EPA/540/2-89/014
     SUPERFUND TREATABILITY
            CLEARINGHOUSE
               Document Reference:
Atlantic Research Corp. "Engineering and Development Support of General Decon
 Technology for the U.S. Army's Installation/Restoration Program." Prepared for
  USATHMA under contract DAAK11-80-C0027. Four volumes with a total of
            approximately 500 pp. April-June 1982.
              EPA LIBRARY NUMBER:

           Superfund Treatabillty Clearinghouse -EUWW-1

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               SUPERFUND TREATABILITT CLEARINGHOUSE ABSTRACT


Treatment Process:       Thermal Treatment - Incineration

Media:                   Soil/Lagoon Sediment

Document Reference:      Atlantic Research Corp.   "Engineering and Develop-
                        ment Support of General  Decon Technology for the
                        U.S. Army's Installation/Restoration Program."
                        Prepared for USATHMA under contract DAAK11-80-
                        C0027.   Four volumes with a total of approximately
                        500 pp.  April-June 1982.

Document Type:           Contractor/Vendor Treatability Study

Contact:                Wayne Sisk
                        U.S. DOD/USATHAMA
                        Aberdeen Proving Ground,  MD  21010-5401
                        301-671-2054

Site Name:              Louisiana Army Ammunition Plant (NPL - Federal
                        facility)

Location of Site:        Atlantic Research Corp.,  Alexandria, VA

BACKGROUND;  This  document reports on the results of bench-scale tests of
treatment technologies for explosive-containing  sediment located in lagoons
at Army ammunition plants.  A companion literature search identified the
appropriate explosives remediation technologies  to be evaluated.  Cost
estimates for various treatment technologies were made based on the
laboratory data.
OPERATIONAL INFORMATION:  Sediment samples contaminated with the explosives
TNT, RDX, tetryl  and nitro cellulose from the Louisiana Army Ammunition
Plant were used in the laboratory tests.  Explosive levels in lagoon #4
sediments were at  or below 1000 ug/g.  Samples from lagoons 9 and 11 had
much higher RDX and TNT levels (1000 to 109,000  ug/gm of soil).  The report
contains a detailed QA/QC plan and analytical protocol.
PERFORMANCE;  Incineration tests were conducted  by placing approximately 4g
of sediment in a  crucible and placing the crucibles in a muffle furnace for
varying amounts of time.  Residues were analyzed for contaminants of inter-
est.  Table I shows the results of the incineration tests.  Incineration at
temperatures as low as 300-500C for 30 minutes  time can remove all the
contaminants from  the sediments.  While all of the explosives can be
reduced to their  detection limits at the lower temperatures, it is possible
that some toxic decomposition products may remain.  It is, therefore,
important to use  temperatures which reduce the total organic contents as
measured by chemical oxygen demand (COD) to acceptable levels.  This can be
accomplished at temperatures of 500 -700C and reaction times of 30 min-
utes.  Since explosive volatilization may occur,  it will be important in a
pilot scale study  to determine whether any vaporized explosives can be
detected in the exhaust gases.   Costs for treatment can vary from $100,0007
3/89-28                                            Document Number:  EUVW-1

   NOTE:  Quality assurance of data may not be appropriate for all uses.

-------
year to $2,000,000/year depending on the water content of the slurry that
is incinerated.
    In addition  to incineration,  acetone extraction,  gamma irradiation, wet
air oxidation, and water extraction tests were conducted and results
reported in this document.   Of the five procedures tested only incineration
and acetone extraction proved effective in removing contaminants from sedi-
ments.  Incineration equipment is available and pilot tests were
recommended.

CONTAMINANTS;

Analytical data  is provided in the treatability study report.  The
breakdown of the contaminants by  treatability group is:
Treatability Group

W06-Nitrated Aromatics and
     Aliphatics
VIO-Non-Volatile Metals



Wll-Volatile Metals

W12-0ther Inorganics
CAS Number

121-82-4

118-96-7

479-45-8

7440-47-3

7439-92-1

7440-43-9
COD
Contaminants

Hexahydro-1,3,5-trinitro-
 1,3,5-triazine (RDX)
Trinitrotoluene (TNT)

Trinitrophenylmethyl-
 nitramine (tetryl)
Chromium

Lead

Cadmium
Chemical Oxygen Demand
3/89-28                                            Document Number:  EUW-1
   NOTE:  Quality assurance of data may not be appropriate for all uses.

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                                 TABLE  I

            INCINERATION OP  LAGOON  9  SEDIMENT - EXPLOSIVES LEVELS


                                     Concentration  in Dry Sediment
Temperature
No heat
200


300


500


700


900


Time
(min)

5
30
60
5
30
60
5
30
60
5
30
60
5
30
60
TNT RDX
(ug/g) (ug/g)
424,000 159,000
10,000 <1
1,500 <1
1,350 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
<2 <1
Tetryl
(ug/g)
15,800
114
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
COD
(ug/g)
206,000
124,500
116,500
149,200
55,200
52,300
30,000
5,900
2,190
1,280
8,720
1,310
2,320
12,200
2,410
1,670
Note:  This is a partial listing of data.  Refer to the document for more
       information.
3/89-28                                            Document Number:  EUWV-1

   NOTE:  Quality assurance of data aay not be appropriate for all uses.

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DRXTH-TE-   C_^                  /+<                 AD
   )   ENGINEERING AND DEVELOPMENT SUPPORT OF GENERAL DECON

  H          TECHNOLOGY FOR THE U.S. ARMY'S INSTALLATION

                          RESTORATION PROGRAM
       Task 2.   Treatment of Explosives Contaminated Lagoon Sediment
                Phase IL  Laboratory Evaluation
                              Randall S. Wentsel
                              Suzette Sommerer
                              Judith F. Kitchens
                    ATLANTIC  RESEARCH  CORPORATION
                         -Alexandria, Virginia823M
                                  June 1982  c


                       Unclassified/Limited Distribution
                                Prepared  for:

          U.S.  ARMY TOXIC AND HAZARDOUS MATERIALS  AGENCY
                   Aberdeen Proving Grounds-Maryland
             ATLANTIC RESEARCH CORPORATION
                       ALEXANDRIA,VIRGINIA

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                                     Disclaimer

       The views opinions and/or findings contained in this report are those of
the authors and should not be construed as an  official  Department of  the  Army
position, policy  or decision unless so designated by other documentation.

       The use of trade names  in this report does not constitute an official
endorsement or  approval of the  use of such commercial products.  This  report
may not be cited for purposes of advertisement.


                                     Disposition

       Destroy  this report when it  is no longer needed.  Do not return it to the
originator.

-------
        UNCLASSIFIED
SECURITY CLASSIFICATION 0? THIS PAGE r7in Dt Enttrtd)
             REPORT DOCUMENTATION PAGE
                                                               READ INSTRUCTIONS
                                                            BEFORE COMPLETING FORM
         NUMBER
                                         2. GOVT ACCESSION NO,
                                                           3 RECIPIENT'S CATALOG NUMBER
 4. TITLE <** subnn) Engineering and  Development Support
  of General Decon Technology for the U.S. Army's
  Installation Restoration  Program.   Task 2.  Laboratory
  Evaluation -  Phase II
                                                       5.  TYPE Of REPORT * PERIOC COVERED
                                                        Final Report
                                                        November - July 1981
                                                       e.  PERFORMING ORG. REPORT NUMBER
                                                        49-5002-02-0002
 7. AUTHORC*;

  Randall  S.  Wentsel, Suzette Sommerer,  and
  Judith F. Kitchens
                                                           8. CONTRACT OR GRANT NUMBESri;
                                                         DAAK11-80-C-0027
 9- PERFORMING ORGANIZATION NAME AND ADDRESS
   Atlantic Research Corporation
   5390  Cherokee Avenue
   Alexandria, Virginia   22314
                                                        to. PROGRAM ELEMENT. PROJECT. TASK
                                                          AREA ft WORK UNIT NUMBERS
 II. CONTROLLING OFFICE NAME AND ADDRESS
  DCASR  Philadelphia
  P.O.  Box 7730
  Philadelphia, Pennsylvania  19101
                                                        12. REPORT DATE
                                                         June 1982
                                                        13. NUMBER OF PAGES

                                                         142
 14.  MONITORING AGENCY NAME  ADDRESS^// dlllunal Irem Controlling Otllct)
  U.S. Army Toxic and  Hazardous  Materials  Agency
  Aberdeen  Proving  Ground,
  Maryland  21010
                                                           IS. SECURITY CLASS, 'at thu rtpon)
                                                         UNCLASSIFIED
                                                        IS. OECLASSIFICATION' DOWHIBRAOING
                                                           SCHEDULE
 16.  DISTRIBUTION STATEMENT (ol (hit Rtport)

  Unclassified/Limited Distribution
 '?.  DISTRIBUTION STATEMENT (ol th* taftruct *ntrrfn D*<* *>'<*)

-------
        UNCLASSIFIED
SECURITY CLASSIFICATION OF THIS f AGCrmiwi < n(.rd)
   toxic  byproduct.  Gamma irradiation  was not  effective at the  high explosives levels
   tested,  and water extraction would.be  prohibitively expensive.
                                                  2        UNCLASSIFIED

                                               SECJRI'Y CLASSIFICATION Of THIS PGE--hen Car Ente--a

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                                    SUMMARY
       The objective of  this  study  was  to continue  the  evaluation  of promising
technologies for the treatment of explosives  containing sediment.  After a literature
evaluation  to  identify  appropriate  methods,  several  techniques were  chosen  for
laboratory  study.  This report summarizes the findings of the laboratory experiments
and recommends further evaluation for those processes which proved most effective on
a small scale.

       Five  treatment processes were  evaluated  to decontaminate  lagoon  sediment
containing  TNT,  RDX, and  tetryl or containing nitrocellulose,   or the five,  only
incineration  and  acetone extraction are  recommended fojj^vfur^herconsio^ration.
Incineration represents established technology for disposal of waste explosives and has
been  proven to  be effective  in completely  destroying  such  compounds.   Acetone
extraction  is a rapid and effective method  of removing  the  explosives {rom  the
sediment.  While the process  has not yet been demonstrated on a  commercial scale for
lagoon sediment decontamination, it is expected that conventional solvent extraction
equipment  can  be  used.   The major disadvantage of acetone  extraction  is 4hat the
waste explosives  are not destroyed and will  require  some other  method of ultimate
disposal or re-processing.

       The remaining  processes,  wet-air  oxidation,  gamma  irradiation  and  water
extraction, are  not recommended for  further study  for  various reasons.   Wet-air
oxidation effectively destroyed RDX, tetryl and nitrocellulose, but it converted TNT to
a more toxic by-product, 1,3,5-trinitrobenzene.   Gamma  irradiation was  not  effective
enough to  be  useful  for  the  highly  contaminated  sediments  tested  in  this study,
however, it may  find  application in treating low  levels of explosives contamination.
Water extraction at high temperature and pressure  was effective at removing TNT,
RDX and tetryl from lagoon sediment, but the process would be expensive to implement
and may  have some serious safety problems.

       Revised cost estimates based on the laboratory data were made for the various
treatment methods.  For comparison pirpoMSj )^&P*MyLjgd^npual  operating costs  were
based on a scenario in ^rtHfcn eleven standard IsfoonsvVHMiaiCir the report, are
treated per year.
                                         -3

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                              ACKNOWLEDGEMENTS


        The laboratory study   experimental effort   for decontamination of explosives
in lagoon sediment was  conducted over an eight month period  and  required  a  coopera-
tive  effort.  The assistance  of the following personnel in accomplishing this  task is
greatly  appreciated:

        Carl Gulp - water extraction  equipment design and construction
        Alice DeSouza - quality  control for analysis
        Antoine  Ennis -  preparation of samples for explosives  analysis
        William  E.  Harward,  HI - incineration,  acetone extraction, water
                                 extraction  experimental work
        William  E.  Jones, III - analysis of explosives and by-products
        Debra  Price -  wet chemical analysis
        Janet Mahannah  - editing
        Richard  Miller,  IT Enviroscience - wet-air oxidation
        James Pierce,  Sandia  Laboratories - gamma irradiation

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                              TABLE  OF CONTENTS
I.         Introduction	       11
           A.    Objective	       11
           B.    Background	       11
           C.    Standard Lagoon Scenario	       11
           D.    Experimental Approach	       11
II.         Lagoon Sediment  Analysis	       13
III.         Incineration	       20
           A.    Process Description	       20
           B.    Objective	       25
           C.    Experimental Procedure	       25
           D.    Results	       27
           E.    Conclusions	       32
           F.    Future Work	       36
           G.    Economic Analysis	       36
IV.         Gamma Irradiation	       40
           A.    Process Description	       40
           B.    Experimental Procedure	       40
                1.    Sample  Preparation and Irradiation	       40
                2.     Analysis of Irradiated and Control
                     Slurries   	       43
           C.    Results and  Discussion	       43
           D.    Conslusions	       46
           E.    Future Work	       49
           F.    Economic Analysis	       49
V.         Wet-Air Oxidation	       51
           A.    Process Description	       51

