-------
TABLE 3
MATERIALS OP CONSTRUCTION
POR THE
WET AIR OXIDATION PROCESS
NOMINAL
ALLOT CHEMICAL COMPOSITION
Cr Mi Mo C Cu
316-L STAINLESS
20 cfa-3
625
HAS7ZLLOY C-276
TITANIUM - 2
bai
bai
3
;
18
20
22
16
CCMMEr.CIALLY
13
34
bai
bai
PURE TI
2
2
.25
.5
9
16
TANIUH
0.
0.
0.
0.
0.
03
03
05
02
01
3.5
-
-
36
-------
TABLE A
MATERIAL TESTING
280 "C for 100 hours
GENERAL RATE COMMENTS
MPT
316-L <1.0 NO LOCALIZED CORK.
20cb-3 <1.0 NO LOCALIZED CORK.
6:- <1.3 NO LOCALIZED CORK.
c-:76 <1.0 NO LOCALIZED CORK.
NO LOCALIZED CORR.
37
-------
Figure 1
2 Factorial Testing
320°C -
Oxidation
Temperature
300'C
i
:ao»c
e. Minutes
38
-------
t'igurtt 2
WET AIR OXIDATION
GENERAL FLOW DIAGRAM
CJ
CD
OXIPIZABLE f^
WASTE
FEED
PUMP
D
PROCESS
HEAT
.EXCHANGER
REACTOR
AIR COMPRESSOR
APCV
j-JU_fc.
WASTEWATER
-------
REFERENCES
1. Standard Methods for the Examination of Vater and Vastevacer
16th Ed., AFHA, AtfVA. VPCF, 1985.
2. Methods for Chemical Analysis of Water and Vastes, U.S. EPA
EPA-600/4-79-020, Marcn, 1979.
3- Flynn, B.L., "Vet Air Oxidation of Waste Streams," Chemical
Engineering Progress. April, 1979, pp. 66-69
<« Copa, V.M., e_t. al., "Simultaneous Sludge Disposal and Carbon
Regeneration," presented at the AIChE National Meeting, New
York, 1987
5- Force, J.M. ed., "Vet Air Oxidation - A Rediscovered
Technology," REACTOR. No. 65, May 1989, p.4
6. Dietrich, M.J., e_t. al.. "Vet Air Oxidation of Hazardous
Organics in Vastevater," Environmental Proeress. Vol.A, No. 3,
August, 1985, p. 171
40
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BENCH SCALE STIRRED AUTOCLAVE
WET AIR ODODATICN DEMONSTRATION
CM INDIANA HARBOR SEDIMENT SLUDCS
FOR
SCIENCE APPLICAnON INTERNATIONAL CORP.
PHASE II
SAIC SUBCONTRACT NO. 16-920034-51
Se^srr^er 27, 1991
2IMPRO
PASSAV^MMT
ENVIRONMENTAL SYSTEMS. INC.
An AfflUBc of tne Blacx Oawion Co.
301 XV. Military ftaM.-RotnurtkL \M 544W
41
-------
TABLE OF CONTENTS
I. INTRODUCTION 1
II. WET AIR OXIDATION PERFORMANCE 1
III. EXPERIMENTAL PROCEDURES . ' 3
IV. PROCESS DESCRIPTION 3
V. DESIGN BASIS 6
VI. SCOPE OF OFFERING 7
VII. ESTIMATED UTILITIES 15
VIII. PRICING 15
REFERENCES.
IZIMPRO
PASSAVA/SJT
42
-------
£N"i..tujXn-'X'j,CN
Zimpro Passavant Environmental Systems, Inc. (ZIMPHO) perfonned
laboratory wet air oxidation tests on dredged sediments from the
Indiana harbor. The test work was perfonned for Science.
Applications International Corporation (SAIC) under contract with
the U.S. EPA. The principal objectives for this Phase II study
were to produce a volume of oxidized samples at the optimal
operating conditions. The operating conditions were determined by
a series of shaking autoclave tests perfonned under the Phase I
study. The Phase I study concluded that the optimal condition
was a reactor temperature of 280eC and a hydraulic detention time
of 90 minutes. The oxidized effluent from Phase II shall be
analyzed by others. The results from the testing are to be
presented to the EPA for evaluation of the wet air oxidation
technology for treatment of the sediment sludge.
This report includes the procedures used and analytical results
obtained from the Phase II wet air oxidation testing of the
sediment sludce.
WET ATR OXJUJftTICN PERFORMANCE
The "as received" feed samples were well mixed and divided out
into eight (8) portions. Separate stirred autoclave oxidations
were performed using six (6) of the eight (8) samples. The
samples were diluted using HPLC grade water. The dilutions were
made to produce an autoclave feed sample with a suspended solids
concentration of approximately ten percent (10%). A list of the
feed samples charged to the stirred autoclave and the volumes
discr.arced is reoorted in Table 1.
TABLE 1: VI'IWMHJ AUTOCLAVE GBODATICN INFOHMATTCN
SAMPLE CHARGED SAMPLE REMOVED OFF GAS ANALYSES,
Sample Sedi.-r.ent Water Solids Filtrate CO. 0. N. CO
>Juir.cer Gra.T.s Grams Grams Grans '
1 225 625 56 545 13.1 3.7 32.0 nd 173
2 253 597 88 682 14.3 2.1 32.1 0.5 229
3 225 625 107 703 13.3 2.0 82.6 nd 150
4 250 601 84 685 13.4 2.8 82.3 r.d 19"
5 125 650 51 615 11.1 5.4 78.6 r.d I'O
6 123 650 43 657 9.2 8.4 79.2 nd 190
*
Pump tuning leaked causing seme less of sample
nd = net detected
r ZIMPRO
PASSAVAJVT
43
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Following the oxidation, effluent samples were decanted from the
stirred autoclave using a peristaltic pump with silicon tubing.
The samples were then vacuum filtered using Whatman fl filter
paper. The mass of both filtrate and filter cake was individually
measured. The filter cake samples were placed in a glass bottle
and the filtrate was pumped into a Tedlar bag. Blending of all
the filtrate samples, and cake samples, was performed on
completion of the" stirred autoclave testing. Sampling of the
blended filter cake and blended filtrate samoles was performed by
SAIC.
Analyses were performed on the oxidized filter cake and filtrate
by Enviroscan Corporation. The tabulation of the obtained data is
located in Table 2. Comparing the results from Phase I to Phase
II, the testing indicates that the filtrates had equivalent CODs.
The remaining 6,136 mg/1 of COD in the filtered effluent would
have to be reduced further. The remaining COD appears to be very
biodegradable. The filtrate had a BOD5/COD ratio of 0.55,
indicating that biological treatment may be acceptable as a
polishing step. The filter cake sample "had a higher COD when
compared to the Phase I results (187 mg/g verses 96 rag/g). Little
more can be said about the samples due to the limited scope of the
analyses. A more complete analytical evaluation of the effluents
will be performed by SAIC once they have obtained the results from
their outside laboratcrv.
TABLE 2: ANALYTICAL RESULTS FPCK PHASE II
filtrate Cake
Analytical No. 56,517 56,518
Oxidation Temperature, 5C 280 280
COD 6,135 mg/1 187 mg/g
BOD; 3,372 .7.9/1
pH sm2
Total Solids 4,563 mg/1 56.8%
Total Asn 2.£44 mg/1 90.2%
ZIMPRO
44
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III. KXf taOMEUTRL PRDCCTURES
All wet air oxidation tests were performed in laboratory titanium
stirred autoclaves eacn having a capacity of 3,780 mis. The
autoclaves are equipped with a magnetic stirring device which
helps diffusion of oxygen into the lio^iid and keeps the solids in
solution. The stirring mechanism is on continuously throughout
the oxidation. The autoclaves were charged with the waste and
sufficient compressed air to result in excess residual oxygen
following oxidation. The charged autoclaves were then heated to
the desired oxidation temperature by electric heating bands and
held for the specified reaction time. Immediately following
oxidation, the autoclaves were cooled to room temperature by
internal water cooling roils and then depressurized.
All analyses included as part of the oxidation testing were
performed by the ZIMFRO analytical laboratory, Enviroscan Corp.,
according to Standard ;ietnods: or EPA Methods for the Chemical
Analysis of Water and Waste' .
IV. PROCESS DESCRIPTION
Wet air oxidation is an aqueous phase oxidation of organic and
inorganic compounds by dissolved molecular oxygen at elevated
temperatures and pressures. The oxygen is typically supplied to
the system as compressed air; however, pure gaseous oxygen has
also been used in specific applications. Depending on the overall
desired treatment level, the oxidation reactions will occur at
moderate temperatures (400 - 600T) and at pressures ranging from
300 to over 3000 pounds per square inch. As the oxidation
temperature is increased, a larger portion of the organic
compounds will be oxidized -/mien will correspond to a higher
overall chemical oxygen demand (CCD) reduction. The wet air
oxidation process will oxidize simple organic compounds to carbon
dioxide and water wnile seme complex compounds are partially
oxidized to simpler rcqpcur.ds, such as acetate, which are more
readily biodegradable.
Figure 1 presents the rasic wet air oxidation system process flow
scr.eme. The proposed flew scr.eme recommends the utilization of an
equalization tanx to provide snort term storage during maintenance
snutdcwns and to damper, cut ±ne effects of periodic changes in
waste characteristics. The waste is transferred from the
equalization tanx to a -igr. oressure diapnragm pump oy means of a
centrifugal low pressure pumc. The pressurized discnarge from tr.e
nign pressure pump 13 "mrir.ed with tne air stream from tr.e
process air ccmcressor t.-.erecv fermine a twopnase stream.
Z1MPRO
45
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I <
I I
t t.KD/
milKH
IIKAT
I! II
AIIXIUARY
HEAT EXiTIIANtiCH
TANK
' IIM:II rut .'.MIII
mo PUMP
111* I'tlV.V.IHIt
n.i:n ruur
(k)
OIT CHS
l(t.ACT()K
runs
HEAT HUNSFU SYMltl
01IDI1CD irrLUCHT TO
rOST TltATBtHT SISTKN
|BY OTHERS)
oxiora.T>
WASTE four
I-KOCCSS AIH
COUVRESSUR
rKELIHIHMI>
MET Mil UXlDKTIUtl SYSTEM
DIAGRAH
> ZIWIPRO
PASSAW
ricuie
-------
The two-phase air/waste stream passes through the tubeside of the
feed/effluent heat exchanger. The feed/effluent is used to
transfer the sensible heat from the oxidized effluent to the un-
reacted waste and air mixture. The heated mixture is then routed
through an auxiliary heat exchanger. The auxiliary heat exchanger
is used, when necessary, to supplement the thermal energy
transferred to the air/waste mixture. The supplemental thermal
energy is supplied by a thermal fluid heat transfer system which
may be either fuel-fired or electrically heated. The thermal
fluid heat transfer system is used to initially bring the system
up to operating temperature.
The heated air/waste mixture is then introduced in the process
reactor vessel. The reactor vessel is a vertically-oriented
column type pressure vessel. The reactor contents are mixed by
the action of the gas phase rising through the liquid. As the gas
phase rises and mixes with the liquid, oxygen is dissolved into
the liquid. The dissolved oxygen is then available to take part
in the oxidation reactions. The reactor is sized to provide
sufficient hydraulic detention time to allow the oxidation
reactions to proceed to the desired level.
The oxidized liquid, oxidation product gases, and spent air leave
the process reactor and are routed througn the shell side of the
previously mentioned feed/effluent heat exchanger. A substantial
cooling of the reactor effluent is achieved in the feed/effluent
heat excnanger; additional cooling is accomplished by the process
cooler. In the process cooler, additional sensible heat energy is
transferred from the reactor effluent to a cooling water stream.
It should be mentioned that the system is still at an elevated
pressure at this point.
The cooled reactor effluent is throttled through a pressure
control valve, thereby depressurizing the flow, into the process
separator. The reactor effluent is separated into a gaseous
stream and a liquid stream oy tne process separator.
The gaseous stream from the prccess separator is routed through
the process off-gas cooler. The off-gas cooler is a vertically
oriented packed column. The process gases enter the base of the
column and flow counter-current to a flow of service water. The
service water cools the process gases causing some Higher boiling
point constituents to condense cut and exit the off-gas cooler
witn the service water; trie lisuids leavinc the off-gas cooler
are discnarged into the prccess senarator.
ZIMPRO
itPASSAVAJVT
47
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At this point in the flew scheme, the process separator liquids
are pumped beyond the treatment system's boundary limits;
typically another treatment process receives these liquids. The
receiving process varies depending on the chemical characteristics
of the oxidized liquids (ODD, BOD, pH, suspended solids, etc.).
Typically, liquids with a high suspended solids are sent through a
clarifier to settle out participate matter. It should be noted
that the oxidized liquid may still contain a relatively high
concentration of biological nutrients, further treatment of these
oxidized liquids by a biological system may be required prior to
discnarge to the final receiving system (lake, river, POTW).
V. DESIGN BASIS
ZIMFEO and SAIC mutually developed three scenarios for the full
scale wet air oxidation of the dredged sediments. These scenarios
were based on the laboratory findings that the wet air oxidation
process could adequately handle sediments at a solids
concentration of approximately ten percent (10%). The dredged
sediment is produced at a solids concentration of approximately
forty (40) percent. Therefore, the sediment would require a three
(3) to one (1) dilution using water from the harbor that is being
dredged. The three scenarios involve the treatment of total
dredgings of 10,000; 40,000; and 100,000 yd1 [all at forty percent
(40%) total solids). It was determined that wet air oxidation
units of ten (10), twenty (20), and forty (40) gallons per minute
[at ten percent (10%) total solids) capacity would be adequately
sized to process these volumes of dredgings as shown in the
following taole.
TTXE TC PF.CCZSS DREDGING, YES
WAG Cacacitv, =cn 10.300 vd1 40.000 vd5 100,000 vd'
10 2.25 6.75 22.50
20 1.12 3.38 11.25
40 0.35 1.59 5.52
Eacr. of the three '3! prcposed wee air oxidation systems covered
under these scenarios vas aesisr.ed based en SIMFEO's experience in
the construction of sirr-iiar systems. Each proposed system snail
be constructed to the standards of ZIT*.F?.0 and all appiiracls
national cedes.
characteristics as lister; ir. Tacie 3.
48
-------
TABLE 3: WASTE CHARACTERISTICS
Average COD, (g/1): 40.0
Total Suspended Solids, [wt %J: 10.0
pH: 7
Chlorides,[ppmj: 12
The design parameters for the proposed systems are presented in
Table 4.
TABLE 4: SYSTEM DESIGN PARAMETERS
Design Flowrate, [U.S. G?M): 10.0 SYSTEM 1
20.0 SYSTEM 2
40.0 SYSTEM 3
Operating Schedule: 24 hours/day
5 days/week
50 weeks/year
Normal Operating .M.ode: Autothennal
Reactor Hydraulic Detention Ti.-e, ;minutes 1: 90
COD Reduction, [%]: 83
Mechanical Design Temperature, \°~}: 570
Mecnanical Design Pressure, [psigj: 2,000
Operating Temperature, {°T}: 536
Operating Pressure, [psigj: 1,500
Material of Construction
for Waste Wetted Surfaces: 316L
SCCPE OF OFFERING
proposes tc crevice ail engineering, design, equipment
supply and start-up services necessary to complete and install tne
wet air oxidation systeir. tc tr.e extent described herein.
ZIMPRO
rBASSAVAJVT
49
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The proposed major equioment pieces and/or system components to be
furnished and installed" by ZIMPRO for each system and included in
the proposed price, as stated hereafter, are listed in Table 5.
5: MAJOR EQUIFMEUT LIST
Quantity
Alloy Material of
Construction
- If Annlicable
1.
<- .
3.
4 .
5.
6.
^
8.
a _
10.
11 .
1 7
12 .
14.
T^Z _
15.
17.
18.
Lew Pressure Feed Pumr>
High Pressure Feed Pumn
Process Air Compressor"
Feed/Zf fluent Heat Exchanger
Auxiliary Heat Exchanoer
Thermal Heat Transfer System
Thermal Fluid
Recirculation Pump
Process Reactor
Process Cooler
Pressure Control Valve/Pot
Process Separator
Off gas Cooler
Separator Bottoms Pumc
Instrument Air Ccmcresscr
Interconnecting Pice
Valves
Motor Control Center
Instrumentation
2 (1 standby)
1
1
1
1
1
2 ( 1 standby )
1
1
2
I
i_
2 (1 standby i
^
1 lot
1 lot
1
1 lot
316L SS Wetted
316L SS Wetted
316L SS
316L SS Tube/CS
316L SS Clad CS
316L SS Tube/CS
316L SS
316L SS
316L SS
As Required
As Required
As Required
Parts
Parts
Shell
Shell
The majority of the ecuirment listed above shall be orepiped and
wired 3n equipment sxids to facilitate field erection and/or
installation of the system by 3IMPF.O. Other equipment shall be
provided as individual items. Skids and individual equipment
items, as provided, are designed to be erected on concrete
fcur.cations provided ov the FURCHASr?.. Table 6 is a listing of
the equipment skids -vnicn are anticipated to be provided for the
orcpcsed svstem.
r ZIMPRO
PASSAVA/VT
50
-------
6:
1. Air Compressor Skid
2. Equipment Skid
3. High Pressure Pump
4. Thermal Fluid Heat
System Skid
1. Air Compressor Skid
2. Equipment Skid
3. Hisn Pressure Pump
4. Thermal Fluid Heat
System Skid
SYSTEM 1-10
Otv
1
1
Skid 1
Transfer
1
SYSTEM 2-20
Otv
1
1
Skid 1
Transfer
1
GPM
Approximate
Dimension
each
(L x W)
in feet
17 x 10
10 x 11
14 x 8
7x8
GPM
Approximate
Dimension
each
(L x W)
in feet
23 x 10
15 X 10
14 x 8
7x8
Approximate
Weight
each
Ibs.
21,500
30,000
25,000
7,000
Approximate
'weight
each
Ibs.
36,000
35,000
25,000
7 , 000
I
SYSTEM 3 - 40 GrM
Approximate
1. Air Compressor Skid
2. Equipment Skid
3. Hicn Pressure Pump
4. Thermal Fluid Heat
Svsrem Skid
Otv
1
1
Skid 1
Transfer
i
Dimension
eacn
(L x W)
in feet
23 x 10
16 x 12
14 x 10
X 3
Acoroximate
"weight
eacn
Ibs.
i
37,000
40,000
2~,000
7 , 000
ZIMPRO
51
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Individual equicment items and/or system components such as the
reactor, feed/effluent heat exchanger, auxiliary heat exchanger,
process cooler, field valves, and field instrumentation will be
fabricated and shipped to the project site for installation,
erection and/or independent mounting by ZIMFRO on separate
concrete foundations to be provided by the PURCHASER. Table 5
lists major individual equipment items being offered for the
proposed wet air oxidation systems which will require independent
mounting and/or installation. Figures 2-A, 2-B, and 2-C are
preliminary plot plans showing the suggested equipment layout and
building size. ZIMPRO will also supply all pipe retired to make
interconnections between skids and free-standing equipment.
TABLE 5: FREE-STANDING EQUIPMENT
SYSTEM 1-10
Qtv
Process Heactcr 1
Feed/Effluent Heat Excr.ar.cer 1
Process Ccoler 1
Auxiliary Heat Excr.anger 1
svs '. : - 20
:tv.
GPM
Approximate
Dimension
each
(L x W)
in feet
3 (diam. )
3.5 x 2.0
2.5 x 2.0
1.5 x 2.0
GPM
Approximate
Dimension
each
(L x W)
in feet
Approximate
Weight
each
Ibs.
27,000
7,500
4,100
1,000
Approximate
Weight
eacn
Ibs.
Process Eeactor
Feed/Effluent Heat
Process Cooler
Auxiliary Heat txc
Excr.ar.csr
r.anser
1 4 'diam. !
1 3.3 x 2.3
1 4.3 x 2.3
1 2.3 x 2.3
53,300
21,100
10,300
7,130
ZIMPRO
52
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i r
tn
CO
t '
I i.
©
SCAt£: I/B- - I*
I *
1 ^
WCT kin oximricM SISTOI
run
10 crri S»STDI
"1 ir
III.
Ha.
1
1
1
4
5
i
1
1
ti|ut|«ent
MW SKID
eouimcNT SIID
ntfXXSS MR COMJUESSOII SKID
niEraiM. nino HEAT TDAxsrai
SYSTDI
REACTOR VESSEL
nxD/frniiENr IKAT txaiMca
MniLlMt ICAT txauucai
rrocrsj anux
~r
mSSAV^Ni
n
fiaiyr. 7-*
i~
-------
qtldlNIZGS,
Mii'-;»'j ui'» u;
I 1IHJ AUVMIWI 11 1,1
U7IOCD SSXJOUJ
O.VJII
1V3U iro/ruji/cuaj
KUSNMU xvju auru Tvutaia
aiis vossm-iuao mw
a i us juu
» I I
-------
en
01
uocxai
IAVKTCRT
rn TO
I .
EOUlFHDfT (KID
raooss AIR omrussot s*to
nmwM. runo BEAT Twucrai EYSTDI
ms/trrunxt BTAT
MniUAmr HEAT naiwcn
SCAltl !/" -
WET MK n«in*TICN STSTtn
PPEI inniMit nor lAtaurr
-------
SYSTEM
Process Reactor
Feed/Effluent Heat Exc.-.anger
Process Cooler
Auxiliary Heat Exchanger
3-40
Qtv.
1
2
1
1
1
GPM
Approximate
Dimension
each
(L x W)
in feet
4.5 (diara. )
5.0 x 2.5
6 x 2.5
4.0 x 2.5
5.0 x 2.5
Approximate
Weight
each
Ibs.
104,000
27,000
24,000
24,000
26,000
Please note that tr.e dimensions and weights
approximations only and are suo^ect to change.
given are
Instrumentation and valves associated with the skid mounted
equipment will be installed and pre-piped on the appropriate skids
to tr.e extent practical. Skid mounted instruments and start-stop
stations shall be preared to skid mounted terminal strips/boxes.
ZIMPP.O shall supply a control panel for each proposed wet air
oxidation system and cerfcrm all wiring necessary to provide a
complete system. The control panel shall be mounted on an
equipment skid.
ZIJ1PP.O has included tr.e cost of a building in each of the proposed
systems. Costs not included with the building are: foundations,
pili.-.gs. site preparation, site dewaterir.g, or equipment pads.
The PURCHASER shall re required to supply utility connections at a
poi.-.t not greater tr.ar. a one '!) foot distance from the building
-ail. Utilities -.- ce supplied by the PURCHASES shall include I
480 Volt, 3 Phase electrical service; 120 volt, 1 Phase electrical
service; ccr.diticr.ee reeling water at 55sr,- service -vater; and
natural gas. Table ? _s a listing jf .^ajor system comnonents and
the required utilitv services.
56
-------
TABLE 6: REQUIBED UTILITY SERVICES
Item Reouired Utility Services
1. Air Compressor Skid 480 Volt 3* Electrical, 65eF
(max.) Cooling Water
2. Equipment Skid 480 Volt 3* Electrical. 120 Volt
1* Electrical, 65°F (max) Cooling
Water, Service Water
3. High Pressure Pump Skid 480 Volt 3* Electrical, 65°F
(max) Cooling Water
4. Thermal Fluid Heat
Transfer System Skid 480 Volt 3$ Electrical, Natural
Gas
5. Process Cooler S5°F (max) Coolino Water
VII. ESTIMATED UTILITIES
;::^??.0 estimates that the proposed wet air oxidation systems will
require the utility duties presented in Table 7. Please note that
these are estimates cr.iy and are sucnect to change.
TABLE 7: ESTIMATED UTILITY DUTIES
i SYSTEM 1 I SYSTEM 2 I SYSTEM 3
| Natural Gas - Start-uc Cr.iv I | |
| '=i:00 3TU/SCF, !scf-"i: I 3 10 I 36
|Cc=li.-.= Water j | |
iar fr;r, [U.S. gem): ] 135 j 275 | 550
iCpersting Power, [kWh Hr :: 130 j 255 j 530
T.K.e ouagetary price i~- t.-.e supply ar.d installation cf the
proposed wet air oxiostior. systems as defined anove is:
SYSTZr: 1 - 10 G?.M.: "our .'".illion five Hundred Thousand and
:c :c: ^o._ars ,54.500,0001.
ZIMPRO
rPASSAVANT
57
-------
SYSTOI 2-20 GFM: Five Million Six Hundred Thousand and
00/3.00 Dollars ($5.600,000) T
STEM 3-40 GPM: Seven Million Three Hundred Thousand and
00/100 Dollars ( 7 , 300 .
These prices do not include provisions for the following items:
1. Any applicable state, local, or federal taxes, permits,
bends, fees or duties.
2. Design or supply of foundations, civil work, sumps, concrete
lining, or sewers.
3. Design, supply, or installation of equalization tanks.
4. Design, supply, or installation of the post-treatment system.
5. Equipment storage necessitated due to action of the
PURCHASER.
5. Any operational spare parts other than the spare rotating
equipment previously listed.
7. Any piping or wiring beyond the proposed system boundary
Units.
58
-------
REFERENCES
1. Standard Methods for the Examination of Water and Wastewater,
16th Ed., APHA, AWHA, WFCF, 1985.
