.264N2 - (02 - 0.5 CO) (1)
Where %EA is percent excess air, 0_ is percent oxygen in the dry
stack gas, CO is percent carbon monoxide in the dry stack gas, and
N_ is percent nitrogen in the dry stack gas. For these
calculations, the CO term can be ignored because proper combustion
reduces CO to less than .002-.005% at an absolute maximum (20-50
ppmv CO). Nitrogen concentration can be taken at 79 percent.
Consequently, the expression can be simplified to the following:
%EA = 100 x 02/(20.856-02) (2)
Solving this equation for various levels of excess air provides
the following values:
4-5
-------
SEA %02
25
30
35
40
50
75
4.2
A. 8
5.4
6.0
7.0
8.9
The research by Kramlich et al. (1984) previously cited demonstrates
that PICs are minimized and DREs are maximized with excess air in the
30 to 40 percent range. Below and above that range, PICs increase in
dramatic quantities, as is shown in Figure 4.2-1.
The minimum concentration of 02 in the stack gas is selected at 5.4
percent, corresponding to the apparent optimal value shown in
Figure 4.2-1. This level can be set for the carrier gas in the
experiment. It corresponds to a C02 level of 15.6 percent. Further,
because 5.4 percent 02 is an apparent minimum point, selection of any
value below this depiction of 35 percent excess air would seriously
distort efforts at limited extrapolation. Such distortions would make
the results of excess air levels greater than 35-50 percent appear to
be more favorable than would be expected under actual operations.
The maximum concentration of 0_ is set at 7.0 percent, corresponding
to common firing practices of many combustion systems. Further, this
representation of 50 percent excess air represents a practical upper
bound beyond which ORE levels of 99.99 percent could not practically be
expected (see, for example, Figure 4.2-1). Finally, the spread between
35 and 50 percent excess air does provide sufficient data for limited
extrapolation to levels between 50 percent and 75 percent.
It should be noted that the values of 5.4 percent and 7.0 percent
represent oxygen concentrations expected for the postflame region.
Should it become necessary in order to demonstrate 99.99 percent ORE,
4-6
21AOE
-------
^2000
(U
0>
>»
X
o
I/I
I/I
0)
5 1500
o
o
4->
V
o
o>
1000
•o
c
03
l/t
c
o
o
o
•o
500
O co
A Hydrocarbons as CH^
Q Test Compound (Average of four)
100
0.02
0.02
-------
one experiment will be run at 5 seconds and 1,250°C with air as the
carrier gas in order to more closely approximate flame mode oxygen
concentrations.
4.2.A Test Execution
The regimes established above will be tested on the contaminated soils
fractions. Two runs will be made per sample in selected cases in order
to ensure adequate data on all hazardous organics identified. Such
tests will be run at 1,250°C for 5 seconds at 5.4% 02, 1,250°C for 2
seconds at 5.4% CL, 900°C for 5 seconds at 5.4% 02> and 900°C for 2
seconds at 5.4% 0 . POHCs will be selected for single run tests at
7% 0 in the carrier gas, and for tests at 650°C. Once a rough
optimum regime has been determined for contaminated soils, it will be
tested on the liquids (where two runs are contemplated), on sludges
(two runs), and on a proportionate mixture of all materials found at
Basin F. The two runs on the proportionate mixture of all materials
will be at 5 second residence time and at 900°C and 1,250°C
temperatures in the afterburner.
4.3 SELECTION OF PRINCIPAL ORGANIC HAZARDOUS COMPOUNDS (POHCs)
POHCs are used as compounds that can measure the fate of all hazardous
chemicals to be destroyed. They are chosen based upon thermal stability and
concentration. Various ranking schemes commonly proposed for the selection
of POHCs include:
o Heat of combustion of the hazardous chemical;
o Autoignition temperature;
o Theoretical kinetics; and
o Thermal decomposition data.
Each methodology has its strengths and weaknesses. Heat of combustion
permits evaluation of all compounds either by experimentally determined
values in kcal/g, or by calculated values. Heat of combustion, however,
does not deal with the issue of thermal stability. Autoignition
4-7
-------
temperature, theoretical kinetics, and thermal decomposition data provide
additional insights. Unfortunately, the database is incomplete for such
properties with respect to the compounds found in Basin F.
The U.S. Environmental Protection Agency (EPA) utilizes heat of combustion
for selection of POHCs according to the following formula:
POHC rank = (%C) + 100/Hc (3)
Where %C represents percentage of concentration in the waste and He is
heat of combustion in kcal/g. This formula is used here in the absence
of more analytically precise kinetics and thermal decomposition data.
It is used to recognize that He and thermal stability are not neces-
sarily correlated. This formula is more sensitive to He than
concentration with respect to Basin F wastes due to the low concentra-
tions of materials (typically in the ppb and ppm ranges).
Table 4.3-1 is a compilation of heats of combustion for the hazardous
organics in the soils sampled at Boring No. 1 and in the liquids found
in Basin F. Of these, aldrin has an He of 3.75 kcal/g and endrin, has
an He of 3.46 kcal/g (Dellinger et al. 1984). These chemicals, along
with dieldrin, can be classified as POHCs. Because of the critical
nature of these tests, however, and the lack of absolute precision in
using the He value to determine appropriateness of any POHC with
respect to incinerability, the bench-scale tests will be performed
initially for all identified compounds in the soils obtained from
Basin F Borehole No. 01. This testing for all compounds necessitates
multiple (4) runs. Based on these runs, the POHCs will be determined
for the remaining tests.
4-8
-------
TABLE 4.3-1
I/
HEATS OF COMBUSTION FOR HAZARDOUS WASTES -
Compound
VOLATILE HALO ORGANICS
Chloroform (trichloromethane)
1,1 - Dichloroethane
(ethylidene chloride)
1,2 - Dichlorethane
(ethylene chloride)
1,1,1 - Trichloroethane
(methylchloroform)
1,1,2 - Trichloroethane
(vinyltrichloride)
Tetrachloroethylene
(perchloroethylene )
Carbon tetrachloride
(tetrachloromethane)
1,2 - Trans-dichloroethylene
(acetylene dichloride)
Dichloromethane
(methylene chloride)
Hexachlorobutadiene
Hexachloroethane
VOLATILE AROMATICS
Benzene (benzol)
Toluene (methylbenzene)
Xylene (0-Xylol)
Ethyl benzene (phenylethane)
Formula
CHC13
CH3CHC12
C1CH2CH2C1
CH3CC13
C12CHCH2C1
C12CCC12
CCl,
C1CHCHC1
CH2C12
C«C16
C2C16
C6H6
C6H3CH3
C6H^(CH3)2
C6H5C2H5
Btu/lb
1,350
5,405
5,405
3,585
3,585
2,145
430
4,865
3,065
3,820
830
18,070
18,270
18,450
18,500 2/
Kcal/gram
0.75
3.00
3.00
1.99
1.99
1.19
0.24
2.70
1.70
2.12
0.46
10.03
10.14
10.24
10.27
2140E
-------
TABLE A.3-1 (Continued)
HEATS OF COBUSTION FOR HAZARDOUS WASTES
Compound
CHLORINATED AROMATICS
Chlorobenzene (phenyl chloride)
Hexachlorobenzene
(perchlorobenzene)
1,2,3,4 - Tetrachlorobenzene
1,2,4 - Trichlorobenzene
1,2 - Dichlorobenzene
ORGANOCHLORINE PESTICIDES
Aldrin "kl
Endrin 4/
Dieldrin ^J
Isodrin &
Chlordane ~U
Malathion &/
Parathion 2/
Azodrin (monocrotophos)
Vapona (DDVP) iS/
Hexachlorocyclopentadiene
Atrazine il/
DDTI2/
DDE13/
Oxathiane
Formula
C6H5C1
C6C16
C6H2Cl4
C6H3C13
C6H4C12
C12H8C16
C12H8C160
C12H8C160
C12H8C16
C10H6C18
C10H1906PS2
C10H1AN05PS
C6HU05NP
C4H7C12O^P
C5C16
C8H1AN5C1
(C1C6H^,)2CHCC13
C14H8C14
N/A
Btu/lb
11,890
3,225
4,700
6,125
8,235
6,755
6,235
10,200
N/A
4,880
N/A
6,505
N/A
N/A
3,785
N/A
8,125
9,100
N/A
Kcal/gram
6.60
1.79
2.61
3.40
4.57
3.75
3.46
5.66
N/A
2.71
N/A
3.61
N/A
N/A
2.10
N/A
4.51
5.05
N/A
2140E
-------
TABLE 4.3-1 (Continued)
HEATS OF COtffiUSTION FOR HAZARDOUS WASTES I7
Compound Formula Btu/lb Kcal/gram
Dithiane N/A N/A N/A
Nabam M/ C^H^NaS^
Maneb il C^H6MnN2S4
Zineb ii/ C4H6MnN2S4Zn
NONCHLORINATED ALIPHATIC SOLVENTS
Methylethyl Ketone (butanone) C4H80 14,538 8.07
Acetone (propanone, C3HgO 13,300 27 7.38
dimethyl ketone)
Methylisobutyl Ketone (hexone)
Dimethyldisulfide
(2,3,-dithiabutane)
OTHERS
Acetonitrite (methyl cyanide)
Acrylonitrile (vinyle cyanide)
Methane
Pyridine
Ethane
Aniline (phenylamine)
Nitrobenzene
(CH2)2CHCH2COCH3
CH3-S-S-SH3
CH3CN
CH2CHCN
CHA
NCHCHCHCHCH
C2H6
C6H5NH2
C6H502N
N/A
N/A
13,280
14,285
23,879 2/
14,105
22,320 U
15,730
10,810 2/
N/A
N/A
7.37
7.93
13.25
7.83
12.39
8.73
6.00
I/ All heat contents from determination of the thermal decomposition
properties of 20 selected hazardous organic compounds Dellinger et al.