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          B.    Experimental Procedure	       51
                1.    Slurry  Preparation and Wet-Air Oxidation Treatment
                     Methodology	       51
                2.    Sample  Analysis	       55
          C.    Results and  Discussion	       55
          D.    Conclusions	       64
          E.    Future  Work	       64
          F.    Economic  Analysis	       64
VI.        Acetone Extraction	       66
          A.    Process Description	       66
          B.    Experimental Procedure	       68
          C.    Results   	       72
          D.    Conclusions	       75
          E.    Future  Work	       75
          F.    Economic  Analysis	       79
VII.       Water Extraction	       82
          A.    Process Description	       82
          B.    Experimental Procedure	       82
          C.    Results	       84
          D.    Conclusions	       84
          E.    Cost Analysis	       84
          F.    Future  Work	       84
vni.       Conclusions and Recommendations	       87
IX.       References	       89
Appendix  A.   Analytical Methods	       A-l
Appendix  B.   Wet Chemistry  Methods	       B-l
Appendix  C.   Raw  Data from Incineration and  Acetone Extraction
              Experiments	       C-l

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                                LIST OF TABLES

Number                                                                  Page
1.      Characteristics of the Standard  Lagoon	      12
2.      Core  Sample Analysis  for LAAP  Lagoon 4	      15
3.      Core  Sample Analysis  for LAAP  Lagoon 9	      16
4.      Core  Sample Analysis  for LAAP  Lagoon 11	      17
5.      Core  Sample Analysis  for LAAP  Lagoons -  Metals	      18
6.      Detection Limits for  Analytical Methods	      19
7.      Elemental Analysis and Heating Values  of Sediments	      28
8.      Incineration of Lagoon 9 Sediment - Explosives Levels	      29
9.      Incineration of Lagoon 11 Sediment - Explosives Levels	      30
10.    \blatilization of Explosives at 200C	      31
11.    Incineration of Lagoon 9 Sediment - Metals Levels	      33
12.    Incineration of Lagoon 11 Sediment - Metals Levels	      34
13.    Incineration of Nitrocellulose Contaminated Sediment	      35
14.    Incineration Costs	      37
15.    Effect of Sediment Water Content on  Fuel Costs	      38
16.    Incinerator Operating Temperatures and Excess  Air Requirements.      39
17.    Characteristics of Unslurried LAAP Lagcon 9 and Spiked Nitro-
       cellulose Sediments	      42
18.    Experimental Design for Gamma Irradiation Study	      44
19.    Effects of Gamma Irradiation on TNT/RDX Sediment Slurries .  .      45
20.    Effects of Gamma Irradiation on Nitrocellulose Slurries	      47
21.    Duncan's  Multiple Range Test for  Nitrocellulose Sediment  ...      48
22.    Capital Costs for Gamma Irradiation	      50
23.    Annual Operating Costs for Gamma Irradiation	      50
24.    Treatment Scheme for Wet-Air  Oxidation of Sediment Slurries  .      54
25.    Wet-Air Oxidation Treatment  of LAAP Sediment	      56
26.    Evaluation of Wet-Air Oxidation Data  of Duncan's  Multiple
       Range Test	      59
27.    Off-Gas Analysis for Wet-Air Oxidation of TNT/RDX Sediment
       Slurries	      61

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Number
28.    Wet-Air  Oxidation of Nitrocellulose Sediment	      62
29.    Off-Gas  Analysis for Wet-Air Oxidation of Nitrocellulose Sediment
       Slurries	      63
30.    Capital Costs for Wet-Air Oxidation	      65
31.    Annual Operating Costs  for Wet-Air Oxidation   	      65
32.    Solubility of Explosives in Acetone	      67
33.    Acetone  Extraction  of TNT/RDX/Tetryl Contaminated  Sediment .      73
34.    Serial  Acetone Extraction	      74
35.    Acetone  Extraction  of Nitrocellulose Contaminated  Sediment  .  .      76
36.    Experimental Conditions to Establish TNT/RDX/Tetryl
       Equilibrium  Curves	      78
37.    Experimental Conditions to Establish Nitrocellulose  Equilbrium
       Curves	      78
38.    Capital Costs for Acetone Extraction	      80
39.    Acetone  Extraction  Annual Operating Costs	        81
40.    Water  Extraction	      85
C-l.   Sediment Weights for Incineration Experiments	      C-2
C-2.   Acetone  Extraction  of TNT/RDX/Tetryl Sediments - Raw Data  .      C-3
C-3.   Acetone  Extraction  of Nitrocellulose - Raw Data	      C-4

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                                LIST  OF FIGURES

Number                                                                   page

1.     Sample  Points at Louisiana Army  Ammunition  Plant	       14
2.     Rotary  Hearth  Incinerator	       21
3.     Multiple Hearth Incinerator	       22
4.     Electric Furnace	       23
5.     Fluidized Bed Incinerator	       24
6.     Rotary  Kiln	       26
7.     Gamma Irradiation  Treatment System  for Dried Sewage Sludge.  .       41
8.     Schematic of Catalyzed  Wet-Air Oxidation  Batch  Reactor ....       52
9.     Picture of Wet-Air Oxidation Reactor	       53
10.   Picture of Wet-Air Oxidation Control  Equipment	       53
11.   GC-MS of Slurry Water  Extract Before Wet-Air Oxidation
      Treatment	       58
12.   GC-MS of Slurry Water  Extract After Wet-Air Oxidation at
      250C/980 psig	       59
13.   Two Steps in the Operating  Cycle of  an  Extraction Battery ...       69
14.   Rotocel Solvent Extractor	       70
15.   Dorr  Thickener	       7i
16.   Water Extraction Apparatus	       83
                                         10

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                               I.  INTRODUCTION

 A.      Objective

        The objective of this study was to determine  on a  laboratory scale the
 effectiveness of several decontamination processes for explosives containing lagoon
 sediments.  Five processes  were recommended for laboratory study after an initial
 literature  search  to  identify  possible  treatments (Wentsel et_al., 1982 ).  These
 processes were incineration, wet-air oxidation, gamma irradiation, acetone extraction,
 and  water extraction.

 B.      Background

        For many years, solid and liquid  wastes from Army Ammunition Plants have
 been stored  in  waste lagoons.   Since most  of these lagoons were  not lined, the
 sediments  on the  bottoms of these lagoons have  become  highly contaminated with
 explosives and  explosives by-products.  The toxicity of these compounds and  the
 potential  for their  leaching into  the  local  ground  water  present  some  serious
 environmental problems.   Treatment  of these sediments  to remove explosives  is
 required if the environmental hazards  associated  with them are to be avoided. Two
 types of sediments which must be treated have  been identified at Army  Ammunition
 Plants.  One  type of sediment contains 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene
 (DNT), hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX), and tetryl.   The  other  contains
 nitrocellulose.

 C.      Standard Lagoon Scenario

        In order to compare capital and operating costs  for  the various treatment
 systems, calculations  were  made on   the  basis of treating 11  standard  lagoons  as
 defined in Table 1.  This standard lagoon  is  intended to be a typical explosives waste
 lagoon,  and its characteristics were defined on the basis of the best  data that were
 available at the  time.  Capital costs include the cost of equipment for removing the
 sediment  from  the  lagoon and processing it.  Operating costs are  calculated on  an
 annual basis.

 D.      Experimental  Approach

        The laboratory experiments conducted  in this study  were not  intended  to
simulate the operation of commercial-scale equipment.  Instead, the contaminated
sediments were subjected to  simple, small-scale experiments which indicated whether
or not  the process  was an effective  treatment method.   In addition,  process
 parameters were optimized as much as possible on this scale.   All of the processes
 recommended for additional  study will require  further development and demonstra-
 tion  before they are  ready  for  field use.
                                       11

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             Table  L  Characteristics of the  Standard Lagoon



Size

    30.5 m x 45.7 m x 2.7 m  deep (100 ft x  150 ft x 9 ft.)

Depth of Sediment to be  Treated

    0.3  m (1 ft)

Volume of Sediment  to be Treated (wet)

    447.5  m3 (118,200 gal)

Weight of Sediment  to be Treated (wet)

    499,400  -  544,800  kg  (1,100,000 - 1,200,000  Ib)

Sediment Characteristics

     moisture content:     50-80%
     composition:  (dry basis)

          10%  TNT
           5% RDX
          10%  other  organics
          75% ash

     heat content (dry  basis):    1028  kcal/kg (1850  Btu/lb)

 Treatment rate (11 lagoons/yr,  300 days/yr,  24 hr/day)

     763 kg/hr (1680  Ib/hr)
     684 1/hr (180 gal/hr)
                                     12

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                        n.  LAGOON  SEDIMENT ANALYSIS


        Sediment core samples were collected from  waste lagoons at Louisiana Army
 Ammunition Plant (LAAP) to select sediment for the laboratory phase of Task 2.  The
 sediment sampling sites  are presented in Figure  L  Sediment samples were taken with
 a core  sampler  at two different sites  in Lagoons 4, 9 and  1L  Each core sample  was
 divided into three 6-inch (15.2 cm) segments.

        The sediment  samples were analyzed for TNT,  RDX,  nitrate, COD, percent
 volatiles and metals.  The methods used in  these  analyses are detailed in Appendix A.
 The data  from  lagoon  4  are  presented in  Table  2.   Explosive levels in lagoon
 4 sediments were at or below 1000  yg/g.  COD  levels  ranged from  8100-37,900yg/g.
 The highest  explosive   levels  were   found  in lagoon 9 (Table 3).    In  the  top
 six   inches  of  site   1,  TNT   and   RDX  levels  were 109,000 and  91,900 yg/g,
 respectively. However, explosive levels  at  site 2 were less  than 1000 yg/g.   Lagoon 11
 was moderately contaminated with  explosives (Table 4).  In the top six inches (15.2  cm)
 of sediment, TNT and RDX  levels ranged  from  1000 to  8,000 yg/g.

        The core samples from the three lagoons showed a great degree of variability
 in explosive concentrations.  Explosive  concentrations varied at different lagoon sites,
 core depths, and between lagoons.

        The results of the analysis for metals in the lagoon sediments are presented  in
 Table 5.  Lagoon 9 sediment had elevated  zinc levels.  Site 1 of Lagoon 11 had higher
 than normal lead and  chromium  levels.

        Actual field samples of nitrocellulose contaminated sediment were not available
 for  these  laboratory studies.  Therefore sediment samples were obtained from a pond
 located near Atlantic Research  Corporation and spiked by addition of solid  nitro-
 cellulose to the sediment followed  by mixing  of  the sediment  to  evenly disperse the
 nitrocellulose.   Nitrocellulose  concentrations in  the  sediment   ranged  from  13,800
yg/g for the incineration  studies to  approximately 60,000 yg/g for the wet-air  oxidation
 tests.

        All  analyses   were  conducted  according  to  the  procedures  presented   in
 Appendices A and B.   The  methods in  Appendix A  were  verified according to the
 USATHAMA QC  plan.   Detection  limits were calculated according to  the method of
 Hubaux and Vos.  These detection b'mits are summarized  in  Table  6.  Several analyses
 were performed for  which the detection limit determinations were not  deemed to be
 necessary  by  the Project Officer.   These  analytical  procedures  are  presented  in
 Appendix  B.
                                        13

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c/5
   D

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Table 2.  Core Sample  Analysis  for LAAP  Lagoon 4
Site
4-1


4-2


Depth
(cm)
0
15.2
30.5
0
15.2
30.5
- 15.2
- 30.5
- 45.7
- 15.2
- 30.5
- 45.7
TNT
(^g/g)
510
330
610
1050
1050
780
RDX

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Table  3.   Core Sample Analysis for  LAAP  Lagoon 9
Depth
Site (cm)
9-1 0
15.2
30.5
9-2 0
15.2
30.5
- 15.2
- 30.5
- 45.7
- 15.2
- 30.5
- 45.7
TNT

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Table 4.   Core Sample Analysis for LAAP Lagoon 11
Site
11-1


11-2


Depth
(cm)
0 - 15.2
15.2 - 30.5
30.5 - 45.7
0 - 15.2
15.2 - 30.5
30.5 - 45.7
TNT
(pg/g)
7110
810
620
1400
930
830
RDX
(Pg/g)
8020
4010
2710
990
680
960
Nitrates
(Pg/g)
57
36
45
22
22
22
COD
(pg/g)
47,700
14,000
14,000
39,600
12,300
10,200
Vo la tiles
(%)
4.4
2.2
2.0
3.1
4.7
3.3

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                             Table 5.  Core Sample Analysis  for LAAP  Lagoons -  Metals
00
Site
4-1
4-2
9-1
9-2
ll-l
11-2
Lead
(pg/g)
20.8
6.2-8.8
9.6-35.0
12.1-34.0
54.9-86.7
33.6
Chromium
(pg/g)
23.2
21.7
25.5-30.6
20.4-35.2
64.4-113.0
16.1-21.7
Zinc
(Mg/g)
NA
NA
132-209
845-1408
195
NA
Cadmium
(yg/g)
NA
NA
2.5-4.0
14.9-23.0
NA
NA
             NA - not  analyzed

-------
     Table  6.  Detection  Limits for  Analytical  Methods

         Methods                            Detection Limits

Nitrate in Water                               0.2     yg/ml
Lead in  Water                                 0.25    yg/ml
Chromium in  Water                             0.3     yg/ml
Cadmium in  Water                             0.050   yg/ml
Zinc in Water                                 0.2     yg/ml
Nitrate in Sediment                             2      yg/g
Lead in  Sediment                               7      yg/g
Chromium in  Sediment                 -         7      yg/g
Cadmium in  Sediment                           3      Ug/g
Zinc in Sediment                               5      yg/g
Nitrocellulose in Sediment                      17      yg/g
TNT in Sediment - High Level                  178      yg/g
RDX in  Sediment  - High Level                 490      yg/g
TNT in Sediment - Low Level                   2      yg/g
RDX in  Sediment  - Low Level                   1      yg/g
Tetryl in Sediment -  Low Level                 0.3     yg/g
                             19

-------
                                III.   INCINERATION
A.      Process Description

        Incineration or  high  temperature  oxidation  of  materials  is an  extremely
effective decontamination method.  When oxidation of the  explosives of  interest is
complete, gaseous carbon dioxide, nitrogen oxides, and water are the only products.  For
explosives contaminated sediment, most of the inorganic portion of the sediment will
remain  as ash.