2. Methods for Chemical Analysis of Water and Wastes, U.S. EPA,
EPA-600/4-79-020, March, 1979.
iZIMPRO
rPASSAVAJVT
59
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APPENDIX B
EXPERIMENTAL DESIGN - ZIMPRO PASSAVANTS
WET AIR OXIDATION TREATMENT TECHNOLOGY
FOR
GLNPO - ASSESSMENT AND REMEDIATION OF CONTAMINATED
SEDIMENT TECHNOLOGY DEMONSTRATION SUPPORT
May 1991
Submitted to:
U.S. Environmental Protection Agency
Great Lakes National Program Office
230 S. Dearborn
Chicago, Illinois 60604
Submitted by:
Science Applications International Corporation
635 West Seventh Street, Suite 403
Cincinnati, Ohio 45203
EPA Contract No. 68-C8-0061, Work Assignment No. 2-18
SAIC Project No. 1-832-03-207-40
60
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TABLE OF CONTENTS
SECTION
List of Tables and Figures iii
1.0 TECHNOLOGY DESCRIPTION 1
2.0 TEST PLAN 3
2.1 Purpose 3
2.2 Approach 3
2.3 Phase I 4
2.4 Phase II 7
3.0 RESIDUAL MANAGEMENT 11
4.0 FINAL REPORT 12
APPENDIX A - ENVIROSCAN Environmental and Analytical Services Brochure
APPENDIX B - Phase I Letter Report on Process Variables
61
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TABLES
NUMBER
2-1 Zimpro Passavant's Analysis Schedule for the Phase I
Wet Air Oxidation of Indiana Harbor Sediment
2-2 Zimpro Passavant's Analysis Schedule for the Phase II
Wet Air Oxidation of Indiana Harbor Sediment
2-3 SAIC's Analysis Schedule for the Phase II
Wet Air Oxidation of Indiana Harbor Sediment
FIGURES
NUMBER
1-1 Wet Oxidation Flow Diagram
2-1 22 Factorial Experimental Design for
Wet Air Oxidation of Indiana Harbor Sediment
62
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SECTION 1
1.0 TECHNOLOGY DESCRIPTION
Wet air oxidation is a process that accomplishes an aqueous phase oxidation of organic or inorganic
substances at elevated temperatures and pressures. The usual temperature range varies from approximately
350° to 600° F (175° to 320° C). System pressures of 300 psig to well over 3000 psig may be required.
However, testing has been done at temperatures exceeding the critical point for water to limit the amount
of evaporation of water, depending on the desired reaction temperature. Compressed air or pure oxygen
is the source of oxygen that serves as the oxidizing agent in the wet air oxidation process.
The basic flow diagram for a conventional wet air oxidation process is shown in Figure 1-1. In
processing an aqueous waste, the wastestream containing the oxidizable material is first pumped into the
system using a positive displacement, high pressure pump. Next, the waste is preheated in a heat
exchanger with the hot oxidized effluent. The compressed air or oxygen is injected into the wastestream
either at the discharge of the high pressure pump or at the inlet to the reactor. A vertical bubble column
is commonly used as the reactor which provides the required hydraulic detention time to effect the desired
reaction. The desired reaction may range from a mild oxidation, which requires a few minutes, to total waste
destruction, which requires an hour or more detention time. Exothermic heat of oxidation is released to the
wastestream during oxidation. This heat release usually raises the temperature of the wastestream to the
desired level in the reactor. The hot, oxidized effluent exits the reactor and is cooled in the process heat
exchangers. The cooled effluent then exits the system through a pressure control valve. The oxidized liquid
and non-condensible offgases are separated in a separator tank and discharged through separate lines.
The products of wet air oxidations vary with the degree of oxidation that is accomplished. For low
degrees of oxidation, oxidizable organic matter is converted to low molecular weight organic compounds
such as acetic acid. For high degrees of oxidation, oxidizable organic matter is chiefly converted to carbon
dioxide and water. Organic or inorganic sulfur is converted to sulfate. Organic nitrogen is converted
primarily to ammonia. The halogens in halogenated organics are converted to inorganic halides.
The commercial applications of wet air oxidation are chiefly in the disposal of aqueous wastes.
However, some applications employ wet air oxidation for recovery of chemicals and energy production,
simultaneously with waste disposal.
63
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Q
«,
HIGH
PRESSURE
PUMP
AIR COMPRESSOR
HOT WATER
REACTOR
H^lq-
Figure 1-1. Wei Oxidation Flow Diagram (Source: Zimpro Passavant)
rVENT
"
SEPARATOR
I »» OXIDIZED
LIQUOR
-------
SECTION 2
2.0 TEST PLAN
2.1 Purpose
The primary objective of these tests is to determine the feasibility and cost effectiveness of Zimpro
Passavant's Wet Air Oxidation process for treating and removing polyaromatic hydrocarbons (PAH's) from
sediments. The Great Lakes National Program Office (GLNPO) has obtained and homogenized sediments
collected for the Indiana Harbor near Gary, Indiana. The wet air oxidation process is not expected to treat
polychlorinated biphenols (PCBs), another known primary contaminant group detected in the sediments.
The bench scale treatability tests of the treatability study are designed to provide data that closely
simulates full scale performance. The data generated by the tests allows Zimpro Passavant and EPA to
evaluate feasibility of the process and to estimate treatment costs for full scale performance.
The Bench Scale Treatability Test objectives are:
To record observations and data to predict full-scale performance of Zimpro
Passavant's wet air oxidation process.
Take samples during the oxidation tests and conduct analysis sufficient to allow for
calculation of mass balances for oil, water, solids and other compounds of interest.
To calculate the oxidation efficiency of target compounds, specifically determining
the level of destruction of organic contaminants, principally PAHs. PCBs, the other
primary organic contaminant group in the sediments are not expected to be treated
by the wet air oxidation technology.
To supply GLNPO with treated solids (300 grams dry basis), and filtrate (water), for
independent analysis.
2.2 Approach
In order to accomplish the test objectives a two phased approach will be used. Phase I is a
preliminary phase conducted by Zimpro Passavant to determine the optimum conditions to be used during
Phase II. Phase II is the treatability test at optimum conditions and GLNPO, through its contractor Science
Applications International Corporation (SAIC), will obtain samples of the untreated sediments and treated
residuals for analysis by an independent laboratory. All analyses for this treatability study program
(consisting of seven treatability studies utilizing four technologies on four sediments) will be conducted by
the same laboratory. This arrangement will eliminate intertaboratory variation from the comparison of the
performance of these technologies. In addition representatives of both GLNPO and SAIC are scheduled to
observe the conduct of Phase II of each treatability study.
65
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2.3 Phase I
2.3.7 Procedures
In Phase I, Zimpro Passavant will analyze the Indiana Harbor sediment for the parameters shown
below in Table 2-1. This Phase I analyses will be conducted by Zimpro Passavant since this initial phase
serves as an optimization step for their wet air oxidation process.
Table 2-1. Zimpro Passavant's Analysis Schedule for the Phase I
Wet Air Oxidation of Indiana Harbor Sediment
Oxidized
Analysis
COD
BOD
Total Solids and Ash
Suspended Solids and Ash
PH
Oil/Grease
PAHs
Chloride
Feed
Slurry
1
1
1
1
1
1
1
1
Filtrate
5
5
5
-
5
5
5
0
Solids
5
-
5
-
-
5
5
0
Total No.
of Samples
11
6
11
1
6
11
11
1
Zimpro Passavant will conduct the Phase I wet air oxidation treatability study in a shaking autoclave
at temperatures ranging from 280° C to 320° C using reactor residence times of 30 to 90 minutes. The
batch shaking autoclaves are fabricated from various corrosion resistant alloys, including 316 stainless steel,
nickel, Inconel 600 and 625, Hastelloy C-276, and titanium. The shaking autoclaves have total volumes of
0.5 liters and 0.75 liters.
Each wet air oxidation test will be conducted by placing approximately one hundred (100) ml of
slurried sediment in the shaking autoclave. The autoclave will be closed and pressurized with air so that
an amount of oxygen equivalent to 125 percent of Chemical Oxygen Demand (COD) is charged to the
autoclave. The autoclave will then be placed in a heater shaker mechanism and heated to the desired
reactor temperature. The autoclave will be held at temperature for the desired reaction residence time, after
which, ft will be cooled to room temperature. The non-condensible gas will be analyzed for oxygen,
nitrogen, carbon dioxide, carbon monoxide, total hydrocarbons, and methane. After completing the offgas
66
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analysis, the autoclave will be de-pressurized and opened. The oxidized effluents from each oxidation
condition will be composited. The composite samples will be filtered using a laboratory vacuum filter funnel
and collection flask. The feed sediment slurry, oxidized filtrates, and solids will be analyzed by Zimpro
Passavant according to the analysis schedule presented in Table 1-1, Section 1.3.
The feed sediment slurry will be prepared by diluting the sediment that is provided to approximately
ten (10) percent solids, using distilled water.
2.3.2 7esf Conditions, Process Variables and Schedule
Zimpro Passavant will require approximately 500 grams of sediment solids (dry weight basis) to
complete Phase I, which is equivalent to approximately 1300 grams of wet Indiana Harbor sediment (the
Indiana Harbor sediment has a reported moisture content of approximately 39%).
The Phase I test plan consists of a 22 factorial experimental design which will determine the effect
of temperature and time at temperature on the destruction of organic contaminants in the sediment. The
test plan will consist of the following autoclave oxidation conditions:
Temperature °C Time at Temperature. Minutes
280 30
280 90
300 60
320 30
320 90
A temperature-time diagram of the experimental plan is shown in Figure 2-1. It is estimated by
Zimpro Passavant that five oxidations will be conducted at each condition to obtain sufficient samples which
will be used for analysis purposes.
The Phase I work, including sample analysis, can be completed in approximately six (6) weeks after
receipt of the sediment solids. The Phase I work can be initiated within two (2) weeks after receipt of
contract and notification to proceed.
67
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Figure 2-1. 2* Factorial Experimental Design for Wet Air Oxidation of Indiana Harbor Sediment
O
LU
CC
D
r-
<
CC
HI
CL
2
LU
r-
320
300
280 -
260
0 30 60 90 120
TIME AT TEMPERATURE, MIN.
The process variables for Phase I test plan include the following:
Temperature (280° - 320° C)
Time at Temperature (0.5 hours - 1 .5 hours)
Note: Percent solids for feed (2 to 20 percent or maximum pumpable slurry concentration) was not
included as a test variable because the destruction of organic contaminants is not concentration
dependent. Also, pressure (300 to 3000 psig) is not included as a test variable because the
destruction of organic contaminants is not dependent on the system pressure, provided excess
oxygen is present.
2.3.3 Report
At the completion of Phase I, a letter report specifying the wet air oxidation conditions required for
Phase II testing will be prepared and sent to SAIC. These would include, but would not necessarily be
limited to reaction temperature(s) and reactor residence time(s), and will reflect those conditions (process
variables) that produced the maximum destruction of target compounds, as determined in Phase I.
68
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2.4 Phase II
2.4.1 Procedures
Zimpro Passavant will conduct Phase II of the wet air oxidation treatability study in stirred
autoclaves. The stirred autoclaves are fabricated from 316 stainless steel and titanium. The one-gallon
capacity of the stirred autoclave will facilitate the production of larger quantities of oxidized effluents. Zimpro
Passavant proposes to conduct the stirred autoclave test using the wet air oxidation conditions that produce
the maximum destruction of the polynuclear aromatic hydrocarbons, as determined in Phase I.
In Phase II, the stirred autoclave will be charged with approximately two (2) liters of slurried
sediment (10 percent suspended solids). The stirred autoclave would be charged with sufficient air to
provide an amount of oxygen equivalent to 125 percent of the COD. The stirred autoclave will then be
heated to the desired temperature and kept at temperature for the desired length of time. After completion
of the reaction time, the stirred autoclave will be cooled and the non-condensible gas will be analyzed for
oxygen, nitrogen, carbon dioxide, carbon monoxide, total hydrocarbons, and methane. After completion
of the gas analysis, the stirred autoclave will be de-pressurized. The oxidized effluent will be withdrawn and
saved for analysis by SAIC and Zimpro Passavant. It is anticipated that two (2) stirred autoclave oxidations
will be conducted using the chosen wet air oxidation conditions. The combined oxidation effluent will
produce approximately four (4) liters of filtrate and 400 grams of solids. Zimpro Passavant will require
approximately 250 ml of filtrate and 10 grams of solids for analytical purposes.
2.4.2 Tesf Conditions and Process Variables
Zimpro Passavant will require approximately 500 grams of sediment solids (dry weight basis) to
complete Phase II as described herein.
The Phase II work can be completed in three (3) weeks, approximately four (4) working days for
preparation of equipment and one (1) working day for conducting the stirred autoclave tests. The remaining
two (2) weeks will be required to complete the sample analyses, develop cost information, and report all of
the wet air oxidation test results to SAIC.
The process variables for the Phase II test plan include oxygen content (equivalent to 125% of the
COD), the percent solids used, the presssure of the stirred autoclaues, a specified temperature, and a
desired length of time. The latter two variables will be determined from the Phase I test.
2.4.3 Sediment Sample Characterization and Analyses
There will be two separate analytical matrices conducted on the Indiana Harbor sediment during
Phase II, one by Zimpro Passavant and one by SAIC's subcontract laboratory, Battelle. Zimpro Passavant
will conduct analyses on the treated sediment according to the analytical matrix shown in Table 2-2.
69
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Table 2-2. Zimpro Passavant Analysis Schedule for the Phase II
Wet Air Oxidation of Indiana Harbor Sediment
Oxidized
Analysis
COD
BOD
Total Solids and Ash
Suspended Solids and Ash
pH
Feed
Slurry
1
1
1
1
1
Filtrate
1
1
1
-
1
Solids
1
-
1
-
"
Total No.
of Samples
3
2
3
1
2
At the beginning of the Phase II treatability test, SAIC personnel observing Phase II will pack and
ship untreated Indiana Harbor sediment per written detailed instructions supplied to the SAIC on-site
representative. This sample will be obtained from a separate unopened container of the sediments sent for
Phase II. The analyses to be conducted on these sediments through SAIC's subcontract laboratory are
listed in Table 2-3.
Following the Phase II treatability test, SAIC's subcontract laboratory will conduct analysis on the
untreated sediments and end products. The number of analyses conducted on the anticipated residuals are
also outlined in Table 2-3.
2.4.4 Quality Assurance (QA)
Zimpro Passavant will conduct their portion of this study according to the quality assurance/quality
control procedures of their subsidiary laboratory, ENVIROSCAN, Inc. (Wisconsin Department of Natural
Resources Certification No. 737 053 130). ENVIROSCAN's QA program includes the following internal
controls.
Sample protocols
Sample handling procedures
Chain of Custody
Sample receipt, preservation, and storage
Analytical procedures
Reporting results
Laboratory quality control programs
On-going employee training
70
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Table 2-3. SAIC's Analysis Schedule lor the Phase II Wet Air Oxidation of Indiana Harbor Sediment
QC. Simple ( )
»nd
* fulho./ Blank
Not Analyzed
(1) - Number of Analyses
1 Indiana Harbor Sediment
MS '-Matrix Spike *
MSD - Matrix Spike Duplicate
-------
SAIC has developed and GLNPO has approved a QA project plan for this project. This QA project
plan is available as a separate document. Additional information on Zimpro Passavant's analytical laboratory
(ENVIROSCAN) is included in the ENVIROSCAN brochure (Appendix A).
72
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SECTION 3
3.0 RESIDUAL MANAGEMENT
The anticipated residuals from the wet air oxidation treatability studies are of very small quantity
(estimated at approximately 400 grams of dry solids and 4 liters of filtrate). A portion of the Zimpro
Passavant complex is a permitted hazardous/toxic waste storage, treatment, and disposal facility (WI/EPA
Registration No., WID044393114). The pilot plant facilities, where the treatability tests will be conducted, are
within the same complex, thus Zimpro Passavant has in-house residual management capabilities.
73
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SECTION 4
4.0 FINAL REPORT
Upon completion of the bench scale treatability program, Zimpro Passavant will prepare a Final
Report. The Final Report will contain the following:
Zimpro Passavant's wet air oxidation process description, test procedures, operating
parameters, sampling locations and frequencies
Test results discussion with analytical data
Mass balance calculations, if applicable
Projected full scale system configuration and operating parameters that would be used to
treat site waste materials
Treatment cost estimates in dollars per unit volume of soil for the Indiana Harbor type soil,
based on the lowest cleanup level which can reasonable be achieved
The following data will be presented in tabular form:
Initial contaminant concentrations; along with the moisture contents and pH values
and other relevant data
Final analytical results for all streams generated from the extracts of each sample
Percentages of individual contaminants extracted for each sample, as well as a
calculation of total PAHs oxidized
Oxidation efficiency for each contaminant
Log books and chromatograms if generated.
74
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APPENDIX C
QUALITY ASSURANCE PROJECT PLAN
FOR
GLNPO - ASSESSMENT AND REMEDIATION OF
CONTAMINATED SEDIMENT TECHNOLOGY
DEMONSTRATION SUPPORT
Revision II
February 15, 1991
Submitted to:
U.S. Environmental Protection Agency
Great Lakes National Program Office
230 S. Dearborn
Chicago, Illinois 60604
Submitted by:
Science Applications International Corporation
635 West Seventh Street, Suite 403
Cincinnati, Ohio 45203
EPA Contract No. 68-C8-0061, Work Assignment No. 2-18
SAJC Project No. 1-832-03-207-50
75
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GLNPO - QAPJP
Section No.: Q
Revision No.: 2
Date:
Paiic:
Feb. 15. U>91
1 of 2
TABLE OF CONTENTS
SECTION
REVISION DATE
1 1) INTRODUCTION
2.0 PROJECT DESCRIPTION
3.0 QUALITY ASSURANCE OBJECTIVES . . .
4.0 SAMPLE TRANSFER AND PREPARATION
PROCEDURES
5 0 ANALYTICAL PROCEDURES AND
CALIBRATION
0.0 DATA REDUCTION. VALIDATION AND
REPORTING
7.0 INTERNAL QUALITY CONTROL CHECKS
8.0 PERFORMANCE SYSTEMS AUDITS
9.0 CALCULATION OF DATA QUALITY
IMPLICATORS
10 ii CORRECTIVE ACTION . . .
11.0 QA/QC REPORTS TO MANAGEMENT . . .
APPENDIX A - TECHNOLOGY SUMMARIES
12
1/9/91
2/15/91
2/15/91
1/9/91
2/15/91
1/9/91
1 '9/91
1 "»/91
I/1', '91
76
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QUALITY ASSURANCE PROJECT PLAN APPROVALS
QA Projeer Plan Title: GLNPO Assessment and Remediation of Contaminated
Sediment Technolooy Demonstration Suooort
Prepared by: Science Applications International Corporation (SAIC)
QA Project Category:
II
Revision Date: January 9, 1990
SAIC'3 Vcrx. Assignment Manager (print,
C'yrie J. Diai
SAIC's QA Manager (print)
/Dace
v?/
ure
Steve Y
orr. Group Chair (print)
signature
Sf'an Scnurnacre1"
Af.CS QA Officer (print)
Signature
E?A. IMSL-1V, N'RD QA Officer .print;
^?A .ecr.nicai rroiect Manager (print.
Signature
?ave Ccwoi'
'-&*
77
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DISTRIBUTION LIST:
Gene Easterly
Brian Schumacher
Tony Kizlauskas
Thomas Wagner
Clyde Dial
Steve Garbaciak
Dennis Timberlake
Steve Yaksich
David Cowgill
Gary Baker
Vic Eneleman
U.S. EPA. EMSL (Las Vegas)
LOCKHEED (Las Vegas)
SAIC (Chicago)
SAJC (Cincinnati)
SAIC (Cincinnati)
U.S. COE (Chicago)
U.S. EPA, RREL (Cincinnati)
U.S. COE (Buffalo)
U.S. EPA, GLNPO (Chicago)
SAIC (Cincinnati)
SAJC (San Diego)
GLNPO - QAPjP
Section No.: Q_
Revision No.: 2_
Date:
Page:
Feb. 15. 1991
2 of:
78
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GLNPO - OAPjP
Section No.: l_
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 2
1.0 INTRODUCTION
The Great Lakes National Program Office (GLNPO) leads efforts to carry out the
provisions of Section 118 of the Clean Water Act (CWA) and to fulfill U.S. obligations
under the Great Lakes Water Quality Agreement (GLWQA) with Canada. Under Section
118(c)(3) of the CWA. GLNPO is responsible for undertaking a 5-year study and
demonstration program for contaminated sediments. Five areas are specified for priority
consideration in locating and conducting demonstration projects: Saginaw Bay, Michigan;
Sheboygan Harbor. Wisconsin: Grand Calumet River, Indiana (aka: Indiana Harbor);
Ashtabula River, Ohio; and Buffalo River, New York. In response, GLNPO has initiated
an Assessment and Remediation of Contaminated Sediments (ARCS) Program. The ARCS
Program will be carried out through a management structure including a Management
Advisory Committee consisting of public interest, Federal and State agency representatives,
an Activities Integration Committee which is made up of the chairpersons of the technical
work groups, and technical work groups.
In order to obtain the broadest possible information base on which to make
decisions, the ARCS Program will conduct bench-scale and pilot-scale demonstrations and
utilize opportunities afforded by contaminated sediment remedial activities by others, such
as the Corps of Engineers and the Superfund program, to evaluate the effectiveness of those
activities. These bench-scale and pilot-scale tests will be developed and conducted under
the guidance of the Engineering/Technology (ET) Work Group for ARCS.
SAIC has been contracted to supply technical support to the ET Work Group. The
effort consists of conducting bench-scale treatability studies on designated sediments to
evaluate the removal of specific organic contaminants.
79
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GLNPO - QAPjP
Section No.: j_
Revision No.: 1
Date: Jan. 9. 1991
Page: 2 of 2
Sediments have been obtained by GLNPO from various sites and represent the type
of material that would be obtained for onsite treatment. The primary contaminants of these
sediments are polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons
(PAHs). Analyses to date show PCB concentrations are less than 50 ppm. These sediments
have been homogenized and packaged in smaller containers by EPA.
80
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GLNPO - QAPJP
Section No.: 2_
Revision No.: 2
Date: Feb. 15. 1991
Page: 1 of 12
2.0 PROJECT DESCRIPTION
2.1 Background
SAJC and its subcontractors will conduct seven (7) bench-scale (several liters) tests
on wet contaminated sediments using four treatment technologies.
The seven treatability tests (as currently planned) will utilize sediments from 4 sites
(Saginaw River, Buffalo River, Indiana Harbor Canal, and Ashtabuia River). Five
sediments have been collected from these sites by GLNPO. These samples have been
homogenized by the U.S. EPA and are being stored under refrigeration in 5 gallon
containers by EPA in Duluth, MN.
These five sediments are currently being analyzed in the U.S. EPA, Environmental
Research Laboraton' in Duluth. The Duluth Laboratory is analyzing the sediments for total
organic carbon/total inorganic carbon (TOC/TIC), particle size, density of dry material,
total sulfur, acid volatile sulfide. oil and grease (O & G), total PCBs. PAHs (10), and metals
including mercury. Table 2-1 is a summary of the data received to date.
A portion (small vial) of each residual of each treatability test may be retained and
sent to the GLNPO office for "show" purposes. If available, sub-regulated quantities of the
solid and oil residuals from each test treatability study may also be retained and shipped to
EPA for possible further treatment studies.
The following is a list of technologies and the proposed number of sediment samples
to be tested by each technology:
a. B.E.S.T. Extraction Process on three samples (Buffalo River, Indiana
Harbor, Saginaw TRP 6)
b. Low Temperature Stripping (RETEC) on one sample (Ashtabuia River)
c. Wet Air Oxidation (Zimpro Passavam) on one sample (Indiana Harbor)
d. Low Temperature Stripping (Soil Tech) on two samples (Buffalo River and
Indiana Harbor)
Summaries of these technologies are included in Appendix A.
81
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TABLE 2-1 a. Preliminary Analytical Results on ARCS Sediments
00
to
Description
Saginaw 221
Saginaw TRP6
Ashlabula River
Indiana Harbor
Buffalo River
Concentration (Mg/kgm)(a)
Total
PCB
0.6
6.0
C
0.2
0.4
Total
PAH
1.2
3.1
C
96
5.6
Cu Cd
33 0.9
81 4.7
55 3.0
320 9.4
85 1.9
Ni
76
110
96
150
57
Fe(%)
1.4
09
3.7
16
3.9
Cr
140
200
550
540
110
Zn
240
200
240
3300
200
Pb
30
47
48
780
94
Concentration
TOO
1.4
1.2
2.6
21
2.0
O&G
O.I
0.3
1.7
5.8
0.5
(%)(*)
Moisture (b)
40.3
31.1
52.9
61.0
41.5
(a) Concentration in ppm and dry weight basis unless otherwise indicated.
(b) As received basis.
TABLE 2-lb. Preliminary Particle Size Distribution (%)
Description
Buffalo River
Particle Size (a)
>50u 50-20 u 20-5 u 5-2 u 2-0.2 u 0.2-0.08 u < 0.08 u
19.8 12.1 29.0 11.8 24.3 2.4 0.6
Median
Diameter, u
9.3
s, TJ
(a) u micarons
-------
GLNPO - QAPjP
Section No.: 2_
Revision No.: 2
Date: Feb. 15. 1991
Page: 3 of 12
2.2 Testing Program for Chemical Characterization
SAIC shall be primarily responsible for the physical and chemical characterization
of both the sediment samples prior to testing and the residuals created during the tests.
Analyses conducted by the vendors or subcontractors will not be depended on, but such data
shall be reported whenever available.
Two different sets of chemical analyses will be conducted during the performance of
the treatability tests: optimization test analyses and performance evaluation analysis. The
Phase I optimization test analyses will be conducted by the subcontractor or vendor during
the series of initial technology tests. The Phase II performance evaluation analyses will be
conducted by SAIC (or its analytical subcontractor) on the raw sediment sample prior to the
treatability test run at optimum conditions and on the end products produced by that
particular test. These tests are described further in this section.