1984.
2/ Chemical Processes. Felder and Rousseau. 1978.
3/ l,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4,5,8-dimethanon
aphthalene
2140E
-------
TABLE A.3-1 (Continued)
HEATS OF COMBUSTION FOR HAZARDOUS WASTES I/
4/ l,2,3,4,10,10-hexachloro-6,7-epoxy,l,4,4a,5,6,7,8,8a-octahydro
1,4,5,8-endo-endo,dimethanonaphthalene)
5/ l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l,4,5,8-
dimethanonaphthalene
6/ 1,2,3,4,10,10-hexachloro-l,4,4a,8,8a hexahydro-1,A,5,8-endo-
dimethanonaphthalene
7/ 1,2,4,5,6,7,8,8-octachloro-A,7,methano-3a,4,7,7a-tetrahydroindane
8/ S - (1-2 dicarbethoryethyl) 0,0-dimethyldithiophosphate
9/ 0,0-dietlyl 0-P-nitrophenylphosphorothioate
10/ 0,0-dimethyl 0-(2,2-dichlorovinyl phosphate)
ll/ 2-chloro-4-ethylamino-6-isopropyl amino-s-triazine
12/ l,l,l-trichloro-2,2-bis(p-chlorophenyl) ethane
137 l,l-dichloro-2,2-bis-(p-chlorophenyl)ethylene
14/ Ethylenebis (dithiocarbamic acid) disodium salt
15/ Manganous ethylenebis (dithiocarbonate)
16/ Zinc ethylenebis (dithiocarbamate)
2140E
-------
4.4 SELECTION OF ANALYTICAL PARAMETERS
The analyses that will be performed to achieve the objectives of the waste
incineration tests were selected to meet the following criteria:
o Maximize the information;
o Minimize number of analytical procedures;
o Utilize current laboratory certification; and
o Minimize certification efforts.
The analytical program will support four (4) phases of testing:
o Initial screen of waste feedstock;
o POHC evaluation tests;
o Incinerator optimization tests; and
o Incineration under optimum conditions.
The complete organic analysis will be performed for four (4) test burns
which will cover the full range of test conditions to establish the
appropriate POHCs. The initial screen of the feedstock wastes has been
discussed in Section 3.2.2. Optimization of the incinerator operating
conditions requires rapid analytical response to guide subsequent test
burns. To achieve a rapid turn-around of the results during the
optimization phase, only POHCs will be tested for in the feedstock, the
solid residue fraction, and the off-gas. These analyses will not be
certified but will be performed using approved methods. However, while
certification may not be necessary, some demonstration of the laboratory's
ability to detect the required levels will be required.
The 99.99% ORE level in the optimization phase and optimum conditions phase
will be determined from the initial feedstock screening analyses. The
99.99% ORE level, will be used to determine the analytical detection limit.
The actual DREs will be calculated for the POHC from the analysis of the
individual feed sample.
4-9
2140E
-------
A table of 99.99% ORE levels will be calculated from the initial feedstock
v screening data for all POHCs that are selected for analysis during the
optimum conditions phase. After the optimum conditions for incineration
have been established, the following analytical procedures will be performed
at HEAI on the feedstock and the incineration by-products:
o Chlorinated Hydrocarbon Analysis (GC/ECD)
o Organosulfur Compound Analysis (GC/FPD)
o Organophosphorous Compound Analysis (GC/NPO)
o Volatile Organic Analysis (GC/PID and GC/Hall detector)
o Hydrogen Halides (F~ & Cl")
o Cyanide (Distillation/Colorimetric)
o Metals (Arsenic by furnace AA, Mercury by cold vapor AA, general
metals by ICP)
o GC/MS Screen
Furthermore, the above procedures will be used to analyze data for feedstock
at the time of each optimum conditions burn. Because HEAI has not proposed
to certify the above methods, the data resulting from the analysis can
provide only a rough estimate of the quantity of analyte present. This will
be necessary to establish the best estimate of POHC concentration at time of
the burn. The incineration off-gas and residues will be tested to acquire
quantitative data to better estimate the destruction and removal efficiency
at optimum conditions.
A more detailed discussion of the procedures is described in Section 5.2.
The methods were selected based upon the ideal instrument detection limits
that each procedure is capable of producing under optimized analytical
preparatory conditions.
A GC/MS screen of the organic fraction of the incineration gas sampling
train and of the solid residues will be performed on selected test runs.
This screen will not continue to be utilized if the desired detection limits
cannot be achieved. However, through a GC/MS screen, more data may be
aquired about compounds which are detected but not identified by the GC/EPD,
Vs-k
NPD, FPD, or Hall detector analyses.
4-10
-------
5.0 ANALYTICAL DETAILS
5.1 SAMPLE HANDLING AND SAMPLE FLOW
Hittman/Ebasco Associates Inc. (HEAI) will be the lead laboratory on sample
handling and processing. Samples shipped from the field will be homogenized
and properly stored under refrigerated conditions by HEAI until analysis or
incineration testing. For initial feedstock analysis, the sample will be
shipped by overnight express to the approved laboratory. Figure 5.1-1
illustrates the flow of the sample from RMA to the laboratories for analysis.
The soil sample collected will be from a known area of high contamination to
facilitate the bulk homogenization and storage of one sample. Sludge and
liquid samples should be of a more consistent contaminant concentration
range, although "hot" spots can be expected. After aliquoting for feedstock
analysis, the samples will then be aliquoted into separate bottles for each
test incineration run. The samples will be maintained in tightly sealed
glass containers under refrigerated conditions. The lid of each container
will be wrapped with Teflon tape and then a layer of parafilm around that to
prevent loss of volatiles. However, it can be assumed that some contaminant
concentration levels will drop during this period of optimizing the
incinerator burns.
The laboratories performing analyses will be CAL, UBTL, and HEAI. HEAI will
have the lead on sample preparation and shipment for feedstock analyses. A
full set of organic and metal analyses will be performed on each initial
soil, sludge, and liquid feedstock sample. HEAI will be responsible for all
incinerator test burn sample analysis. The solid and gas fractions
collected from the test burns will be analyzed by methods developed at
HEAI. Table 5.1-1 summarizes in tabular form, the tests which will be
performed and Table 5.1-2 summarizes the number of analyses to be performed.
5-1
91 />or
-------
VGA/Matrix
to CAL
Sample Shipped
from RMA
I
Received by
HEAI
Samples combined
by Matrix type
I
Bulk sample
Homogenized
I
Analytical and Incineration
Test Aliquots Prepared
I
semi-volatile/matrix
to HEAI
Results to HEAI
Incineration tests
I
Analysis
metal/matrix
to UBTL
FIGURE 5.1-1
SAMPLE ANALYTICAL FLOW
-------
TABLE 5.1-1
ANALYTICAL METHODOLOGY
Analysis/Matrlx/Analytes
Volatile Organlcs/Sollds
1,1-Oichloroethane
Dlchl o row thane
1 , 2-Olchloroethane
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Carton tetrachloride
Chloroform
Tetrachloroethylene
Trichloroethylene
Trans-1 , 2-Oichloroethylene
Benzene
Toluene
Xylene (3 isomers)
Ethylbenzene
Chlorobenzene
Methylisooutyl ketone
Dlmethyldisulfide
Blcycloneptadiene
Dlcyclopentadiene
Semi-Volatile Organics/Solids
Aldrin
Endrln
Oieldrin
Isodrln
p.p'-OOT
p.p'-OC
Chlorophenylmethyl sulfide
Chlorophenylmethyl suUoxide
Chlorophenylmethyl sulfone
Detection
Limit*
o.s ug/g
O.Sug/g
0.5 ug/g
0.5ug/g
0.5 ug/g
0.5 ug/g
0.5 ug/g
0.5 ug/g
0.5 ug/g
0.5 ug/g
0.5 ug/g
0.5 ug/g
o.s ug/g
0.5 ug/g
0.5ug/g
0.5 uq/9
0.5 ug/g
o.s ug/g
0.5ug/g
0.5 ug/g
0.5 ug/g
o.s ug/g
O.Sug/g
0.5 pg/g
0.5ug/g
0.5 ug/g
o.s ug/g
0.5 ug/g
High Range Level of
Concentration Hold Time Certification Reference Methods
7 days for Semi- EPA 624 (2)
25 u g/g the solid Quantitative (A) EPA 8240 with
25ug/q and 40 days EPA 5030
25 ug/g for the extraction (1)
25 ug/g extract (1) CAL-K9
25 ug/g
25 ug/g
25 ug/g
25 ug/g
25 u g/g
25 ug/g
25 ug/g
25 ug/g
25 ug/g
25 ug/g
25 ug/g
25 ug/g
25 ug/g
25 ug/g
25 yg/g
7 days for Semi- EPA 8270 with
100 ug/g the solid ft Quantitative (A) EPA 3540
100 ug/g 40 days for extraction (1)
100 ug/g the extract HIAI-X9-A
loo ug/g (l)
50 ug/g
100 ug/g
loo ug/g
50 uo/cj
100 ug/g
Principle of Method
A 10 gram portion of the sample is obtained with
a minimum of handling. The sample is shaken for
4 hours with 10 ml methanol. An aliquot of the
methanol extract Is Injected into 5 ml of water
and analyzed by purge-trap GC/MS using a packed
column. Surrogates and internal standards are
used. Unknowns are identified.