        Several incinerator types  have  been proposed for the  incineration of explosives
contaminated lagoon sediment. Those  which were examined  in  the Phase I report of
this study (Wentsel et  aL, 1S82) are the air curtain incinerator, the cyclone or rotary
hearth  furnace, the multiple  hearth furnace, the electric furnace, the  fluidized  bed
incinerator and the rotary kiln. A brief description  of each type of equipment  is given
below.

        The cyclone furnace  or rotary hearth furnace, shown in Figure 2, is a refractory
lined steel cylinder  with a single  rotating hearth.  Wastes are introduced  at the outer
edge of the  hearth and are gradually moved inward  by a fixed plow toward  an  ash
discharge chute at  the center of the  hearth.   Combustion air  is injected above  the
hearth at high tangential velocity in the opposite direction to hearth  rotation.  The air
sweeps  over  the burning waste, then spirals upward toward the exhaust. The cyclone is
operated  at  high  temperatures with exit  gases  leaving the  system at around 820C
(1500F) (EPA,  1979).   Combustion products must pass  through  this high  temperature
central vortex  before  leaving the  furnace,  and this  passage  essentially  completes
combustion  of all organics without any need  for an afterburner  (Stribling,  1972).

        A schematic drawing of a multiple hearth incinerator is presented in Figure 3.
The furnace  is a  refractory-lined  steel cylinder containing a  number of horizontal
refractory hearths  stacked vertically.  Internally  air cooled rabble arms pivot about the
center, raking  burning material spirally towards the  center  or towards  the  edge  on
alternating  hearths.   Waste material  enters  the top of  the furnace, dropping from
hearth  to hearth through  the drying zone (310 to 540C),  the combustion  zone (760C
to  980C), and the ash cooling zone (200C to  315C)  (EPA, 1979). Combustion air is
introduced at the  bottom of the incinerator, and  may be preheated by  first  circulating
as  cooling air through  the rabble arms.

        The  electric furnace,  shown in Figure 4,  has a horizontal metal mesh conveyor
belt which passes under a  series of electric heating  elements.  The steel shell  is lined
with ceramic  fiber insulation  which can  be heated and  cooled very rapidly  without
damage.  Waste material enters  at one end of the furnace,  and combustion air is
admitted to the other to  provide countercurrent exchange of heat and oxygen.

        A fluidized bed incinerator, shown in  Figure 5, is a vertical  refractory-lined
cylinder with a bed of sand or  some  other  particulate suspended by air  flowing  up
through the  bottom of  the incinerator.  Burners  above the fluidized bed at the air inlet
provide  heat   to raise  tne oed temperature ana to provide comoustion heat to low
                                          20

-------
                 EXHAUST
COMBUSTION AIR
          TANGENTIAL
          AIR PORTS
                BURNER (TYP)
                                                                      CYCLONIC ACTION

                                                                      ROTATING HEARTH

                                                                      FIXED PLOW
                                                                 SLUDGE
                                                                 INLET
                                                 ASH DISCHARGE IN
                                                CENTER OF FURNACE
                  Figure  2.  Rotary Hearth  Incinerator (EPA,  1979)
                                             21

-------
               COOLING AIR
               DISCHARGE
SLUDGE CAKE,
SCREENINGS,
AND GRIT-
SCUM
                                                    RABBLE
                                                    ARM
                                                    DRIVE
AUXILIARY
AIR PORTS

RABBLE ARM
2 OR 4 PER
HEARTH

   GAS FLOW
    CLINKER
    BREAKER
                                                           BURNERS
                                                           SUPPLEMENTAL
                                                           FUEL

                                                           COMBUSTION AIR
                                                          SHAFT COOLING
                                                          AIR RETURN
                                                          SOLIDS FLOW
           DROP HOLES
             ASH
       DISCHARGE
           Figure 3.  Multiple Hearth Incinerator (EPA, 1979)
                                22

-------
to
CO
BELT
DRIVE -
SLUDGE FEED
Ox\ j
AIR
GAS
EXHAUST  |
1

LOCK --TfTjr



RADIANT
INFRARED
ROLLER HEATING r- WOVEN WIRE
- LEVELER ELEMENTS (TYP) \ CONTINUOUS BELT
COOLING 1 COOLING I
AIR 1 AIR I
r- RABBLING j 111
} \DEVICE j^^ 	 \ j, I
\i> oooooooooooooooo \
LJ

r i i "r j

	 > COMBUSTION
	 ^ AIR
ASM
DISCHARGE
                                           Figure 4.   Electric  Furnace (EPA, 1979)

-------
                                        ^-EXHAUST AND ASH
         SAND/M
         FEED^S
  THERMOCOUPLE
   SLUDGE
   INLET
FLUIDIZING
AIR INLET
                          FLUiDIZED/v/:':'.;/
                          SAND BED .':::/::
                                               PRESSURE TAP
                                             ^SIGHT
                                             Y GLASS
                                                  BURNER
                          REFRACTER
                            ARCH
                    TUYERES

                   FUEL
                   GUN
                  PRESSURE TAP
WINDBOX
   STARTUP
h-i PREHEAT
  DBURNER
_TFOR HOT
   WINDBOX
           Figure 5.  Fluidized Bed Incinerator (EPA, 1979)
                             24

-------
heating value wastes (EPA, 1979).  Sludge is fed either  into the fluidized sand or  into
the freeboard space above the sand bed  (EPA,  1979).   Bed temperature  is maintained
between 750C and 850C (Dawson, 1978). The  excellent mixing of the system and the
uniform  high bed temperature  generally  make an  afterburner  unnecessary.   Ash  is
carried from the bed by the  fluidizing air and is then removed from the gas stream by
a particulate scrubber, electrostatic precipitator, or baghouse.

        A rotary kiln is a horizontal refractory-lined cylinder which rotates on a  pair
of steel tires. The  kiln is sloped downward from inlet to exit,  with  combustion  air inlet
and the burner usually located at the lower end (Conway and Ross, 1980). The rotational
speed and angle of  incline determine the residence  time of waste  material in the  kiln
(Conway and Ross, 1980)  which  varies from several seconds to  several hours (Scurlock
etaL, 1975).  Combustion temperatures  can range  from 810  -  1650C (Dawson, 1978).
A  small  skid-mounted rotary kiln unit  is shown in  Figure 6.

        Air pollution is a  potential difficulty which must be considered in the design of
any incineration system.   Incomplete combustion  of the material  and entrainment of
particulates  in the  exhaust gas  can pose serious environmental problems.  Incomplete
combustion and volatilization of the waste materials are corrected by the addition of
an afterburner.  Ash  particles carried by the gas stream can  be removed by scrubbers,
electrostatic precipitators, and baghouses. Vaporized metals can be removed  from the
exhaust by a baghouse  after  the gas has been  cooled.

B.      Objectives

       The  objectives of the laboratory  incineration experiments were to demonstrate
the feasibility of incineration as a  sediment decontamination process and to  establish
the temperatures and  treatment times required to obtain complete destruction of the
explosives. Because the  process conditions in most  types of  incinerators  are   non-
homogeneous, they  are difficult to duplicate on  a small scale.  Air/sediment mixing
patterns  and appropriate heating distributions  are among the  most difficult of the
process parameters to  modeL  The incineration experiments in this  study, therefore,
made no attempt to  simulate the operation of commercial incinerators.

C.     Experimental  Procedure

       For  the  incineration  experiments, large samples (approximately 100 g) of each
of  the sediments from  LAAP lagoons 9  and 11  and the spiked  nitrocellulose  sediment
were  taken.   These  samples  were  thoroughly   mixed  to  increase the  explosives
uniformity and air dried.  Duplicate subsamples of each  of the  three sediment samples
were  taken  and sent  to Galbraith Laboratories in  Knoxville, Tennessee  for elemental
analysis and  bomb  colorimetry for heating value  determinations.

       Incineration tests were conducted by weighing approximately 4 g  subsamples  of
the dried  sediments into preweighed open ceramic crucibles.  Each crucible was heated
in  a muffle   furnace for the  prescribed  time. The  subsamples were treated in random
order at  200C, 300C, 700C and  900C for intervals of 5, 30 and 60 minutes.  After
the treatment  interval, the  crucibles  were removed from the furnace, cooled  in a
                                         25

-------
Figure  6.  Rotary  Kiln (C-E Raymond, 1980)
                   26

-------
desiccator and reweighed. The heated subsamples were analyzed for residual explosives
and  heavy metals  by the methods described in Appendix  A. The  chemical oxygen
demand (COD) of each subsample was determined by the method described in Appendix
B.  The  residual explosives concentrations were  then compared to the concentrations
in non-heated control subsamples  to determine the effectiveness  of  heat treatment.

D.     Results

       The  results  of  the  elemental  analyses and  heating value  determinations
performed by Galbraith  Laboratories on  TNT/RDX/tetryl containing sediments from
Lagoons  9 and 11 and on  sediment  spiked with nitrocellulose are listed in Table 7.  The
sediment  from Lagoon 9  contained high levels of explosives and consequently  had  high
percentages of carbon, nitrogen and oxygen and a high heating value.  The sample from
Lagoon 11 contained only  small amounts of organic material and had a very low heating
value.   Sediment  spiked  with approximately 1.5%  nitrocellulose had an intermediate
heating value.   Very  little sulfur  was  found  in any of  the samples.

       The  results  of incineration  experiments on sediment  from  Lagoon 9  (which
contained high  levels  of  TNT, RDX  and tetryl) are presented in Table 8.   Sample
weights before   and  after  treatment  are presented in  Table  C-l of Appendix C. At
200"C, 0.3% of the  original TNT remained after  one  hour.  Liquid chromatography
analysis detected no RDX  or tetryl in these  samples.   After heating at  temperatures
of 300C  and higher, the explosives could not be detected, even after contact times
as snort as five  minutes.  Chemical oxygen demand at each temperature was generally
reduced  with increasing  treatment  time, however, some exceptions  were  observed.
These exceptions were most likely  due to variations in the original sediment and to the
fact that the lowest  COD levels reported  were close  to  the minimum that can be
determined with the  analytical procedure.  Reaction temperature  had  a much larger
effect  on  COD levels than did reaction time. COD reductions ranged from only 30-40%
at 200C  to  more than 99%  at  500C  to 900C for reaction  times  of 30  minutes or
more.

       Results  of  incineration experiments  on Lagoon 11 sediment  are presented in
Table 9.   Explosives in  these  experiments  did  not decompose as rapidly as  in  the
previous experiments with Lagoon 9 sediment and COD levels did not  drop as rapidly
or as completely.  After 30 minutes at a temperature of 500C, 0.04% of the original
TNT, 0.06% of  the  original RDX  and 0.04% of the original  tetryl  remained  in  the
sediment.  Increasing reaction time had little effect on the remaining explosives, but
COD was  reduced.  Similar results were observed at 700C.   While explosives reduction
was  dramatic,  TNT  and  RDX were  both detectable  in the  treated  sediment.  One
possible  explanation  for  the  more rapid  and  complete combustion   of  the highly
contaminated Lagoon 9 sediment is that the large amount of heat released by oxidation
of the  explosives  drives  the temperature of the sample higher  than the controlled
furnace temperature. This excess heat results in spontaneous combustion of the residual
explosives in the sample.

       One  area  of concern  was the potential  for volatilization of  the explosives
instead  of decomposition.   To  determine  if  explosives  volatilization  occurs   and
therefore  the necessity of an afterburner, a volatilization experiment was performed on
Lagoon 9  sediment.  The results of this experiment  are  presented in  Table 10. Exhaust
                                        27

-------
to
oo
                          Table 7.  Elemental Analysis and Heating  Value  of  Air-Dried  Sediments
                                                                                                                   Heating Valu<

Lngoon 9

Lagoon 11

Nitrocellulose

C
Ave
17.49 15.82
14.14
0.36 0.37
0.38
4.86 4.87
4.88
H
Ave
1.22 1.14
1.06
0.11 .11
0.10
1.06 1.04
1.01
% N
Ave
10.28 9.25
8.21
0.18 .17
0.15
1.08 1.10
1.01
% S
Ave
0.01 .01
0.01
0.05 .06
0.06
0.06 .06
0.06
% 0
Ave
17.52 17.88
18.23
2.45 2.55
2.65
14.34 14.35
14.35
BTU/lb.