In order to assure objectivity and consistency of data obtained from multiple vendors
running different technology tests. SAIC shall conduct analyses as described in Table 2-2 for
characterization of the sediments and the end products of the treatability tests at optimum
conditions (Phase II).
The analyses described for the solid fraction in Table 2-2 shall be performed by
SAIC's analytical subcontractor once on a subsample taken from each sample sent to each
vendor or subcontractor for treatability tests (Phase II). This subsample will be taken at the
same time that the sample for the Phase II treatablility study is taken by the vendor. This
data will serve as the measure of the raw sediment quality for comparison to analyses of
treated end products from each technology' test that may be conducted on sediments from
a particular area of concern.
Each bench-scale technology test may actually involve the performance of multiple
laboratory simulations. During the initial tests (Phase I), any analyses performed b\ the
83
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GLNPO - QAPJP
Section No.: 2_
Revision No.: 2
Dale: Feb. 15. 1991
Page: 4 of 12
vendor or subcontractor shall be reported, as available. For the tests run at optimum
conditions (Phase II), SAIC shall conduct the full suite of analyses, as detailed in Table 2-2,
on the end products if sufficient quantities are produced by the technology. Quotes solicited
for each technology specified that a minimum 300 grams dry basis of treated solid had to
be produced for SAIC's analyses. Table 2-3 shows the apportionment of the 300 grams for
the solid analyses. The quantity of water is depended on the sediments and the individual
technologies. To do all the analyses listed in Table 2-2, and associated QC, approximately
10 liters of water are required. Table 2-4 listed specified sample volumes for each analysis,
and gives a priority to each analysis. It is possible that only the PCB and PAH analysis and
associated QC will be performed on the water samples. If any oil residue is produced, it
will be analyzed by dilution with appropriate sample cleanup steps for PCBs and PAHs.
The data generated by SAIC's analyses of the untreated sediment and the treated end
products from the test at optimum conditions will be primarily relied upon to determine
treatment efficiencies. Vendor- or subcontractor-generated data will not be relied upon but
shall be reported when available.
2.3 Required Permits
Because of the small quantities of sediments required for the bench-scale treatability
tests, SAIC anticipates that no formal permits will be required to conduct these tests. If this
is not the case and permits (such as TSCA. RD&D or RCRA permits) are required, the
subcontractor will notify SAIC and the TPM will be notified to obtain approval for
acquisition of the permit(s).
All unused sediment samples requested by SAIC for the treatability test and all
testing residuals, except those requested by the TPM for "show" purposes and those
requested by the TPM for possible further testing, will be properly disposed of per federal
and state regulations.
84
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GLNPO - QAPjP
Section No.: 2_
Revision No.: 2
Date: Feb. 15. 1991
Page: 5 of 12
TABLE 2-2
Parameters and Detection Limits for Analysis of ARCS Technologies
Parameter
TOC/TIC
Total Solids4
Volatile Solids4
Oil & Grease4
Total Cyanide
Total Phosphorus
Arsenic4
Barium4
Cadmium4
Chromium4
Copper4
Iron (total)4
Lead4
Manganese4
Mercury4
Nickel4'
Selenium4
Silver4
Zinc4
PCBs (total & Aroclors)4
PAHs (16)4-5
PH
BOD5
Total Suspended Solids4
Conductivity
Solid1
300
1000
1000
10
0.5
50
0.1
0.2
0.4
0.7
0.6
0.7
5
0.2
0.1
2
0.2
0.7
0.2
0.02
0.2
full range
Water Qift-
1000
1000
1000
10
10
1
2
4
7
6
7
50
2
0.01
20
1
7
?
0.07 0.1
2 0.1
full range
1000^
1000
full range
NOTES:
Tlfli t o/*ti /~*n li t-rt i »c- r*~\ ^ r- *% 1 1 /-4 r- n ^ A »-*»-n-i-i / r*^ rt 1 \s n /)»* * *tr^»rrli^ti\ ' 1 ~h & i^ T * e rr%^ TT^ A+«^lr rV^/^nt/-!
be obtainable by TCP except for As, Se, and Hg. If GFAA is used, the D.L.'s will be
2 mg/kgm except Hg, Cd, and Ag which will be 0.1 mg/kgm.
Detection limits for water are ppb (ug/1). The D.L's for metals should be obtainable
by ICP except for As, Se, Hg. If GFAA is used D.L's will be 1 ug/L except Hg
which will be 0.01 ug/L.
Detection limits for oil are ppm (mg/1).
Parameters tentatively identified for QC analyses.
Polynuclear aromatic hydrocarbons to be analyzed are the 16 compounds listed in
Table 5-2.
85
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GLNPO - QAPjP
Section No.: 2.
Revision No.: 2.
Date:
Page:
TABLE 2-3
Solid Sample Quantities for Analyses
Feb. 15. 1991
6 of 12
Parameter
TOC/TIC
Total + Volatile Solids
Oil & Grease
Total Cyanide
Total Phosphorous
Metals (except Hg)
Hg
PCBs + PAHs
PH
Subtotals
Reserve
TOTAL
Initial
Sample (g)
15
5
20
10
5
5
1
30
20
111
--
--
OC (g)
..
10
40
~
15
3
90(60)3
--
158(128)
--
Total (g)
15
15
60
10
5
20
4
90
20
269(239)
31(61)
300
OC Approach
None1
Triplicate/Control
Triplicate/Control
None2
None2
MS/Triplicate
MS/Triplicate
(3)
None"1
1 For sample set II that does not have such a limited quantity of solid. The QC described in
footnote 3 will be implemented.
2 For sample set II. MS/triplicate QC will be implemented.
3 Quality control for untreated solids is Triplicate and spike and for treated solids matrix spike
and matrix spike duplicate.
For sample set II, Triplicate/Control sample QC will be implemented. The control sample
may be an EPA QC check sample, an NBS - SRM, a standard laboratory reference solution.
or other certified reference material.
86
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GLNPO - QAPJP
Section No.: 2.
Revision No.: 2_
Date:
Page: 7 of 12
Feb. 15. 1991
TABLE 2-4
Sample Volumes Required and Priority Ranking for Water Analyses
Parameter
Priority
Analysis
Volume, ml
QC
Volume, ml
QC
Approach
TOC/TIC
Volatile Solids
Oil & Grease
Total Cyanide
Total Phosphorus
Arsenic
Barium
Cadmium
Chromium
Copper
Iron (total)
Lead
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
PCBs (total & Aroclors)
PAHs (16)
PH
BOD
Total Suspended Solids
Conductivity
7
5
6
7
7
4
7
2
2
_
2
2
2
3
7
4
2
T
1
1
7
7
5
7
25
d
1000
500
50
100
100
b
b
b
b
b
b
100
b
c
b
b
1,000
a
25
1,000
200
100
d
2000
«
300
300
b
b
b
b
b
b
300
b
c
b
b
2.000
a
400
~~
None (e)
Triplicate/Control
Triplicate/Control
None (f)
None (f)
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/MSD
MS/MSD
None (f)
None (f)
Triplicate/Control
None (f)
Note:
a) same aliquot as PCBs e)
b) same aliquot as Barium f)
c) same aliquot as Arsenic
d) same aliquot as Total Suspended Solids
see footnote 2, Table 2-3
see footnote 4, Table 2-3
87
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GLNPO - QAPJP
Section No.: 2_
Revision No.: 2
Date: Feb. 15. 1991
Page: 8 of 12
2.4 Purpose of Phase I Experimental Design
The purpose of the Phase I technology experimental design is for each subcontractor
to establish a range of variables best suited for feasibly implementing their technology on
a full-scale basis (Phase II). SAIC will send a quantity (specified by the vendor) of each
sediment to the vendor to accomplish this. All data generated by the vendor during Phase
I will be supplied to SAIC for inclusion in the report for that technology. This information
will include the operating conditions/parameters, the input/output data for the contaminants
of interest to show the range of effectiveness associated with various operating conditions,
and the quantities of the input material and the various residuals resulting from the test.
The optimum set of conditions to be used for Phase II will be reported to SAIC along with
appropriate revisions to the Phase I experimental design to make it applicable to Phase II.
2.5 Purpose of Phase II Treatabiiity Test
SAIC will send another container of sediment(s) to the vendor (quantity to be
specified by the vendor). This container will not be opened until a representative of SAIC
arrives for the scheduled treatability test(s). Other observers from U.S. EPA, COE and/or
the GLNPO may also be present during the Phase II treatability test(s).
The new sample will be homogenized and a sample equivalent to a minimum of 300
gm of dry solids will be set aside for characterization analyses (Table 2-2) by SAIC. SAIC
will observe the treatability tests and obtain samples of process residuals for analyses (Table
2-2). The bench-scale test(s) must produce enough solid residual for all vendor
requirements and a quantity equivalent to 300 gm of dry solids for SAIC analyses. SAIC
can utilize up to 10 liters of water for analysis and 25 ml of the oil residual. The actual
quantities of water and oil that will be produced are dependent on the initial sediment and
the technology. All technologies except wet air oxidation are expected to produce an oil
residual. Also, if additional solid and/or oil residue is available, EPA may ask for these
materials to be sent to them for storage for possible future evaluation.
88
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GLNPO - QAPJP
Section No.: 2_
Revision No.: 2
Date: Feb. 15. 1991
Page: 9 of 12
All data generated by the vendor during Phase II is to be supplied to SAIC for
inclusion in the report for that technology. The vendor must stipulate in their work plan,
prior to conducting the test(s), the process locations to be sampled, the frequency and the
information being obtained.
All other residuals from both phases of the treatability study, including any untreated
sediment, will be properly disposed of by the vendor.
SAIC shall oversee the treatability test assessment(s) by vendors or subcontractors,
including all QA/QC aspects, monitoring and analysis. SAIC shall ensure compliance with
the specific experimental design during the tests conducted by vendors or subcontractors.
SAIC will make specific notes regarding the equipment being used, any pretreatment of the
sediment(s), the operation of the equipment, and any post treatment of the residuals. SAIC
personnel will pack the untreated sediment sample and the end product samples from the
Phase II test for each technology in an appropriate fashion for shipment from the vendor
or subcontractor to the laboratory SAIC is using for the analysis. Proper chain-of-custody
procedures will be developed in the QAPjP and strictly followed by SAIC personnel.
SAIC plans to take photos of the equipment while at the vendor's location for
inclusion in the report.
SAIC shall perform limited interpretation of technology test results, specifically the
development of material and energy balances. No test of air or fugitive emissions will be
done. For material balances, estimates of the mass distribution of the analytes of interest
(Table 2-2) among the residuals will be made. The term energy' balance is interpreted to
mean an estimation by the vendor of the energy input into the process at a pilot- or full-
scale.
89
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GLNPO - QAPjP
Section No.: 2_
Revision No.: 2
Date: Feb. 15. 1991
Page: 10 of 12
SAIC shall collect any information available from the vendor or subcontractor
concerning the actual or estimated costs of constructing and operating full-scale versions of
the technology tested.
The purpose of this project is to test five technologies for removing organic
contaminants (PCBs and PAHs) from sediments typical of locations around the Great Lakes.
GLNPO is specifying the technologies and the sediment(s) to be treated by each technology.
This study is only one part of a much larger program, and it is not necessarily intended to
evaluate the complete treatment of these sediments. Other aspects or treatment options are
being evaluated by a number of agencies, contractors, etc.
Therefore, this study is based on the following assumptions:
The percent removal of the PCBs and PAHs from the solid residual is the
most important object of this study.
The untreated sediments and solid residuals are the most important matrices.
If water and oil residuals are generated by a technology, the existence of an
appropriate treatment or disposal option for these residuals is assumed.
PAHs and PCBs will be determined in these residuals as a cross check of
their fate in treating the solids.
Based on the intents of this study, the critical measurements are PAHs, PCBs. metals.
total solids, volatile solids, and oil and grease in the untreated and treated solids.
2.6 Organization and Responsibilities
A project organization and authority chart is shown in Figure 2-1. The
Environmental Monitoring Systems Laboratory (EMSL) is cooperating with GLNPO and
SAIC on this evaluation. Mr. Thomas Wagner is the SAIC Work Assignment Manager and
is responsible for the technical and budgeting aspects of this work assignment. Mr. Clyde
Dial is QA Manager and is responsible for QA oversight on this work assignment.
90
-------
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GLNPO - QAPJP
Section No.: 2.
Revision No.: 2.
Date:
Page:
Feb. 15. 1991_
11 of 12
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91
-------
GLNPO - QAPjP
Section No.: 2_
Revision No.: 2
Date: Feb. 15. 1991
Page: 12 of 12
2.7 Schedule
The Phase I experimental designs are scheduled for mid to late February 1990, and
the Phase II Treatability Tests are scheduled for March and April 1991.
92
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GLNPO - OAPJP
Section No.: 3_
Revision No.: 2
Date: Feb. 15. 1991
Page: 1 of 2
3.0 QUALITY ASSURANCE OBJECTIVES
3.1 Precision. Accuracy. Completeness, and Method Detection Limits
Objectives for accuracy, precision, method detection limits, and completeness for the
critical measurements of solids are listed in Table 3-1. Accuracy (as percent recovery) will
be determined from matrix spike recovery for PAHs, PCBs and metals, and from laboratory
control samples (certified reference material- CRM) for the remaining analyses. Precision
(as relative standard deviation) will be determined from the results of triplicate analyses for
PAHs, PCBs, solids (total, volatile and/or suspended), oil and grease, and metals. Matrix
spike and matrix spike duplicate analyses will be used for treated solids for PCBs and PAHs.
The completeness will be determined from the number of data meeting the criteria in Table
3-1 divided by the number of samples that undergo performance evaluation analyses.
3.2 Representativeness and Comparability
Representativeness and Comparability are qualitative parameters. The sediment
samples have already been collected and have been reported to be representative of the
areas to be remediated. The data obtained in this program will be comparable because all
the methods are taken from a standard EPA reference manual and all the analyses will be
conducted at the same laboratory. Reporting units for each analysis are specified in Section
6 of this document and are consistent with standard reporting units in this program.
3.3 Method Detection Limits
The target detection limits (TDLs) were specified by GLNPO (Table 2-2). Based on
the analytical methods appropriate for the analyses and the amount of samples specified in
the methods, the detection limits listed in Table 3-1 should be achievable. Generally the
instrument detection limits are defined as 3 times the standard deviation of 15 blanks or
standards with a concentration within a factor of 10 of the IDL.
93
-------
TABLE 3-1. Qusility Assurance Objectives for Critical Measurements
(Sediments and Treated Solids)
Parameter
Total Solids
Volatile Solids
Oil & Grease
Arsenic
Barium
Cadmium
Chromium
Copper
Iron (total)
Lead ,
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
PCBs (total
& Aroclors (e)
PAHs (Table 5-2)
Method (a)
160.3
160.4
9071
3050/7060
3050/6010
3050/6010
3050/6010
3050/6010
3050/6010
3050/6010
3050/6010
7471
3050/6010
3050/7740
3050/6010
3050/6010
3540 or
3550/8080
3540 or 3550/
8270 or 8 100
Accuracy (b)
(as % recovery)
80-120
80-120
80-120
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
70-130
70-130
Precision (c)
%
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Method
Detection Limit (d)
(mg/kgm)
1000
1000
10
0.1
0.2
0.4
0.7
0.6
0.7
5
0.2
O.I
2
0.2
0.7
0.2
0.02
0.2
Completeness
%
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
(a) References are to "Methods for Chemical Analysis of Water and Wastes", EPA/600/4-79/020 or "Test Methods for
Evaluating Solid Waste", SW-846. 3rd. Ed.
(b) Determined from MS or MS/MSD analyses for metals, PAHs, and PCBs; others determined from
laboratory control samples.
(c) Determined as relative percent standard deviation of triplicate analyses, except PAHs and PCBs
in treated solids where MS/MSD will be used.
(d) See Footnotes 1 and 2 of Table 2-2
(e) Detection limits based on extraction of 30 gram samples.
z z
o ° O
-------
GLNPO - QAPJP
Section No.: 4_
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 4
4.0 SAMPLE TRANSFER AND PREPARATION PROCEDURES
As described in Section 2, SAIC will receive a number of 5 gallon containers of
previously homogenized sediments from the U. S. EPA in Duluth, Minnesota. The number
of containers of each sediment is dependent on the final determination by GLNPO of which
sediments will be tested by the various technologies. Only if smaller portions of sediments
are requested by the vendors will these containers be opened by SAIC. If smaller portions
are required, SAIC will resuspend the solids and water within an individual container by
rolling, tumbling, and stirring of the contents. The final stirring will be in the original
containers using a metal stirrer as would be used to mix a 5 gallon container of paint. The
metal stirrer is appropriate because metals are not the primary constituents of concern in
these treatability tests.
The Chain of Custody Record shown in Figure 4-1 will be completed for each cooler
shipped to the subcontractor or vendor that will conduct the optimization and performance
evaluation tests. The samples obtained from the vendor for analysis will be labeled as
shown in Figure 4-2. The labels will document the sample I.D., time and date of collection,
and the location from where the sample was taken. The amount/type of preservative that
was added will also be recorded.
SAIC personnel will pack and ship the untreated sediment and the end product
samples (residuals) from the optimum conditions test for each technology. The amount of
preservative will be recorded. Samples will be labeled (see Figure 4-2) and shipped by
overnight deliver}' service to the laboratory in coolers containing ice. If "blue ice" is used
in the coolers, samples will be initially cooled with regular ice prior to being packed in the
coolers with blue ice. The Chain of Custody Record (Figure 4-1) will be completed for each
cooler shipped to the laboratory.
95
-------
GLNPO - QAPJP
Section No.: 4_
Revision No.: J_
Date:
Page:
Jan. 9. 1991
2 of 4
Solid, sediment and oil samples require no preservative other than cooling to 4° C.
The appropriate types of containers (solid and liquids), holding times, and preservatives for
water samples are listed in Table 4-1.
TABLE 4-1. Sample Containers, Preservation and Holding Times
Parameter
TOC
Solids (Total,
Volatile &
Suspended
Oil and Grease
Total Cyanide
Container
P.G
P,G
G
P,G
Preservation of Water Samples
Cool
Cool
Cool
Cool
4°
4°
4°
4°
C.
C
C.
C.
H:SO4
H2S04
NaOH
to pH
to pH
to pH
< 2
< 2
> 12
Holding Time
28 days
7 days
28 days
14 davs
Total Phosphorous P,G
P,G
Metals
(except Cr VI)
Cr (VI)
P.G
PAHs & PCBs
BOD5
PH
Conductivity
G teflon
lined cap
P,G
P,G
P,G
0.6g Ascorbic acid
Cool 4° C, H:SO4 to pH <
HNO3 to pH < 2
Cool 4° C
Cool 4° C, store in dark
Cool 4° C
Cool 4° C
28 days
6 months except Hti
(Hg 28 days)
24 hours
Extract within 7 days
Analyze within 40 days
48 hours
Performed immediately
28 davs
96
-------
' Science J»ppllc»l/on»
/nlomallonal Corporation
An Empfci
Chain -of- Custody Record
Dale Page ol
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OBSERVATIONS. COMMENTS.
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-------
GLNPO - QAPjP
Section No.: 4_
Revision No.: j_
Date: Jan. 9. 1991
Page: 4 of 4
635 W. 7th Street, Suite 403, Cincinnati. OH 45203
Sample No.:
Sample Location/Date/Time:
Project Location/No.:
Analysis:
Collection Method: Purge Volume:
Preservative:
Comments:
Collector's Initials
Figure 4-2. Example Sample Label
98
-------
GLNPO - QAPjP
Section No.: 5_
Revision No.: 2
Date: Feb. 15. 1991
Page: 1 of 3
5.0 ANALYTICAL PROCEDURES AND CALIBRATION
Analytical procedures for all critical measurements are referenced in Table 3-1. The
non-critical measurements are for any residual water and oil remaining after the
performance evaluation tests and some additional analyses on the solid samples. The EPA
procedures are specified in Table 5-1.
The required calibration for all analyses are specified in the methods and will be
followed. All instruments will be calibrated as specified in the methods prior to performing
any analysis of the samples. Internal QC checks, including initial calibration and continuing
calibration checks, for the critical measurements are listed in Table 7-1.
Table 5-2 contains the minimum list of the sixteen PAHs that must be determined
by either analytical method. Additional compounds may be included, but none of these
sixteen may be deleted from the target list.
The laboratory is responsible for maintaining a preventive maintenance program
consistent with manufacturers recommendations for all instruments required for this
program. In addition, they are responsible for having a sufficient supply of routine spare
parts necessary for the operation of the analytical equipment in order to complete the
analysis in a timely fashion.
99
-------
GLNPO - QAPjP
Section No.: .5
Revision No.: 2
Dale: Feb. 15. 1991
Page: 2 of 3
TABLE 5-1
Analytical Methods for Critical and Non-critical Measurements
Methods-
Pammeter
Solid
Water
Oil
TOC
Total Solids
Volatile Solids
Oil and Grease
Total Cyanide
Total Phosphorous
Arsenic
Mercury
Selenium
Other Metals
PCBs
PAHs
pH
BOD
Total Suspended Solids
Conductivity
9060
160.3
160.4
9071
9010
365.2
3050/7060
7471
3050/7740
3050/6010
3540 or
3550/8080
3540 or 3550/
8270 or 8lOOb
9045
NA
NA
NA
9060
NA
160.4
413.1
9010
365.2
7060
7470
7740
3010/6010 (7760 Ag)
3510 or
3520/8080
3510 or 3520/
8270 or 8100h
9040
405.1
160.2
9050
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
3580/8080
3580/8270
NA
NA
NA
NA
(a) References are to "Methods for Chemical Analysis of Water and Wastes", EPA/600/4-
79/020 or "Test Methods for Evaluating Solid Waste", SW-846, 3rd. Ed.
(b) Where options for methods are given,-Either is acceptable if the detection limits given
in Table 2-2 can be achieved.
NA - Not analyzed
100
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GLNPO - QAPjP
Section No.: 5_
Revision No.: 2
Date: Feb. 15. 1991
Page: 3 of 3
TABLE 5-2
List of PAHsa
Acenaphthene Chrysene
Acenaphthylene Dibenzo(a,h)anthracene
Anthracene Fluoranthene
Benzo(a)anthracene Fluorene
Benzo(a)pyrene Inden(l,2,3-cd)pyrene
Benzo(b)fluoranthene Naphthalene
Benzo(k)fluoranthene Phenanthrene
Benzo(ghi)perylene Pyrene
PAH analyses must determine these 16 compounds at a minimum.
101
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GLNPO - OAPjP
Section No.: §_
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 1
6.0 DATA REDUCTION, VALIDATION AND REPORTING
Data will be reduced by the procedures specified in the methods and reported by the
laboratory in the units also specified in the methods. The work assignment manager or his
designer will review the results and compare the QC results with those listed in Table 3-1.
Any discrepancies will be discussed with the QA Manager.
Ail data will be reviewed to ensure that the correct codes and units have been
included. All organic and inorganic data for solids will be reported as mg/kgm except TOC,
oil & grease (O&G), moisture and iron that will be reported as percent and pH that will
be reported in standard pH units. All metals and organics in water samples will be reported
as ug/1. TOC, solids (suspended and volatile), O&G, cyanide, phosphorus, and BOD will
be reported as mg/1. Conductivity will be reported as umhos/cm and pH as standard pH
units. After reduction, data will be placed in tables or arrays and reviewed again for
anomalous values. Any inconsistencies discovered will be resolved immediately, if possible.
by seeking clarification from the sample collection personnel responsible for data collection.
and/or the analytical laboratory.
Data Tables in the report will be delivered in hard copy and on discs. The discs will
be either in Lotus files or WordPerfect 5.1 files.
102
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GLNPO - QAPJP
Section No.: _7_
Revision No.: 2
Date: Feb. 15. 1991
Page: 1 of 7
7.0 INTERNAL QUALITY CONTROL CHECKS
The internal QC checks appropriate for the measurement methods to be utilized for
this project are summarized in Table 7-1. These items are taken from the methods and the
QC program outlined in Section 3 of this QAPjP.
For the GLNPO program, the following QC measures and limits are employed:
on-going calibration
checks
method blanks
matrix spikes
replicates
beginning, middle, and end of sample set for metals, pH,
TOC/TIC, total cyanide, and total P
mid-calibration range standard
± 10% limit unless otherwise stated
± 0.1 pH unit for pH
± 10 umhos/cm for conductivity at 25° C
beginning, every 12, and end of sample set for PCBs and
PAHs
mid calibration range standard
± 10% limit
one per sample set for PCBs and PAHs
< MDL limit unless otherwise stated
beginning, middle and end for metals, TOC/TIC, total
P, total cyanide, and pH
beginning, middle and end for conductivity with
acceptance limits of < 1 umho/cm
one per sample set
1 to 1.5 times the estimated concentration of sample
± 15% limit for metals; ± 30% for PCBs and PAHs
triplicate analyses
RSD <, 20% unless otherwise stated
one per sample set
± 0.1 pH unit for pH
± 2 umhos/cm for conductivity
103
-------
GLNPO - QAPJP
Section No.: T_
Revision No.: 2
Date: Feb. IS. 1991
Page: 2 of 7
QC sample - - minimum of one per sample set
(CRM) - ± 20% of known CRM
- ± 0.1 pH unit for pH
- ± 1 umhos/cm for conductivity
surrogate spikes - added to each sample
(PCBs and PAHs only) - ± 30% recovery
The surrogate for PCB analysis is tetrachlorometaxylene and the internal standard is 1,2,3-
trichlorobenzene.