Surrogates are:
d2 - Methylene chloride
1 ,2-Oichloroethane-d4
djQ - Ethylbenzene
The internal standard will be
1 , 2-dibromoethane-d^ .
A 15 aram portion of the sample is obtained with
a minimum of handling and mixed with 30 grams of
anhydrous sodium sulfate. The sample is soxhlet
extracted for 8 hours with 300 ml of methylene
chloride. The extract is reduced to a final
voline of 10 •! In a K-0 aparatus. An aliquot
of the extract is analyzed by fused silica
capillary colim GC/MS. Surrogates and internal
standards are used. Unknowns are identified.
-------
TABLE 5.1-1 (Continued)
Analysls/Matrlx/Analytes
Hexachlorocyclopentadlene
Oxathlane
Olthlane
Malathion
Parathlon
Chlordane
Azodrin
Vapona
Supona
OIMP
Atrazlne
ICP Metal Screen/Solids
Cadmium
Chromium
Copper
Lead
Zinc
Aluminum
Iron
Detection
Limit*
0.5 ug/g
0.5 ug/g
0.5 pg/g
0.5 \ig/g
0.5 ug/g
0.5 ug/g
0.5|ig/g
0.5 ug/g
0.5 ug/g
0.5 ug/g
0.5uq/g
0.5 ug/g
5 ug/g
5 ug/g
5 ug/g
5 ug/g
Interelement
Interelement
High Range Level of
Concentration Hold Time Certification Reference Methods
100 ug/g
100 ug/g
100 u g/g
loo ug/g
100 ug/g
100 y g/g
100 u g/g
100 ug/g
100 ug/g
so ug/g
loo ug/g
6 mos (5) Quantitative (B) USATHAMA 7S
500 ug/g UBTL-P9
500 ug/g
500 ug/g
500 ug/g
500 ug/g
Correction
Correction
Principle of Method
Surrogates are:
d^-1 , 3-Oichlorobenzene
d^-Diethylphthalate
d^-2-Chlorophenol
d4 Di-n-Octyl Phthalate
The internal standard will be d,0 Phenanthrene
A 1 gram portion is digested with 3 ml repeated
portions of KNO? and finished with HC1. The
sample is filtered to a final volume of 50 ml.
The sample Is analyzed by ICP.
•
Arsenic/Solids
10 ug/g 6 mas Quantitative (B) EPA 7060 with
EPA 3050
extraction (2)
UBTL-B9
A one gram portion of the sample Is digested with
HN03. The digest is analyzed by GF/AA.
-------
TABLE 5.1-1 (Continued)
Analysis/Matrix/Analytes
Detection High Range Level of
Limit* Concentration Hold Time Certification Reference Methods
Principle of Method
Mercury/Solids
O.lgg/g 1 gg/g 28 days (5) Quantitative (B) EPA 245.5 (5)
UBTL-Y9
A one gram portion is weighed out and treated
with aqua regla followed by potassium perman-
ganate. Excess permanganate is reduced with
hydroxylamlne sulfate. The mercury is reduced
with stamous chloride and determined using the
cold vapor technique.
Extraction Procedure Toxiclty
Incinerator Residues/Solids
7 days
None
EPA 1310(1)
EPA Method C004 (6)
HEA1
A 100 gram portion of incinerator residues is
extracted for 24 hours with 1.6 liters of
deionlzed water which is maintained at pH
5-0.2 using acetic acid. The extract is
analyzed by USATHAMA certified liquid methods
shown in Table 6.1-2 for the eight elements,
four pesticides and two herbicides listed in
40 CFR 261.24.
Ignltablllty/Sollds
7 days
None
Corrosivity/Solids
7 days
None
EPA 1010(1)
EPA Method COO2 (6)
ASTM Method
093-77
HEAI
EPA 1110(1)
EPA Method C002(6)
NACE Standard
TM-10-69
HEAI
A sample is heated at a slow constant rate with
continual stirring in a cup. A small flame is
directed into the cup at regular Intervals with
simultaneous interruption of stirring. The
flash point is the lowest temperature at which
application of the flame ignites the vapor above
the sample.
Coupons of SAE Type 1020 steel are exposed to
the sample and by measuring the degree to which
the coupon has been eroded, determines the
corroslvity of the sample.
-------
TABLE 5.1-1 (Continued)
Analysis/Matrix/Analytes
Detection
Limit*
High Range
Concentration Hold Time
Level of
Certification Reference Methods
Principle of Method
Reactivity (Total
and Amenable
Cyanide; and Sulfides)/SolIds
7 days
None
EPA 9010 and
EPA 9030(1)
EPA Method C003(6)
HEAI
Total and Amenable Cyanides: Two 100 gm samples
are hrought to a 500 ml volume in ASTM type II
water. Each sample is then distilled to remove
interferences. During distillation cyanide is
converted to HCN which is trapped in a scrubber
containing 50 ml 1.25 N NaOH. 10-12 drops of
rhodamine indicator are added to the scrubber
contents. The solution is titrated with
standard silver nitrate solution to the first
change in color from yellow to brownish pink
against an ASTM type II water blank.
Sulfides Excess iodine is added to a 50 om
sample which has been treated with zinc acetate
to produce zinc sulfide and suspended in 200 ml
distilled water. Two ml of 6 N HC1 is added to
the sample. The iodine oxidizes the sulfide to
sulfur under acidic conditions. Excess iodine
is back trltrated with sodium thlosulfate using
the starch indicator, until the blue color
disappears.
-------
TABLE 5.1-1 (Continued)
Analysis/Hatrlx/Analytes
Detection High Range Level of
Limit* Concentration Hold Time Certification
Reference Methods
Principle of Method
Proximate Analysis:
Moisture/Solids
7 days
None
EPA Method
AOOla (6)
HEAI
Ash (Loss on Ignition)/Solids
7 days
None
Elemental Composition/Solids
7 days
None
EPA Method
AOOlb (6)
HEAI
EPA Method
A003 (6)
A 10 gm soil or 25 gm sludge aliquot is
transferred to a tared porcelain evaporating
dish. The sample and dish are weighed, then
heated on a hot plate to evaporate the sample to
near dryness without boiling. The sample and
dish are then transferred to a 103°C oven to
complete evaporation. Periodically the sample
is removed from the oven, cooled in a desiccator
and weighed. Dryness is considered complete
when weight loss is<4« of previous weight.
After removing a 50 mg aliquot for elemental
analysis, the weighed solids from the moisture
analysis and porcelain dish are ignited for 30
minutes at 600°C. The ash is cooled in a
desiccator and weighed.
A 50 mg sample of dried solids are analyzed to
determine the percent concentration of the
following elements: carbon, nitrogen,
phosphorus, sulfur, and halogens (i.e. iodine,
chlorine, fluorine, bromine).
Heating Value of the Waste/Solids
7 days
None
EPA Method
A006 (6)
A 1 gm sample is placed in a bomb calorimgrer
and ignited. The amount of heat released by the
burning waste, the activation energy, is
expressed as Btu/lb.
-------
TABLE 5.1-1 (Continued)
Analysls/Matrlx/Analytes
Volatile Halo Organlcs/Mater
Chlorobenzene
Chloroform
1 , 1-Olchloroethane
1 , 2-Olchloroethane
1,1, 1-Trlchloroethane
1 , 1 ,2-Trichloroethane
Tet rachlo roct hy lene
Trlchloroethylene
1 , 2-trans-Olchloroethy lene
Dichloromethane
Carbon tetrachlorlde
Volatile Arom. Organlcs/Water
Benzene
Toluene
Xylenes
Ethyl benzene
Organochlorlne Pesticides/Water
Aldrln
Endrin
Dieldrln
Isodrln
Chlordane
Hexachlorocyclopentadlene
p.p'-OOT
p.p'-OOE
Detection
Limit*
Ipg/L
1 yg/L
1 wg/L
lpg/L
1 pg/L
1 wg/L
1 ug/L
1 pg/L
1 pg/L
1 pg/L
1 ug/L
lug/L
l ug/L
l wg/L
lpg/L
0.1 ug/L
0.1 pg/L
0.1 pg/L
0.1 pg/L
0.1 ug/L
0.1 pg/L
0.1 pg/L
0.1 pg/L
High Range Level of
Concentration Hold Time Certification Reference Methods
14 days (2) Quantitative EPA 601 (2)
50Mg/La
50pg/La
50pg/La
50 u g/La
50 p g/La
50Mg/La
50ug/La
50pg/La
50ug/La
50yg/La
50 u g/La
7 days (2) Quantitative EPA 602 (2)
50wg/La
50gg/La
50pg/La
50pg/La
7 days for Quantitative EPA 608 (2)
10pg/La the water
10pg/La and 40 days
10gg/La for the
10pg/La extract (2)
10pg/La
10ug/La
10pg/La
10pg/La
Principle of Method
Purge and Trap GC/Hall Detector with a packed
column (1% SP-1000 on Carbopack B) 1,2-dibromo-
ethane or other suitable internal standard will
be used based on Phase I experience to monitor
purge efficiency.