2326
2255
58
63
763
728
Av
2291

61

751


-------
                          Table 8.  Incineration of Lagoon 9  Sediment - Explosives  Levels

                                                                Concentration in  Dry Sediment
NS
CO
Temperature

-------
Table 9.  Incineration of Lagoon 11 Sediment  -  Explosives Levels
                                         Concentration in Dry Sediment
Temperature Time
(C) (min)
No heat
200 5
30
60
300 5
30
60
500 5
30
60
700 5
30
60
TNT
(pg/g)
47,300
27,800
1,290
1,170
<178
<178
40
20
20
35
30
3
<1
RDX
(Mg/g)
15,900
4,430
< 490
146
< 490
< 490
20
10
10
10
20
5
30
Tetryl
fcg/g)
2,100
780
< 70
< 70
< 70
< 70
6
< .3
.9
< .3
.8
< .3
< .3
COD
(pg/g)
81,800
32,800
46,900
50,900
57,700
29,800
2,100
16,800
13,400
300
14,000
12,200
8,100

-------
Table 10-     Volatilization  of Explosives at 200C
Explosive
TNT
RDX
Tetryl
Explosive Level
Before Heating
(Pg/g)
218,000
32,200
6,600
Explosives in Sediment
After Heating
(%)
34.6
27.3
19.0
Explosives
Volatilized
(%)
14.5
3.3
< 30

-------
gases were  passed through a  condenser  and the  condensate was  rinsed  with  known
quantities of acetone and the rinse  analyzed  for explosives.   After one hour at 200C,
19-35% of each of the  original explosives remained  in the sediment  and 3.3%  of  the
RDX and 14.5% of the TNT were recovered in the condensate. Tetryl was not detected
in the condensate, but the low  initial level of tetryl  and  the dilution  of  the rinse
required  that more  than  30%  of the  original amount be  present for detection.   This
experiment  shows  that some  volatilization without combustion can occur.    If  the
incinerator is one in which the exhaust gases will  not pass through  a  high temperature
region to complete  combustion, an afterburner will be  required to  ensure  complete
destruction  of the explosives.

        Another  possibility which  must  be  considered  in incineration  design  is  the
potential for vaporization of heavy metals.  Lagoon  9 and Lagoon 11 sediment samples
were analyzed for several metals  before and after  the incineration experiments. The
results of these  analyses  are presented  in Tables  11 and 12.   Metal levels before and
after treatment  remained approximately the same  up to temperatures of 700C for
sediments from both Lagoons 9 and 11.  Increases  in metal levels after treatment are
the  result of burning away the organic portions of the sediment but  leaving the same
total amount of  metals.  Other variations in the data are due primarily  to variations
in the orignal sediment.  At 900C, lead, chromium, and cadmium levels were reduced
 significantly, indicating that all three metals were vaporized  or carried out in dust with
 the  air  stream  during  treatment. In a  commercial  scale    incinerator,  either  the
 temperature  will have to be controlled to prevent  metals vaporization or the  metals
 will have to be recovered from the gas stream. Such recovery  can  be accomplished by
 a baghouse after the gas has  been cooled.

        The results  of incineration experiments on sediments spiked with nitrocellulose
are  shown in Table 13.   At  all treatment temperatures  and  times,  nitrocellulose was
reduced  to  below its detection limits. COD levels  were  reduced by longer treatment
times at any  given temperature, but as was observed with the sediments from Lagoons
9 and 11, furnace temperature produced a much larger effect.   At  900C, COD  levels
were reduced by  99.8% at treatment  times  of  30  and 60  minutes. At 200C, the COD
level was reduced by 83%  after one  hour.

 E.      Conclusions

        These experiments demonstrated that incineration is an effective method for
 destroying  TNT, RDX,  tetryl  and  nitrocellulose in  lagoon  sediment.    Essentially
 complete decontamination of the sediment  for  all of  the  explosives tested can  be
 achieved at temperatures of  300-500C with treatment  times of 30  minutes or less.
 While all of the explosives can be reduced to their detection limits at the  lower
 temperatures, it is  possible  that some toxic decomposition products may remain.  It is
 therefore important to use temperatures which  reduce  the  total  organic content  as
 measured by COD to acceptable levels.  This can be accomplished at temperatures of
 500-700C and reaction times  of 30 minutes.  Since explosives volatilization may occur,
 it  will  be   important  in  a pilot  scale  study  to determine  whether any  vaporized
 explosives can be detected  in the exhaust gases.

        Metals are vaporized  if the  sediment  is incinerated  at  900C,  but are  not
 vaporized  if  the  temperatures are maintained  at  700C  or  less.  Vaporization  can be
 minimized  by controlling  incineration temperature at/or  below 700C.  Alternatively,
 the incinerator  could  be operated  at  higher  temperatures if a cooling system  and
 baghouse were provided to recover the vaporized  metals.  The incineration laboratory
 studies were conducted on dried sediment containing relatively high  concentrations of
 explosives.   The dried  sediment represents a worst case from a potential  hazards point
 of view.  However, in the field, the sediment will contain significant amounts of water
 e.g. 20-80%. This water wiU render  the sediment  safer  to handle in the digging, mixing


                                          32

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                                  Table  11.    Incineration of Lagoon 9 Sediment  -  Metals Levels
CO
GO
Temperature
(C)
No heat
300


500


700


900


Time
(min)

5
30
60
5
30
60
5
30
60
5
30
60
Lead
(ug/g)
75
74
99
74
93
120
84
90
100
160
81
5.2
18
Chromium

-------
                                  Table   12.   Incineration of Lagoon 11 Sediment - Metals  Levels
CO
.fc.
Temperature Time
(C) (min)
No heat
200 5
30
60
300 5
30
60
500 5
30
60
700 5
30
60
Lead
(Pg/g)
31
16
28
18
19
29
31
33
26
31
21
26
21
Chromium
(pg/g)
24
7
10
10
10
7
10
30
10
10
20
40
5

-------
                              Table  13.    Incineration of  Nitrocellulose  Contaminated Sediment
CO
en
Temperature
No heat
300


500


700


900


Time
(min)

5
30
60
5
30
60
5
30
60
5
30
60
Nitrocellulose COD
(Pg/g) (ug/g)
13,800 106,000
< 17 38,400
<17 22,200
<17 17,900
<17 12,000
<17 3,500
<17 1,200
<17 2,600
<17 690
<17 1,020
<17 2,500
<17 220
<17 200

-------
and incinerator feed stages.  The largest problem will be the amount of energy required
to simply vaporize  the water.'  Incinerator design or optimization of sediment through-
put will  thus  largely be based on  the energy requirements  to vaporize the  water and
heat the sediment to the desired temperature. Essentially the explosives  will go along
for the ride.

       Incineration has been demonstrated on  a commercial scale for destruction of
waste  explosives,  and  equipment  i  available  which  would  not   require  signifi-
cant modification to process explosives contaminated sediment.  Of  all the processes
evaluated, incineration is the one  which could  be directly implemented at an  Army
Ammunition Plant  most quickly and  with the least developmental costs.

F.      Future Work

        Pilot  scale  tests of  incineration to treat TNT/RDX/tetryl  and  nitrocellulose
containing sediments are scheduled for this fall.  Tests will probably  be  conducted in
a rotary kiln incinerator, a  piece  of equipment which has been  used in the past for
munitions incineration.   A  subcontractor  will  provide  facilities   and personnel  to
perform    pilot scale    incineration  tests  of TNT/RDX/tetryl and   nitrocellulose
contaminated sediments.   The  results  of  the   tests  will be used  to determine the
technical  feasibility,  scale-up  potential  and   costs  of  incinerating  approximately
5,500,000  kg/yr (12,100,000 Ib/yr) of  sediment.

        Each  of the two sediment types will be tested at a minimum of four different
incineration  conditions for at  least two  hours  after  stabilization  of the  system.
Temperature, air flow, fuel consumption,  and feed rate will be monitored during the
tests.    The  ash,  exhaust gas, and  any scrubber  or other  effluents  will be sampled
periodically.  These samples will be  analyzed by ARC to  monitor system  performance.
 After  the pilot scale tests are  completed, the results will be used to  provide a  better
estimate  of  incineration  costs  and appropriate operating parameters for treating
explosives  containing sediments.

G.      Economic  Analysis

         Capital and operating costs (based on the limited labortory tests) to treat the
 sediment from 11 standard lagoons per year are  presented in Table 14.   Capital costs
 include  a dredge,  a holding tank, a  flat bed trailer on which to carry  the  equipment
 and the  incinerator with afterburner and/or other pollution  control devices.  Operating
 costs  were calculated  on the basis of  the sediment composition and moisture content
 described for the  standard lagoon.  Capital and operating costs are roughly equivalent
  for all of  the incinerators evaluated so ability  of the system to handle  the  explosives
  contaminated sediments  will be  the  major  factor in  choosing between them.   The
  effects of sediment moisture content on fuel costs, a major component of the operating
  costs, are shown  in Table 15.  These costs were based  on the excess air requirements
  and operating temperatures for the various systems, as listed in Table 16.  The  rotary
  kiln has a maximum fuel cost higher than the other incinerators because it can operate
  at  temperatures  up  to 1650C.   The high  explosives  level sediment  is capable of
  sustainiiig combustion  without  additional  fuel when  it  is  dry,  while  the  low level
  sediment requires $100,000 - $200,000 per year  in fueL  ^,watar..$oatejit,goes up, fuel
  
-------
                  Table  14.  Incineration Costs  (1980 Dollars)
      Incinerator                     Capital  Costs          Annual Operating Costs






Rotary Hearth Furnace                $ 705,800                $310,000  -  $440,000






Multiple  Hearth Furnace               $ 751,000                $460,000  -  $500,000






Electric  Furnace                      $ 560,000                $380,000  -  $550,000






Fluid  Bed Incinerator                  $ 891,000                $430,000  -  $490,000






Rotary Kiln                           $ 496,000                $370,000  -  $420,000

-------
CO
00
                               Table 15.  Effect of Sediment Water  Content on Fuel Costs
                                                    Annual Costs in Thousands of Dollars/Year (1980  Dollars)
Incinerator
High Heating Value (2000 Btu/lb)
Rotary Hearth
Multiple Hearth
Electric Furnace
Fluidized Bed
Rotary Kiln
Low Heating Value (100 Btu/lb)
Rotary Hearth
Multiple Hearth
Electric Furnace
Fluidized Bed
Rotary Kiln
Dry Sediment

0
0
0
0
0

104-156
115-168
92-152
92-113
104-256
60% Solid Slurry

20-91
25-102
1-86
1-34
'"-265

305-377
304-388
286-371
286-320
305-552
15% Solid Slurry

1525-1736
1483-1747
1460-1730
1460-1586
1524-2485

1810-2021
1768-2032
1745-2016
1745-1871
1810-2771

-------
         Table  16.   Incinerator Operating Temperatures and Excess
                    Air Requirements
   Incinerator
Temperature  Range
Excess Air Requirements
Rotary Hearth

Multiple  Hearth

Electric  Furnace


Fluidized Bed


Rotary Kiln
     820

     760-980

     760-980



     750-850



     810-1650
         30-80

         95-100

         20-70



         20-30



         30-50
                                    39

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                            IV.  GAMMA IRRADIATION
A.     Process Description

       Gamma  irradiation can  breakdown  organic  molecules  by either direct  or
indirect methods.  Direct ionization by gamma rays  will often cleave chemical bonds
leading to the formation of free  radicals.  Gamma irradiation also produces H and OH
free radicals which can react to form ozone and hydroperoxide.  These oxidizing agents
also contribute to the degradation process  through  oxidative  break  down of organic
matter present in the medium.

       Two  isotopes,  Cesium-137  (Cs-137)  and  Cobalt-60  (Co-60),  are  currently
employed as sources in the gamma irradiation systems used in  sludge  disinfection
treatment processes.  Cs-137 is available as a  by-product from the processing of nuclear
weapon wastes.  Co-60 is produced by  exposing cobalt  metal to  accelerated  neutrons
(EPA, 1979).

       Gamma irradiation, unlike some other ionization processes, is very penetrating.
Sixty-four cm of  water are required to  stop 90% of the  radiation  from a Co-60 source.
This penetration range makes gamma irradiation useful for  the  treatment of relatively
significant amounts of sediment  or sludge.

       Two  types of gamma  irradiation  systems are  used  to disinfect sludge.  One
system, located in Germany, uses a Co-60 source and pumps  liquid sludge around  the
source.    Another system,  shown  in Figure  7, is located at  Sandia  Laboratories in
Albuquerque, New Mexico.  This  unit has a one-million curie  source of Cs-137 and  can
process up to 8 tons of dried sludge per day.  The sludge is loaded onto a conveyor and
passed by the source.   The exposure is determined by the speed  of the conveyor. The
Sandia sludge treatment system  was used  for irradiation of sediment samples for this
study.  Sandia also has a 90,000 curie Co-60 source which is used for research purposes.
Several sediment  samples  were also irradiated with  this source.