Table 7-2 shows an analytical matrix that will be completed for each technology
tested. For example, consider the case of a bench scale treatability test of (1 kilogram)
Indiana harbor sediment by low temperature stripping. Based on the data presented in
Table 2- la and assuming complete separation and recovery of oil. water, and solid, a 1
kilogram sample of untreated sediment will produce 58 grains of oil, 610 ml of water, and
332 grams of dry treated solids. For the purpose of this program, this sample set consists
of 1 untreated solid, 1 treated solid, and the water and oil generated by the process. Table
7-3 is a completed analytical matrix for this test. Table 7-3 is based on Tables 2-2 and 2-4
and the QC approach described in this QA plan. The analysis of the water sample in this
example is severely limited by the relatively small amount of sample obtained.
Table 7-4 is a matrix summarizing the anticipated samples to be analyzed for this
project. The sets for each technology (see section 2.1) are:
I B.E.S.T.
II ReTec
III Wet Air Oxidation
IV Soil Tech
The Soil Tech process will process treated soils at two distinct points. Therefore,
four treated solids are produced from the two untreated sediments.
104
-------
lAHI.li 7-1. Internal QC Checks for Measurements
o
en
Parameter
Solids
(Total &
Volatile
Oil & Grease
Metals
Metals
PCBs (b)
PAHs
Method (a)
160.3
160.4
f
9071
6010
7000
series
8080
8270 or
8100
Initial
Calibration
Balance
(Yearly)
See Above
2 points
4 points
5 points
5 points
Calibration
Checks
Balance
Each Day
See Above
Every 10th
Sample
Every 10th
Sample
Every 10th
Sample
Every 12
Hours
Method
Blank
Yes
Yes
Yes
Yes
Yes
Yes
MS/MSD
NA
NA
MS only
MS only
Yes (treated)
MS only (untreated)
Yes (treated)
MS only (untreated)
Triplicate
Sample
Analysis
Yes
Yes
Yes
Yes
NA (treated)
Yes (untreated)
NA (treated)
Yes (untreated)
QC
Sample
Yes
Yes
Yes
Yes
Yes
Yes
Surrogate
Spikes
NA
NA
NA
NA
Yes
Yes
(a) References are to "Methods for Chemical Analysis of Water and Wastes", EPA/600/4-79/020
or "Test Methods for Evaluating Solid Waste", SW-846, 3rd. Ed.
(b) Second column confirmation of positive results is required.
NA - Not Applicable
fli
"
O : O
:. >
T3
n
er
-------
TA11LH 7-1. Internal QC Checks for Measurements (continued)
o
o>
Parameter
pli
Conductivity
Cyanide
Phosphorous
TOC/TIC
Method (a)
9045/9040
9050
9010
365.2
9060
Initial
Calibration
2 points
1 point
7 points
9 points
3 points
Calibration
Checks
Every 10th
Sample
Every 15th
Sample
Every 15th
Sample
Every 15th
Sample
Every 15th
Sample
Method
Blank
NA
NA
Yes
Yes
Yes
MS/MSD
NA
NA
NA
NA
NA
Triplicate
Sample
Analysis
NA
NA
NA
NA
NA
QC
Sample
Yes
Yes
Yes
Yes
Yes
Surrogate
Spikes
NA
NA
NA
NA
NA
(a) References are to "Methods for Chemical Analysis of Water and Wastes", EPA/600/4-79/020
or "Test Methods for Evaluating Solid Waste", SW-846, 3rd. Ed.
NA - Not Applicable
o B r
*?
«
-------
Section No.:
Revision No.:
Date:
Page:
15. 1991
5 of 7
^
C
ts
I
r-
107
-------
TABLE 73. Example
o
trimeters
oUl Solids
Moisture)
/olttile Solids
rtettls
Alls
TOC
ToUl Cyinide
ToUl Photphorous
PlL
BOD
ToUl Suspended
Solids
Conductivity
QC Sample
tnd
.fel/iod Blank
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Untreated
Sediment
MS
X
>
l^i
Tripli-
cate
X
Treated
Solids
MS
x
MSD
t*r
X
c*te
Wtter
MS
MSD
'ripli-
ctle
-o D 50
w u o
O B r
B 2
2?;
p : C
-------
TABLE 7-4. Analytical and QC Sample Matrix for GIJNPO Trcalabilily Studies (numbers of samples)
SAMPLE SET
SET I
Untreated S.
Treated S.
Water
Oil
SET IV
Untreated S.
Treated S.
Water
Oil
SET II
Untreated S.
Treated S.
Water
Oil
SETHI
Untreated S.
Treated S.
Water
TOTALS
Solids
Water
Oil
TOC/TIC
() QC(b)
3
3
2
4
1
1
1
1
16
1
-
I
3
2
3
-
5
3
TOTAL
SOLIDS
S QC
3
2
4
1
1
1
1
16
2
3
2
3
2
3
2
20
VOL
SOLIDS
S QC
3
2
4
1
1
1
1
16
1
2
3
2
3
2
3
3
2
20
3
OAO
S QC
3
2
4
1
1
1
I
16
1
2
3
2
3
2
3
3
2
20
3
TOTAL
YANIDE
S QC
3
2
4
1
1
1
1
16
1
-
-
3
3
3
-
6
3
ror/tL
fHOS
S QC
3
2
4
1
1
1
1
16
-
-
3
3
3
-
6
3
METALS
S QC
3
2
4
1
1
1
1
1
16
1
3
3
3
3
3
3
3
3
24
3
PCBs
S QC
3
3
3
2
4
2
2
1
1
1
1
1
16
7
6
2
1
3
3
2
I
3
3
2
2
3
3
2
2
20
6
9
PAH
S QC
3
3
3
2
4
2
2
1
1
I
16
7
6
3
2
1
3
3
2
I
3
3
2
2
3
3
2
2
20
6
9
pH
S QC
3
3
2
4
I
1
1
1
16
1
-
-
3
2
3
-
S
3
BOD
S QC
-
-
1
-
1
-
-
3
-
3
TSS
S QC
-
-
1
-
1
-
-
3
-
3
COND
S QC
-
-
1
-
-
-
3
-
3
r? o so % o
mis
"d
o
" o
:- ^
(a) Number of original simples.
(b) Number of quality control samples. A "3" represent) two additional replicates (triplicate determination) ind spike or control
sample analysis resulting in an additional Ituee QC analyses. A "2' represents matrix spike/matrix spike duplicate analysis
scheme resulting in an additional two QC analyses. A * I * indicates a blank spike or other control sample analysis resulting
in one additional QC analysis.
(c) Treated and untreated solids does not apply, and only one control sample per set will be analyzed.
^J
o
S
-------
GLNPO - QAPjP
Section No.: 8_
Revision No.: 2
Date: Feb. 15. 1991
Page: 1 of 1
8.0 PERFORMANCE AND SYSTEM AUDITS
The laboratory will perform internal reviews by the QA officer or a designee. These
reviews should include, as a minimum, periodic checks on the analysts to assess whether they
are aware of and are implementing the QA requirements specified in the ARCS QA
program.
The laboratory will be prepared to participate in a systems audit to be conducted by
the SAIC QA Officer or his designee and/or ARCS QA Officer.
The vendors of the various technologies have all been advised that a number of
representatives from SAIC. GLNPO. and other organizations will be present during
Phase II of the treatabilit\ studies. Thus the ARCS QA officer can be present during
Phase II of anv or all of the treatabilirv studies.
110
-------
GLNPO - QAPJP
Section No.: 9_
Revision No.: 1
Date: Jan. 9. 199]
Page: 1 of 3
9.0 CALCULATION OF DATA QUALITY INDICATORS
9.1 Accuracy
Accuracy for PAHs, PCB and metals will be determined as the percent recovery of
matrix spike samples. The percent recovery is calculated according to the following
equation:
% R = 100% xC' ~£? _
where
9tR = percent recovery
C, = measured concentration in spiked sample aliquot
C0 = measured concentration in unspiked sample aliquot
C, = actual concentration for spike added
Accuracy for the other critical measurements will be determined from laboratory
control samples according to the equation:
9c R = 1009c i
C,
where
%R = percent recovery
Cm = measured concentration of standard reference material
C, = actual concentration for standard reference material
9.2 Precision
Precision will be determined from the difference of percent recovery values of MS
and MSDs for PAHs and PCBs or triplicate laboratory analyses. The following equations
will be used for all parameters:
111
-------
GLNPO - QAPjP
Section No.: £_
Revision No.: J_
Date:
Page:
Jan. 9. 1991
2 of 3
When 2 values are available:
RpD = [Q - C2] x 100%
[C, + C,]/2
where
RPD = Relative percent difference
Cj = The larger of two observed values
C, = The smaller of the two observed values
When more than 2 values are available:
S =
N
I
i = 1
N
i r x
N i = l
N - 1
where
S = standard deviation
X, = individual measurement result
N = number of measurements
Relative standard deviation may also be reported. If so, it
will be calculated as follows:
RSD = 100
X
112
-------
GLNPO - QAPJP
Section No.: 9_
Revision No.: 1
Date: Jan. 9. 1991
Page: 3 of 3
where
RSD = relative standard deviation, expressed in percent
.S = standard deviation
X = arithmetic mean of replicate measurement.
9.3 Completeness
Completeness will be calculated as the percent of valid data points obtained from the
total number of samples obtained.
% Completeness = VDP x 100
TDP
where
VDP = number of valid data points
TDP = total number of samples obtained.
113
-------
GLNPO - QAPjP
Section No.: 10
Revision No.: 1
Date: Jan. 9. 1991
1 of 2
10.0 CORRECTIVE ACTION
Corrective actions will be initiated whenever quality control limits (e.g., calibration
acceptance criteria) or QA objectives (e.g., precision, as determined by analysis of duplicate
matrix spike samples) for a particular type of critical measurement are not being met.
Corrective actions may result from any of the following functions:
Data Review
Performance evaluation audits
Technical systems audits
Interlaboratory/imerfield comparison studies
All corrective action procedures consist of six elements:
Recognition that a Quality Problem exists
Identification of the cause of the problem
Determination of the appropriate corrective action
Implementation of the corrective action
Verification of the corrective action
Documentation of the corrective action
For these treatabiliry studies after initial recognition of a data quality problem, the
data calculation will be checked first. If an error is found, the data will be recalculated and
no further action will be taken. If no calculation error is found, further investigation will
be conducted. Depending on the cause and the availability of the appropriate samples.
reanalysis or flagging of the original data will be utilized.
114
-------
GLNPO - QAPJP
Section No.: 10
Revision No.: 1
Date: Jan. 9. 1991
Page: 2 of 2
All corrective action initiations, resolutions, etc. will be implemented immediately and
will be reported in Sections One and Two (Difficulties Encountered and Corrective Actions
Taken, respectively) in the existing monthly progress reporting mechanisms established
between SAIC, EPA-RREL, GLNPO, AND THE ARCS QA officer and in the QA section
of the final report. The QA Manager will determine if a correction action has resolved the
QC problem.
115
-------
GLNPO - QAPjP
Section No.: 11
Revision No.: 1
Date: Jan. 9. 1991
Paue: 1 of 1
11.0 QA/QC REPORTS TO MANAGEMENT
This section describes the periodic reporting mechanism, reporting frequencies, and
the final project report which will be used to keep project management personnel informed
of sampling and analytical progress, critical measurement systems performance, identified
problem conditions, corrective actions, and up-to-date results of QA/QC assessments. As
a minimum, the reports will include, when applicable:
Changes to the QA Project Plan, if any.
Limitations or constraints on the applicability of the data, if any.
The status of QA/QC programs, accomplishments and corrective actions.
Assessment of data quality in terms of precision, accuracy, completeness,
method detection limit, representativeness, and comparability.
The final report shall include a separate QA section that summarizes the data
quality indicators that document the QA/QC activities that lend support to
the credibility of the data and the validity of the conclusions.
For convenience, any QA/QC reporting will be incorporated into the already well-
established monthly progress reporting system between SAIC and EPA-RREL for all TESC
Work Assignments. In addition, copies of monthly reports will be sent to the ARCS QA
officer. Any information pertaining to the above-listed categories will be reported under
Sections One through Three (Difficulties Encountered. Corrective Actions Taken, and
Current Activities, respectively) in the monthly reports.
116
-------
GLNPO - QAPjP
Section No.: Appendix A
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 3
APPENDIX A
TECHNOLOGY SUMMARIES
117
-------
GLNPO - QAPJP
Section No.: Appendix A
Revision No.: 1
Date: Jan. 9. 1991
Page: 2 of 3
B.E.S.T. Process Description
The B.E.S.T. process is a patented solvent extraction technology utilizing triethylamine
as the solvent. Triethylamine is an aliphatic amine that is produced by reacting ethyl
alcohol and ammonia. The key to success of the B.E.S.T. process is triethylamine's
property of inverse miscibility. At temperatures below 65°F, triethylamine is completely
soluble with water. Above this temperature, triethylamine and water are only partially
miscible. The property of inverse miscibility can be utilized since cold triethylamine can
simultaneously solvate oil and water.
The B.E.S.T. process produces a single phase extraction solution which is a homogeneous
mixture of triethylamine and the water and oil (containing the organic contaminants, such
as PCBs. PNAs, and VOCs) present in the feed material. In cases where the extraction
efficiencies of other solvent extraction systems are hindered by emulsions, which have the
effect of partially occluding the solute (oil containing the organic contaminants),
triethylamine can achieve intimate contact at nearly ambient temperatures and pressures.
This allows the B.E.S.T. process to handle feed mixtures with high water content without
penalty in extraction efficiency. This process is expected to yield solid, water, and oil
residuals.
Low Temperature Stripping
Low-temperature stripping (LTS) is a means to physically separate volatile and semivolatile
contaminants from soil, sediments, sludges, and filter cakes. For wastes containing up to
10% organics or less, LTS can be used alone for site remediation.
LTS is applicable to organic wastes and generally is not used for treating inorganics and
metals. The technology heats contaminated media to temperatures between 200-1000°F,
driving off water and volatile contaminants. Offgases may be burned in an afterburner,
condensed to reduce the volume to be disposed, or captured by carbon adsorption beds.
For these treatability studies, only processes that capture the contaminants driven off will
118
-------
GLNPO - QAPJP
Section No.: Appendix A
Revision No.: 1
Date: Jan. 9. 1991
Page: 3 of 3
be considered. The process (for these treatability studies) is expected to yield solid, water,
and oil residuals.
Wet Air Oxidation
Wet air oxidation is a process that accomplishes an aqueous phase oxidation of organic or
inorganic substances at elevated temperatures and pressures. The usual temperature range
varies from approximately 350 to 600°F (175 to 320°C). System pressures of 300 psig to well
over 300 psig may be required. However, testing has been done at temperatures exceeding
the critical point for water to limit the amount of evaporation of water, depending on the
desired reaction temperature. Compressed air or pure oxygen is the source of oxygen that
serves as the oxidizing agent in the wet air oxidation process. This process is expected to
yield only solid and water residuals.
119
-------
ro
o
SAIC-GLNPO (CF #361)
CONVENTIONALS IN UNTREATED SEDIMENT
ZIMPRO
MSLCode Sponsor ID
MX
361 26/27, Rep 1 I-US-ZP. Rep 1
361-26/27. Rep 2 I-US-ZP. Rep 2
361-26/27. Rep 3 1 US ZP. Rep 3
Method Blank
STANDARD REFERENCE MATERIAL
MESS 1 SRM
In-house Concensus value tt
MATRIX SPIKE RESULTS
Amount Spiked
361-26/27
361-26/27 + Spike
Amount Recovered
% Recovery
REPLICATE ANALYSES
361-26/27, Rep 1 1 US-ZP, Rep 1
361-26/27, Rep 2 I-US-ZP, Rep 2
361-26/27, Rep 3 1 US-ZP, Rep 3
RSD%
% Moisture
001%
54.97
55.12
NA
NA
NA
NA
NA
NA
NA
NA
54.97
NA
NA
NA
% Total
pH Volatile Solid
NA 0 00%
7.67
NA
NA
NA
NA
NA
NA
NA
NA
NA
7.67
NA
NA
NA
14.73
15.28
15.12
NA
NA
NA
NA
NA
NA
NA
14.73
15.28
15.12
2%
Oil & Grease
(mg/kg)
20.0
9811
10016
9851
20 U
NA
17944
9811
12005
2194
12% x
9811
10016
9851
1%
TOC
% weight
0.007
19.25
NA
NA
0.014
2.12
2.3
NA
NA
NA
NA
NA
19.25
NA
NA
NA
Total Cyanide Total Phosphorus
(mg/kg) (mg P/kg)
0.2 0002
223
24.9
NA
0.2 U
NA
343.0
22.3
357.5
335.2
98%
22.3
NA
NA
NA
2919
NA
NA
0.005
NA
4177
4743
9007
4264
102%
2919
NA
NA
NA
NA = Not analyzed
U = Below detection limit
H = Value based on past in-house anulysus ot MfcSS-1. Not statistically dotormined
x = Most likely analyst error and spiko not addud
NOTE: Convenlionals results roportod on dry woiyhl basis.
TJ
TJ
rn
o
x
-------
SAIC GLNPO (CF #361)
CONVENTIONALS IN TREATED SEDIMENT
ZIMPRO
MSLCode Sponsor ID
MTL
361 29. REP 1 I-TS-ZP
361 29, HEP 2 I-TS-ZP
361-29. REP 3 1-1 S ZP
Method Blank
STANDARD REFERENCE MATERIAL
MESS-1 SRM
In-house Concensus value #
MATRIX SPIKE RESULTS
Amount Spiked
361-26/27
361-26/27 + Spike
Amount Recovered
% Recovery
REPLICATE ANALYSES
361-29, Rep 1 I-TS-ZP. REP 1
361-29. Rep 2 I-TS ZP. REP 2
361-29, Rep 3 I-TS-ZP. REP 3
RSD%
% Moisture
001%
43 3
NA
NA
NA
NA
NA
NA
NA
NA
NA
433
NA
NA
NA
% Total
pit Volatile Solid
NA 0 00%
6.51
6.52
NA
NA
NA
NA
NA
NA
NA
NA
6 51
NA
NA
NA
7.78
7.19
7.05
NA
NA
NA
NA
NA
NA
NA
7.78
7.19
7.05
5%
Oil & Grease
(mg/kg)
20 0
1058
1093
702
20 U
NA
17944
9811
12005
2194
12% x
1058
1093
702
23%
TOC
% weight
0 007
9 28
NA
NA
0 014
2.12
23
NA
NA
NA
NA
NA
9.28
NA
NA
hC
Total Cyanide Total Phosphorus
(mg/kg) (mg P/kg)
02 0 002
145
NA
NA
02 U
NA
343.0
22 3
357.5
335.2
98%
14.5
NA
NA
N3
4743
NA
NA
0.005
NA
4177
4743
9007
4264
102%
4743
NA
NA
N3
NA - Not analyzed
U « Below detection limit
# - Value based on past In-house analyses ol MESS-1.
X =» Most likely analyst error and spike not added
NOTE: Conventionals results reported on dry weight basis.
Not statistically determined
-------
SAIC GLNPO (CF »361)
METALS IN UNTREATED SEDIMENT
(Conconlrations In ug/g dry weight)
ZIMPHO
MSLCode Sponsor ID
MDL
36126/27, Rep 1 1 US ZP. Rep 1
361 26/27, Rep 2 1 US ZP. Hop 2
361 26/27. Hop 3 1 US ZP. Rop 3
Method Blank
STANDARD REFERENCE MATERIAL
-4646 SRM
yj
VB)U«
MATRIX SPIKE RESULTS
Amount Spiked
361 26/27 *
361 26/27 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-26/27. Rep 1 1 US ZP. Rop 1
361 26/27, Rep 2 1 US ZP, Rop 2
361 26/27. Rep 3 1 US ZP. Hop 3
RSO%
Ag
AA
0 007
4 78
4 90
4 81
0 20
0 11
NC
2
4 83
7 12
229
115%
4 78
4 90
4 81
1%
As
2 5
21 6
34 6
26 6
NA
1 1 26
11 6
±1 3
NS
NS
NS
NS
NS
21 6
34 6
26 6
24%
Ba
43
282
281
287
NA
387
NC
rC
NS
NS
NS
NS
NS
282
281
287
1%
Cd
AA
0 006
7 71
8 17
7 35
0 006
0 40
0 36
10 07
2
7 74
9 88
2 14
107%
7 71
8 17
7 35
5%
Cr
33
1082
1047
1096
NA
66
76
13
NS
NS
NS
NS
NS
1082
1047
1096
2%
Cu
5 5
267
250
244
NA
21 4
18
±3
NS
NS
NS
NS
NS
267
250
244
ET/o
%Fo
0 26
17 45
17 12
17 22
NA
3 38
3 35
10 1
NS
NS
NS
NS
NS
17 45
17 12
17 22
1%
Hg
CVAA
0 0003
1 385
1 369
1 439
0 00013
0 066
0 063
10 012
1 984
\ 398
3 257
1.859
94%
1 385
t 369
1 439
3%
Ml
Ml
56
1920
1910
1890
NA
345
375
±20
NS
NS
NS
NS
NS
1920
1910
1890
1%
Nl
at
7 5
1 19
1 13
1 12
NA
308
32
13
NS
NS
NS
NS
NS
119
1 13
112
3%
Pb
6 2
764
707
766
NA
27 5
28 2
±1 8
NS
NS
NS
NS
NS
764
707
766
4%
So
AA
0 22
5 38
5 54
5 41
0 22 U
0 74
NC
NC
2 70
5 44
8 44
3
111%
5 38
5 54
5 41
2%
Zn
Xf
7 8
3090
2930
3070
NA
122 4
138
16
NS
NS
NS
NS
NS
309C
293C
307(
3°X
U - Below detection limits
NA - Not analyzed
NC - Not cerlihed
NS - Not spiked
' - Moan ot triplicated sample
x - Sample was inadvertently not spikud
NOTE All metals results aro blank corrected
-------
SAIC GLNPO (CF »36t)
METALS IN TREATED SEDIMENT
(Concentrations In ug/g dry weight)
ZIMPRO
MSL Code Sponsor ID
MX
361 29, Rep 1 I-TS-ZP. Rep 1
361 29. Rep 2 1 TS ZP. Hop 2
361 29, Rep 3 1 TS ZP. Hop 3
Method Blank
1646 SRM
cetllllBd
valua
MATRIX SPIKE RESULTS
Amount Spiked
361 29m
361 29 4 Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-29, Rep 1 I-TS-ZP. Rep 1
361 29. Rep 2 1 TS ZP, Hep 2
361 29, Rep 3 1 TS ZP. Rep 3
RSD%
Ag
AA
0007
697
6 72
704
002
0 12
NO
SC
2
691
563
-1 28
NA x
6 97
6 72
704
2%
As
»F
2 5
202
35 0
32 2
NA
12 1
11 6
±1 3
NS
NS
NS
NS
NS
20 2
35 0
32 2
27%
Ba
43
351
367
387
NA
393
NC
N3
NS
NS
NS
NS
NS
351
367
387
5%
Cd
AA
0006
13.47
12 69
12 80
0006 U
0 41
0 36
±0 07
2
130
153
23
115%
13 47
12 69
12 80
3%
Cr
MT
33
1471
1467
1372
NA
98
76
±3
NS
NS
NS
NS
NS
1471
1467
1372
4%
Cu
55
299
360
392
NA
21 4
18
13
NS
NS
NS
NS
NS
299
360
392
13%
%Fe
0 26
21 6
22 7
23 7
NA
3 39
3 35
±0 1
NS
NS
NS
NS
NS
21 6
22.7
23.7
5%
Hg
CVAA
0 0003
2 286
2 253
2 241
0 00013
0 065
0 063
±0 012
1 967
2 260
4 303
2 043
103%
2 286
2 253
2 241
1%
Ml
Mf
56
2570
2700
2760
NA
323
375
±20
NS
NS
NS
NS
NS
2570
2700
2760
4%
Nl
XHF
7 5
126
150
138
NA
36 1
32
±3
NS
NS
NS
NS
NS
126
ISO
138
9%
Pb
6 2
938
1080
1266
NA
26 8
28 2
11 8
NS
NS
NS
NS
NS
938
1080
1266
15%
Se
AA
0 22
701
6 41
6 59
0 22 U
0 87
NC
rC
2 73
6 67
9 47
28
103%
701
6 41
6.59
5%
Zn
7 8
3720
4260
4890
NA
131 4
138
16
NS
NS
NS
NS
NS
3720
4260
489C
14%
U - Below detection limits
NA - Not analyzed
NC - Not certified.
NS - Not spiked.
* - Mean ol triplicated sample.
x Sample was inadvertently not spikod
NOTE. All metals results are blank corrected
-------
SAIC GLNPO (CF »36()
ZIMPRO
to
PAH IN UNTREATED SEDIMENT
Low Molecular Welghl PAHs (nq/q dry welqhl)
MSL Coda
361-26/27, Rep 1
361 26/27. Rep 2
361 26/27. Rep 3
Method Blank 3
Sponsor ID
I-US-2P. Rep 1
I-US-ZP. Rop 2
I-US-ZP. Rep 3
Naphthalene Acenaphthytone Acenaphlhene
4479 0
4269 D
3749 0
921 CU
3011 0
2975 D
3347 D
987 OJ
4404 D
4214 D
4525 D
1389 (XI
Fluorene Phenanthrene Anthracene
4891 D
4592 D
5120 D
1163 DU
16498 D
14979 D
16191 D
681 OJ
6282 D
6056 D
6955 D
773 DU
STANDARD REFERENCE MATERIAL
SRMNIST1941
carlllled value
364
NC
54 U
NC
60 U
NC
63 U
NC
550
577
164 U
202
MATRIX SPIKE RESULTS
Amount Spiked
361 26/27 «
361-26/27 4 Spike
Amount Recovered
Percent Recovery
4237 D
4172 D
7960 D
3808
90%
4237 D
3111 D
8037 D
4926
116%
4237 D
4381 D
8814 D
4433
105%
4237 D
4868 D
9668 D
4800
1 1 3%
4237 D
15889 0
22250 D
6361
150% '
4237 D
6431 D
12387 D
5956
141%'
REPLICATE ANALYSES
361-26/27. Rep 1
361 26/27, Rep 2
361-26/27, Rep 3
1 US ZP. Rep 1
1 US ZP. Rep 2
I-US-ZP. Rep 3
RSD%
4479 D
4289 D
3749 D
9%
3011 D
2975 D
3347 D
7%
4404 D
4214 D
4525 D
4%
4891 D
4592 D
5120 D
9-/o
16498 0
14979 D
16191 D
95i
6282 D
6056 D
6955 D
7%
D - Samples diluted 110 and re-run
U - Below detection limits
t - Mean ol triplicated samples
NC - Not certified.