Purge and Trap/GC/PID with a packed column (IX
SP-1000 on Carbopack B, to permit runs in
conjunction with EPA 601). A suitable internal
standard will be used based on Phase I experi-
^
ence to monitor purge efficiency.
An 800 ml portion of water is extracted with 3 x
50 ml methylene chloride. The extract is reduced
in volume and exchanged with iso-octane. The
final volume Is 10 ml or less. The concentrated
extract is analyzed by GC/EC using a fused silica
capillary column. Cleanup procedure will be
f ?)
applied as required. A suitable Internal
standard will be selected based on Phase I
Q
experience to monitor purge efficiency.
-------
TABLE 5.1-1 (Continued)
Detection
Analysls/Matrlx/Analytes Limit*
Dicyclopentadiene and 0.3 pg/L
Bicycloheptadienc/Water
Organosulfur Compounds/Water
Chlorophenylmethyl sulfide 2 pg/L
Chlorophenylmethyl sulf oxide 2 pg/L
Chlorophenylmethyl sulf one 2pg/L
1,4 oxathlane 2 pg/L
dithiane 2 pg/L
Phosphorates /Water
Oil sopropylmethylphosphonate 2 p g/L
Olmethylmethylphosphonate 2 pg/L
Organophosphorous Pesticides/Water
Malathlon 0.1 pg/L
Parathion 0.1 pg/L
High Range
Concentration
25 ug/L
50 pg/L
50 pg/L
50 pg/L
50 pg/L
50 ug/L
100 pg/L
100 pg/L
5 pg/L
5 pg/L
Level of
Hold Time Certification Reference Methods
Extract Quantitative Developed by MRI
within 7 for USATHAMA
days, Certification
analyze
within 40.
See 4 (1)
Extract Quantitative USATHAMA 4P
within 7
days,
analyze
within 30.
See EPA 625
(1)
7 days Quantitative USATHAMA 4S for
See EPA 625 DIMP
(1)
ESE will develop
method for DMMP
7 days Quantitative EPA 8140(2)
See EPA modified for
625 (1) water
Principle of Method
A 100 ml portion of sample is extracted with 5
ml of methylene chloride. The extract is
analyzed by GC/FID using a fused silica
capillary column. A suitable internal standard
will be specified based on Phase I experience to
monitor purge efficiency.
An 800 ml portion is extracted three times with
50 ml methylene chloride. The volume is reduced
in a K-0 apparatus and exchanged for Isooctane.
The Isooctane extract is analyzed by GC/FPD-S
using a packed column (5X SP-1000 on Chromosorb).
A suitable internal standard will be specified
based on Phase I experience to monitor purge
efficiency.
An 800 ml portion of the sample Is extracted
three time with 500 ml methylene chloride. The
extract is reduced in volume and exchanged with
Isoctane. The final volume is 5 ml. The
extract is analyzed bya GC/NPD using a fused
silica capillary column. Vapona will be added
if indicated by Phase I experience. A suitable
internal standard will be specified based on
Phase 1 experience to monitor purge efficiency.
An 800 ml portion of the samples is extracted
three times with 50 ml methylene chloride. The
extract Is reduced In volume and exchanged with
Azodrin
Supona
Vapona
0.1 ug/L
0.1 pg/L
0.1
5
5 ug/L
5 pg/L
isooctane. The final volume is 5 ml. The
extract is analyzed by GC/NPD using a fused
silica capillary column. A suitable internal
standrd will be specified based on Phase 1
experience to monitor purge efficiency.
-------
TABLE 5.1-1 (Continued)
Analysis/Matrix/Analytes
Detection High Range Level of
Limit* Concentration Hold Time Certification Reference Methods
Principle of Method
Metals by AA/Hater
Arsenic
Mercury
lOgg/L 100Mg/L 6 mos (5) Quantitative EPA 206.2 (A)
O.lug/L lOyg/L 28 days (5) Quantitative EPA 245.1 (4)
A 100 ml aliquot of sample is digested with H20,
and HMO,. The digest is analysed by GF/AA.b
A 100 ml aliquot is treated with H2S04, HNOj,
KMn04, KjSjOg. Excess KMn04 is destroyed with
hydroxylamine sulfate. The mercury is reduced
with stannous sulfate and analyzed by CV/AA.b
Metals by ICP/Kater
Chromium
Cadmium
Lead
Zinc
Copper
Magnesium
Calcium
Sodium
50(i g/L
50 p g/L
50 pg/L
50gg/L
50 \t g/L
10 mg/L
100 mg/L
100 mg/L
5000 Mg/L
5000 g g/L
5000 y g/L
5000 yg/L
5000 v g/L
1000 g g/L
1000 g g/L
1000 y g/L
6 mos (5) Quantitative
EPA 200.7 (4)
All samples will be treated by adding HNO? + Ha
and heating before analysis to dissolve precipi-
tates that may have formed after sampling.
Magnesium, calcium and sodium may be certified
at lower levels if required.
Ignltabllity/Water
7 days
None
EPA 1010 (2)
ASTM Method
D93-77 and
EPA Method
C001(6)
A liquid sample is heated at a slow constant
rate with continual stirring in a cup. A small
flame is directed into the cup at regular
Intervals with simultaneous Interruption of
stirring. The flash point is the lowest
temperature at which application of the flame
ignites the vapor above the sample.
Corroslvity/Water
7 days
None
EPA 1110 (2)
NACE Standard
TM-01-69 and
EPA Method C002 (6)
Coupons of SAE Type 1020 steel are exposed to
the sample and by measuring the degree to which
the coupon has been eroded, determines the
corrosivity of the sample.
-------
TABLE 5.1-1 (Continued)
Analysis/Matrix/Analytes
Detection High Range
Limit" Concentration Hold Time
Level of
Certification
Reference Methods
Principle of Method
Reactivity (Total and
Amenable Cyanide, and
Sulfide)/Water
7 days
None
EPA 9010
EPA 9030 (2):
and EPA Method
C003 (6)
Proximate Analysis:
Moisture/Mater
7 Days
None
EPA Method
A001a(6)
Total and Amenable Cyanides: Two 500 ml samples
preserved with 2 ml IN NaOH are prepared. One
is chlorinated to destroy succeptable
complexes. Each sample is then distilled to
remove interferences. During distillation,
cyanide is converted to HCN which Is trapped In
a scrubber containing 50 ml 1.25N NaOH. Ten to
twelve drops of rhodamlne Indicator are added to
the scrubber contents. This solution is
titrated with standard silver nitrate solution
to the first change in color from yellow to
brownish pink against an ASTM Type II water
blank.
Sulfides; Excess iodine is added to a 200 ml
sample which is treated with zinc acetate to
produce zinc sulfide. Two ml of 6N HC1 is added
to the liquid. The iodine, oxidizes the sulfide
to sulfur under acidic conditions. Excess
iodine is back titrated with sodium thiosulfate,
using the starch Indicator, until the blue color
disappears.
A 100 ml liquid aliquot is transferred to a
tared procelain evaporating dish. The sample
and dish are weighed, then heated on a hot plate
to evaporate the sample to near dryness without
boiling . The sample and dish are then
transferred to a 103°C oven to complete
evaporation. Periodically the sample Is removed
from the oven, cooled in a desiccator and
weighed. Dryness is considered complete when
weight loss is < « of previous weight.
-------
TABLE 5.1-1 (Continued)
Analysis/Matrlx/Analytes
Detection High Range Level of
Limit* Concentration Hold Time Certification Reference Methods
Principle of Method
Ash (Loss on Ignition)
7 days
None
Elemental Composition/Mater
7 days
None
Heating Value of the Haste/Water
7 days
None
Viscosity/Water
7 days
None
EPA Method
A00lb(6)
EPA Method
A003C6)
EPA Method
A006(6)
EPA Method
A005(
-------
TABLE 5.1-1 (Continued)
Analysis/Matrlx/Analytes
Detection High Range Level of
Limit* Concentration Hold Time Certification
Reference Methods
Principle of Method
Volatile Organics/Off-Gas
4 weeks In None
freezer
The front and back sections of the Tenax tubes
are combined and thermally desorbed. The
desorbed organics are analyzed by GC Hall using
a fused silica capillary column.
Acid Gases/Off-Gas
28 days None
The O.ln NaOH sorbent from the stack gas
impinger is assayed by specific ion probe for
chloride.