B.      Experimental Procedure

        1.    Sample  Preparation and Irradiation

             Actual samples from  LAAP lagoon 9 were used for TNT/RDX contamin-
ated sediment. Uncontaminated sediment was  spiked with nitrocellulose (10% by weight)
for use in the gamma  irradiation study.  Analysis of the LAAP  lagoon 9 and the  spiked
nitrocellulose sediments are presented  in  Table 17.

             For  the gamma irradiation studies, aqueous slurries  containing 10% solids
(w/w) were formulated from these  sediments  according  to the following  procedure.  A
weighed amount  of  dried sediment  was  placed  in a two-gallon Helicone  mixer.
Distilled water was added to the  sediment in the proper  ratio.  The sediment and water
were slowly agitated  to wet the particles.   After the  initial mixing, the mixer speed
was increased to 185 rpm to evenly suspend the particles and  provide a uniform slurry.
One hundred ml aliquots of the slurry  were dispensed from the valve in  the bottom of
the mixer  into preweighed polyethylene  bottles. Agitation was continued  during sample
                                         40

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         Input
                                 Conveyor

                     "Source Plaque
Figure 7.   Gamma Irradiation Treatment  System for Dried
           Sewage Sludge (Morris et  al.,  1979)
                           41

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 Table  17.  Characteristics of Unslurried LAAP  Lagoon 9 and Spikea
           Nitrocellulose Sediments
                                   TNT/RDX        Nitrocellulose
                                   Sediment           Sediment
ND - Not Determined
TNT
  (yg/g, dry wt)                     287,000

RDX
  (ug/g, dry wt)                      58,000

Nitrocellulose
  (ug/g, dry wt)                        -               34,000

COD  (yg/g)                         470,000           166,000

Nitrate  (pg/g)                            4.5                2

Chromium (ug/g,  dry  wt)                   4              ND

Cadmium (yg/g, dry wt)                    5              ND

Lead (ug/g, dry wt)                       40              ND

Zinc (yg/g, dry wt)                      500              ND

Percent Volatiles                          37.7                8.4
                                42

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withdrawal.  The  polyethylene bottles  were reweighed, capped, labelled and refriger-
ated until treatment.   Thirteen bottles of  each sediment type were prepared in this
manner.   Two samples (a and  b) were irradiated at each set of conditions excepting the
samples  receiving 4.1  megarads.   These  samples were  included to provide additional
information and were not in the laboratory  test plan.  Samples were  randomly assigned
aeration or non-aeration labels and the  dosage levels of 0, 0.5, and 1.5 megarads.  The
experimental design is  presented  in Table  18.

             The  non-aerated samples  were  irradiated  by the Cs-137  sludge  treat-
ment unit. The samples were irradiated  in two batches.  The first batches were exposed
for 45 minutes and received 0.5 megarads.  The second batch received 1.5 megarads in
135 minutes of irradiation.   Because only sealed bottles could  be treated  on the Cs-137
sludge plant, the aerated samples were exposed  to a Co-60 source.  The samples were
aerated during exposure by bubbling air  through the solution via airstones and  a fish
tank pump.  These samples received 0.5, 1.5  or  4.1 megarads with treatment times of
4, 13, and 35  minutes,  respectively.  After treatment,  the samples  were refrigerated
and transported to Atlantic Research Corporation for  analysis.

       2.    Analysis of Irradiated  and Control Slurries

             The analyses of  the irradiated  and control slurry samples were accom-
plished  in  the  following  manner.   The  water and  sediments  were  separated  by
decantation and filtration. The sediments were air dried on the dull side of aluminum
foil. The volume of water and the weight of the sediment were then determined. Each
sediment  and  water  sample  was then  analyzed  in  duplicate  for   the  following
parameters:

                  explosives (TNT, RDX and  tetryl, or  nitrocellulose)

                  Chemical Oxygen Demand (COD)

                  Nitrate

Analyses  were  according to the procedures presented in Appendices A and B. For the
non-aerated samples, the air above  the liquid  was  sampled  and analyzed to determine
if any CO,  C02 or  NOX was  produced upon  irradiation.

C.     Results and  Discussion

       The  characteristics  of  the TNT/RDX slurries formulated  from  lagoon  9
sediment  are presented in  Table 19.  The sediment from lagoon 9 had highly variable
explosives concentrations from sample  to sample.  This variability  was obvious when
the dried  sediment was examined  since crystals  and lumps  of TNT and RDX could be
observed  in the dried material.   The slurries formulated from the sediment were also
high variable  in explosive  concentrations.   A one  way  analysis  of  variance  was
performed on  the  TNT, RDX,  tetryl and  COD data to  determine if any of the treated
samples was significantly  different from the control  or any other  treated  samples.
None  of  the treated values was  significantly different although  it  appears  that the
higher  dose rate (4.1 megarads) had some effect on the degradation  of the explosives.
                                         43

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         Table  18.  Experimental Design for  Gamma  Irradiation Study
                          RDX/TNT                   Nitrocellulose
dose (megarads)	aeration    Non aeration	aeration     Non aeration
0
0.5
1.5
4.1
a
a
a
a
b
b
b

a
a
a

b
b
b

a
a
a
a
b
b
b

a b
a b
a b

     a   =   Sample  bottle a

     b   =   Sample  bottle b
                                     44

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                   Table  19.  Effects of Gamma Irradiation on TNT/RDX Sediment Slurries
                     Dose       Water Volume    Sediment    
-------
        The  nitrocellulose  slurries  characteristics  are  summarized  in  Table  20.
Nitfocellulose concentrations  in this table  are  presented  as  nitrite  and have not  been
converted back  to nitrocellulose.  In the analysis of nitrocellulose, the nitroceDulose is
hydrolyzed and reduced to nitrite.  If the numbers are converted  back to nitrocellulose,
the data would  show an increase in the nitrocellulose concentration.  This increase is
due to the breakdown of the  nitrocellulose by  gamma irradiation. The products of the
irradiation evidently are easier to hydrolyze  than the  nitrocellulose (25%  hydrolysis
efficiency) yielding a higher nitrite leveL This explanation is further supported by the
COD  data.  * COD  levels were greater  in the treated  sediment than in the control
sediment.  Nitrocellulose is poorly oxidized  by the COD method.  Gamma irradiation
partially degrades the nitrocellulose rendering it  more susceptible to oxidation by the
COD  procedure. Nitrate levels in the slurry  water also  increased.

        The nitrocellulose data were subjected to one-way  analysis of variance.  This
analysis showed  that the nitrite  data was significant at the less  than  1%  level, the
nitrate  data at  the  3% level, and the COD data at the 2% level. A table  of  means for
the  Duncan's  Multiple  Range  Test  is  presented in Table  21.  These  data  show  a
significant difference in nitrite  and COD levels  between the  controls and the  non-
aerated samples at a dose of 0.5 megarads.  At a dose of 1.5 rnegarads, the data  were
not significantly different than the  controls.

        Analysis of the air above  the solutions  in the non-aerated irradiated samples of
both  Lagoon 9 and  nitrocellulose sediment samples did  not  show the presence of any
CO.  In addition, CO2  and NOX levels were  not significantly  different  between the
control and irradiated samples.

D.      Conclusions

        The  gamma  irradiation  treatment of  TNT/RDX  contaminated sediment  was
partially effective at a dose of 4.1 megarads.  Approximately 30% of the explosives and
COD levels  were degraded.   The  high amount  of explosives (over one-third of the
sediment weight) made it difficult for the  method  to be effective.   Nitrocellulose was
also  partially  degraded in  the  sediment  by  gamma   irradiation.   However,  the
exact quantity of  nitrocellulose degraded  by the gamma   irradiation could  not  be
determined,  due to  problems associated with the analytical method for nitrocellulose.

        Overall, gamma irradiation did  not reduce the explosive levels in  the sediment
to acceptable levels in these experiments.   Extrapolation of the data indicate that  a
dose  of 16.2  megarads or greater  would probably  be required to completely degrade the
explosives.  This dose would require a holding time of about 140 minutes in the presence
of the  1,000,000 Curie  Co-60 source with aeration or 24.7 hours in the presence of the
90,000  Curie Cs-137 source.  This treatment procedure may  be effective  for removing
low levels of explosives contamination in soils, sediment  or liquids.   However, reaction
conditions must  first be optimized before this  method can be useful in toxic materials
destruction.
                                           46

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                  Table  20.   Effects of Gamma Irradiation on Nitrocellulose  Sediment Slurries
                                                                             Nitrocellulose
Sample
Control a
b
Control a
b
Non-aerated a
b
Non-aerated a
b
Aerated a
b
Aerated a
b
Dose
(megarads)
0
0
0
0
0.5
0.5
1.5
1.5
0.5
0.5
1.5
1.5
Water Vol.
(mL)
78
91
94
92
85
87
83
88
84
82
54
87
Sediment
dry wt. (g)
7.70
7.92
7.11
7.75
7.97
6.92
5.45
7.11
6.22
7.03
6.38
7.84
% Solids
in Slurry
11.3
8.7
4.8
7.5
9.4
8.0
6.6
8.1
7.4
8.6
11.8
9.0
Expressed as
Nitrite (mg/g)
8.6
8.4
8.7
8.9
26.0
24.7
12.2
23.3
13.0
11.0
18.5
14.0
COD
(mg/g)
167
167
170
160
225
227
204
156
163
163
191
194
Nitrate
(ug/mL)
1.0
0.3
0.5
0.3
0.5
1.0
2.0
1.0
1.0
1.0
1.0
2.0
Aerated     a
4.1
105
8.67
                                                                  8.3
                                                           12.3
                                                            190
                                                           3.0

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00
                           Table 21.  Duncan's Multiple Range Test for Nitrocellulose Sediment
                                                            Parameter Measured
                Dosage  (megarads)         COD (ug/g)            Nitrite (mg/g)            Nitrate (ug/mL)
Non-aerated 0
0.5
1.5
Aerated 0.5
1.5
4.1
166,000 b
226,000 a
180,000 b
163,000 b
192,500 a.b
190,000 a.b
8,650 c
25,350 a
17,750 a.b
12,000 b.c
16,250 b
12,300 b,c
0.5 c
0.8 c
1.5 b
1.0 b,c
1.5 b
3.0 a
             Values within a column  not followed by the same letter are significantly different at the  5% level
             of probability according to Duncan's Multiple  Range  Test.

-------
E.      Future Work

        Gamma irradiation  is not  an effective method for decontaminating  lagoon
sediments containing  high levels of  explosives.   To obtain complete degradation, large
doses  of  radiation are required,  driving  equipment  costs  up  as  residence  time  is
increased.   Since  the process  has not  been used in the past  to destroy explosives, a
considerable  amount  of  experimentation  and  process development  is  required  to
optimize the system configuration and operating conditions.  For these reasons, further
development of gamma irradiation  is not recommended for this application.  In other
situations where explosives levels are low and would require shorter residence times for
a particular source, gamma  irradiation may prove to be a very inexpensive  treatment
method which would  warrant further development.

F.      Economic  Analysis

        Capital costs for a gamma  irradiation  facility  using a Cs-137 radiation source
to process 900 kg/hr of explosives contaminated lagoon sediment are presented in Table
22.  Costs for the facility include  an insulated concrete building, an emergency water
dump  tank  for source shielding, cesium  capsules,  a  source handling  pool, aeration
equipment,  control equipment, pumps, piping, flow meters, a radiation alarm and a fire
suppression  system (EPA, 1979).  Annual operating costs, including annual costs for
replacement Cs-137, are presented  in Table 23.  Costs in the literature (EPA, 1979) for
gamma irradiation facilities are based on a  system which delivers only a 1 megarad
dose.  To provide  a 16.2 megarad dose, the required size of  the system was increased
to give a much longer residence time.   The major  operating cost  for  this system  is
labor which can probably be  reduced if there  is other work available not related to the
process to  which the  operators   can devote  any extra  time.    Projected  labor
requirements  for a system of this size are only 2,400  man-hours per year (EPA, 1979),
much less than the 6,000 operator  man-hours and  2,000 supervisor man-hours provided
in this estimate.  Further cost reductions  can be made if  Cs-137 can be obtained at
reduced rates from the processing wastes of  nuclear weapons manufacturing.  While a
gamma irradiation  facility  would   be  expensive  to  build,  it  would  be  relatively
inexpensive  to operate once the system  was installed.
                                        49

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                  Table 22, Capital  Costs for Gamma Irradiation
           Equipment
Cost
Reference
Dredge:  Porta-Dredge, 1136 L/min      $   58,800

Holding Tank                             145,600


Gamma Irradiation Facility              1,200.000


TOTAL COST                         $1,404,400
                  Salemink, 1980

                  Peters and Timmerhaus,
                  1968

                  EPA, 1979
              Table  23.  Annual  Operating Costs  for Gamma Irradiation
              Cesium-137

              Electricity (70,000  kwh/yr @ $0.07/kwh)

              Maintenance (3% of capital)

              Labor

              TOTAL COST
                 $ 42,000

                    4,900

                   42,000

                  210,000

                 $298,900
                                        50

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                             V.   WET-AIR OXIDATION
A.      Process  Description

        Wet-air  oxidation  is a  process  which uses a catalyst and oxygen  to  destroy
organic compounds in aqueous  mixtures  at  elevated temperatures and pressures.  The
waste  slurry is  pumped  by means of a  high  pressure pump through a heat exchanger
where  it is heated to reaction temperatures.  It then passes to a  high pressure  reactor
along with compressed air.  Specific catalysts are added to the mixture to increase the
reaction rate. Retention times in the reactor are on the order of 40 to 60 minutes.  The
treated slurry is passed from the reactor through the heat exchanger where it is cooled.
The  cooled slurry  then  goes to a  gas-liquid separator where  gaseous products  are
removed.  Depending on the type of waste, the gaseous or liquid  products may require
further treatment before they  are released into the  environment.  Slurries containing
between 5 and 10  percent  solids are treated by this process.  Higher amounts of solids
create problems with mixing and mass  transfer of the  oxygen.