- Value outside ol Internal QC limits (40 120%)
-------
ro
en
SAICGINPO (CF *361)
PAH IN UNTREATED SEDIMENT
High Molecular Weighl PAHs (ng/g dry woighl)
ZIMPRO
MSL Code Sponsor ID
361 26/27. Rep 1 I-US-ZP.
361 26/27. Hop 2 1 US ZP.
361 26/27. Hep 3 1 US ZP.
Method Blank- 3
Rep t
Hop 2
Rop 3
Fluor an
thane
32492 D
31816 D
35549 0
446 UJ
Indono Dibonzo
Pyrene Benzo(a) Chrysene Benzo(b) Benzo (k)- Benzo(a)- (1.2.3.c.d) (a.h) Benzo(g.h.l)
anliuacone lluoranlhpne Biioranlhorw pyrene pyrene anthracene ooivlene
32303 D
31993 D
34572 D
465 DU
20662 0
21303 D
22074 D
439 DJ
28641 D
29430 D
29878 D
418 DU
24190 D
25225 D
25514 D
335 DU
15552 D
15889 D
17357 D
275 DU
26124 0
28986 D
27576 D
357 DU
18664 0
19499 D
20438 D
367 DU
6622 D
7985 0
6654 0
360 DU
13355 D
15571 D
14165 D
243 D
STANDARD REFERENCE MATERIAL
SHM NIST1941
c»rllll»d
MATRIX SPIKE RESULTS
Amount Spiked
361 26/27 II
361 26/27 t Spike
Amount Recovered
Percent Racovory
REPLICATE ANALYSES
value
361-26/27, Rep 1 1 US ZP. Rep 1
361 26/27. Rep 2 1 US ZP. Rop 2
361 26/27. Rep 3 1 US ZP, Rep 3
BSD*
1114
1220
4237 D
33286 D
43798 D
10512
248% '
32402 D
31816 D
35549 D
&/.
1034
1080
4237 D
32956 D
41981 0
9025
2U% '
32303 D
31993 D
34572 D
4%
481
550
4237 D
21083 0
29133 D
8051
190% '
20862 D
21303 0
22074 D
3%
703
NC
4237 D
29136 D
36811 0
7676
181% '
28841 D
29430 D
29878 D
2%
766
780
4237 D
24976 D
33607 0
8631
204% '
24190 D
25225 0
25514 D
3%
603
444
4237 D
16266 D
22897 D
6631
157% '
15552 O
15889 D
17357 D
6%
500
670
4237 D
27562 D
35567 D
8005
189% '
26124 D
28986 D
27576 D
5%
498
569
4237 D
19534 D
27151 D
7617
180% *
18664 D
19499 D
20438 D
5%
141
tc
4237 D
10725 D
13977 D
3252
77% | ', .
6622 D
7985 0
6654 D
11%
421
516
4237 D
14364 D
18877 D
4513
107%
13355 D
15571 D
14165 D
8%
D - Samples diluted 1:10 and re run
U - Below detection limits
* - Mean ol triplicated samples.
NC - Not certified.
' - Value outside ol Internal QC limits (40 120%)
-------
SAIC GLNPO (CF »361)
ZIMPRO
PAH IN UNTREATED SEDIMENT
MSLCode
361-26/27,
361 26/27.
361 26/27.
Sponsoi ID
Rep
Rep
Hop
1
2
3
1 US ZP,
I-US-2P.
1 US ZP.
Rep
Rep
Rop
Surrogate Recovery %
D8 Naph-
thalene
1 31%
2 29%
3 21%
010
D'
D'
D-
Acenaph-
thalene
65%
61%
61%
D12 Perylene
D
D
D
112%
1 08%
110%
D
D
D
Method Blank 3
STANDARD REFERENCE MATERIAL
SRM NIST1941
25% D'
28% '
24% D'
47%
90% D
74%
to
MATRIX SPIKE RESULTS
Amount Spiked
361 26/27 I
361-26/27 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361 26/27, Rep 1
361-26/27. Rop 2
361 26/27, Rep 3
I US ZP. Hep 1
I US ZP. Rop 2
I US ZP. Hep 3
RSD%
D - Samples diluted 1 10 and re-run
» > Mean ol triplicated samples
NC - Not certified
- Value outside ol Internal QC limits (40 120%)
NA - Not applicable
NA
27% D-
37% D '
NA
NA
NA
62% D
72% D
NA
NA
NA
110% D
112% D
NA
NA
31% D'
29% D'
21% D'
20%
65% D
61% D
61% D
4%
112% D
108% 0
110% D
2%
-------
SAICGUNPO (CF »361)
ZIMPRO
to
PAH IN TREATED SEDIMENT
Low Molecular Weight PAHs (ng/q dry weigh!)
MSL Code Sponsor ID
361 29 R I-TS ZP
Method Blank R
STANDARD REFERENCE MATERIAL
SHMNIST1941
c»rtlll»d v«lu*
MATRIX SPIKE RESULTS
Amount Spiked
361 29 R
361 29 + Spike
Amount Rocoveied
Percent Recoveiy
Amounl Spiked
361 29 R
361 29 + Spike DUP
Amounl Recovered
Percent Recovery
Naphthalene Acenaphlhylene Aconaphlhene
30
1 1
364
NC
3049
30
1931
1902
62%
3623
30
1063
1034
29% '
145 U
11 U
54 U
rC
3049
145 U
2139
2139
70%
3623
145 U
1418
1418
39% *
22 U
16 U
60 U
NC
3049
22 U
2376
2376
78%
3623
22 U
1588
1588
44%
Fluotene Phenanlhrene
18 U
13 U
63U
NC
3049
18 U
2628
2628
86%
3623
IB U
2194
2194
61%
174
9
550
577
3049
174
3074
2899
95%
3623
174
3260
3086
85%
Anlhracone
39
9 U
164 U
202
3049
39
2322
2282
75%
3623
39
2295
2256
62%
R - Re extracted sample results
U - Below detection limits
NC - Not collided
* . Value outside of Internal QC limits (40 120%)
-------
SAICGLNPO(CF »361)
PAH IN TREATED SEDIMENT
High Molecular Welghl PAHs (nqfr dry weighl)
ZIMPRO
MSL Code Sponsor ID
361-29 R I-TS-2P
Method Blank R
Indeno
Fluoran- Pyrene Benzo(a)- Chrysene Beruo(b) Benzo(k)- Benzo(a)- (1.2,3.c.d) Diberuo(a.h)- Benzo(g.h,l)-
Ihune anthracene Huoranlhone lluoranlhene pyrene pyrene anthracene perylene
114 181 241 840 286 4U 273 116 168 189
9 9 SUS 6 5 5 5 4U 6
STANDARD REFERENCE MATERIAL
SHMNIST1941
ro
00
ccrtlllid vilu*
1114
1220
1034
1080
MATRIX SPIKE RESULTS
Amount Spiked
361 29 R
361 29 t Spike
Amount Recovered
Percent Recovery
Amount Spiked
361 29 R
361 29 + Spike DUP
Amount Recovered
Percent Recovery
R > Re-extracted sample results.
U - Below detection limits
NC - Not certilied.
* - Value outside ol Internal QC limits (40 120%)
481
550
703
766
780
498
569
141
421
516
3049
1 14
3031
29)8
96%
3623
1 14
3436
3322
92%
3049
181
3060
2879
94%
3623
181
3459
3278
90%
3049
241
3265
3024
99%
3623
241
3541
3300
91%
3049
840
3283
2443
80%
3623
840
3499
2659
73%
3049
286
2785
2499
82%
3623
286
3220
2934
81%
3049
4 U
2351
2351
77%
3623
4 U
2853
2853
79%
3049
273
2205
1932
63%
3623
273
3092
2820
78%
3049
1 16
2755
2640
87%
3623
116
2931
2816
78%
3049
168
381 1
3643
119%
3623
168
3944
3776
104%
3049
189
2846
2658
87%
3623
189
2942
2753
76%
-------
SAICGLNPO (CF »361)
ZIMPRO
PAH IN TREATED SEDIMENT
MSLCode
Sponsor ID
Surrogate Recovery %
D8 Naph- DtO Acenaph- D12 Perylene
thalene thalene
361-29 R I-TS ZP
Method Blank H
STANDARD REFERENCE MATERIAL
23% '
51%
34%"
62%
76%
72%
SRM NIST1941
28%
47%
74%
10
MATRIX SPIKE RESULTS
Amount Spiked
361 29 R
361 29 + Spike
Amount Recovered
Percenl Recovery
Amount Spiked
361 29 R
361 29 + Spike DUP
Amount Recovered
Percent Recovery
R - Re extracted sample results
* - Values outside ol Internal QC limits (40-120%)
NA - Not applicable
MA
23% '
30% '
NA
NA
NA
23% '
25% '
NA
NA
NA
34% '
66%
NA
NA
NA
34% '
41%
NA
NA
NA
76%
64%
NA
NA
NA
76%
73%
NA
NA
-------
SAICGLNPO (CF #361)
PAH IN WATER
ZIMPRO
Low Molecular Weight PAHs (ng/l)
CO
O
MSI Code Sponsor 10
361-30 I-WR-ZP
Method Blank 7
MATRIX SPIKE RESULTS
Amount Spiked
361-30
361 30* Spike
Amount Recovered
Percent Recovery
Amount Spiked
Blank 7
Blank 7 + Spike
Amount Recovered
Percent Recovery
Naphthalene Acenaphlhylene Acenaphlhene
956
266 U
25000
956
5987
5031
20% '
25000
266 U
8947
8947
36% '
152 U
275 U
2SOOO
152 U
8313
8313
33% '
25000
275 U
10024
10024
40%
218 U
395 U
25000
218 U
7027
7027
28% '
25000
395 U
10259
10259
41%
Fluorene Phenanlhrene Anthracene
192 U
348 U
25000
192 U
12931
12931
52%
25000
348 U
11685
11685
47%
1037
230 U
25000
1037
20485
19448
78%
25000
230 U
15262
15032
60%
142U
258 U
25000
142U
14663
14663
59%
25000
258 U
16941
16941
68%
U - Below detection limits
- Value outside ol internal QC limits (40 120%)
-------
SAIC GLNPO (CF *361)
PAH IN WATER
High Molecular Weigh! PAHs (ng/l)
ZIMPRO
MSL Code Sponsor ID
361-30 1 WH ZP
Method Blank- 7
MATRIX SPIKE RESULTS
Amount Spiked
361 30 I-WR-ZP
361 -30 f Spike
Amount Rocovoied
Percent Recovery
Amount Spiked
Blank 7
Blank 7 + Spike
Amount Recovered
Pel cent Recovery
Fluoran-
Ihune
162
175 U
25000
162
23080
22910
92%
25000
175 U
22732
22732
91%
Pyrena Beruo(a)
anthracene
137
181 U
25000
137
22094
21957
88%
25000
181 U
22303
22303
89%
98 U
177 U
25000
98 U
23216
23216
93%
25000
177 U
27433
27433
110%
Chrysene Bonzofb) Benzo (k)-
fluoranlhone rluoranlhene
95 U
171 U
25000
95 U
22754
22754
91%
25000
171 U
24443
24443
98%
70 U
127 U
25000
70 U
22338
22338
89%
25000
127 U
24350
24350
97%
61 U
11 1 U
25000
61 U
20690
20690
83%
25000
111 U
22597
22597
90%
Indent)
Bonzo(a) (1.2.3.c.d) Diberao(a.h)- Beruo(g.h.i)
pyrene pyrene anthracene oeivlone
79 U
143 U
25000
79 U
15479
15479
62%
25000
143 U
23230
23230
93%
72 U
131 U
25000
72 U
20532
20532
82%
25000
131 U
23647
23647
95%
92 U
166 U
25000
92 U
26638
26638
107%
25000
166 U
30175
30175
121% '
70 U
142
25000
70 U
1S953
18953
76%
25000
142
22117
2197S
88%
U - Below detection limits
- Value outside ol Internal QC limits (40-120%)
-------
SAIC GLNPO (CF »361)
PAH IN WATER
ZIMPRO
MSLCode Sponsor 10
Surrogate Recovery %
D8 Naph-
thalene
361-30 1 WR-ZP 35%
Method Blank 7 16%
DID Aconaph-
thalene
47%
18% '
012 Perylene
58%
80%
CO
ro
MATRIX SPIKE RESULTS
Amount Spiked
361 30
361 30* Spike
Amount Recovered
Percent Recovery
Amount Spiked
Blank 7
Blank-7 + Spike
Amount Recovered
Percent Recovery
' - Value outsldo ol Internal QC limits (40 120%)
NA . Not applicable
NA
35% '
20% *
NA
NA
NA
16%
22% '
NA
NA
NA
47%
27%
NA
NA
NA
18% '
27%'
NA
NA
NA
58%
60%
NA
NA
NA
80%
80%
NA
NA
-------
co
CO
RE-PROCESSED RESULTS (1/92)
PCDi IN UNTREATED SEDIMENT
Conconlrollons In un/kn dry wolghl
ZIMPRO
SAIC-GLNPO (CF II3G1)
2/12/92
% Surrogate rtocovory
MSLCoda
361-26/27. Rep 1 D
361-26/27. Rep 2 D
361-26/27. Rep 3 D
Blank-6
Sponsor ID
I-US-ZP. Rop 1
I-US-ZP. (tap 2
I-US-ZP. Hop 3
Aroclor
1242
2000 U
2000 U
2000 U
200 U
Aroclor Aroclor Aroclor
1240 1254 1260
9470 D 1000 U 1000 U
9GOO D 1000 U 1000 U
1 1300 D 3106 D 1000 U
200 U 100 U 100 U
Tolrachloro- Oclachloro-
m-Xylone naphthalene
84.0% 91 6%
01 4% 73 0%
80.9% B9 4%
53.0% 02.1%
STANDARD REFERENCE MATERIAL
SRM 5 (US 2)
MATRIX 8PIKE RESULTS
Amount Splkod
361-26/27 *
361-26/27 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
381-26/27. Rep 1 D
381-26/27, Hop 2 D
361-26/27. Rop 3 D
certified value
I-US-ZP, Rop 1
l-US ZP, Rop 2
I-US-ZP. Hop 3
RSDV.
100 U
N3
MS
NS
NS
N3
NS
2000 U
2000 U
2000 U
0%
100 U G9 50 U
he 111 itf;
NS 4237 NS
hS 3106 D NS
NS 6019 NS
NS 3633 NS
NS 06% NS
67 6% 96 2%
N3 N3
NA NA
021% 04.7%
07.3% 91.5%
NA NA
NA NA
0470 D 1000 U 1000 U 04.0% 01.6%
0000 D 1000 U 1000 U 01.4% 73.0%
11300 D 3100 D 1000 U 00.0% 00.4%
10% 73% 0% 2% 12%
D Samples diluted 1:10 and ro-run.
U Below detection limits.
- Value outside ol Inlornal QC limits (40-120%).
NC - Not corllllod.
II - Moon ol ropllcDlod onmplo.
NS - Not aplkod NA - Not applicable.
-------
RE-PROCESSED RESULTS (1/92)
PCBs IN TREATED SEDIMENT
Concentrations In uq/kg dry weight
ZIMPRO
SAIC-GLNPO (CF #361)
2/12/92
% Surrogate Recovery
MSL Coda Sponsor ID
381-20 I-TS-ZP
BLANK-8
STANDARD REFERENCE MATERIAL
SRM-S (H3-2)
certified voluo
MATRIX SPIKE RESULTS
Amount Spiked
361-29
361-29 + Spike
Amount Recovered
Percent Recovery
Amount Splkod
361-29 DUP
361-29 + Spike DUP
Amount Recovered
Percent Recovery
Aroclor
1242
200 U
200 U
100 U
1C
NS
he
NS
NS
NS
NS
he
NS
NS
NS
Aroclor Aroclor Aroclor
12-18 1254 1200
4008 3555 100 U
200 U 100 U 100 U
100 U 00 50 U
N3 111 rC
NS 3876 NS
NS 3555 NS
NS 7630 NS
NS 4075 NS
NS 105% NS
NS 3049 NS
NS 3555 NS
NS 4052 NS
NS 1207 NS
NS 43% NS
Tolrachloro- Oclachloro-
m-Xylono naphlholono
87.1% 73.1%
53.9% 821%
87.6% 00.2%
N3 NO
NA NA
67.1% 73.1%
61 .6% 93.0%
NA NA
NA NA
NA NA
67.1% 73.1%
03.0% 57.7%
NA NA
NA NA
U - Below detection limits.
* - Value oulsldo of Internal QC limits (40-120%).
NC - Nol corllllod.
NS - Nol eplked. NA - Not applicable.
-------
RE-PROCESSED RESULTS (1/92)
PCBi IN WATER SAMPLES
Concentrations In ug/L
ZIMPRO
SAIC-GLNPO (CF #361)
2/12/92
% Surrogate Recovery
MSLCode Sponsor ID
381-30 I-WR-ZP
Blank-7
MATRIX SPIKE RESULTS
Amount Spiked
361-30
381-30 + Spike
Amount Recovered
Percent Recovery
Aroclor
1242
0.2 U
0.2 U
NS
NS
NS
NS
NS
Aroclor Aroclor Aroclor
1240 1254 1260
0.2 U 0.1 U 0.1 U
0.2 U 0.1 U 0.1 U
NS 25 NS
NS 0.1 U NS
NS 21 NS
NS 21 NS
NS 0-1% NS
Telrachloro- Oclachloro-
m-Xylone nophlhalono
85.8% 900%
20 2% * 90 0%
NA NA
85.8% 90.0%
67.4% 77.8%
NA NA
NA NA
U » Betow detection limits.
* > Value outside ol Internal QC limits (40-120%).
NC - Not certified.
NS - Nol spiked. NA » Not applicable.
-------
Appendix E
QUALITY ASSURANCE/QUALITY CONTROL
In order to obtain data of known quality to be used in evaluating the different technologies for
the different sediments, a Quality Assurance Project Plan (QAPP) was prepared. The QAPP specified
the guidelines to be used to ensure that each measurement system was in control. In order to show
the effectiveness of the different technologies, the following measurements were identified in the QAPP
as critical - PAHs, PCBs, metals, total solids, oil and grease and volatile solids in the untreated and
treated sediments. Other parameters analyzed in the sediments included pH, TOO, total cyanide, and
total phosphorus. If water and oil residuals were generated by a technology, then polynuclear aromatic
hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined as a check on their fate
resulting from in treating the sediments. Each of these measurements and the associated quality
control (QC) data will be discussed in this section. It should be noted that the ZIMPRO technology
developers do not claim that the process will remove PCBs. Therefore PCB analysis is not critical in
demonstrating the effectiveness of this technology.
Also included in this section are a discussion of the QC results, modifications and deviations
from the QAPP, and the results of a laboratory audit performed. Any possible effects of deviations or
audit findings on data quality are presented.
Attached to this appendix is an abridged version of the Data Verification report completed by
the ARCS Program QA Officer. Copies of the entire Data Verification report are available from GLNPO.
PROCEDURES USED FOR ASSESSING DATA QUALITY
The indicators used to assess the quality of the data generated for this project are accuracy,
precision, completeness, representativeness, and comparability. All indicators will be discussed
generally in this section; specific results for accuracy and precision are summarized in later sections.
Accuracy
Accuracy is the degree of agreement of a measured value with the true or expected value.
Accuracy for this project will be expressed as a percent recovery (%R).
Accuracy was determined during this project using matrix spikes (MS) and/or standard
reference materials (SRMs). Matrix spikes are aliquots of sample spiked with a known concentration of
136
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target analyte(s) used to document the accuracy of a method in a given sample matrix. For matrix
spikes, recovery is calculated as follows:
where: C, = measured concentration in spiked sample aliquot
C0 = measured concentration in unspiked sample aliquot
C, = actual concentration of spike added
An SRM is a known matrix spiked with representative target analytes used to document laboratory
performance. For SRMs, recovery is calculated as follows:
%R = °m x 100
where: Cm = measured concentration of SRM
C, = actual concentration of SRM
In addition, for the organic analyses, surrogates were added to all samples and blanks to
monitor extraction efficiencies. Surrogates are compounds which are similar to target analytes in
chemical composition and behavior. Surrogate recoveries will be calculated as shown above for SRMs.
Precision
Precision is the agreement among a set of replicate measurements without assumption of
knowledge of the true value. When the number of replicates is two, precision is determined using the
relative percent difference (RPD):
RPD=
where: C, = the larger of two observed values
C2 = the smaller of two observed values
137
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When the number of replicates is three or greater, precision is determined using the relative standard
deviation (RSD):
RSD= S x 100
where: S = standard deviation of replicates
X = mean of replicates
Precision was determined during this project using triplicate analyses for those samples
suspected to be high in target analytes (i.e., untreated sediments). Matrix spike and matrix spike
duplicate (MSD) analyses were performed on those samples suspected to be low in target analytes
(i.e., treated sediments). A MSD is a second spiked sample aliquot with a known concentration of
target analyte used to document accuracy and precision in a given sample matrix.
Completeness
Completeness is a measure of the amount of valid data produced compared to the total amount
of data planned for the project. For the ZIMPRO treatability studies, no samples were lost due to field
or analytical problems. Though all guidelines for QA objectives were not met, all data generated was
deemed useable.
Representativeness
Representativeness refers to the degree with which analytical results accurately and precisely
represent actual conditions present at locations chosen for sample collection. Sediment samples were
collected prior to this demonstration and were reported to be representative of the areas to be
remediated. Samples of untreated and treated sediment and residuals were taken by SAIC personnel
during Phase II of these tests. Samples were shipped under chain-of-custody to Battelle Marine
Sciences Laboratory in Sequim, Washington. Therefore, the data is representative of material actually
treated.
Comparability
Comparability expresses the extent with which one data set can be compared to another. As
will be discussed in more detail in the section Modifications and Deviations From the QAPP, the data
generated are comparable within this project and within other projects conducted for the ARCS
138
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Program. However, because specialized procedures were used in some instances, the data may not
be directly comparable to projects outside the ARCS Program.
ANALYTICAL QUALITY CONTROL
The following sections summarize and discuss analytical procedures and the results of the QC
indicators of accuracy and precision for each measurement parameter for the ZIMPRO technology
evaluation.
PAHs
PAH Procedures
Sediments and waters were extracted and analyzed using modified SW-846 procedures as
described in the section Modifications and Deviations From the QAPP. Three isotopically-labelled PAH
surrogates were added to all samples and blanks prior to extraction. Daily mass tuning was performed
using decafluorotriphenylphosphine (DFTPP) to meet the criteria specified in Method 8270. The
instrument was calibrated at five levels for the sixteen PAHs. The RSD of the response factors for
each PAH was required to be <25 percent. Calibrations were verified every 12 hours for each PAH;
criteria for % difference from the initial calibration was <25 percent for each PAH. An internal standard,
hexamethyl benzene, was added prior to cleanup and was used to correct PAH concentrations for loss
during cleanup and extract matrix effects. Quantification was performed using Selective Ion Monitoring
(SIM).
PAH QC Results and Discussion
Surrogate recoveries for all PAH samples for the ZIMPRO demonstration are summarized in
Table QA-1. If more than one of the three surrogates fell outside the control limits used, corrective
action (reanalysis) was necessary. (This criteria was not applied by Battelle to method blanks.)
Surrogate recoveries were generally low for samples and method blanks, indicating a possible
analytical problem rather than matrix effects. An investigation indicated possible problems with the
evaporator used to concentrate the extracts. In summary, low surrogate recoveries indicate that PAH
target concentrations may be biased somewhat low. Since both the untreated and treated sediments
were affected similarly, relative removal percentages should be valid.
It should also be noted that surrogate recoveries for both the initial analysis and the re-
extracted analysis for the treated solid (I-TS-ZP) did not meet acceptance criteria.
As required by the QAPP, triplicate analyses of the Indiana Harbor untreated sediment (I-US-
ZP) were performed to assess precision. These results are summarized in Table QA-2. A matrix spike
139
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TABLE QA-1. PAH SURROGATE RECOVERIES
d8-Naphthalene
Sample (%)
I-US-ZP
I-US-ZP
I-US-ZP
Method Blank
I-TS-ZP (Re-extract)
Method Blank
I-WR-ZP
Method Blank
31*
29*
21*
25*
23*
51
35*
16*
dIO-Acenaphthalene d12-Perylene
(%) (%)
65
61
61
24*
34*
62
47
18*
112
108
110
90
76
72
58
80
Control Limits
(%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
* Outside Control Limits
was performed on this same sample to assess accuracy. These results are included in Table QA-2.
All RSDs fell within the control limits specified. Several matrix spike recoveries fell outside control limits
due to inappropriate spiking levels. For several compounds, the spiking level was between 10 and 30
percent of the sample concentration. Recoveries for these compounds may not be indicative of actual
matrix interferences.