Volatile Metals/Off-Gas
Chromium
Cadmium
Lead
Zinc
Cooper
6 mos
None
EPA 200.7(5)
50 ug
50 ug
50 ug
50 yg
50 ug
500 ug
500 vg
500 yg
500 yg
SOOyg
An aliquot of silver catalyzed ammonium
persulfate sorbent is treated with HNOj + HC1
and heated before analysis to dissolve
precipitates and analyzed by ICP.
Volatile Metals/Off-Gas
Arsenic
1 yg
10 yg
6 mos
None
EPA 206.2 (5)
An aliquot of silver catalyzed ammonium
persulfate sorbent is treated with H^O, and
HNO-. The digest is assayed by GF/AA.
Volatile Metals/Off-Gas
Mercury
0.1 ug
lOyg
28 days None
EPA 245.1 (5)
An aliquot of silver catalyzed ammonium
persulfate sorbent is treated with H^O^
HMO,
and
Excess
KMN04 is destroyed with hydroxylamine
sulfate. The mercury is reduced with stannous
sulfate and analyzed by cold vapor AA.b
-------
TABLE 5.1-1 (Continued)
Analysis/Matrlx/Analytes
Detection High Range
Limit* Concentration
Hold Time
Level of
Certification Reference Methods
Principle of Method
Organophosphorous Compounds/
Off-Gas
Organosulfur Compounds/Off-Gas
Organochlorlne Compounds/Off-Gas
Qualitative Developed by HEAI
Qualitative Developed by HEAI
Qualitative Developed by HEAI
XAD-2 sorbent, incinerator residues, fly ash,
and water extracted (if necessary). All
extracts combined to one sample concentrate.
Solvent exchanged as necessary to perform
instrumental analysis. Analyses by GC with
specific detectors as described under liquid
matrix.
•Actual detection limits for certified methods are Identified in Volume IV of the RMA Procedures Manual (Project Specific Analytical Methods Manual) for
each laboratory. Detection limits for uncertified methods and methods to be certified are desired detection limits.
a Reflects an estimate of the linear range of the method and is proposed to minimize dilutions.
b To be developed during USATHAMA Phase II certification.
References:
(1) EPA SW-846, 2nd ed., "Test Methods for Evaluating Solid Waste".
(2) EPA-«X)/4-82-057, July 1982 "Methods for Organic Chemical Analysis of Principal and Industrial Wastewater".
(3) Personal Communication from Chris Weathington, Ebasco QA Manager.
(4) ESE-AMP^-UD-HjO.l, July 22, 1982.
(5) EPA-600/4-79-020, Revised March 1983, "Methods for Chemical Analysis of Water and Wastes".
(6) EPA-600/8-M-OO2, February 1984, Sampling and Analysis Methods for Hazardous Waste Combustion.
Notes:
(A) Semi-Quantitative: See Section III of the Litigation Technical Support and Services Rocky Mountain Arsenal Procedures Manual, Seciton 11.2.2.1.
(B) Quantitative: See Section III of the Litigation Technical Support and Services Rocky Mountain Arsenal Procedures Manual, Section 11.2.2.1.
-------
Table 5.1-2
Number of Analyses
Feedstock
Test Phase
Initial Screen of
Waste Feedstock
POHC Evaluation Tests
Optimization Tests
Test of Optimum
Conditions
•
Analysis
VOA-GC/MS1
Semi vol. -GC/MS2
Metals3
VOA-GC/MS
Semi vol. -GC/MS
GC/ECD4
GC/FPD5
GC/NPD6
GC/PIO7
GC/ECD
GC/78
VOA-GC/MS
Semi vol. -GC/MS
GC/ECD
GC/FPD
GC/NPD
GC/PID
Metals
Solid
1
1
1
4
4
—
—
-
12
12
1
1
_
_
-
-
1
Liquid^
1
1
1
—
_
_
—
—
-
<•»
-
1
1
_
_
-
-
1
Sludge
1
1
1
—
—
—
_
_
-
_
-
1
1
_
_
_
_
1
Residual
Ash
—
-
—
_
4
4
4
4
12
12
—
_
3
3
3
3
3
Off-
Gas
—
-
_
_
4
4
4
4
12
12
^
_
3
3
3
3
3
1. VOA-GC/MS: Volatile Organic Analyses by Gas Chromatography/Mass Spectrometer.
2. Semivol. - GC/MS: Semivolatile Organic Analyses by Gas Chromatography/Mass
Spectrometer
3. Metals: Selected metals by inductively coupled plasma and atomic absorption.
4. GC/ECD: Chlorinated Hydrocarbons by Gas Chromatography with Electron Capture
Detector.
5. GC/FPD: Organosulfur Compounds by Gas Chromatography, with Flame Photometric
Detector.
6. GC/NPD: OrganoPhosphorous Compounds by Gas Chromatography with Nitrogen Phosphorous
Detector.
7. GC/PID: Volatile Organic Analysis by Gas Chromatography with Photolonlzation
Detector.
8. Detector depends on selected POHCs.
-------
5.2 ANALYTICAL PROTOCOL SUMMARY
The following is a summary of the analytical procedures which will be
followed to support the Task 17 objectives. All soil, sludge, sediment,
incineration residue, and solid matrices were considered as soils for
analytical purposes. Analytical methods, target analytes, and desired
target detection limits for liquid matrix analytes are discussed in this
section as well.
The off-gas analytical procedures have not been developed in detail but a
summary of the analytical approaches and procedures that may be expected to
meet the requirement of Task 17 are listed.
5.2.1 Volatile Organics in Soil and Solid Samples by Gas
Chromatography/Mass Spectrometry (GC/MS)
The volatile organics method for solids was based on EPA Method 8240
(EPA SW-846). This method was PMO certified for soils and solids at
the semiquantitative level for the Task 17 Program (USATHAMA Method N9
for UBTL and K9 for CAL).
In this method, a 10-gram portion of the sample will be obtained with
minimum of handling and placed into 10 ml of methanol in a volatile
organic acid (VOA) septum vial, spiked with the surrogates: methylene
chloride-d2; 1,2 Dichloroethane-d.; and ethyl benzene-d.Q> capped
with a teflon lined lid, and shaken for four hours. A 20-ug aliquot of
the methanol extract will be removed, spiked with 200 ug of
1,2-dibromoethane-d. as an internal standard, and injected into 5 ml
of organics-free water and contained in a syringe. The contents of the
syringe will then be injected into a purging device, purged, and
analyzed on a packed column (1% SP-1000 on Carbopack B) by GC/MS. Each
sample will be assayed for target compounds at detection limits
identified in Table 5.1-1.
5-2
2140E
-------
In addition, the total ion current profile will be screened for all
major unknown peaks. An attempt will be made to identify the largest
of these major unknown peaks which are present in excess of ten percent
of the area of the internal standard peak. Each of these major unknown
peaks will be reported as the purity, fit and probability to match the
three most likely candidate compounds from the Environmental Protection
Agency/National Bureau of Standards/National Institute of Health
(EPA/NBS/NIH) Mass Spectral library computer program.
5.2.2 Semivolatile Organics in Soil and Solid Samples bv Gas
Chromotography/Mass Spectrometry (GC/MS)
This analytical technique was based on EPA Method 8270 for solids (EPA
SW-8A6) and was PMO certified for soils and solids at the
semiquantitative level for the Task 17 program (USATHAMA Method L9 for
UBTL, X9 for CAL, and X9-A for HEAI).
Using this method, a 15-gram portion of the sample will be obtained
with a minimum of handling and spiked with the surrogates:
2-chlorophenol-d^, 1,3-dichloro-benzene-d^, diethyl phthalate-d ,
and di-n-octyl phtalate-d^. The sample will be mixed with anhydrous
sodium sulfate (30 grams or more depending on sample moisture content)
then the soxhelet extracted for 8 hours with 300 ml methylene
chloride. The extract is reduced to a final volume of 10 ml in a
Kuderna-Danish (K-D) apparatus. An aliquot of this concentrate will be
spiked with phenanthrenerd._ as an internal standard and analysed on
a fused silica capillary column by GC/MS. Samples will be assayed for
target analytes at the detection limits shown in Table 5.1-1. In
addition, the total ion current profile will be scanned for major
unknown peaks. As discussed for volatile organics, an attempt will be
made to identify these unknown major peaks.
5.2.3 Metals in Soil and Solid Samples by Inductively Coupled Argon
Plasma (ICP) Emission Soectrometrv
The ICP method, based on USATHAMA Method 7S, is PMO certified at the
quantitative level (USATHAMA Method P9 for UBTL and A9 for CAL).
5-3
-------
In this procedure, a one-gram portion of sample will be digested in a
watch glass covered Griffin beaker with 3 ml of concentrated nitric
acid. Contents of the beaker will be heated to near dryness and
repeated portions of concentrated nitric acid will be added until the
sample is completely digested. The digestion process is finished with
two ml of 1:1 nitric acid and 2 ml of 1:1 hydrochloric acid. The
sample digest will be filtered, the beaker and watch glass rinsed with
deionized water, and the rinsate passed through the filter. The
digestate is brought to a final volume of 50 ml and assayed by ICP.