B.      Experimental Procedure

        L    Slurry  Preparation  and Wet-Air Oxidation  Treatment  Methodology

             The wet-air oxidation experiments were conducted at IT-Enviroscience in
Knoxville,  Tennessee.  The reactions were carried out  in  a stirred  one-liter titanium
clad  reactor.  The reactor, catalyst addition system  and associated equipment  are
shown  in Figure  8.  Photographs of the  reactor and control equipment are presented in
Figures 9 and 10.

             Ten percent   Lagoon  9  sediment slurries in water were formulated as
described for the gamma irradiation study.  The  same sediments were used  in  the
formulation.  Aliquots of 350 ml (TNT/RDX)  or 150 ml  (nitrocellulose)  were dispensed
from the mixer  into pre-weighed polyethylene bottles.  The bottles were  re-weighed,
capped, labelled and refrigerated until  treatment.

             The  treatment scheme  for the  wet-air  oxidation studies is presented in
Table 24.  The experimental procedure  consisted of adding  the catalyst mixture to the
catalyst addition tanks.   The catalyst  mixture typically consisted of 3.81 g of  MnSO4
  HoO, 35.47 g of  70.5% HNO3, 6.75 g of 47.2% HBr, and 67.2 g of deionized H2O.   The
sediment slurry sample was added to the reactor along with deionized  water rinses (50
g) of the sample bottle.  The reactor was sealed and pressurized with helium  to 800 psig
to check the system for  leaks.  The reactor was vented and batch-purged with cylinder
oxygen to remove inerts. It  was then pressurized to 200 psig with cylinder  oxygen and
heated  to the desired reaction  temperature.   The catalyst mixture was added to the
reactor with helium pressure to initiate the  catalyzed  oxidation of the sample.   The
reaction was terminated after  the desired  length of  time  by  cooling the reactor  with
cooling water through  the reactor  jacket.  The  reactor  was cooled to 20C before
venting the  final  reactor gas   through  a sampling valve  into a  gas  sample  bag for
analysis  by  gas  chromatography for  C02-   The final liquid reaction effluent  was
aspirated into a clean bottle.  These samples and the final gas  samples were  shipped
to Atlantic Research Corporation for analysis.
                                         51

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0
OXYGEN/CATALYST
ADDITION VALVE
                                                                          VENT/CATALYST
                                                                          ADDITION VALVE
                                                                                                 VENT TO BUILDING ALLEY
en
ro
CHECK
VALVES
j
J\

-T-V-^ w
i, [) sssasr ssa?
? TANK 9 ?
1 , r [^ 1 	 n
RELIEF
OXYGEf| PRESSURE GAGE VALVE
CYLINDER
r in-
COOLING WATER!
DRAIN
	 ^
MAGNETICALLY
r j COUPLED \
{ \ AGITATOR <
of
fl
_ I !
1 ^^
1,
1 LITER


RUPTURI
VENT/CATAI

-------
      Figure  9.   Picture of Wet-Air  Oxidation  Reactor
Figure 10.  Picture of Wet-Air  Oxidation Control Equipment
                          53

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 Table  24.  Treatment Scheme  for Wet-Air Oxidation of  Sediment  Slurries
Order
Sediment Type
Temperature (C)/
 Pressure (psig)
Treatment Time
    (min)
1 RDX/TNT
2 RDX/TNT
3 RDX/TNT
4 RDX/TNT
5 RDX/TNT
6 RDX/TNT
7 Nitrocellulose
8 Nitrocellulose
9 Nitrocellulose
10 Nitrocellulose
200/600
225/750
225/750
200/600
250/980
250/980
200/600
165/450
200/600
165/450
60
60
90
90
90
60
60
60
90
90
                                   54

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        2.    Sample  Analysis

             The  sample  handling  and  analysis procedures  for  the  slurries  were
 essentially the same  as described under gamma  irradiation.

             Analysis was also conducted for by-products from  the wet-air oxidation of
 the TNT/RDX sediment.  Ten ml of water from two sediment slurries (before and after
 wet-air treatment) were extracted with 1 ml of methylene chloride and the extracts
 concentrated  to  0.25  ml.   This  extract was  analyzed  by gas chromatography-mass
 spectrometry  using a Hewlett-Packard  5992A Mass Spectrometer and  the following
 conditions:

        Column:        2% Dexsil  300  GC  on Anakrom  Q packed  in a
                       6 ft.  by  0.25 in and 2 mm  I.D.

        Gas Flow:      Helium (9.  15 cc/min

        Temperatures:
             injector:   210C
             column:    160C to 240C <.  15C/min

 C.      Results and Discussion

        The results of  the wet-air oxidation  treatment of TNT/RDX  contaminated
 sediment are  presented  in  Table  25.   The data indicate  that  RDX  and tetryl were
 reduced to below detection limits of the GC analysis method at the lowest treatment
 scheme of  200C/600  psig.   The low levels of RDX and tetryl in the final product could
 not be determined by the more sensitive HPLC method because the presence of large
 quantities of TNT breakdown  and  addition products  obscured the peaks.

        The TNT  was rapidly decarboxylated in the wet-air oxidation reaction. No TNT
 was  observed  in  any  of   the  product  solutions  or  sediments.    However,  1,3,5-
 trinitrobenzene (TNB) was observed in  large amounts.  The TNB residual decreased as
 the treatment temperature and pressure increased.   At the highest treatment scheme
 of  250C/980  psig,  the  trinitrated   ring  (from  TNT  or TNB)  was reduced  by
 approximately 99%. At  this treatment  level, COD was also reduced by 90-95%.

             A one-way analysis  of variance  table  showed that  the  data for TNB
removal  by treatment and time  interaction  were  significant  at  the   0.004%  level.
 Further evaluation of the data by Duncan's  Multiple Range Test is presented in Table
 26.  Temperature/ pressure combinations had a significant effect on the  disappearance
of TNB, however, treatment times above 60  minutes at a specific temperature/pressure
combination had no increased effect on TNB  disappearance.

       The chromatrograms of the slurry water  extracts from before and  after wet-
air oxidation are  presented  in Figures  11 and 12.  Before wet-air oxidation,  only three
 main peaks  were  observed.  These  peaks were identified as TNT,  RDX and tetryl by
comparison  with  SARM materials.   After  wet-air oxidation,  no  RDX  or  tetryl  was
observed.   1,3,5-Trinitrobenzene, 2,4-dinitrobenzene, bromodinitrobenzene and dibromo-
                                       55

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               Table  25.   Wet-Air Oxidation Treatment of LAAP Sediment
                                                Remaining   After  Treatment
Pressure (psig)
Control
200/600
200/600
225/750
225/750
250/980
250/980
(min)
0
60
90
60
90
60
90
TNB (Mg/g)
_*
89,000
+5,600
87,000
+18,000
142,000
+27,000
172,000
+21,000
2,600
+1,600
1,800
+1,700
RDX (Mg/g)
42,000
+14,300
< 490
< 490
< 490
< 490
< 490
< 490
Tetryl (Mg/g)
10,400
+3,000
<75
<75
<75
<75
<75
<75
COD (Mg/g)
172,000
NA
NA
NA
NA
7,900
17,000
NA  -  Not Analyzed



*Initial TNT walues 236,000 + 25,000 Mg/g

-------
                 Table 26.  Evaluation  of  Wet-Air Oxidation  Data by
                            Duncan's Multiple  Range Test
Treatment  Temperature (C)/       Treatment Time     Trinitrated Ring Structure  After
      Pressure (psig) _ (min) _ Treatment
        200/600                           0                        230177 a
                                         60                         80171 c
                                         90                         76743 c

        225/750                           0                        237428 a
                                         60                        123976 b
                                         90                        155322 b

        250/980                           0                        239030 a
                                         60                          1634 d
                                         90                          2586 d
 Values with a column not  followed by the same letter are significantly  different at
 the 5% level of probability according to Duncan's Multiple  Range Test.
                                         57

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                                 TETRYL
Figure 11.  GC-MS of Slurry Water  Before Wet-Air Oxidation  Treatment
                                58

-------
     dlbromonitrobenzene
                           bromodinitrobenzene
Figure  12.  GC-MS of Slurry  Water Extract After  Wet-Air
           Oxidation at  250C/980 psig
                               59

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nitrobenzene  were identified as the  main constituents of this extract. Thus, it appears
that the  mechanism  for  TNT destruction  by  wet-air  oxidation  proceeds via rapid
oxidation  of  the methyl group followed  by decarboxylation to form TNB.  This initial
step is  followed by removal of the nitro group and in some cases a substitution of
bromide for the nitro.  The  compounds formed  from wet-air oxidation of TNT are more
hazardous than TNT itself.  TNB and dinitrobenzene (DNB) are explosives,  and are more
soluble  in water than TNT  (460 mg/1 for 1,3-DNB and 278 mg/1 for TNB compared to
130 mg/1 for  TNT) (Wentsel et aL, 1979; U.S.  Army, 1967).  TNB and 1,3-DNB are known
to be toxic to humans.  Both  compounds are  potent methemoglobin formers (Wentsel
et aL. 1979).

        The  reactor  air  analysis  from  the  treatment of  TNT/RDX  sediments is
presented in  Table 27. The  initial atmosphere in the reactor was pure oxygen. The CO 2
levels  for the treated sediment ranged  from  12.6%  of  the  total gas  volume  at
200C/600 psig for 60 minutes to 34.1% at 250C/980 psig for 90 minutes.  Overall the
C02 levels increased as the temperature and  treatment time increased. A brown gas
was also observed in  the air sampler bags.  This gas was identified as bromine from
the catalyst.  The bromine  gas was  not  quantified. No significant  quantities of NO or
     were found.
       The amounts of CO2 and N2 which could theoretically be released by complete
decomposition of the explosives present in the treated slurry were  calculated to be 5.18
g CO2 and .895 g of N2  At the highest temperature/pressure/time conditions, 34.1%
of the reactor  exhaust was C0%. If this number is adjusted for the  pressure, 5.36 g of
CO2 were given off.  This  amount is 0.18  g  greater  than the theoretical.   Thus, it
appears that a high percentage  of  the explosives  was  essentially completely  oxidized
and that other organic material present in the sediment was also oxidized.  The actual
amount of N2  measured (adjusted  for pressure) was 1.10 g.  Again  the actual amount
measured was  slightly higher than  the theoretical.  The additional N could be the
result  of leakage or  could have been produced from  the nitric  acid.   In the higher
temperature/pressure reactions,  all of  the atmospheric constituents were not accounted
for by expected breakdown  products of the  explosives.  Bromine was present in the
atmospheres  of  these samples  and was  probably the  major  portion  of the missing
constituents.

       The results of the wet-air  oxidation treatment of nitrocellulose sediment are
presented in Table 28.  A treatment of 200C/600 psig for  90  minutes reduced the
nitrocellulose or nitrate  levels in the sediment by 96%.  COD  levels were also lowered
by a  similar amount  at  these conditions.

       The  data on the  percent  reduction of nitrocellulose  in the  sediment  were
transformed  into log  form.  An  ANOVA  table  was  then  constructed.   Treatment
pressure/temperature were not  significant,  but treatment time was significant at the
0.15%  level.   In other  words,  the  lowest  temperature/pressure  was as effective in
degrading nitrocellulose  as the higher temperature/pressure scheme.  Further  evaluation
of the data  by  Duncan's Multiple  Range  Test showed  that the time 0 and  60  or 90
minute data were significantly different  at the 5% level of  probability  but the 90
minute data were not significantly different from the 60 minute data.