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MD) analysis was
performed for the treated Indiana Harbor sediment (I-TS-ZP). These results are presented in Table
QA-3. Recoveries were generally acceptable. RPDs for the lighter compounds were outside the
guidelines specified in the QAPP. As minimal or none of these compounds were present in the sample,
project results should not be affected.
A matrix spike analysis was performed on the Indiana Harbor water residual (I-WR-ZP). These
results are summarized in Tables QA-4.
One certified National Institute of Science and Technology (MIST) standard reference material
(SRM) was extracted and analyzed with the sediment samples. The recoveries for this standard are
summarized in Table QA-5.
Method blanks were extracted and analyzed with each set of samples extracted. Minimal
quantities of several PAHs were found in all three PAH method blanks; total concentrations are
140
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TABLE QA-2. PAH REPLICATE AND SPIKE RESULTS FOR I-US-ZP
Compound
Naphthalene
Acoriaphthylene
Acenaphthene
Fluor ene
Phenanthrene
Anthracene
Fluoianthene
Pyrene
Boi i/o(a)anthracene
Chiysene
Bonzo(b)1luoranthene
Bi -n/o(k)f luoranthene
Beii7o(a)pyrene
lnd'3no(1 ,2,3,c,d)pyrene
Dibenzo(a,h)anthracene
Bon7O(g,h,i)perylene
* Outside Control Limits
(1) Spiking level ranged from
Replicate 1
dry ppb
4480
3010
4400
4890
16500
6280
32500
32300
20900
28800
24200
15600
26100
18700
6620
13400
1 0 to 30 percent
Replicate
dry ppb
4290
2980
4210
4590
15000
6060
31800
32000
21300
29400
25200
15900
29000
19500
7980
15600
of sample
2 Replicate 3
dry ppb
3750
3350
4520
5120
16200
6960
35500
34600
22100
29900
25500
17400
27600
20400
6650
14200
concentration.
Mean
4170
3110
4380
4870
15900
6430
33300
33000
21100
29100
25000
16300
27600
19500
7090
14400
RSD
(%)
9
7
4
5
5
7
6
4
3
2
3
6
5
5
11
8
Precision
Control
Limits (%)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Recovery
(%)
90
116
105
113
150*{1)
141*
248*(1)
213*(1)
190*(1)
181*(1)
204*(1)
157*(1)
189*(1)
180*(1)
163*
107
Accuracy
Control Limits
(%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
-------
TABLE QA-3. PAH MS/MSD RESULTS FOR I-TS-ZP
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranathene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
MS
Recovery
(%)
62
70
78
86
95
75
96
94
99
80
82
77
63
87
119
87
MSD
Recovery
(%)
29*
39*
44
61
85
62
92
90
91
73
81
79
78
78
104
76
RPD
73*
57*
56*
34*
11
19
4
4
8
9
1
3
21*
11
13
13
Accuracy
Control
Limits (%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
Precision
Control Limits
(%)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Outside Control Limits
TABLE QA-4. PAH MS RESULTS FOR I-WR-ZP
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a) anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,0,00 pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
MS Recovery (%)
20
33
28
52
78
59
92
88
93
91
89
83
62
82
107
76
Control Limits (%)
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
142
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TABLE QA-5. PAH SRM RESULTS
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluor anthene
Pyrene
Benzo(a) anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Recovery (%)
NC
NC
NC
NC
95
NR
91
96
87
NC
98
136*
75*
88
NC
82
Control Limits (%)
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
NC = Not Certified
* = Outside Control Limits
NR = Not Recovered- certified value near detection limit.
unaffected. No corrections were performed for method blanks as no consistent significant contamina-
tion problems were observed.
PCBs
PCB Procedures
Sediments and waters were extracted and analyzed using modified SW-846 procedures as
described in the section Modifications and Deviations From The QAPP. Two surrogates, tetrachloro-m-
xylene and octachloronaphthalene, were added to all samples and blanks prior to extraction. The gas
chromatograph (GC) employed electron capture detection (ECD) and was calibrated at three levels for
each of four Aroclors (1242, 1248, 1254, 1260). The RSD of the response factors for each Aroclor was
required to be <25 percent. Calibrations were verified after every ten samples; criteria for percent
143
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difference from the initial calibration was <25 percent. An internal standard, dibromooctafluorobiphenyl,
was added prior to cleanup and was used to correct PCB concentrations for loss during cleanup and
extract matrix effects.
Quantification of Aroclors was performed on two columns (DB-5, primary and 608, confirmation) as a
confirmation of their presence.
PCB QC Results and Discussion
Surrogate recoveries for all PCB samples for the ZIMPRO demonstration are summarized in
Table QA-6. If both recoveries fell outside the control limits used, correction action (reanalysis) was
necessary. All samples were acceptable with respect to the surrogate criteria used.
TABLE QA-6. PCB SURROGATE RECOVERIES
Sample
I-US-ZP Rep.1
I-US-ZP Rep.2
I-US-ZP Rep.3
Method Blank
I-TS-ZP
Method Blank
I-WR-ZP
Method Blank
Tetrachloro-m-xylene
(%)
84
81
81
54
67
54
86
20
Octachloronaphthalene
(%)
92
73
89
82
73
82
90
90
Control Limits
(%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
« = Outside Control Limits
NC = Not Certified
NR = Not recovered - certified value near detection limit.
As required by the QAPP, triplicate analyses of the Indiana Harbor untreated sediment (I-US-
ZP) were performed to assess precision. These results are summarized in Table QA-7. A matrix spike
using Aroclor 1254 was performed on the same sample to assess accuracy; these results are included
in Table QA-7. The RSD and recovery for individual Aroclors are both within control limits. The RSD
for total PCBs is 25 percent.
144
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TABLE QA-7. PCB REPLICATE AND SPIKE RESULTS FOR I-US-ZP
en
Replicate 1 ppb Replicate 2 ppb Replicate 3 ppb RSD
Aroclor dry . dry dry Mean (%)
1242 2000 U 2000 U 2000 U 2000 U NC
1248 9470 9680 11300 10200 10
1254 1000 U 1000 U 3190 NC NC
1260 1000 U 1000 U 1000 U 1000 U NC
U = Undetected
* = Outside Control Limits
NC Not Calculated
NS Not Spiked
TABLE QA-6. PCB MS/MSD RESULTS FOR
MS Recovery MSD Recovery
PCI! (%) (%) RPD
Aroclor 1254 105 43 84*
Precision Accuracy Control
Guideline Limits Recovery Limits (%)
(%) (%)
20 NS 40-120
20 NS 40-120
20 86 40-120
20 NS 40-120
I-TS-ZP
Accuracy Control Limits Precision Guideline Limits
(%) (%)
40-120 20
U Undetected
* Outside Control Limits
NC Not Calculated
NS Not Spiked
-------
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MSD) analysis was
performed for the treated Indiana Harbor sediment combustor solids (I-TS-ZP). These results are
presented in Table QA-8. Matrix spike recoveries were within guidelines but the RPO was not. No
explanation was determined. As PCBs were not critical to meeting project objectives, no reanalyses
were performed.
A matrix spike analysis was performed on the Indiana Harbor water residual (I-WR-ZP). These
results are summarized in Table QA-9.
One standard reference material (SRM) certified by the National Research Council of Canada
(NRCC) for Aroclor 1254 was extracted and analyzed with the sediment samples. A recovery of 62%
was obtained.
Method blanks were extracted and analyzed with each set of samples extracted. No PCBs were
found in any method blanks.
TABLE QA-9. PCB MS RESULT FOR I-WR-ZP
MS Recovery Control Limits
PCB (%) (%)
Aroclor 1254 84 Not Specified
METALS
Metals Procedure
Sediments were prepared for metals analysis by freeze-drying, blending, and grinding.
Sediments for Ag, Cd, Hg, and Se were digested using nitric and hydrofluoric acids. The
digestates were analyzed for Ag, Cd, and Se by graphite furnace atomic absorption (GFAA) by SW-846
Method 7000 series using Zeeman background correction. The digestates were analyzed for mercury
by cold vapor AA (CVAA) using SW-846 Method 7470.
Sediments for As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were analyzed by energy-diffusive X-Ray
fluorescence (XRF) following the method of Sanders (1987). The XRF analysis was performed on a
0.5 g aliquot of dried, ground sediment pressed into a pellet with a diameter of 2 cm.
146
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Metals QC Results and Discussion
Triplicate analyses of the Indiana Harbor untreated sediment (I-US-ZP) and treated sediment
(I-TS-2P) were performed to assess precision. Matrix spikes were analyzed for the same samples to
assess accuracy. Results are summarized in Tables QA-10 and QA-11. It should be noted that the
sediments were not spiked for XRF analysis as spiking is not appropriate for that analysis.
Accuracy and precision results for metals were acceptable with only a few minor exceptions, as
shown in Tables QA-10 and QA-11. RSD results outside limits are due to concentrations near the
analytical detection limits. These exceptions have little, if any, impact on data quality and project
results.
One NIST certified standard reference material (SRM) was digested and analyzed twice with
the sediment samples for XRF, GFAA, and CVAA analyses. These results are presented in Table QA-
12.
Method blanks were digested and analyzed for the metals analyzed by GFAA and CVAA.
(Method blanks are not applicable to XRF analysis). If analyte was detected in the method blank, blank
correction was performed. Minimal amounts of some metals were detected; data quality is not affected.
OIL AND GREASE
Oil and Grease Procedures
Sediment samples were extracted with freon using Soxhlet extraction according to SW-846
Method 9071. The extract was analyzed for oil and grease by infra-red (IR) as outlined in Method
418.1 (Methods for Chemical Analysis of Water and Wastes, 1983).
Oil and Grease QC Results and Discussion
Both the untreated and treated Indiana Harbor sediment (I-US-ZP and I-TS-ZP) were analyzed
for oil and grease in triplicate. In addition, a matrix spike was performed for I-US-ZP. Results are
presented in Table QA-13. As indicated, I-US-ZP was probably not spiked due to laboratory error. The
RSD for I-TS-ZP was outside control limits; removal efficiencies may be affected minimally.
147
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TABLE QA-10. METALS REPLICATE AND SPIKE RESULTS FOR I-US-ZP
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe{1)
Hg
Mn
Ni
Pb
So
Zn
Method
GFAA
XRF
XRF
GFAA
XRF
XRF
XRF
CVAA
XRF
XRF
XRF
GFAA
XRF
Replicate 1 .
ppm dry
4.78
21.6
282
7.71
1080
267
17.4
1.38
1920
119
764
5.38
3090
Replicate 2,
ppm dry
4.90
34.6
281
8.17
1050
250
17.1
1.37
1910
113
707
5.54
2930
Replicate 3,
ppm dry
4.81
26.6
287
7.35
1100
244
17.2
1.44
1890
112
766
5.41
3070
Mean
4.83
30.9
283
7.74
1080
254
17.3
1 40
1910
115
746
544
3030
RSD
1
24*
1
5
2
5
1
3
1
3
4
2
3
Precision
Control Limits
20
20
20
20
20
20
20
20
20
20
20
20
20
Recovery
115
NS
NS
107
NS
NS
NS
103
NS
NS
NS
111
NS
Accuracy
Control Limits
85-115
85-115
85-115
85-115
NS - Not Spiked
* Outside Control Limits
(1) - Results in Percent for Fe
-------
TABLE QA-11. METALS REPLICATE AND SPIKE RESULTS FOR I-TS-ZP
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe(1)
Hg
Mn
Ni
Pb
Se
Zn
Method
GFAA
XRF
XRF
GFAA
XRF
XRF
XRF
CVAA
XRF
XRF
XRF
GFAA
XRF
Replicate 1 ,
ppm dry
6.97
20.2
351
13.5
1470
299
21.6
2.29
2570
126
938
7.01
3720
Replicate 2,
ppm dry
6.72
35.0
367
12.7
1470
360
22.7
2.25
2700
150
1080
6.41
4260
Replicate 3,
ppm dry
7.04
32.2
387
12.8
1370
392
23.7
224
2760
138
1270
6.59
4890
Mean
691
29.1
368
13.0
1440
350
22.7
226
2680
138
1100
6.67
4290
RSD
2
27*
5
3
4
13
5
1
4
9
15
5
14
Precision
Control Limits
20
20
20
20
20
20
20
20
20
20
20
20
20
Recovery
NS
NS
NS
115
NS
NS
NS
103
NS
NS
NS
103
NS
Accuracy
Control Limits
85-115
85-115
85-115
85-115
NS = Not Spiked
* Outside Control Limits
(1) Result in Percent for Fe
-------
TABLE QA-12. METALS SRM RECOVERIES
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Se
Zn
SRM-1
(%)
NC
97.1
NC
111
86.8
119
101
105
92.0
96.2
97.5
NC
88.7
SRM-2
(%)
NC
104
NC
114
128*
119
101
103
86.1
113
95.0
NC
95.0
Control Limits
(%)
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
* = Outside control limits
NC = Not Certified
TABLE QA-13. OIL AND GREASE REPLICATES AND SPIKE RESULTS FOR
I-US-ZP AND I-TS-ZP
Replicate 1, Replicate 2, Replicate 3,
Sample ppm dry ppm dry ppm dry
Mean
Precision Accuracy
Control Control
RSD Limits Recovery Limits
I-US-ZP
I-TS-ZP
9810
1060
10000
1090
9850
702
9890
951
1
23*
20
20
12*(1) 80-120
NS 80-120
NS = Not Spiked
* = Outside Control Limits
(1) = Laboratory results indicated that the sample probably was not spiked
TOTAL VOLATILE SOUDS
Total Volatile Solid Procedures
Sediments were analyzed for total volatile solids (TVS) following the procedures in Method
160.4 (Methods for Chemical Analysis of Water and Waste, 1983) modified for sediments. An aliquot
of sediment was dried and then ignited at 550°C. The loss of weight on ignition was then determined.
Total Volatile Solid QC Results and Discussion
Both the Indiana Harbor untreated and treated sediment (I-US-ZP and IT-TS-ZP) were analyzed
for TVS in triplicate. Results are summarized in Table QA-14. Both RSDs fell within specified control
limits.
150
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TABLE QA-14. TVS REPLICATES FOR I-US-ZP AND I-TS-ZP
Sample
I-US-ZP
I-TS-ZP
Replicate 1 ,
%dry
14.7
7.78
Replicate 2,
% dry
15.3
7.19
Replicate 3,
%dry
15.1
7.05
Mean
15.0
7.34
RSD
(%)
2
5
Control Limits
(%)
20
20
OTHER ANALYSES
Sediment samples were analyzed for pH using SW-846 Method 9045. Sediment and water
were combined in a 1:1 ratio and mixed prior to pH determination.
Total Organic Carbon (TOG)
Sediment samples were analyzed for TOC using SW-846 Method 9060. One SRM was
analyzed with the sediments, yielding a recovery of 92.2 percent.
Total Cyanide
Sediment samples were analyzed for cyanide by SW-846 Method 9010. Approximately 5 g of
sediment was distilled; the distillate was analyzed spectrophotometrically. A matrix spike was analyzed
for I-US-ZP; a recovery of 98 percent was obtained.
Total Phosphorus
Sediment samples were analyzed for phosphorus by EPA Method 365.2. Approximately 1 g of
sediment was digested; the digestate was analyzed spectrophotometrically. A matrix spike was
analyzed for I-TS-ZP; a recovery of 102 percent was obtained.
Total Phosphorus
Sediment samples were analyzed for Phosphorus by EPA Method 365.2. Approximately 1 g of
sediment was digested; the digestate was analyzed spectrophotometrically. A matrix spike was
analyzed for I-TS-ZP; a recovery of 102 percent was obtained.
AUDIT FINDINGS
An audit of the Battelle-Marine Sciences Laboratory was conducted on September 25 and 26,
1991 . Participants included EPA, GLNPO, and SAIC personnel. The path of a sample from receipt to
reporting was observed specifically for samples from these bench-scale treat ability tests. Two concerns
151
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were identified in the organic laboratory: 1) the preparation, storage, record-keeping, and replacement
of standards is not well-documented; and 2) the nonstandard procedures used to extract, clean up and
analyze samples needs to be documented with reported data.
During the audit, the use of nonstandard procedures was discussed. It was concluded that
data comparability within this project and within the ARCS program should not be an issue, as the
Battelle laboratory has performed all analyses to date. However, comparability to data generated
outside the ARCS program is not possible.
MODIFICATIONS AND DEVIATIONS FROM THE QAPP
Laboratory activities deviated from the approved QAPP in two areas-analytical procedures and
quality assurance (QA) objectives. Specific deviations and their effect on data quality are discussed in
this section.
ANALYTICAL PROCEDURES
The Assessment and Remediation of Contaminated Sediments (ARCS) Program was initiated
by the Great Lakes National Program Office (GLNPO) to conduct bench-scale and pilot-scale demon-
strations for contaminated sediments. To date, all laboratory analyses performed in support of the
ARCS Program have been done at the Battelle-Marine Sciences Laboratory (MSL) in Sequim,
Washington. Standard procedures used by Battelle-MSL often do not follow those procedures identified
in SW-846 and the QAPP. While these nonstandard procedures yield results of acceptable quality,
comparability with analyses performed outside the ARCS Program is not possible.
PAH Analysis
Samples were co-extracted with PCB samples using a modified SW-846 extraction
procedure which entailed rolling of the sample in methylene chloride and an additional
clean-up step using high pressure liquid chromatography (HPLC). An internal standard,
hexamethyl benzene, was added prior to this clean-up step to monitor losses through
the HPLC. Final results were corrected for the recovery of this internal standard. A
second internal standard, d12-phenanthrene, was added prior to analysis; however, no
corrections were made based on its recovery. Neither of these internal standards are
specified in Method 8270.
SW-846 Method 8270 was modified to quantify the samples using Selective Ion
Monitoring (SIM) Gas Chromatography/Mass Spectrometry (GC/MS). This modification
results in improved detection limits.
Three isotopically-labelled PAH compounds were used as surrogates rather than those
recommended in Method 8270. Recoveries of these compounds should better repre-
sent the recoveries of target PAHs.
152
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PCB Analysis
Samples were extracted using the modified extraction procedures as described for the
PAH analysis. An internal standard, dibromooctafluorobiphenyl, was added prior to the
HPLC clean-up to monitor losses. Final results were corrected for the recovery of this
standard. A second internal standard, 1,2,3-trichlorobenzene (required by QAPP) was
added prior to analysis; however, no corrections were made based on its recovery.
Quantification of PCBs was not done on a total basis as required by SW-846 Method
8080 but by quantifying four peaks for each Aroclor and averaging these results.
Peaks were considered valid if the peak shape was good, if there was no tailing, and if
there was little or no coelution with other peaks. A definite Aroclor pattern was
necessary for quantification of PCBs.
A three-point calibration for each peak was used instead of the five-point calibration
required by Method 8080. This modification should have minimal effect on data quality.
The surrogate required by the QAPP, tetrachloro-m-xylene, was used. A second
surrogate, octochloronaphthalene, was also added to monitor extraction efficiency.
Metals Analysis
Nine of the 13 metals analyzed for sediment samples were measured by energy-
diffusive X-Ray fluorescence (XRF) - As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn. This
procedure yields a total metals concentration instead of the recoverable metals
determined by SW-846 methods.
Sediments for Ag, Cd, Hg, and Se were subjected to an acid digestion using nitric and
hydrofluoric acids. This digestion again yields total rather than recoverable metals.
Oil and Grease
Oil and grease extracts for sediments were analyzed using infrared (IR) detection rather
than the gravimetric procedures specified in the QAPP. This should have no effect on
data quality.
QUALITY ASSURANCE OBJECTIVES
Many of the guideline QA objectives and internal QC checks criteria guidelines specified in the
QAPP (particularly for organic analyses) are not routinely achievable by standard or nonstandard
methods. To avoid excessive reanalyses (both costly and time-consuming), some acceptance criteria
established internally by Battelle were used for this project. These internal limits are adequate for use
in determining whether or not project results are valid.
PAH Analysis
Both surrogate and matrix spike objectives for PAHs were specified in the QAPP to be
70 to 130 percent. For surrogates, Battelle actually used internal limits of 40 to 120,
with one percent of the three surrogates out of limits being acceptable. If more than
153
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PCB Analysis
one surrogate did not fall within 40 to 120 percent, reanalysis was required. For matrix
spikes, internal limits of 40 to 120 percent were also used; no reanalyses however,
were performed based on exceedences of these limits.
Limits for continuing calibration checks were specified as ±10 percent in the QAPP;
limits of ±25 percent were used.
Both surrogate and matrix spike objectives for PCBs were specified in the QAPP to be
70 to 130 percent. For surrogates, Battelle actually used internal limits of 40 to 120
percent. If both surrogates exceeded these limits, re-extraction was performed. For
matrix spikes, internal limits of 40 to 120 percent were also used; no reanalyses,
however, were performed if these limits were exceeded.
Limits for continuing calibration checks were specified as ±10 percent in the QAPP;
limits of ±25 percent were used.
Metals Analysis
Samples analyzed by XRF cannot be spiked. Therefore, no measure of sample
accuracy was obtained for those metals previously identified as being analyzed by XRF.
An SRM was analyzed, providing a means to measure method accuracy for eight of the
nine metals determined by XRF (all but Ba).
SAMPLE HOLDING TIMES
Water Samples
The QAPP specified holding times for water samples only. All water extractions and analyses
for the critical parameters were performed within these holding times (from the time of sample receipt).
Sediment Samples
Though holding times for organics in sediment samples were not specified in the QAPP, the
referenced SW-846 methods do require that extractions be done within 14 days and that the analysis of
the extracts be performed within 40 days after extraction. Any analyses exceeding these criteria for the
critical parameters will be discussed below.
PAHs
Initial triplicate analyses of the Indiana Harbor untreated sediments yielded concentrations for
several compounds above the calibration range. Dilutions were analyzed approximately two months
past the 40 day extract holding time. No significant differences were observed between the original
analysis and the diluted analysis; removal efficiencies should not be affected.
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The Indiana Harbor treated sediment was re-extracted over two months past the 14 day
extraction holding time due to unacceptable surrogate recoveries. (Surrogate recoveries for the re-
extracted sample also did not meet acceptance criteria.) The re-extracted values were approximately
60 percent of the initial values. Because of the minimal amounts of PAHs present after treatment
relative to the amount in the feed, the accuracy of the results for the treated sediment is less critical. If
the concentration of total PAHs were actually two to five times higher than the reported value; removal
efficiencies would still be greater than 95 percent.
CONCLUSIONS AND LIMITATIONS OF DATA
Upon review of all sample data and associated QC results, the data generated for the ZIMPRO
treatability study has been determined to be of acceptable quality. In general, QC results for accuracy
and precision were good and can be used to support technology removal efficiency results.
As discussed previously, the analytical laboratory used several specialized methods when
analyzing samples from the ZIMPRO treatability study. These same methods, however, have been
used in analyzing all samples generated to date in support of the ARCS Program. Therefore, while the
data generated for the ZIMPRO treatability study may not be comparable to data generated by standard
EPA methods, it is comparable to data generated within the ARCS Program.
The abridged version of the Data Verification Report prepared by the ARCS Program
QA Officer follows.
155
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Data Verification Report For Assessment and
Remediation of Contaminated Sediment Program
Report Number 8
(SAIC, Bench-Scale Tests)
By
M. J. Miah, M. T. Dillon, and N. F. D. O'Leary
Lockheed Environmental Systems and Technologies Company
980 KelJy Johnson Drive
Las Vegas, Nevada 89119
Version 1.0
Work Assignment Manager
Brian A. Schumacher
Exposure Assessment Research Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89193
Environmental Monitoring Systems Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Las Vegas, Nevada 89193
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ABSTRACT
Data submitted by the Science Applications International Corporation
(SAIC) of Cincinnati, Ohio, have been verified for compliance of the QA/QC
requirements of the Assessment and Remediation of Contaminated Sediment
(ARCS) program. This data set includes results from bench-scale technology
demonstration tests on wet contaminated sediments using four treatment
technologies, namely, B.E.S.T. (extraction process), RETEC (low temperature
stripping), ZIMPRO (wet air oxidation), and Soil Tech (low temperature
stripping). The primary contaminants in these sediments were polychlorinated
biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs). In addition,
metal contents and conventionals (% moisture, pH, % total volatile solids, oil and
grease, total organic carbon (TOC), total cyanide, and total phosphorus) in these
sediments were also considered for this project. The objective of the bench-scale
technology demonstration study was to evaluate four different treatment
techniques for removing different organic contaminants from sediments. Both
treated and untreated sediment samples were analyzed to determine treatment
efficiencies.
A total of seven sediment samples from four different areas of concerns
(Buffalo River, Ashtabula River, Indiana Harbor, and Saginaw River) uere
analyzed under the bench-scale technology demonstration project. The samples
from these areas of concern (AOCs) were collected by the Great Lakes National
Program Office (GLNPO) in Chicago, IL, and sample homogenization was
performed by the U. S. EPA in Duluth, MN. SAIC was primarily responsible
for the characterization of the sediment samples prior to testing and for the
residues created during the test. The solid fraction analyses were performed by
SAIC's analytical subcontractor Battelle-Marine Sciences Laboratory of Sequim,
Washington, and Analytical Resources Incorporated of Seattle, Washington.
The submitted data sets represent analyses of untreated sediments, as well
as solid, water, and oil residues obtained by using different treatments. The
verified data set is divided into several parameter groups by sampled media. The
data verifications are presented in parameter groups that include: metals, PCBs,
conventionals, and PAHs.
The results of the verified data are presented as a combination of an
evaluation (or rating) number and any appropriate data flags that may be
applicable. The templates used to assess each individual analyte are attached in
case the data user needs the verified data of a single parameter instead of a
parameter group.