The sample will be assayed for target metals at detection limits
identified in Table 5.1-1.
5.2.A Arsenic in Soil and Solid Samples by Graphite Furnace Atomic
Absorption (AA) Spectroscopy
The arsenic method for soils and solids was developed from EPA Method
7060 (EPA-SE-846). Using this method, a one-gram sample will be
digested with hydrogen peroxide and concentrated nitric acid. The
digest will be filtered and assayed by graphite furnace atomic
absorption spectroscopy. The target detection limit for arsenic will
be 1 ug/g. This method is PMO certified at the quantitative level
(USATHAMA Method B9 for UBTL and G9 for CAL).
5.2.5 Mercury in Soil and Solid Samples by Cold Vapor Atomic
Absorption (CVAA) Spectroscopy
This mercury method, developed from EPA Method 245.5 (EPA
600/4-82-057), is PMO certified at the quantitative level (USATHAMA
Method Y9 for UBTL and J9 for CAL). In the method, a one-gram sample
portion will be digested with aqua regia followed by treatment with
potassium permanganate. Excess permanganate will be reduced with
hydroxylamine sulfate. Mercury will be reduced with stannous chloride
and assayed by CVAA. The target detection limit for mercury will be
0.1 ug/g.
5-4
2140E
-------
5.2.6 Extraction Procedure (EP) Toxicity Protocol for Soils.
Incineration Residues, and Solids
This extraction procedure is based upon EPA Method 1310
(EPA-SW-846) and EPA Method C004 (EPA-600/8-84-002). The
procedure will not be PMO certified. In the extraction
procedure, a 100-gram portion of the sample is extracted for a
period of 24 hours with 1.6 1 of deionized water which is
maintained at pH 5.0 +0.2 using 0.5 N acetic acid and monitored
throughout the course of the extraction. The sample slurry is
allowed to stand to permit the solid phase to settle and the
liquid portion to be decanted for filtration. The filtered
liquid is the extract. This liquid will be assayed using PMO
certified methods for arsenic, cadmium, chromium, endrin, lead,
and mercury, and approved methods for selenium, silver, barium,
lindane, methoxychlor, toxaphene, 2,4-dichlorophenoxy acetic
acid, and 2,4,5-trichlorophenoxy propionic acid.
5.2.7 Ignitability in Soil and Solid Samples
This method is based on EPA Method 1010 (SW-846). Ignitability is
determined by heating a sample at a slow, constant rate with continual
stirring in a Pensky-Martin closed-cup tester. A small flame is
directed into the cup at regular intervals with a simultaneous
interruption at which the test flame ignites the vapor above the
sample. This method will not be PMO certified.
5.2.8 Corrosivity Toward Steel in Soil and Solid Samples
The corrosivity method is based on EPA Method 1110 (SW-846). In the
method, coupons of SAE Type 1020 steel are exposed to the waste to be
evaluated and, by measuring the degree to which the coupon has been
dissolved, the corrosivity of the waste is determined. This method
will not be PMO certified.
5-5
21AOE
-------
5.2.9 Reactivity in Soils and Solid Samples
Reactivity for soils and solids in this task is defined in terms of
cyanide or sulfate concentrations. The assay employs EPA Method 9010
(EPA-SW-846) for total and amenable cyanide and EPA method 9030
(EPA-SW-846) for sulfide. For cyanide, a sample will be split into
two, 100-gram aliquots, each brought to a 500 ml volume with ASTM Type
II water in a 1-liter boiling flask. One aliquot is chlorinated with
calcium hypochlorite to destroy susceptable complexes. Each aliquot is
distilled to remove interferences and 25 ml of concentrated sulfuric
acid is slowly added to each flask. During distillation, cyanide is
converted to HCN which is then trapped in a scrubber containing 50 ml
1.25 N NaOH. Ten to twelve drops of rhodamine indicator are added to
the scrubber contents. This solution is titrated with standard silver
nitrate solution to the first change in color from yellow to brownish
pink against an ASTM Type II water blank.
Sulfides are determined by adding excess iodine to a 50-gram sample
suspended in 200 ml distilled water which has been treated with zinc
acetate to produce zinc sulfide. Two ml of 6N hydrochloric acid is
added to the sample. The iodine oxidizes the sulfide to elemental
sulfur under acidic conditions. Excess iodine is back titrated with
sodium thiosulfate using starch indicator until the blue color
disappears. These methods will not be PMO certified.
5.2.10 Proximate Analysis of Soils and Solid Samples
The proximate analysis provides data relating to the physical form of
the sample and provides an approximate mass balance as to its
composition. This analysis is based upon EPA Method AOOla for
particulate and moisture, EPA Method AOOlb for ash (loss on ignition),
EPA Method A003 for elemental composition, and EPA Method A006 for the
heating value of the sample (EPA-600/8-84-002). Proximate analyses
procedures will not be PMO certified.
In the particulate and moisture method (EPA AOOla), 10 grams of soil
and 25 grams of sludge are placed in a tared porcelain evaporation
5-6
2140E
-------
2140E
dish. The sample and the dish are weighed, then heated on a hot plate
to evaporate the sample to the near dryness without scorching. The
sample and dish are then transferred to a 103°C oven to complete
evaporation. Periodically, the sample and dish are removed from the
oven, cooled in a desiccator and weighed. Dryness is considered
complete when weight loss is less than 4% of the previous weight.
Ash (loss on ignition) content (EPA AOOlb) is determined on the weighed
solids from the moisture analysis. After removing a 50-mg aliquot for
elemental analysis, the solids and procelain dish are ignited for 30
minutes at 600°C. The resultant ash and porcelain dish are cooled in a
desiccator and weighed.
The elemental composition method (EPA A003) uses 50 mg of dried solids
to determine the percent concentrations of carbon, nitrogen,
phosphorous, sulfur, and halogens (iodine, chlorine, fluorine, and
bromine). Carbon is determined by measuring carbon dioxide and water
upon combustion (ASTMD-3178-73). Nitrogen is determined by the
Kjeldahl digestion method (ASTM D-3179-73), and oxygen by the
difference method (ASTMD-3176-74). Phosphorous is determined by the
spectroscopic method (ASTMD-2795), sulfur by sulfate titration
(ASTMD-3177), and halides by halide titration (ASTMD-2361-66).
Heating value of the sample will be determined using the ASTMD-2015
method. In the method, a one-gram sample is placed in a calibrated
isothermal jacket bomb calorimeter under controlled conditions.
Calorific values (Btu) will be computed from temperature observations
made before, during, and after combustion of the sample.
5.2.11 Unknown Identification in Soil. Solid, and Sludge Samples by
Gas Chromatography/Mass Spectrometry (GC/MS)
The total ion current profile will be screened for all major unknown
peaks. The laboratories will report (RT Code, estimated concentrations
and print MS traces) all unknowns with peaks greater than 10 percent of
the internal standard response. Each of these major unknown peaks
greater than 10 percent of the internal standard response (excluding
obviously meaningless peaks, e.g., column bleeds) will be reported as
5-7
-------
the purity, fit, and probability to match the three most likely
candidate compounds from the Environmental Protection Agency/National
Bureau of Standards/National Institute of Health (EPA/NBS/NIH) Mass
Spectral library computer program.
5.2.12 Volatile Halogenated Organics in Liquid Samples
The analytical method for volatile halogenated organics in water will
be based on EPA Method 601 (EPA 60074-82-057). This analytical
procedure will be a purge and trap method, assayed on a packed column
(1% SP-1000 on Carbopack B) by GC equipped with a Hall electrolytic
conductivity detector. Water samples will be spiked with
1,2-dibromethane, or another suitable internal standard based on
project experience, to monitor purge efficiency.
Volatile halogenated organic analyses and desired detection limits are
identified in Table 5.1-1.
5.2.13 Volatile Aromatic Organics in Liquid Samples
The volatile aromatic hydrocarbon methods will be based on EPA Method
602 (EPA 660/4-82-057) for water and EPA Method 8020 (EPA-SW-846) for
soil and solids. Analysis of volatile aromatics in water will be a
purge and trap method, analyzed by GC equipped with a photoionization
detector using a packed column (1% SP-1000 on Carbopack B).
Table 5.1-1 lists the volatile aromatic organic constituents and target
detection limits.
5.2.14 Organochlorine Pesticides in Liquid Samples
The analytical methodology for organochlorine pesticides will be based
on EPA Method 608 (EPA 600/4-82-057) and EPA Method 8080 (EPA
600/4-82-057) for water and EPA Method 8080 (EPA-SW-846) for soil and
solid samples. An 800-ml portion of water will be extracted three
times with 50 ml of methylene chloride. The extract shall be reduced
5-8
2140E
-------
in volume and exchanged with hexane to a final volume of 10 ml or
less. The concentrated extract will be analyzed by GC with an electron
capture detector using a fused silica capillary column.
Organochlorine pesticides and their target detection limts are listed
in Table 5.1-1.