       The air analysis  data for the nitrocellulose sediment treatments are presented
in Table 29.  Oxygen was  initially  present in the reactor.  As treatment temperatures
increased, the amount of CO2 increased.  CO% levels for the four  treatment conditions
ranged from 10.9 - 14.5  percent of the total gas volume.
                                       60

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Table 27.   Off-Gas  Analysis for Wet-Air Oxidation  of TNT/RDX
            Sediment Slurries
                                     Percent
Treatment
(C/psig)
200/600
200/600
225/750
225/750
250/980
250/980
Time
(min)
60
90
60
90
60
90
C02
12.60
19.85
29.10
31.97
28.86
34.13
2
79.71
65.40
46.37
26.39
46.82
43.21
N2
6.54
12.56
13.65
10.86
13.62
11.04
CO
0.1
0.1
0.1
0.4
0.1
0.1
Summation
(percent)
98.95
97.91
89.22
69.62
89.40
88.48

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                     Table 28.  Wet-Air Oxidation of Nitrocellulose Sediment
                                                      Remaining   After   Treatment
Temperature (C)/
Pressure (psig)
Control
165/450
165/450
200/600
200/600
Treatment Time
(min)
0
60
90
60
90
Nitrocellulose
Mg/g
59,800 f 12,800
3,250 + 500
2,280 + 260
2,320 + 540
2,250 + 180
COD Sediment
Wg/g
163,500
NA
NA
32,300
3,400
COD Liquid
ug/ml
19,200
NA
NA
255
260
NA - Not Analyzed

-------
                Table 29.  Off-Gas  Analysis for Wet-Air Oxidation of Nitrocellulose  Sediment Slurries
                                                                        Percent
Treatment
(C/psig)
165/450
165/450
200/600
200/600
Treatment
Time (min)
60
90
60
90
CO2
10.91
13.18
14.05
14.50
<*
79.54
81.23
78.87
70.56
N2
3.29
5.13
6.29
16.37
CO Summation
.30 94.04
.14 99.68
<.10 99.31
<.10 101.53
o>
CO

-------
D.     Conclusions

       Wet-air oxidation of the TNT/RDX sediment was effective.  The treatment did
reduce RDX,  TNT and tetryl  levels in the sediment  to below  GC  detection  limits.
GC/MS  analysis  of the  treated slurry  water  indicated  that  the  toxic  compounds
trinitrobenzene and dinitrobenzene were present.   Relatively high and  long treatment
conditions (250C/980  psig) were required for 99%  disappearance of the trinitrated ring
structure.

       Nitrocellulose  levels in the sediment were also  significantly reduced by wet-air
oxidation.  However, the  increase in treatment temperature and time did not seem to
increase  the destruction  of the nitrocellulose.

E.     Future Work

       While wet-air  oxidation is an effective treatment method for RDX  deconta-
mination, it is not a totally acceptable method for use on TNT containing sediments
because of the toxic by-products  formed.  Destruction of nitrocellulose by the process
was not  complete.    In  addition,  both the capital  and  operating costs  for  wet-air
oxidation are extremely  high,  as  can be  seen in the next section.  For these reasons,
wet-air oxidation is  not recommended for  further study in  the decontamination  of
lagoon sediments.

F.     Economic Analysis

       Capital and operating costs  for wet-air oxidation of 3,800 kg/hr of a 10% solids
lagoon sediment  slurry are presented in Tables 30  and 31.  This treatment rate is the
same as that in  the  standard lagoon  scenario except  that water  has been added to
facilitate operation of the wet-air oxidation equipment.  Costs were  taken from  a
report prepared  by IT-Enviroscience (1981) at  the  end  of the  experimental work.
                                       64

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                 Table  30.  Capital Costs  for Wet-Air  Oxidation


     Equipment                   Cost                     Reference


Dredge                       $    58,800               Salemink,  1980


Holding Tank                     145,600               Peters  and Timmerhaus,
                                                      1968



Wet-Air Unit                  8,262,000               IT-Enviroscience, 1981

TOTAL                      $8,466,400
           Table 31.   Annual Operating Costs for Wet-Air  Oxidation
                      (IT-Enviroscience,  1981)
      Maintenance  (5% of capital)                            $  413,000

      Labor (3 operators, 1 supervisor)                           210,000

      Fuel Oil (490  Btu/lb @. $9/M Btu)                         270,000

      Cooling Water (L86 gal/lb @  $25/1000  gal)                 133,000

      Electricity (.05 kwh/lb  @ $0.07/kwh)                       212,000

      HBr (.005  Ib/lb @.  $0.09/lb)                               236,000

      HNOs (.07 Ib/lb @  $0.09/lb)                               381,000

      NaOH (.05 Ib/lb @  $0.06/lb)                               181,000
      TOTAL                                                 $3,036,000
                                      65

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                           VI.   ACETONE  EXTRACTION
A.     Process  Description

       Solvent extraction or leaching is the process of separating soluble compounds
from insoluble  solids by bring.  _:  the  solids into  contact  with an appropriate solvent.
The soluble compounds dissolve and the  solution is then  mechanically separated from
the remaining solids.  Additional process steps may be added to remove the solute from
solution or to recover a solvent which is either undesirable  in the finished product  or
is too expensive to waste.  Important factors influencing the effectiveness  of solvent
extraction processes are the ease with which the solvent can reach the solute and the
ease of separation of desired products from any remaining  solvent.

       Acetone extraction of explosives from  lagoon sediment may be an economical
and effective decontamination method.  As indicated in Table 32, all of the explosives
of interest to this study are either somewhat  soluble or easily  dispersible in acetone
at room  temperature.  Extraction of  the explosives  should be  efficient and safe.
Residual acetone could be removed for recovery by gentle heating.  Since the normal
boiling point of acetone is  well below the  detonation  temperatures of the explosives,
most of the acetone could be recovered by boiling the mixture and then condensing the
vaporized acetone.  Some  acetone would be allowed to remain with the explosives  to
maintain  them in a  wet state  to reduce the  danger  of  accidental detonation.  It  is
essential  that  the  impact and  heat sensitivities of the  explosives in  question when
mixed  with  small  amounts  of  acetone be  carefully examined  before such  a solvent
recovery  scheme is attempted.  The remaining  acetone  and extracted explosives could
be  incinerated to ensure complete  destruction.  Heat  from the incineration  could  be
used to power the solvent  recovery steps.

        As with most mass  transfer processes, continuous countercurrent exchange  is
the most  efficient solvent extraction method in terms of equipment, energy and raw
materials  requirements.    For  solvent  extraction,  continuous  countercurrent ex-
change requires several contacting  stages  in which solvent  and  solid are mixed, then
separated. Solids  move from stage  to stage with a little  more  solute being  extracted
at each stage.   Fresh solvent is introduced  at  the  opposite end  of the process so that
clean solvent contacts nearly solute-free solids in the last stage. Solvent from the last
stage is  fed to the next-to-last stage,  and so on  from stage  to stage  until the most
highly solute-laden solvent contacts the untreated solids in the  first stage.  Counter-
current extraction can produce an essentially solute-free solid  stream and  a solute-
saturated solvent  stream, thus minimizing solvent  requirements.

        Solid-liquid solvent extraction has  been used for a wide variety of separation
processes.  A brief review of several types of solvent  extraction equipment  and their
possible   applications to  decontamination  of  lagoon  sediment  is  presented  in the
following paragraphs.
                                        66

-------
Table  32.    Solubility of Explosives  in Acetone (Departments  of
             the Army and  Air  Force,  1967)
    TNT                     0C              57 g/100 g solvent

                            20C             109 g/100 g solvent

                            25C             132 g/100 g solvent

                            30C             156 g/100 g solvent

                            50C             346 g/100 g solvent

    RDX                    20C               7.4 g/100 g solvent

                            50C              12.8 g/100 g solvent

    Tetryl                   very soluble  in acetone

    Nitrocellulose            not truly soluble,  dispersed to
                            colloidal form in acetone

-------
       One of the  simplest solvent extraction schemes is  the  extraction  battery  or
Shanks system  (Treybal, 1955).  Each stage is  a  percolation tank which is  filled  with
solid through which the solvent can trickle to the  bottom of the tank.  Solvent draining
from  the  bottom of each  tank is pumped  to the  top of the next tank.  At any given
time, one tank will be out of operation for emptying of solute-free  solids and refilling
with  fresh solids. In  the  next step,  the tank of  fresh solids will  receive the  most
concentrated solution  while  the tank which received fresh solvent  in the last step is
emptied and refilled.  The process continues in this fashion until the first tank emptied
is again ready to  be  emptied, and the cycle begins again.  A typical operation of a five
tank extraction battery is shown  in Figure 13.

        A more sophisticated version of  the same type  of  percolation scheme  is shown
in Figure 14.   Designed  for the  extraction  of vegetable seeds such  as soybeans  or
linseeds, the Rotocel  consists  of  18 percolation cells which revolve  about a stationary
compartmented tank (Treybal, 1955).  Solids are continuously loaded,  countercurrently
contacted  with solvent, then  unloaded through hinged  screens in the bottom of each
celL  A complete cycle in the  extraction battery corresponds to one revolution of the
Rotocel. The chief advantage of this scheme is the continuous addition and removal  of
solids.

        Finely  ground  solids  which are readily  suspended can be  leached in a series  of
alternating  agitated  vessels  and   mechanical  separators  such  as  centrifuges  or
thickeners.   Each  agitator  and  separator pair is  a single  stage, and  countercurrent
operation is again the most efficient method  of operation.   Many  types of agitators
have  been used,  but  the turbine  type mixer  is  generally the most suitable (Treybal,
1955).  Continuous centrifuges are  useful for  those solids which are easily separated
from  the  solution, while thickeners are used for more difficult separations, typically for
very fine  solids in dilute suspension.  A thickener  manufactured by Dorr Oliver  is shown
in Figure 15.

        Any of these  three  types of equipment might be useful  for solvent  extraction
of  explosives  from  lagoon  sediment.   Effectiveness  of  the  process  and  economic
considerations  will determine  which is most suitable.

B.      Experimental  Procedure

        The first step in examining  solvent extraction is to determine whether the
process is effective  at removing explosives from contaminated lagoon sediment. Several
temperatures and extraction  times for  sediments contaminated with  TNT,  RDX and
tetryl from LAAP  Lagoon 9 and with nitrocellulose were  examined for a single stage
extraction according  to the following procedure.

        Approximately 10 grams of dry contaminated sediment  were  placed in a 250 ml
round bottom flask  outfitted with a reflux condenser.   Acetone (150 mL) was added  to
the flask  with continuous agitation to ensure  good contact between the acetone and
sediment.  The  flask was placed  in  a  water  bath  for the  required time interval  to
maintain  a constant  temperature.   After the proper time  period, the  250 ml round
bottom flask  was quickly removed  from the water bath and the contents  filtered  to
separate  the sediment and solvent.  A sample of  the solvent was placed in a screw cap
culture tube while the entire sediment filter cake was  recovered with the filter paper
and allowed to dry at room temperature.
                                         68

-------
                                                  Fresh Solid
cr>
CO

1
L Solvent
-''-   
^^___



,
<^


	 -^

i
Solut
Sol

,
.'.' '''





i
s

e-Free
id



Fresh
t Solvent
c ^
 t t


 . . 

Soluto-F
Sol id
i
*\V *.." !".** *.-!* " 
 *.".*."".' * . * i. *  *
.".*. *- *** ~ *."**!
\^_ _^
1
Saturated
Sol vent
{
f 	 ^*x
rep


;

v^^


Fresh
	 Solid
^
' ** x " ''
.* ' " "*
,
  J  ; .
 "" * * "



r
'  *"** "
:" ' ' * : "
'" *.*.*

Saturated
Sol vent

11
-^"**-1 "^*



V
* *' " - ' . ' ' " ,


                                                   Two Si ens  in  the Oncr.-il inp  Cvrlr  oT ,-ni  h'.x I i-.ir i i .-in  K/I

-------
Solids
            t
Solvent and
Solute
                                             Rotating Cells
                       Leached
                       Solids
                                  Solvent
                            Figure  14 .   Rotocel  Solvent  Extractor
                                              70

-------
        TOP VIEW
        SIDE  VIEW
Figure 15.   Dorr Thickener
              71

-------
       The  weights  of  the  sediment before  and after treatment  were recorded along
with  the  amount of  solvent  recovered.   Samples of  the  solvent  and  the  dry
sediment were analyzed for TNT,  RDX and tetryl or for nitrocellulose by the methods
described  in  Appendix  A.

       One set  of serial  extraction experiments was conducted at room temperature
according to  the following procedure.  Approximately 10 grams of  dry TNT/RDX/tetryl
contaminated sediment were weighed  into  each of two 250  ml Erlenmeyer  flasks.
Acetone (150 ml) was added to each  flask and the flasks were sealed with plastic film.
One flask  was shaken  for  15 minutes  while the other was shaken initially and  then
allowed to stand for the  same  length  of time.   Both flasks  were unsealed, and  the
solvent was decanted off leaving  only  the sediment and a small amount of solvent in
the bottom  of each  flask.  Fresh acetone (150  ml)  was added  to each  flask and  the
entire process was repeated. A third 150 ml aliquot of fresh acetone was added to each
flask  and  shaken or  allowed to stand for 15  minutes,  then  the entire contents  of the
flasks were filtered. The  sediment filter cakes were allowed  to  air dry.   Volumes of
solvent recovered  from each extraction were recorded,  together  with the  initial  and
final  weights of the  sediment.  Extracts and  sediment samples were analyzed for TNT,
RDX,  and  tetryl by  the same methods as before.