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INTRODUCTION
The bench-scale technology demonstration project was undertaken to evaluate the
efficiencies of four techniques used for the removal of specific contaminants from wet sediments
collected from designated Great Lakes areas of concern. Four different sediment treatment
techniques, namely, B.E.S.T (Basic Extraction Sludge Technology), RETEC, ZIMPRO, and Soil
Tech were considered for evaluation. B.E.S.T. is a solvent extraction process, RETEC and Soil
Tech are low temperature stripping techniques, and ZIMPRO is a wet air oxidation technique.
Wet sediments were collected by the Great Lakes National Program Office (GLNPO) from four
Great Lakes sites, namely, the Buffalo River in New York, the Saginaw River/Bay (referred to
as Saginaw River throughout the following discussions) in Michigan, the Grand Calumet
River/Indiana Harbor (referred to as Indiana Harbor throughout the following discussions) in
Indiana, and the Ashtabula River in Ohio. The four techniques were used to treat the sediment
samples from these four sites. The sediment samples represent the sediment that would be
obtained for on-site treatment.
The B.E.S.T. process is a patented solvent extraction technology that uses the inverse
miscibility of triethylamine as a solvent. At 65° F, triethylamine is completely soLt'.e in water
and above this temperature, triethylamine and v,a:er are parJa^y r.iscib'e. Th:s rrcr-erty of
inverse miscibility is used since cold triethylamine can simultaneously solvate oil and water.
RETEC and the Soil Tech (low temperature stripping) are techniques to separate volatile and
semivolatile contaminants from soils, sediments, sludges and filter cakes. The low temperature
stripping (LTS) technology heats contaminated media to temperatures between 100 -200° F,
evaporating off water and volatile organic contaminants. The resultant gas may be burned in
an afterburner and condensed to a reduced volume for disposal or can be captured by carbon
absorption beds. For these treatability studies, only the processes that capture the driven off
contaminants were considered. The ZIMPRO (wet air oxidation) process accomplishes an
aqueous phase oxidation of organic and inorganic compounds at elevated temperatures and
pressures. The temperature range for this process is between 350 to 600° F (175 to 320° C).
System pressure of 300 psi to well over 300 psi may be required. In this process, air or pure
oxygen is used as an oxidizing agent.
Samples for the technology demonstration projects were obtained by GLNPO (Chicago,
Illinois) and were analyzed by Battelle-Marine Sciences Laboratory (Battelle-MSL, Sequim, WA)
and by Analytical Resources Incorporated (Seattle, WA). To evaluate the bench-scale
technologies, the sample analyses were divided into four parts: (1) raw untreated sediment
samples, (2) treated sediments, (3) water residues, and (4) oil residues. The amount of residues
available for the analyses depended upon the corresponding sediment samples and on the
individual technology used to treat those sediment samples.
The analyses of sediment and residue parameters for these projects were divided into four
different categories: (1) metals, including Ag. As. Ba. Cd. Cr. Cu. Fe. Hg, Mr.. Ni. ?b. Se.
and Zn; (2) polychlorinated biph.en\is (PCBs;: (5; p-:'.;~._:^ar a::~a::c r.vcrocarrr-.s ?AHsr.
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and (4) conventional*, including percent moisture, pH, percent total volatile, oil and grease, total
organic carbon (TOC), total cyanide, and total phosphorus. Analyses of metals and
convenuonals were performed on treated and untreated sediment samples only for B.E.S.T.,
ZIKfPRO, and Soil Tech, while for the RETEC process, analyses of metals and conventionals
were performed on treated and untreated sediment samples as well as water residue samples.
No oil residues were produced by the ZIMPRO technique (wet air oxidation treatment
technique), while in the other three techniques, oil residues were analyzed after appropriate
sample cleanup steps for PCBs and PAHs.
QUALITY ASSURANCE AND QUALITY CONTROL REQUIREMENTS
The objective behind all quality assurance and quality control (QA/QC) requirements is
to ensure that all data satisfy predetermined data quality objectives. These requirements are
dependent on the data collection process itself. Under the bench-scale technology demonstration
project. QA/QC requirements were established for:
2. Precision,
3. Accuracy,
4. Blank analyses,
5. Surrogate and matrix spike analyses, and
6. Calibration
a) initial
b) ongoing.
Four parameter groups analyzed in the sediment and water residue phases were of interest
in the bench-scale technology demonstration project. These groups included: (a) metals, (b)
PCBs, (c) PAHs, and (d) conventionals. The conventionals included: percent moisture, pH,
percent total volatile, oil and grease, TOC, total cyanide, and total phosphorus. In addition,
total solids, total suspended solids, and conductivity were included in the conventionals group
for RETEC conventional analyses. The analyses for metals and conventionals were performed
for solids only, except for RETEC, where metals and conventionals were analyzed in solid and
water residue phases. Parameter groups analyzed in the oil residue phase are PCBs and PAHs.
The objective of these analyses was to characterize samples both before and after each treatment
was applied.
The detection limits for metals, PCBs, PAHs, and conventionals (where appropriate)
were denned as, three times the standard deviation for 15 replicate analyses of a sample with
an ar.alv.e concentration within a factor of 10 above the expected or required limit of detection.
I";!. -.c _:L ~i~ rr.eter detect:" !:m:ts are presented in the approved quality assurance project plan
:';: 5 -.'.~ '.- f.'.e r. ::.e Gre^: Lixes Nr.:cr.il Program Office in Chicago, IL.
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3
Precision requirements were based on analytical triplicate analyses for all parameters of
sediment samples and treated residues, at the rate of 1 per 20 samples. The results of the
triplicate analyses provided the precision for the analytical laboratory. An acceptable limit was
the coefficient of variation less than or equal to 20 percent. The precision requirement was
established for all variable types in this project. For treated sediments, the relative percent
difference (RPD) between the matrix spike and matrix spike duplicate was used as a measure
of precision with an acceptance limit of less than 20% .
Accuracy was defined as the difference between the expected value of the experimental
observation and its "true" value. Accuracy in this project was required to be assessed for each
variable type using analysis of certified reference materials, where available, at the rate of 1 per
20 samples. Acceptable results must agree within 20 percent of the certified range. Since no
PCBs and PAHs were expected to be detected in the treated sediment, matrix spikes and matrix
spike duplicate analyses were required during the analyses of treated sediment for the organic
parameters. Matrix spike analyses were used as a measure of accuracy for treated sediment
analyses, with an acceptance limit of ±30% from the known value.
Matrix spikes were required to be used at a rate of 1 per 20 samples and to be within
plus or minus 15 percent of the spiking value for meia's and 70 to 130 percent of the spiJcr.g
value for organics (PCBs ard PAHs).
Surrogate spike anahses were onlv required for each sample in organic analyses. The
acceptable limits for the surrogate recover)' was between 70 and 130 percent of the known
concentration.
The observed values should have been less than the method detection limit for each
parameter for method blanks (run at the beginning, middle, and end of each analytical run).
The ongoing calibration checks were required at the beginning, middle, and end of a set
of sample analyses for all variable types. The maximum acceptable difference was ±1056 of
the known concentration value in the mid-calibration range. Initial calibration acceptance limits,
for metals, was the _>.0.97 coefficient of determination for the calibration curve, while a %RSD
of the response factors of less than or equal to 25 % was required for organics.
RESULTS AND DISCUSSION
The ARCS QA program was formally adopted for use when SAIC received final approval
from the GLNPO on May 31, 1991. An evaluation scale, based upon the QA program
developed for the ARCS program, was developed to evaluate the success of the data collection
process in meeting the QA/QC requirements of the ARCS program. The following section
discusses how to interpret the data verification results.
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The Verification Process and Evaluation Scale
For verification purposes, the data set from each technology was divided into 4 different
sample media as follows:
1. Untreated sediment,
2. Treated sediment,
3. Water residue, and
4. Oil residue.
The verification process included QA/QC compliance checking for accuracy, precision,
matrix spike analysis, surrogate spike analysis, blank analysis, detection limits, initial and
ongoing calibration checks, and holding times as well as checks on calculation^ correctness and
validity on a per parameter/analyte basis. Compliance checks were performed to ensure that the
QA/QC measurements and samples: (a) met their specified acceptance limits; (b) had reported
results that were supported by the raw data; and (c) were analyzed following good laboratory
practices, where checking was possible. Upon completion of the verification process, a final
rating was assigned for each of the individual categories. The final ratings are presented as a
ccrr.'rina::?." c:" a number value and a flag list.
T'e r.-T.encal value for the rating of a given parameter was assigned based upon the
success:'.: completion of each required QA/QC sample or measurement. The QA/QC samples
were broken down into four different sample groups, namely, accuracy, precision, blanks, and
spike recoveries. A fifth category was included for QA/QC measurements to address the
successful completion of instrument calibrations (both initial and ongoing) and the determination
of method detection limits. If the laboratory successfully met the acceptance criteria of 50
percent or more of the parameters in a given QA/QC sample group, then the laboratory received
the full value for that category. For example, if 50 percent or more of the reagent blanks for
the metals in sediment analyses had measured values below the method detection limit, then
three points were awarded for that category, assuming reagent blanks were the only blank
samples analyzed by the laboratory. The individual point values for each QA/QC sample type
or measurement and the minimum acceptance levels for each category are presented in Appendix
B. The final numerical rating presented for each parameter category is the summation of the
point values from each of the five categories.
Along with each numerical rating, a list of appropriate flags has been attached to the final
rating value (Appendix C). The flag indicates where discrepancies exist between the laboratory
data and the acceptance limits of the required QA program. Different flags are presented for
each category of QA sample (accuracy, precision, blanks, and spike recoveries) and for the
QA/QC measurements (instrument calibration and detection limit determination). The flags have
a lener and subscript configuration, such as A,. The letter of the flag represents the category
of the discrepancy while the subscript designates the form of the discrepancy. For example, the
A f ::5 .-:.:::e discrepancies in the use of accuracy checking samples, such as reference
- _;:._.: ;- __r:::;s A :".;: v.:-.h a subscnp: of 1 indicates that the laboratory failed to meet
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the acceptance criteria. Using the example of the A, flag, this flag would then indicate a failure
of the laboratory to meet the QA/QC requirements for the use of reference materials in their
appraisal of accuracy. A flag with the subscript 0 indicates that no information was received
(or no standards were available in the case of accuracy) from the analytical laboratory, and
therefore, no points could be allotted towards the final calculated rating value for that particular
category. It should be noted that the 0 flag does not necessarily indicate that the analytical
laboratory did not perform the QA/QC analyses, only that no information was received from the
laboratory.
The subscript 9 flag indicates that the sample category or QA/QC measurement is not
applicable to that particular parameter or parameter group (Appendix C). For example, an S,
flag indicates that a matrix spike for that given parameter or analyte is not applicable, such as
was the case for percent moisture. Where subscript 9 flags occur, an adjustment to the passing
and maximum scores (to be discussed) for a parameter group was made and will be reported in
the appropriate tables.
A complete presentation of the QA/QC rating factors (point values by sample type) and
the various data flags and their subscripts are presented in Appendices B and C, respectively.
A more complete discussion of the rating scale can be found in the report submitted to the
RA'M workgroup by Schumacher and ConkJing entitled. "User's Guide to the Quality
Assurance/Qualitv Control Evaluation Scale of Historical Data Sets."
Individual parameter flags are presented in the templates found in Appendix D. The
objective of the presentation of the individual flag templates is to help the data user make a
determination regarding the useability of the data set for any given purpose and to provide the
data user with a means to assess any individual parameter that may be of specific interest.
The Interpretation and Use of the Final Verified Data Rating Values
The data verification scale was developed to allow for the proper rating of the verified
data and the subsequent interpretation and evaluation of the ratings. Two different
interpretations can be made using the ratings provided in this report, namely, the actual or "true"
rating and the potential rating. The first interpretation is based upon the formal ARCS QA
program, while the second interpretation scale is based upon the "full potential" value of the
submitted data set. In the following sections, each interpretation of the results will be discussed.
Data Interpretation Based upon the Formal ARCS OA Program
For each of the four parameter categories, the data were initially verified for QA/QC
compliance following the requirements specified in the signed QAPP submitted by SAIC and the
ARCS QAMP on file at the GLNPO in Chicago, Illinois.
Table 1 provides the verified data ratings for each variable class for the four different
lechr.olog'.es st-Cied based cr. r.e current ARCS QA progra.r.. The rarr.gs of these variable
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classes are presented to provide the data user with a means for comparing the ARCS QA
program-based verified results with other data sets, using the same or similar parameters, that
were generated prior to and after the initiation of the formal ARCS QA program.
Table 2 provides the data user with the full compliance and acceptable scores presented
for each parameter group based upon the current ARCS QA program. The full compliance score
represents the numerical rating value if all required QA/QC samples and measurements were
performed by the analytical laboratory and successfully met all the QA/QC requirements of the
ARCS QA program. An acceptable score is lower than the full compliance score and accounts
for laboratory error that can be reasonably expected during an analysis of multiple samples.
Any final rating value less than the acceptable score indicates that problems were identified in
the data that could adversely effect the quality of the data. The acceptable score was set at 60
percent of the full compliance score. To determine the percentage of QA/QC samples and
measurements successfully analyzed for a given parameter versus the number analyzed following
the complete ARCS QA protocols, divide the numerical rating received by the full compliance
score. An acceptable data set, in this case, has a rating of 60 percent or greater.
In some cases, all the QA/QC requirements may not be applicable (e.g., matrix spikes
for percent solids are not applicable). If this is the case, a flag with the subscript 9 was used,
and the full compliance and acceptable scores were adj-r.ed by lowering the score on appropriate
number of points for nonrequired sample type, as identified in Appendix B. An example of this
situation is % moisture, as indicated in Table 1, the subscript 9 flag has been applied to
accuracy, blank, detection limit, and spike samples. Therefore, the full compliance and
acceptable scores (Table 2) are only based upon the possible points for the successful completion
of the remaining QA/QC samples that have cumulative points value of 8 (Appendix B).
Data Interpretation Based upon the' Potential* Value of the Data Set
A second interpretation scale has been presented to allow the data user to establish the
"full potential" value of the submitted data set. The numerical value and associated flags
presented in the first interpretation can be considered as an absolute rating for that data set or
parameter. These ratings were based upon all the data submitted to Environmental Monitoring
Systems Laboratory - Las Vegas (EMSL-LV) and to Lockheed for review by the analytical
laboratory. If one or more parameter or parameter groups qualifying flags had the subscript of
5, 6, 9, or 0 (Appendix C), the required information was not available or not applicable at the
time of sample analysis, and consequently was not included during the data verification and
review process. The equivalent point value(s) for each individual sample type may be added to
the reported point sum to give the data user the full potential value of the data set. This process
assumes that if the "missing" QA/QC samples or measurements were performed, the results
would fall within the ARCS QA program specified acceptance limits. For example, if the point
value {including qualifying flags) for the metals was 6-B. C0 D0 S0, then the data user could
potent!illy add 14 points to the score since the blank ar.i!>ses. spike information, detection limit,
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and calibration (initial and ongoing) information was not available for verification. The resulting
data would then have a rating of 20.
TABLE 1. Verified Data Ratings Based on the Current ARCS QA Program
Untreated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Total
phosphorus
PCBs
PAHs
D.t.3. 1
12-QDo
0-A, B, 0, D, Po S,
0-A, B, 0, D, PO S,
6-A,CoD»S,
15-A, Ct
12-C. Po S,
14-Ao P0
14-Ao P0
17-B: D0
17-Do S,
ZIMPRO
12-CoDo
3-A, B, Q D, S,
0-A, B, Q D, P0 S,
3-A, BO Q D, S,
6-A, B, C6 D, S,
12-C6P0S,
14-AoPo
14-.Ao P0
14- A, B; DD
11-B2D0S. S;
Soil Tech
12-CoDo
0-A,B,CoD,P0S,
0-A, B, Co D, P0 S,
6-A, C0 D, S,
6-A, B, C4 D, S0
12-C6P0S,
11-AoPoSo
14-A.Po
14- A, B, Dc
17-D0S:
RETEC
12-CoD0
3-A, B, Q D, S,
3-A, B, C, D, S,
6-A, Q D, S,
9-A, DO Ct So
9-C.D0P0S,
8-Ao D, P, So
11-A.DoSo
11-A, B:D0S5
20.D0
Treated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Total
phosphorus
PCBs
PAHs
12-CoD0
0-A, B, Co D, P0 S,
0-A,B,CoD,P0S,
6-A, Co D, S,
15-A, C6
12-C«P0S,
14-Ao P0
14-Aj Po
14-B, D0 P,
14-D9 P, S-
12-QDo
0-A, B, Q, D, P0 S,
3-A,B,CoD,S,
3-A, BO Q D, S,
6-A, Bj C6 D, S,
12-C. P0 S,
14-Ao PO
14-Ao PO
ll-A^DoP,
17-Do S:
12-QDo
3-A, B, Q D, S,
0-A, B, Q, D, Po S,
6-A,CoD,S,
9-A, B, Ce D,
12-C6P0S,
14-Ao P0
14-Ao P0
14-B:D0P,
14-Do P, S:
12-QDo
3-A,B,CoD,S,
3-A,B,C,D,S9
6-A,C,D,S,
6- A, C, DO P, So
12-C, D, S,
11-AoDoPo
14-Ao D0
14-A, Bj DO
20-D0
-------
TABLE 1. Verified Data Rating Based on the Current ARCS Program
(Continued)
Water
residue
Metals
% Moisture
pH
Total
Suspended
Solids
%TVS
Total Solids
Oil and grease
TOC
Total cyanide
Total
phosphorus
Conductivity
PCBs
PAHs
*
**
»
««
*s
**
««
**
*
*
*
«
*
*«
*
*
**
**
** ** : **
*
**
**
14-Bj D0 P0
ll-A^DoP, S,
<
**
**
14-B, D0 P0
17-DoS,
9 *
«*
**
5-A, B, DO P0 S,
S6
17-Do P0
Oil residue
PCBs
PAHs
11-A.BjDoS,
11-AoBjDoS,
17-B, Do
14-B, DO S,
20
**
3-A, B, Q D, S,
6-A,CoD, S,
6-A, Q, D, S,
6- A, Co D, S,
12-A, C6 D0
9-.\, C. D, S, i
14- ^ D0
14-A^Do
9-A, C. D, S,
5-AoBjDoPoS,
S6
Il-A.D.P.S,
il-^DoP.S,
17-B; DO
* No oil residue was produced by this treatment
** Analyses were not conducted for this treatment
-------
TABLE 2. Full Compliance and Acceptable Scores Based on the Current ARCS QA Program
Variable Class
Metals in Treated Sediment
Metals in Untreated Sediment
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Tc:ai phosphorus
Conductivity
Suspended Solids
Total Solids
PAHs
PCBs
Full Compliance
20
20
8
8
9
17
17
20
20
14
9
9
23
23
Acceptable
12
12
5
5
6
11
11
12
12
9
6
6
14
14
Table 3 presents the verified data ratings for each variable class in the four technologies
based on their full potential value. All data qualifying flags with the subscripts 5, 6, 9, or 0
have been removed. The appropriate point values for each of the 5, 6, or 0 flags (Appendices
B and C) were added to the final rating scores for each parameter or parameter group. In
contrast, the removal of the subscript 9 flags resulted in an adjustment to the full compliance and
acceptable scores, and npj in an addition to the calculated point scores since these analyses were
not applicable to the methodologies used by the laboratory (Table 2).
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10
TABLE 3. Verified Data Ratings Based on the Full Potential of the Data set
Untreated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cvanide
Tool phosphorus
PCBs
PAHs
B«t«o< 1
20
8
8
6
17
17
20
20
20- B,
20-S:
ZIMPRO
20
8
8
6
8-B;D, S;
17
20
:o
17-A. B-
14-B, S, S.
I
Soil Tech
20
8
8
6
11-B-D,
17
20
:o
17-A.B,
20-S:
RETEC
20
8
8
6
17
17
17-P,
:o
17-A.B,
23
Treated
Sediments
Metals
% Moisture
PH
%TVS
Oil and grease
TOC
Total cyanide
Total phosphorus
PCBs
PAHs
20
8
8
6
17
17
20
20
H-B, P,
17-P, S:
20
8
8
6
8-B, D, S,
17
20
20
14-A,B:P,
20- S:
20
8
8
6
11-B,D,
17
20
20
17-B, P,
20-S;
20
8
8
6
9-P,
17
20
20
17-A, B,
23
-------
11
TABLE 3. Verified Data Ratings Based on the Full Potential of the Data set
(continued)
Water
residue
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cvanide
Total phosphorus
i O^u:tr.;r.
.1 Susper.deJ Solids
Total Solids
PCBs
PAHs
»*
*>
**
*
*
**
*
*«
K C
C*
20-B,
17-P,S:
**
*
**
*
*
**
»*
«*
**
«*
**
20-B,
20-S,
Oil residue
PCBs
PAHs
14-A, B, S,
17-B, S,
«
*
**
*
*
*«
*
**
<
M-A.BjS,
23
20-B,
17-8,5,
20
8
8
6
17
17
20
20
14
6
6
20-B,
14-A, P, S,
20-B,
20-B,
* No oil residue was produced by this treatment
** Analyses were not conducted for this treatment
To evaluate the data using the values presented in Table 3, the final ratings should be
compared to the full compliance and acceptable scores presented in Table 2. The data user
should bear in mind that these values are only the potential values of the data set and assumes
that the "missing" QA/QC data could have been or were performed successfully by the
laboratory. Any value falling below the acceptable value presented in Table 2 clearly indicates
that major QA/QC violations were identified and the data should be used with a great deal of
caution bv the data user.
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12
Data Verification Results for Bench-scale Technoloev Demonstration Project
B.E.S.T.
The B.E.S.T. technology was evaluated by analyzing sediment samples and their treated
residues (treated sediments, water residues, and oil residues) for metals, conventionals, PCBs
and PAHs. PCB and PAH analyses were performed for sediments, water, and oil residues. The
metals and conventional analyses were performed for the sediment samples only.
In the majority of the cases studied, the accuracy objective was satisfactory for the metal
analyses in treated and untreated sediments. Of the thirteen metals analyzed, accuracy
information was not available for Ba, Se, and Ag. In both treated and untreated sediments, ten
of the thirteen metal analyses (As, Cd, Cr, Cu, Fe, Pb, Mn, Hg, Ni, Pb, and Zn) satisfied
ARCS specified QA/QC requirements for accuracy. Four of the thirteen metal analyses (Cd,
Hg, Se, and Ag) satisfied QA/QC requirements for blank analyses, while the remaining nine
metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of
the XRF analyses, results from blank sample analyses were not applicable. Both initial and
ongoing calibration for Cd, Hg, Se, and Ag analyses met the ARCS QA/QC specifications for
bo'uh treated and untreated sediments, while for the remaining nine metals (As, Ba, Cr, Cu, Fe,
Mn, Ni, Pb, and Zn) calibration information was not available. Detection limits information for
metal analyses in treated and untreated sediments were not available for verification except for
Cd, Hg, Se, and Ag where detection limits were satisfactory. The precision information for the
metal analyses in treated sediment was not available for Se, but was satisfactory for the
remaining elements, with the exception of Hg, where precision information did not satisfy
QA/QC requirements. The precision information for the metal analyses in untreated sediment
was not available for Se, but was satisfactory for the remaining twelve metal (Ag, As, Ba, Cd,
Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn) analyses. The matrix spike information for both treated
and untreated sediment analyses were satisfactory for Cd, Hg, and Se, were unsatisfactory for
Ag, while the remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed
by XRF techniques. In all of the XRF analyses, results from matrix spike analyses were not
applicable.
Of the seven conventional analyses, the accuracy information in both treated and
untreated sediments was satisfactory for TOC and was not available for total cyanide, and total
phosphorus. In the remaining four conventional analyses, accuracy was not applicable. In both
sediments, five of the seven conventionals (%TVS, oil and grease, TOC, total cyanide, and total
phosphorus) satisfied QA/QC requirements for blank analyses, and the blank information was
not applicable for moisture, pH, and TVS. Both initial and ongoing calibration information was
satisfactory for all conventional analyses in both treated and untreated sediments except for
moisture and pH where calibration information was not available and for TOC and oil and grease
A here ongoing calibration information was not available. Detection limits were satisfactory' for
r'ru: (o:'. ar.d grease, TOC, total cyanide, and total phosphorus) of the se\er. ccr.'. er.ticr.al
-------
13
analyses in treated and untreated sediments, and were not applicable for moisture, pH, and TVS.
The precision information was satisfactory for two (%TVS, oil and grease) of the seven
conventional analyses in treated and untreated sediments. No precision information was
available for the remaining five conventional analyses in treated or untreated sediments. The
matrix spike information for both treated and untreated sediment analyses were satisfactory for
oil and grease, total cyanide, and total phosphorus, while for the remaining four conventional
analyses the matrix spike information was not applicable.
In treated sediments, untreated sediments, and water residues, the accuracy objective for
PCBs was satisfactory for Aroclor 1254 analyses only and could be used to represent the whole
PCB group. No accuracy information was available for the remaining three Aroclor analyses.
In oil residues, accuracy information was not satisfactory for PCB analyses. In both sediments
and in both residues, PCB analyses did not satisfy ARCS specified QA/QC requirements for
blank analyses indicating potential contamination at the laboratory. Initial and ongoing
calibration was satisfactory for all PCB analyses in both treated and untreated sediments as well
as in water and oil residues. Detection limit information were not available for PCB analyses
in treated and untreated sediments and for water and oil residues. In the untreated sediments,
the precision information was satisfactory for Aroclors 1242 and 1254, and no precision
information was available for Aroclors 1248 and 1260. In the treated sediments, the precision
information was not satisfactory for Aroclor 1254, and no precision information was available
for Aroclors 1242, 1248, and 1260. In water residues, no precision information was available
for any of the Aroclors. In oil residues, the precision information was satisfactory for Aroclor
1248, and no precision information was available for Aroclors 1242, 1254, and 1260. The
matrix spike for Aroclor 1254 was satisfactory for both sediment and water residue analyses and
could be used to represent the whole PCB group. The matrix spike for Aroclor 1254 was
unsatisfactory for the analyses of oil residue. In both sediment or residue analyses, no matrix
spike information was available for Aroclors 1242, 1248, and 1260. The surrogate spike
recoveries were satisfactory for PCB analyses in both sediments and residues.