5.2.15 Organosulfur Compounds in Liquid Samples
The organosulfur compounds that will be target analytes are listed in
Table 5.1-1. Methodologies for organosulfur analyses will be developed
from USATHAMA Method 4P for water. In a water matrix, an 800-ml sample
will be extracted three times with 50 ml of methylene chloride. The
extract volume shall be reduced in a K-D apparatus and exchanged with
isooctane. The isooctane extract will be assayed on a packed column
(5% SP-1000 on Chromosorb) by GC with a flame photometric detector.
The target detection limit for organosulfur compounds in water will be
2 ug/1.
5.2.16 Organophosphorous Pesticides in Liquid Samples
Organophosphorous compounds targeted for analysis are listed in Table
5.1-1. Analytical methods for these compounds are derived from EPA
Method 8140 (EPA-SW-846) for water.
In a water matrix, the five Organophosphorous compounds will be
extracted from an 800-ml sample with three 50-ml volumes of methylene
chloride. The extract will be concentrated and exchanged with
isooctane to a final volume of 5 ml. An aliquot of the extract will be
assayed on a packed column 6 feet by 2mm ID 1.5% OV17 + 1.95% QF-1 by
GC equipped with a nitrogen/phosphorous detector. Target detection
limits for the five Organophosphorous pesticides in water will be 0.1
ug/1.
5-9
-------
5.2.17 Phosphonates in Liquid Samples
The phosphonates Include diisopropylmethylphosphonate (DIMP) and
dimethylmethylphosphonate (DMMP). Specific analytical methodologies
for phosphonates will be developed from USATHAMA Method 4S for water.
The sample will be analyzed on a fused silica capillary column by GC
equipped with a nitrogen/phosphorous detector. The target detection
limit for phosphonates in water will be 2 ug/1.
5.2.18 Metals in Liquid Samples
Ten metals will be assayed in liquid matrices. The metals and
principal analytical method will be as follows: arsenic and mercury by
atomic absorption; and cadmium, calcium, chromium, copper, lead,
magnesium, sodium, and zinc by ICP.
The method for arsenic analysis will be derived from EPA Method 206.2
(EPA 600/4-79-020) for water. Using EPA Method 206.2 (EPA
600/4-79-020), a 100-ml sample of water will be digested with hydrogen
peroxide and concentrated nitric acid. The digest will be assayed by
graphite furnace atomic absorption spectroscopy. Target detection
limits for arsenic in water will be 10 ug/1.
The mercury methods will be derived from EPA Method 245.1 (EPA
600/4-79-020) for water. In the water method, a 100-ml sample will be
treated with sulfuric acid, nitric acid, potassium permanganate, and
potassium pursulfate. Excess permanganate will be destroyed with
hydroxylamine sulfate. Mercury will be reduced with stannous sulfate
and assayed by cold vapor atomic absorption spectroscopy. The target
detection limit for mercury in water will be 0.1 ug/1.
The method for ICP metals in water was derived from EPA Method 200.7
(EPA 600/4-79-020). Target analytes and desired detection limits for
ICP metals in the liquid matrix is shown in Table 5.1-1.
5-10
2140E
-------
All Mater samples for ICP metals will be digested by adding nitric and
hydrochloric acid and heating before analyses to dissolve any
precipitates that may have formed after sampling. The sample digest
will be filtered, brought to a final volume of 50 ml, and assayed by
inductively coupled argon plasma emission spectrometry.
5.2.19 lonitabilitv in Liquid Samples
This method is based on EPA Method 1010 (SW-846). Ignitability is
determined by heating a sample at a slow, constant rate with continual
stirring in a Pensky-Martin closed-cup tester. A small flame is
directed into the cup at regular intervals with a simultaneous
interruption of stirring. The flash point is defined as the lowest
temperature at which the test flame ignites the vapor above the
sample. This method will not be PMO certified.
5.2.20 Corrosivity Toward Steel in Liquid Samples
The corrosivity method is based on EPA Method 1110 (SW-846). In the
method, coupons of SAE Type 1020 steel are exposed to the waste to be
evaluated and, by measuring the degree to which the coupon has been
dissolved, the corrosivity of the waste is determined. This method
will not be PMO certified.
5.2.21 Reactivity in Soils and Solid Samples
Reactivity in soils and solids for this task is defined in terms of
cyanide or sulfide concentrations. The assay employs EPA Method 9010
(EPA-SW-846) for total and amenable cyanide and EPA Method 9030
(EPA-SW-846) for sulfide. For cyanide, a sample will be split into
two, 500-ml aliquots in a 1-liter boiling flask. One aliquot is
chlorinated with calcium hypochlorite to destroy susceptable
complexes. Each aliquot is distilled to remove interferences and 25 ml
of concentrated sulfuric acid is slowly added to each flank. During
distillation, cyanide is converted to HCN which is trapped in a
scrubber containing 50 ml 1.25 N NaOH. Ten to twelve drops of
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rhodamine indicator are added to the scrubber contents. This solutions
is titrated with standard silver nitrate solution to the first change
in color from yellow to brownish pink against an ASTM Type II water
flask.
Sulfides are determined by adding excess iodine to a 200-ml sample
which has been treated with zinc acetate to produce zinc sulfide. Two
ml of 6N hydrochloric acid is added to the sample. The iodine oxidizes
the sulfide to elemental sulfur under acidic conditions. Excess iodine
is back titrated with sodium thiosulfate using starch indicator until
the blue color disappears. These methods will not be PMO certified.
5.2.22 Proximate Analysis of Liquid Samples
The proximate analysis provides data relating to the physical form of
the sample and provides an approximate mass balance as to its
composition. This analysis is based upon EPA Method AOOla for
moisture, EPA Method AOOlb for ash (loss on ignition), EPA Method A003
for elemental composition, and EPA Method A006 for the heating value of
the sample (EPA-600/8-84-002). Proximate analyses procedures will not
be PMO certified.
In the moisture method (EPA AOOla), a 100-ml liquid sample is placed in
a tared porcelain evaporation dish. The sample and the dish are
weighed, then heated on a hot plate to evaporate the sample to near
dryness without scorching. The sample and dish are then transferred to
a 103°C oven to complete evaporation. Periodically, the sample and
dish are removed from the oven, cooled in a desiccator, and weighed.
Dryness is considered complete when weight loss is less than 4% of the
previous weight.
Ash (loss on ignition) content (EPA AOOlb) is determined on the weighed
solids from the moisture analysis. After removing a 50-mg aliquot for
elemental analyses, the solids and procelain dish are ignited for 30
minutes at 600°C. The resultant ash and procelain dish are cooled in a
desiccator and weighed.
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The elemental composition method (EPA A003) uses 50 mg of dried solids
to determine the percent concentrations of carbon, nitrogen,
phosporous, sulfur, and halogens (iodine, chlorine, fluorine, and
bromine). Carbon is determined by measuring carbon dioxide and water
upon combustion (ASTMD-3178-73). Nitrogen is determined by the
Kjeldahl digestion method (ASTM D-3179-73), oxygen by the difference
method (ASTMD-2795), sulfur by sulfate titration (ASTMD-3177), and
halides by halide titration (ASTMD-2361-66).
Heating value of the sample will be determined using the ASTMD-2015
method. In the method, a one-gram sample is placed in a calibrated
isothermal jacket bomb calorimeter under controlled conditions.
Calorific values (Btu) will be computed from temperature observations
made before, during, and after combustion of the sample.
Viscosity of liquid samples will be determined using the ASTMD-445
method utilizing a kinematic viscometer and a thermometer. The time
will be measured for the flow of a fixed volume of liquid through the
viscometer.
5.2.23 Volatile Organics in Incineration Off-Gas Samples bv Gas
Choromatography Mass/Spectrometry (GC/MS)
Due to their volatility, analysis for these compounds will be
restricted to incineration off-gas samples collected on Tenax/Charcoal
tubes. In this method, the front and back portions of the
Tenax/Charcoal tubes are thermally desorbed. These desorbed organics
are analyzed by a GC Hall detector using a packed column (1% SP-1000 on
Carbopack B). This procedure will analyze for the volatile halo
organics. This method will not be certified by PMO, but demonstration
will be required to show the detection level that can be achieved.
Other test burns may be used to collect the volatile aromatic organics
for analysis, since the tenax traps will permit only one analytical
run. The volatile aromatics will be analysed by GC/PID upon the same
packed column as described above.
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GC/MS will not be used because it does not have the required
sensitivity to achieve the Task 17 action levels.
5.2.24 Acid Gases in Incineration Off-Gas Samples
This method was developed.by UBTL for the analysis of hydrogen chloride
(EPA-600/8-84-001) in incineration off-gases. The method will not be
PMO certified.
In the method, 0.2 N sodium hydroxide sorbent from an incineration
off-gas impinger is assayed by specific ion probe for the presence of
chloride.
5.2.25 Volatile Metals bv Inductively Coupled Argon Plasma (ICP)
Emission Spectrometry in Incineration Off-Gas Samples
This ICP method, based on EPA method 200.7 (EPA-600M-79-020), is not
PMO certified at the quantitative level. The ICP method has been
certified only for soils and waters, not volatile metals.
In this procedure, an aliquot of silver catalyzed ammonium persulfate
sorbent is placed in a beaker, treated with concentrated nitric acid
and 1:1 hydrochloric acid, and heated to dissolve precipitates that may
have formed. The acidified aliquot will be filtered, the beaker rinsed
with deionized water, and the rinsate passed through the filter. The
digestate is brought to a final volume of 5 ml and assayed by ICP.