In eight of sixteen PAH analyses of treated and untreated sediments, the accuracy
objective was satisfactory. No accuracy information was available for six PAHs (naphthalene,
acenaphthylene, acenaphthene, fluorene, chryscne, and dibenzo{a,h)anthracene) analyses in both
treated and untreated sediments. The accuracy objective was not satisfactory for benzo(k)
fluoranthene and benzo(a)pyrene in treated or untreated sediments. No accuracy information was
available for any of the PAH analyses in water and oil residues. In treated and untreated
sediments, and in water residues, PAH analyses satisfied ARCS specified QA/QC requirements
for blank analyses. In all cases of oil residues, the blank analyses exceeded the MDL indicating
potential contamination at the laboratory. Initial and ongoing calibration limits for PAH analyses
met the ARCS QA/QC specifications for both treated and untreated sediments and water and oil
residue analyses. Detection limit information was not available for PAH analyses in treated and
untreated sediments, nor for water and oil residues. In untreated sediments and oil residues, the
precision information was satisfactory for all PAH analyses, except for acenaphthene in untreated
sediment, and naphthalene in oil residues where no precision information was available. In
:rei:ed sediments, the precision information was satisfactory for fluorene, phenar.threr.e. ar.d
-------
14
anthracene but was unsatisfactory for the remaining PAH analyses. In water residues, no
precision information was available for PAH analyses except for benzo(g,h,i)pyrene where
precision was unsatisfactory. The matrix spike information was satisfactory for twelve of sixteen
PAH analyses in treated sediment and for eight of the sixteen analyses in untreated sediment and
in water and oil residues. Surrogate recoveries were not satisfactory for PAHs in either
sediment and residue analyses.
ZIMPRO
The ZIMPRO technology was evaluated by analyzing sediment samples, treated
sediments, and water residues for metals, conventionals, PCBs, and PAHs. PCB and PAH
analyses were performed for both sediment and water residues. The metals and conventional
analyses were performed for the both sediment samples only.
In the majority of the cases studied, the accuracy objective was satisfactory for the metal
analyses in treated and untreated sediments. Of the thirteen metals analyzed, accuracy
information was not available for Ba, Se, and Ag. In both treated and untreated sediments, ten
of the thirteen metal analyses (As, Cd, Cr, Cu, Fe, Pb, Mn, Hg, Ni, and Zn) satisfied ARCS
specified QA/QC requirements for accuracy. Four of the thirteen metal analyses (Cd. Hg, Se,
ar.d Ag) satisfied QA/QC requirements for blank analyses, while the remaining nine metals (As,
Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of the XRF
analyses, blank sample analyses are not applicable. Both initial and ongoing calibration for Cd,
Hg, Se, and Ag analyses met the ARCS QA/QC specifications for both treated and untreated
sediments while for the remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn),
calibration information was not available. Detection limit information for metal analyses in
treated and untreated sediments was not available for verification except for Cd, Hg, Se, and
Ag where the detection limits were satisfactory. The precision for the metal analyses in treated
sediment was not satisfactory for As, but was satisfactory for the remaining elements. The
precision information for the metal analyses in untreated sediment was satisfactory for all
elements. The matrix spike information for both treated and untreated sediment analyses were
satisfactory for four (Cd, Hg, Se, and Ag) of the thirteen elements while the remaining nine
metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of
the XRF analyses, results from matrix spike analyses were not applicable.
Of the seven conventional analyses, the accuracy information in both treated and
untreated sediments was satisfactory for TOC and was not available for total cyanide, and total
phosphorus. In the remaining four conventional analyses, accuracy was not applicable. In both
sediments, three of the seven conventionals (TOC, total cyanide, and total phosphorus) satisfied
QA/QC requirements for blank analyses. The blank information was unsatisfactory for oil and
grease, was not available for %TVS, and the blank information was not applicable for moisture
and pH. Both initial and ongoing calibration information was satisfactory for all conventional
analyses in both treated and untreated sediments except for % moisture, pH, and TVS where
:il.bra::on information was not available, and for TOC and oii ar.d grease, where cr.gr.rg
-------
15
calibration information was not available. Detection limits were satisfactory for three (TOC,
total cyanide, and total phosphorus) of the seven conventional analyses in treated and untreated
sediments. Detection limits were unsatisfactory for oil and grease analyses in treated and
untreated sediments and were not applicable for % moisture, pH, and %TVS. The precision
information was satisfactory for pH, %TVS, and oil and grease analyses in treated, and for
% moisture, %TVS, and oil and grease analyses in untreated sediment. No precision information
was available for % moisture, TOC, total cyanide, and total phosphorus analyses in treated
sediment and for pH, TOC, total cyanide, and total phosphorus analyses in untreated sediments.
The matrix spike information for both treated and untreated sediment analyses were satisfactory
for total cyanide and total phosphorus, were unsatisfactory for oil and grease while for the
remaining four conventional analyses the matrix spike information was not applicable.
The accuracy objective was unsatisfactory for the PCB analyses in treated and untreated
sediments for Aroclor 1254. No accuracy information was available for the remaining three
Aroclor analyses in treated and untreated sediments. In water residue, the accuracy objective
for PCBs was satisfactory for Aroclor 1254 analyses only and could be used to represent the
whole PCB group. No accuracy information was available for the remaining three Aroclor
analyses in water residues. In water residues and in both treated and untreated sediments, the
blank analyses exceeded the detection limits specified in the QAPP indicating potential
contamination at the laboratory. Initial and ongo;~g calibraticr. uas sa::sfa:'.or> for all PCB
analyses in both treated and untreated sediments as -Aell as in water residues. Detection limits
information were not available for PCB analyses in treated and untreated sediments, nor in the
water residues. In untreated sediment analyses, most PCB observations were below the
instrument detection limits, therefore it was not possible to calculate meaningful precision
information for PCB Aroclors, with the exception of Aroclor 1248 analyses, where precision
information satisfied QA/QC requirements. No precision information was available for PCB
analyses in treated sediments, except for Aroclor 1254 in treated sediment where it did not
satisfy QA/QC requirements. In the water residue, no PCB precision information was available.
The matrix spike for Aroclor 1254 was satisfactory for both sediments, and the water residue
analyses and could be used to represent the whole PCB group. The matrix spike information
for sediments and water residue analyses for Aroclor 1242, 1248, and 1260 were not available
for verification. The surrogate recoveries were satisfactory for PCB analyses in sediment and
residue analyses.
In ten of the sixteen PAH analyses in treated sediment and nine of the sixteen PAH
analyses in untreated sediments, the accuracy objective was satisfactory. No accuracy
information was available for six PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene,
chrysene, and dibenzo(a.h)anthracene) analyses in treated and untreated sediment. The accuracy
objective was not satisfactory for benzo(k)fluoranthene in untreated sediment. Accuracy
information in water residue was unsatisfactory for naphthalene, acenaphthylene, acenaphthene,
phenanthrene, and benzo(a)pyrene. Accuracy was satisfactory for the rest of the PAH analyses
in water residues. In treated sediments and water residues, PAH analyses satisfied ARCS
specified QA/QC requirements for blank analyses. In all cases of untreated sediment analyses,
the blank analyses exceeded the detection limit specified in the QA??. CaJibra:::- I:.T.::S for
-------
16
PAH analyses met the ARCS QA/QC specifications for both treated and untreated sediments,
and also for water residue analyses. Detection limits information were not available for PAH
analyses in treated and untreated sediments, nor for the water residues. The precision
information was satisfactory for PAH analyses in both sediments except for naphthalene,
acenaphthylene, acenaphthene, fluorene, and benzo(a)pyrene analyses in treated sediment and
for naphthalene, acenaphthene, phenanthrene, and benzo(a)pyrene in water residue, where
precision was unsatisfactory. The matrix spike information was satisfactory for fifteen of the
sixteen PAH analyses in treated sediment, for five of the sixteen analyses in untreated sediment
and for eleven of the sixteen analyses in water residues. Surrogate recoveries were not
satisfactory for PAHs in the sediment and residue analyses.
SOIL TECH
The Soil Tech technology was evaluated by analyzing sediment samples and their treated
residues (treated sediments, water residues, and oil residues) for metals, conventional s, PCBs,
and PAHs. PCB and PAH analyses were performed for sediment and residues. The metals and
conventional analyses were performed for the sediment samples only.
In ;-; rr.aiont\ of the cases studied, the accuracy objective v,as satisfactory for the metal
. , r J *
analyses in treated and untreated sediments. Of the thirteen metals analyzed, accuracy
information \vas not available for Ba, Se, and Ag. Four of the thirteen metal analyses (Cd, Hg,
Se, and Ag) satisfied QA/QC requirements for blank analyses, while the remaining nine metals
(As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of the
XRF analyses, blank sample analyses are not applicable. Both initial and ongoing calibration
for Cd, Hg, Se, and Ag analyses met the ARCS QA/QC specifications for both treated and
untreated sediments while for the remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and
Zn), calibration information was not available. Detection limits information for metal analyses
in treated and untreated sediments were not available for verification except for Cd, Hg, Se, and
Ag where detection limits were satisfactory. The precision information for the metal analyses
in treated sediment was not available for Se and Hg but was satisfactory for the remaining
elements with the exception of Cr, where precision information did not satisfy the QA/QC
requirements. The precision information for the metal analyses in untreated sediment was
satisfactory for all metal analyses. The matrix spike information were satisfactory for four (Cd,
Hg, Se, and Ag) of the thirteen elements for treated sediments and two (Cd, Hg) of the thirteen
elements for untreated sediments. The matrix spike information were unsatisfactory for Se and
Ag analyses in untreated sediments. The remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni,
Pb, and Zn) were analyzed by XRF techniques. In all of the XRF analyses, results from matrix
spike analyses were not applicable.
Of the seven conventional analyses, the accuracy information in both treated and
untreated sediments was satisfactory for TOC and was not available for total cyanide, and total
rhespherji. In the remaining four conventional analyses, accuracy was not applicable. In both
sec.-;.".£. :":.: of the sever. con\er.'uonals CSTVS, TOC, toial cyanide, and total phosphorus)
-------
17
satisfied QA/QC requirements for blank analyses, and the blank information was not applicable
for moisture and pH, while blank analyses was not satisfactory for oil and grease. Both initial
and ongoing calibration information was satisfactory for all conventional analyses in both treated
and untreated sediments, except for % moisture, pH, and %TVS where calibration information
was not available. Ongoing calibration information was not available for TOC and oil and
grease. Detection limits were satisfactory for three (TOC, total cyanide, and total phosphorus)
of the seven conventional analyses in treated and untreated sediments. Detection limits were
unsatisfactory for oil and grease and were not applicable for % moisture, pH, and 9&TVS. The
precision information was satisfactory for % moisture, 9&TVS, and oil and grease in treated
sediments. The precision information was satisfactory for %TVS, and oil and grease in treated
sediments. No precision information was available for the remaining conventional analyses in
treated or untreated sediments. The matrix spike information were satisfactory for oil and
grease, total phosphorus, and total cyanide in treated sediment analyses and for total phosphorus
in untreated sediment analyses. The matrix spike information were not available for oil and
grease and total cyanide in untreated sediment analyses. While for the remaining four
conventional analyses, the matrix spike information was not applicable.
The accuracy objective was satisfactory for the PCB analyses in treated sediments and
in oil residue analyses for Aroclor 1254 only and could be used to represent the whole PCB
group. The accuracy objective was unsatisfactory for the PCB analyses in untreated sediments
and in water residue analyses for Aroclor 125-1. No accuracy information was available for the
remaining three Aroclor analyses in sediment or residue analyses. In both residues and in both
treated and untreated sediments, the blank analyses exceeded the detection limits specified in the
QAPP, except for Aroclor 1260 in oil residue. Initial and ongoing calibration was satisfactory
for all PCB analyses in both treated and untreated sediments, as well as in both water and oil
residues. Detection limit information was not available for PCB analyses in both sediments and
residues. In untreated sediment analyses, most PCB observations were below the instrument
detection limits, therefore, it was not possible to calculate meaningful precision information for
PCB Aroclors, with the exception of Aroclor 1248 analyses, where precision information
satisfied QA/QC requirements. No precision information was available for PCB analyses in
treated sediment, except for Aroclor 1254, where it did not satisfy QA/QC requirements. No
precision information was available for PCB analyses in oil and water residues, except for
Aroclor 1248 in oil residue, where precision was satisfactory. The matrix spike for Aroclor
1254 was satisfactory for both sediments and the oil residue analyses and could be used to
represent the whole PCB group. The matrix spike for Aroclor 1254 was unsatisfactory for the
water residue analyses, and the matrix spike information for both sediment and residue analyses
for Aroclor 1242, 1248, and 1260 were not available for verification. The surrogate recoveries
were satisfactory for PCB analyses in sediment and residue analyses, except for water residue
where surrogate information was not available.
In eight of sixteen PAH analyses in treated and untreated sediments, the accuracy
objective was satisfactory. No accuracy information was available for six PAHs (naphthalene,
acenaphthylene, acenaphthene, fluorene, chrysene, and dibenzo<'a.ri)amhracene) analyses in both
treated a^d untreated sediments. The accuracy ob;ecti\e *aj net satisfactory for ber.zoilo
-------
18
fluoranthene in treated or untreated sediments nor for benzo(g,h,i)perylene in untreated
sediment. Accuracy information was satisfactory for the PAH analyses in water and oil
residues. In treated and untreated sediments and water residues, PAH analyses satisfied ARCS
specified QA/QC requirements for blank analyses. In all cases of oil residues, the blank
analyses exceeded the MDL. Calibration limits for PAH analyses met the ARCS QA/QC
specifications for both treated and untreated sediments as well as water and oil residue analyses.
Detection limit information was not available for PAH analyses in treated and untreated
sediments nor for water and oil residues. In untreated sediment and oil residues, the precision
information was satisfactory for all PAH analyses, except for acenaphthene and acenaphthene
in untreated sediment, and naphthalene in oil residues, where no precision information was
available. In treated sediments, the precision information was satisfactory for naphthalene,
acenaphthylene acenaphthene, fluorene, phenanthrene, and anthracene, and was unsatisfactory
for the remaining PAH analyses. In water residues, no precision information was available for
any of the PAH analyses. The matrix spike information was satisfactory for twelve of sixteen
PAH analyses in treated sediment, and for thirteen of the sixteen analyses in untreated sediment
and ten of the sixteen analyses in water and all analyses in oil residues. Surrogate recoveries
were unsatisfactory for PAHs in either sediment and oil residue analyses but were satisfactory
in water residue.
RT~"~T~ T~ f
C i C.
The RETEC technology was evaluated by analyzing sediment samples and their treated
residues (water residues and oil residues) for metals, conventionals, PCBs and PAHs. PCB and
PAH analyses were performed for sediment and residues. The metals and conventional analyses
were performed for both sediment samples and water residues.
In a majority of the cases studied, the accuracy objective was satisfactory for the metal
analyses in treated and untreated sediments. Of thirteen metals analyzed, accuracy information
was not available for Ba, Se, and Ag. In both treated and untreated sediments, ten of the
thirteen metal analyses (As, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Hg, and Zn) satisfied ARCS specified
QA/QC requirements for accuracy. The accuracy objective was satisfactory for all metal
analyses in water, except for Se, where accuracy did not satisfy QA/QC requirements. Four of
the thirteen metal analyses (Cd, Hg, Se, and Ag) satisfied QA/QC requirements for blank
analyses. The remaining nine metal analyses (As, Ba, Cr, Cu, Fe, Pb, Mn, Ni, and Zn) were
analyzed by XRF techniques. In all of the XRF analyses, blank sample analyses are not
applicable. In water residue, blank analyses were satisfactory for all metals except for Fe, Mn,
and Se, where blank analyses exceeded the detection limits specified in the QAPP, and for Ba,
where no information regarding blank analyses was available. Both initial and ongoing
calibration met the ARCS QA/QC specifications for Cd, Hg, Se, and Ag for both treated and
untreated sediments, and for all metals in water residue analyses. While in both treated and
untreated sediments the remaining nine metals (As, Ba, Cr, Cu, Fe, Pb, Mn, Ni, and Zn),
ciJibrr.ic- :",:"::"2::rr: *s:e no: ava'lable. Detection limits information for metal analyses in
::;.: . ; ;.r; _~.-:.y;_ ;=: -e.r.s -ere r:: a\ arable for verification, except for Cd, Hg, Se, and
-------
19
Ag, where detection limits were satisfactory. Detection limits for metal analyses in water
residue were satisfactory, except for Mn, Se, and Zn, where detection limits exceeded the
QA/QC requirements. The precision information for the metal analyses in treated and untreated
sediments, and in water residue was satisfactory for all elements, except for Hg in treated
sediment, and Se and Hg in water residue analyses, where precision information did not satisfy
QA/QC requirements. The matrix spike information for treated sediment analyses were
satisfactory for Cd, Hg, and Ag, and was not satisfactory for Se. The matrix spike information
for untreated sediment analyses were satisfactory for Cd and Hg, and was not satisfactory for
Se and Ag. The remaining nine metals (As, Ba, Cr, Cu, Fe, Pb, Mn, Ni, and Zn) were
analyzed by XRF techniques for treated and untreated sediment. In all of the XRF analyses,
matrix spike analyses are not applicable. The matrix spike information for water residue
analyses was satisfactory for all metals except for Ag where matrix spike information did not
satisfy QA/QC requirement.
Of the seven conventional analyses in both treated and untreated sediments, accuracy
information was satisfactory for TOC, and was not available for total cyanide, or total
phosphorus. In the remaining four conventional analyses accuracy was not applicable. Of ten
conventional analyses in water residue, accuracy information was not available for TOC, total
cyanide, total phosphorus, and conductivity. In the remaining seven conventional analyses
accuracy \vas not applicable. In both treated and ur.treated sediments and in water residue
analyses. rcTVS, oil and grease, TOC, total cyanide, ar.d total phosphorus satisfied QA/QC
requirements for blanks. Also, the blank information was satisfactory for total solids ar.d total
suspended solids in water residue analyses. The blank information was not applicable for the
remaining conventional analyses in sediment and water residue analyses. Both initial and
ongoing calibration information was satisfactory for all conventional analyses in both sediment
and water residue, except for % moisture (in sediment), pH, and TVS, TSS, TS where
calibration information was not available, and for TOC and oil and grease, where ongoing
calibration information was not available. Detection limit information was not available in both
treated and untreated sediments and in water residue for oil and grease, TOC, total cyanide, and
total phosphorus, and was not applicable for the remaining conventional analyses. In treated
sediment, the precision information was not satisfactory for oil and grease and no precision
information was available for total cyanide. In untreated sediment, the precision information
was not satisfactory for total cyanide, and no precision information was available for TOC. The
precision information was satisfactory for the remaining five conventional analyses in treated and
untreated sediments. In water residue, the precision information was satisfactory for all the
conventional, except for moisture, where no precision information was available. The matrix
spike information was not available for oil and grease, and was satisfactory for total cyanide and
total phosphorus in treated sediment analyses. The matrix spike information was not available
for oil and grease, total cyanide, and total phosphorus in untreated sediment analyses. The
matrix spike information was satisfactory for oil and grease, total cyanide, and total phosphorus
in water residue analyses. The matrix spike information for the remaining conventional analyses
was not applicable for sediment and water residue analyses.
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20
The accuracy objective was unsatisfactory for the PCB analyses in treated sediments,
untreated sediments, and oil residue for Aroclor 1254 and could be used to represent the whole
PCB group. No accuracy information was available for the remaining three Aroclor analyses
in treated and untreated sediments. No accuracy information was available for PCB analyses
in water residues. In both sediments and residues, the blank analyses exceeded the detection
limits specified in the QAPP. Both initial and ongoing calibration for PCB analyses met the
ARCS QA/QC specifications for both treated and untreated sediments, as well as for water and
oil residues. Detection limit information was not available for PCB in either sediments or
residue analyses. The precision information for the PCB analyses in treated and untreated
sediment was satisfactory for Aroclor 1254. In all remaining analyses, precision information
was not available. The matrix spike was satisfactory for Aroclor 1254 in treated sediment and
in oil residue analyses, and could be used to represent the whole PCB group. The matrix spike
information was not available for the remaining Aroclors in treated sediment and oil residues.
The matrix spike information was not available for PCB analyses in untreated sediment and in
water residues. The surrogate recoveries were satisfactory for PCB analyses in sediment and
residue analyses.
In ten of the sixteen PAH analyses in treated sediments and in seven of the sixteen PAH
analyses in untreated sediments, the accuracy objective was satisfactory. No accuracy
hformation uas available for six PAHs (naphthalene, acer.aphth\ler.e acenaphthene, fluorene,
chrysene. dibenzo(a.h)anthracene) analyses in treated and untreated sediment. The accuracy
objective was not satisfactory for benzo(lc)fluoranthene, benzo(a)pyrene, and benzo{g,h,i)
perylene in untreated sediment. Accuracy information was satisfactory for fourteen of the
sixteen PAH analytes in oil residue. Accuracy information was unsatisfactory for PAH analyses
in water residue, except for benzo(lc)fluoranthene, indeno(l,2,3,c,d)pyrene,
dibenzo(a,h)anthracene. The blank analyses for the PAHs in treated and untreated sediment was
satisfactory in all cases except for acenaphthylene, acenaphthene, fluorene, phenanthrene, and
anthracene. In water residues, all PAH analyses satisfied ARCS specified QA/QC requirements
for blank analyses. In all oil residues, the blank analyses exceeded the detection limit specified
in the QAPP. Both initial and ongoing calibration information for PAH analyses met the ARCS
QA/QC specifications for both treated and untreated sediments, and also for water and oil
residue analyses. Detection limit information was not available for PAH analyses in either
sediments or residues. The precision information was satisfactory for PAH analyses in treated
sediments, except for benzo(k)fluoranthene, where precision did not satisfy QA/QC
requirements. The precision information was satisfactory for PAH analyses in untreated
sediments except for acenaphthylene and acenaphthene, where precision information was not
available, and for benzo(k)fluoranthene, where precision did not satisfy QA/QC requirements.
The precision information was satisfactory for PAH analyses in oil residue, except for
benzo(k)fluoranthene, where precision information did not satisfy QA/QC requirements. In
water residue, precision was unsatisfactory for PAH analyses except for benzo(k)fluoranthene,
indeno(l,2,3,c,d)pyrene, and dibenzo(a,h)anthracene, where precision was satisfactory. The
matrix spike information was satisfactory for ten of the sixteen PAH analytes in treated
sediment, for fourteen of the ar.ilytes in untreated sediment, for thirteen of the analytes in oil
resid-es. ir.d :c: three of the ar.alvtes in water residues. Surrogate recoveries were satisfactory
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21
for PAHs in both treated and untreated sediments as well as for oil and water residue analyses.
Summary
Based on the compliance with the ARCS QA/QC requirements, SAIC was capable of
supplying acceptable results for metals, conventionals, PCBs, and PAHs. The results received
for all four technologies satisfied ARCS QA/QC requirements.
An examination of results of the bench scale technology demonstration data set indicates,
that SAIC could have successfully provided acceptable data for all parameters. The data user
should be aware that some QA/QC discrepancies were identified, as indicated by subscript 1 and
2 flags in Table 3.
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NOTE
Appendix A - Laboratory Submitted Data Summary Sheets
and
Appendix D - ARCS Data Verification Templates by Parameter
are not included with this report.
Copies are available from GLNPO upon request.
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APPENDIX B
QA/QC Sample Rating Factors
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CATEGORY
RATING FACTORS
CATEGORY
SCORE ACCEPTABILITY LEVEL
Accuracy
Precision
Certified Reference Material
Analytical Replicate
3
3
Acceptable = 3
Acceptable *= 3
Spike Recovery
Blanks
Miscellaneous
Matrix Spike = 3
Surrogate Spike (organics) = 3
Blanks = 3
Instrument Calibration (initial) = 3
Instrument Calibration (on going) = 2
Instrument Detection Limit = 3
Acceptable = 3
(organics) = 6
Acceptable = 3
Acceptable = 3
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APPENDK C
Data Verification Flags
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A = Accuracy Problem
A0 = no standard available/no information available
A, = accuracy limit for the reference materials exceeded
A* = accuracy is not applicable
B = Blank Problem
BO = no information available
Bj = reagent blank value exceeded MDL
B, = blanks are not applicable
C = Calibration Problem
C0 = no information available
C, = initial calibration problem
C, = on-going calibration problem
Cs = no information on initial calibration
C6 = no information on on-going calibration
C, = on-going calibration is not applicable
D = Detection Limit Problem
D0 = no information available
D, = detection limit exceeded
D, = detection limit is not applicable
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H = Holding Times Exceeded
P = Precision Problem
P0 = no information available
P, = precision limit for analytical replicate exceeded the QA/QC
requirements
Pj = MSD exceeded the QA/QC requirement
P, = precision is not applicable
S = Spike Recovery Problem
S0 = no information available on spike
S, = limit of matrix spike recovery exceeded
S2 = limit of surrogate spike recovery exceeded
S5 = no information available on matrix spike recovery
S> = no information available on surrogate spike recovery
S, = spike rece-.ery rot applicable
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