5.2.26 Volatile Metals/Arsenic in Incineration Off-Gas Samples bv
Graphite Furnace Atomic Absorption (AA) Spectrometry
The arsenic method for soils and solids will be developed from EPA
Method 7060 (EPA-SW-846). Using this method, an aliquot of silver
catalyzed ammonium persulfate sorbent will be digested with hydrogen
peroxide and concentrated nitric acid. The digest will be filtered and
assayed by graphite furnace atomic absorption Spectrometry. The target
detection limit for arsenic will be 1 ug/g.
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5.2.27 Volatile Metals/Mercury in Incineration Off-Gas Samples bv Cold
Vapor Atomic Absorption (CVAA) Spectrometrv
This mercury method was developed from EPA Method 245.5 (EPA
600/4-82-057). In the method, an aliquot of silver catalyzed ammonium
persulfate sorbent will be digested with aqua regia followed by
treatment with potassium permanganate. Excess permanganate will be
reduced with hydroxylamine sulfate. Mercury will be reduced with
stannous chloride and assayed by CVAA. The target detection limit for
mercury will be 0.1 ug/g.
5.2.28 Moisture Content in Incineration Off-Gas Samples
The moisture content determinations will not be PMO certified. In this
method, the weight of the condensate collected in the trap is measured.
5.2.29 Organophosphorous. Orgonosulfur. and Organochlorine Compounds
in Incineration Off-Gas Samples by GC/Selective Detectors
After incineration the bottom residue and fly ash, the XAD-2 sorbent
are sohxlet extracted with methylene chloride and the condensate in the
liquid trap is extracted with methylene chloride. The extracts are
concentrated by Kuderna Danish. The concentrates are then solvent
exchanged to isooctane. The final volume will vary from 0.25 ml to
0.50 ml to meet the sensitivity and action levels required of Task 17.
This method will not be PMO certified. Demonstration will be required
to show the detection level that can be achieved.
The concentrate is analyzed for organochlorine, Organophosphorous and
organosulfur compounds. The instrumental conditions are the same as
those described under the respective sections in Table 5.1-1 for liquid
samples.
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5.3 ANALYTICAL RESULTS
X,
5.3.1 System Performance Parameters
A run log will be maintained for the bench-scale test unit. This log
will note the purpose of a particular test run, the set test
conditions, and any abnormalities encountered during the test. The
operating parameters such as temperatures, pressures, and flow rates
will be recorded on a data sheet. Measurements will be made at
appropriate intervals to insure a continuous picture of the operating
conditions.
5.3.2 Analytical Results
The concentrations of the constituents measured in the off-gases and
solid residues will be analyzed for the original sample volume (for
liquids) or weight (for soils). For sludge, the data would be
presented based on a dry weight basis.
v,
5.4 CERTIFICATION
The initial feedstock analyses will be performed by PMO certified methods
and laboratories for those methods which are currently certified. To reduce
the intralaboratory analytical variations and provide the rapid turn around
of analyses, HEAI will perform all of the analyses of the individual feed
wastes and incineration products except for the physical characterization
analyses. No new methods will be certified for this task. However, some
methods demonstration will be required. Hittman/Ebasco will use methods
approved by PMO but will not perform additional certification analyses. If
required to determine the validity of analytical data, qualitative
certification would be recommended.
5.5 QA/QC
For Task 17, the sample handling and analytical activities will comply with
the established QA requirements stated in the RMA Procedures Manual except
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as noted in this test plan. The bench-scale test conditions such as
temperature, gas flow rates, pressures, and oxygen levels will be measured
using industry-acceptable methods and equipment. These methods will be
based on the equipment manufacturers calibration and established procedures.
The analytical procedures for feedstock and solid residues will use QC
procedures outlined in the RMA Procedures Manual (Ebasco, 1985). All
chemical analyses will include:
o Calibration standard;
o Blank; and
o Matrix spike.
During development of procedures for off-gas and residue chemical analysis,
it will be necessary to document the steps used to achieve the required
detection limits. The documented procedure will include:
o Summary of method;
o Instrumentation and operating conditions;
o Reagents and materials;
o Analytes and analytes standard concentration;
o Details of sample preparation;
o Calculation; and
o QC.
For all analyses where the detection or action level is critical, there will
be one standard run at two times the required detection limit. The matrix
spike also will be at two times the detection level or two times the found
analyte concentration.
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6.0 EXPECTED RESULTS
6.1 INTRODUCTION
The test program outlined in the preceding sections is designed to develop
data at the bench-scale that will ensure success of a full-scale
incineration program. It will provide a basis for selecting an appropriate
incineration regime and will therefore contribute to the confirmation of the
selection of the most desirable technology for waste destruction to a ORE of
99.99 percent. Details of these expected results are outlined below.
6.2 EXPECTED DRE RESULTS
The tests identified above will provide detailed information concerning the
ability to remove hazardous organic chemicals from the soils by heating them
to temperatures in the 800-1,000°C region. They will determine the extent
to which such chemicals as aldrin, endrin, dieldrin, isodrin, and other
contaminants can be removed from the soils matrix and put into the vapor
state in order to ensure their destruction in an afterburner.
The tests identified above will provide sufficient analytical data to
determine the DRE for all organics found in the soils as a function of time,
temperature, and oxygen concentration. Specific plots will be as follows:
o DRE as a function of temperature with a residence time of 2 seconds;
o DRE as a function of temperature with a residence time of 5 seconds;
o DRE as a function of time with a temperature of 1,250°C
(afterburner);
o DRE as a function of time with a temperature of 900°C (afterburner);
and
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v
o ORE of certain selected POHCs (e.g., aldrin as a function of
oxygen concentration for constant time and temperature values.
From these data a rough optimal (most cost effective) regime for destruction
of hazardous organics can be developed. This regime will incorporate
thermodynamic data concerning the soils (e.g., heat capacity, thermal
conductivity, specific heat) plus regime results into conceptual evaluations
of fuel consumption (temperature) and equipment volume (residence time)
requirements.
ORE values will also be determined for liquid, sludge, and a mixture of
wastes at a successful regime associated with soils incineration (e.g.,
1,250°C, 2 seconds, 5.4% 02). Such ORE values will confirm the utility of
a selected regime for the entire waste feedstock associated with Basin F.
6.3 EXPECTED TECHNOLOGY SELECTION CONFIRMATION RESULTS
The data above will provide a method for conceptual optimization of the
incineration regime to be scaled up from the bench-scale operations to
either pilot plant or full-scale operation. These data can then be compared
to typical regimes for existing incinerator designs from among the
technologies of countercurrent and cocurrent rotating kilns, fluidized beds,
and multiple and single hearth furnaces.
In addition to the ORE data described above, the PCT data concerning the
soils, sludge, and liquid also will be factored into the evaluation of
technologies. Specific issues will include ash fusion temperature of the
soils. Such data will be used to determine whether a given technology does
or does not have a "fatal flaw" with respect to the wastes found at Basin F.
Such data could be used to rule out a given technology if it cannot provide
sufficient temperature or residence time to ensure 99.99 percent ORE.
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APPENDIX 1
REFERENCES
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6.4 OTHER EXPECTED RESULTS
v
The tests described in preceding sections will contribute by determining
initial regimes to be tested either at the pilot-scale or full-scale
operation. Further, they will be useful in determining conceptual
parameters of a full-scale operation including the following:
Technology Parameter
Rotary Kiln Capacity (volume)
Direction (countercurrent vs. cocurrent)
Angle and rotational speed for residence time
Optimal fuel and combustion regime
Fluidized Bed Capacity (volume)
Optimal fuel and combustion regime
Maximum operating temperature
i
"**N,
Afterburner Capacity (volume)
Optimal fuel and combustion regime
These expected resulted will be essential in developing a cost-effective
incineration program for the complete and safe destruction of the hazardous
chemicals in Basin F at RMA.
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REFERENCES
Babcock and Wilcox. 1978. Steam: Its Generation and Use. The Babcock and
Wilcox Company, New York, NY.
Bonner, T. et al. 1981. Hazardous Waste Incineration Engineering. Noyes
Data Corporation, Park Ridge, NJ.
Dellinger, B. Determination of the Thermal Decomposition Properites of
20 Selected Hazardous Organic Compounds. Prepared by University of
Dayton, Research Institute, Environmental Sciences Group, Dayton, OH.
Prepared for Environmental Protection Agency, EPA-600/2-84-138,
August 1984, 204 pp.
Felder, R. and R. Rousseau. 1978. Elementary Principles of Chemical
Processes. John Wiley and Sons., Inc., New York, NY.
Frankel, I., N. Sanders, and G. Vogel. 1983. Survey of the Incinerator
Manufacturing Industry. Chemical Engineering Process 79(3):44-55.
Kramlich, J. et al. Laboratory-Scale Flame-Mode Hazardous Waste Thermal
Destruction Research. Prepared by Energy and Environmental Research
Corp., Irvine, CA. Prepared for Environmental Protection Agency,
EPA-600/2-84-086, April 1984, 155 p.
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