C.      Results

        The  results  of   the  single   stage  acetone   extraction experiments using
TNT/RDX/tetryl contaminated lagoon sediment are presented in  Table  33.  The  data
shown are  the average  data for two runs at  each set of experimental conditions. Raw
data for these experiments  are presented in Table C-2 of Appendix C.  With a solvent
to  dry sediment  weight  ratio  of  approximately  12:1  (15  ml  acetone/g  sediment),
extraction was essentially complete  for all of the explosives at all of the experimental
conditions. Since only a very small amount of explosives was detected after extraction
at  25C  for 15  minutes,  there  was  little room  for  improvement  at  the  higher
temperatures and  longer extraction  times.  Explosives recoveries  in acetone averaged
70%  for  TNT,  83% for  RDX and  97% for tetryl. Possible reasons  for  incomplete
recovery  of  TNT  and  RDX are  filtration and handling losses and variation  in  the
explosives levels in  the original sediment.

        The results of two room temprature serial extractions using Lagoon  9 sediment
are presented in Table 34.  Only 0.1% of the  original TNT and none of the RDX or
tetryl was detected  in the third extraction of the shaken sample. The sample which  was
not shaken showed a somewhat lower recovery in  the first  extraction and essentially
complete  removal  of  explosives in the second  extraction.  Overall  recoveries of
explosives were  higher than in  the previous experiments.  This  higher recovery  was
probably because a smaller amount  of sediment was mixed and analyzed for the set of
tests, thus  minimizing  variation  in  the inital explosives concentration.
                                        72

-------
                       Table  33.   Acetone Extraction of TNT/RDX/Tetryl  Contaminated
                                   Sediment
Temperature

-------
                               Table  34.    Serial Acetone Extraction
                         Shaken
Not Shaken
TNT RDX Tetryl
fraction (% explosives in acetone) Extraction
First
Second
Third
TOTAL
87.5
2.2
0.1
89.8
97.4
0.9
0
98.3
95.7 First
0 Second
0 Third
95.7
TNT RDX Tetryl
(% explosives in acetone)
78.5
3.3
0.1
81.9
88.2
4.0
0
92.2
99.4
0
0
99.4
Original Explosive Levels in Sediment:




              TNT:         192,700   pg/g




              RDX:         40,000   Mg/g



              Tetryl:       12,700   pg/g

-------
        The results of single stage acetone extraction experiments using nitrocellulose
contaminated sediment are presented in Table  35.  Each entry represents the average
value for  two runs and the raw data from which this table was generated is in Appendix
C as Table C-3.  Extraction efficiencies  were not as high as for the other explosives,
but they  were  high  enough  to  indicate that  acetone extraction may be  a feasible
method of removing nitrocellulose from soiL The data show that increasing temperature
improves  the extraction  efficiency. Nitrocellulose recoveries in the  acetone ranged
from  an average of 27% at 25C to an  average of 73% at 75C.  Increasing contact
time did not  produce  an improvement in extraction efficiency, and in fact the amounts
of nitrocellulose extracted  showed a tendency to be somewhat lower at longer contact
times. Since  nitrocellulose does  not  form a  true solution in  acetone, this reduced
efficiency is probably the result of nitrocellulose falling out of suspension upon standing
after  the initial agitation.

D.      Conclusions

        Acetone extraction is a  very effective  method  of removing  TNT,  RDX and
tetryl  from lagoon sediments.  Extraction efficiencies expressed as percent explosives
recovered in acetone  for TNT,  RDX and tetryl were 70%, 83% and  97% respectively.
The results indicate that acetone extraction of these explosives is relatively easy.  Only
a few  contacting stages  will be required  for essentially  complete extraction.

        Acetone extraction of nitrocellulose from lagoon sediment is not as effective
as extraction of the  other explosives, however,  the process is still technically feasible.
More  contacting stages would be required for nitrocellulose extraction, and care should
be taken in  the equipment design  to ensure  that  nitrocellulose is  not  allowed to
redeposit  on the sediment.

        Commerical extraction equipment is currently available which could be used for
decontamination of lagoon sediment.  The extraction battery and the Rotocel apparatus
are likely to  be useful in this application.   While flammable solvents such as acetone
are avoided  where  possible  in solvent extraction processes, such solvents  have  been
used successfully in  the past.  Technically, acetone extraction of all of the explosives
considered is a  rapid  and effective method of explosives decontamination.

E.      Future Work

        Since acetone  extraction proved  to   be an  effective  method of  removing
explosives from lagoon sediment,  some further  laboratory  tests followed  by a  pilot
scale demonstration of the  process are recommended.  Before a demonstration unit can
be designed,  it is important to experimentally determine the equilibrium curves relating
the concentration of  explosives in the extract,  the concentration of explosives and  the
amount of solvent  associated with  the  solids after  separation, and  the amount of
explosives free  solid  before and after the  extraction step.  This  equilibrium data will
provide the  basis for determining  the number of countercurrent  equilibrium stages
required for  the process.
                                         75

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                       Table  35.     Acetone Extraction  of  Nitrocellulose Contaminated Sediment
                                                     Nitrocellulose
Nitrocellulose
CD
Temperature
(C)
25
25
25
50
50
75
75
75
Time
(min)
15
30
60
15
30
15
30
60
in Sediment
(96 original nitrocellulose)
44.2
36.9
75.3
64.7
37.4
15.6
12.9
20.1
in Acetone
(/-. original nitrocellulose)
27.9
24.0
30.3
38.6
61.5
83.8
71.7
62.5
                     Original Level in Sediment



                          Nitrocellulose:   73,400   pg/g

-------
        To control explosives levels and to provide concentrations over the entire range
 of  interest,  sediment samples  for the  equilibrium .experiments  should be spiked with
 explosives.   Since  TNT and RDX are found at higher levels  in  sediment  and are  less
 soluble in acetone than tetryl, only  the equilibrium  curves for TNT and RDX need be
 determined individually.   Another set of curves should be found  for  TNT,  RDX  and
 tetryl together.   Nitrocellulose equilibrium  curves should be determined separately.
 The experimental procedure and proposed experiments to obtain equilibrium data are
 described below.

        A ten gram sample  of spiked  sediment  is weighed  and placed  in  a  150  ml
 Erlenmeyer flask.  The required volume of acetone is added, and the  mixture is shaken
 for ten minutes.  The mixture  is vacuum  filtered on weighed filter paper, the  volume
 of acetone recovered  is measured, and  the sediment with  filter  paper is weighed wet.
 The sediment is then allowed to air dry  and  is reweighed.  Extract  and sediment are
 analyzed  for  the appropriate explosives.

        The experimental  conditions  which are to be used to generate the equilibrium
 curves  for  TNT/RDX/tetryl containing  sediment  and  for  nitrocellulose  containing
 sediment  are listed in Tables 36 and 37,  respectively.   The  complete  experimental
 program  for TNT/RDX/tetryl  containing sediment  outlined thus far  would  require a
 total of 96 experiments to determine equilibrium  curves  for each explosive individually
 and  864 experiments to find the curves for all of  the  explosives  together.   Running
 these  experiments  in duplicate  boosts these figures  to  200   and  1700  experiments
 respectively.  Since 1700 experiments are  far too  many to  be  practical for the  current
 program,  the earliest experiments should be for one  acetone volume and two explosives
 levels for each explosive,  both individually and in tandem.  If statistical analysis shows
 that the results for each explosive are  not significantly  different when run alone or in
 tandem,  then the  individual  experiments  should  be  sufficient  and   the  tandem
 experiments  should be dropped.  If  the  tandem  experiments are  required,  the total
 number of experiments should  be  reduced to give  a  more manageable experimental
 program.  In addition, for all experiments, if any acetone  volume reduces an explosive
 level to its detection  limit, all experiments using larger volumes of acetone for that
 explosives level should be  dropped.   While such a program does not allow for sample
 randomization, the possibilities for greatly reducing the  total number of samples,  and
 therefore the costs, outweigh any loss in statistical reliability.  While the nitrocellulose
 should be tested alone, the same procedure of throwing out  high volumes of acetone
 if the explosive is not detected in  the sediment should be used.

        Two  possible process difficulties  which should be  addressed  in  the  laboratory
 phase of  this study are the effects  of water on the  extraction efficiencies and  the
 hazards of crystallized explosives under acetone.  Before  the equilibrium experiments
 are conducted, a series of  five experiments should be run to establish  whether moisture
 in the sediment has any significant effect on the extraction. For one acetone  volume
 and one relatively high level of each  explosive (in tandem), experiments should be done
 in which the only variable  is the sediment moisture  level.  If no significant variation is
 observed,  the experimental program  should be continued as planned.   If  water has a
 significant effect on the  extraction, then the program  will have to be redesigned to
 take this  factor into account.   Explosives hazards of the  sediment extracts  should be
determined by boiling  the  acetone  containing  explosives  down to approximately 10% of
 its  original  volume,  then impact  testing the  crystallized  explosives  and  acetone
 mixture.
                                        77

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Table 36.   Experimental  Conditions to Establish TNT/RDX/Tetryl
           Equilibrium Curves
Acetone Volumes
5 ml
10 ml
20 ml
50 ml
75 ml
100 ml
TNT Levels
0.5%
1%
5%
10%
25%
50%
RDX Levels
0.5%
1%
5%
10%
20%
30%
Tetryl Levels
0.5%
1%
5%
10%


  Table  37.  Experimental Conditions  to Establish Nitrocellulose
            Equilibrium Curves
      Acetone Volumes	Nitrocellulose Levels


            5 ml                         0.5%

           10 ml                         1%

           20 ml                         5%

           50 ml                        10%

           75 ml                        20%

          100 ml
                            78

-------
        At this point,  it is necessary to determine whether a bench scale simulation or
pilot scale tests are needed.  Bench scale simulation using an extraction battery would
be relatively simple to set-up.  A separate process vessel is required for each stage as
determined  by  the  equilibrium data.   Each vessel would need a perforated support for
the sediment, a solvent distributor at  the  top of the  vessel, and a collection system and
pump at  the bottom.   Each vessel must also be  easily  opened  to  remove  treated
sediment. A continuous still  at the end of the process line collects waste explosives
under acetone.  The  distilled acetone  is reused in  the process.   Incineration of the
waste explosives  should not be a part of this simulation.   Explosives can be disposed
of by incineration  performed by  Atlantic Research  Corporation's  Propellent  Division.
Information  to  be gained  from  a system on  this  scale  using  actual contaminated
sediment  includes solvent percolation  rates, minimum amounts of acetone required for
desired  extraction, and demonstration of a semi-continuous process.

        If a pilot  scale demonstration  is recommended, the options are for Atlantic
Research  to build or purchase a solvent extraction  unit or to use  the pilot equipment
of a manufacturer.  In either case, equipment must  be added to the system to dispose
of the extracted explosives  immediately. This disposal can be accomplished either with
a liquid incinerator to burn the entire extract or with a solvent recovery still followed
by an incinerator to burn the crystallized explosives.  If  this latter  option is chosen,
it  may  prove more cost effective to skip the pilot  scale demonstration and  purchase
the equipment directly for a  field demonstration.  In this case,  it  might be  possible to
use existing incineration  facilities at the installation to dispose  of test products.

F.      Economic  Analysis

        The capital and yearly  operating costs for acetone extraction are presented in
Tables  38 and 39.    The  capital costs  were obtained  from  the references  shown.
Necessary adjustments for changing economic conditions were made with the use of the
appropriate chemical engineering  plant cost index. The total capital cost in  1981 dollars
for this system is $383,300  and the yearly operating  costs are $394,400. These  costs are
on the same order  as those for the incineration  system.  A major factor contributing
to the relatively high operating costs is  the  cost of the  acetone.
                                       79

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                                   Table  38.    Capital Costs  for  Acetone Extraction
           Quantity
         Equipment
Installed Cost
                                                                                            Reference
oo
o
             5

             5

             1

             1
Dredge:  Porta-Dredge  PD-4LS-
1136 1/min

Holding Tank:  454,200 1
(120,000 gal)  w/75 hp side
entry  turbine

Slurry  Pump:  1/2 hp

Flat Bed Trailer

Incineration System (includes
feed system, incinerator,  after
burner and/or scrubber) (50 gal/
hr)

Percolation Tank:  470  1  (124  gal)

Pump:   12 1/min (3 gal/min)

Still:   148 1 (40 gal)

Heat Exchanger (Shell and Tube)
4 rn2  (44  ft2)
                                                                 $   58,800


                                                                    145,600



                                                                        880

                                                                     11,030

                                                                    150,000
      7,100

      3,640

      5,300

       940
                       Salemink,  1980


                       Peters and Timmerhaus, 1968



                       Peters and Timmerhaus, 1968

                       Peterbilt, 1980

                       Met-Pro, 1981
Peters and Timmerhaus, 1979

Peters and Timmerhaus, 1979

Peters and Timmerhaus, 1979

Popper, 1968
                            TOTAL CAPITAL COST
                                      $ 383,290

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                                Table 39.    Acetone Extraction Annual Operating Costs
                          Labor  (3 operators @ $45,000/man year                   $ 210,000
                                 (1 supervisor @ $75,000/man year)
                           Maintenance  (3% of total capital)                           11,500
                          Electricity
                              (4000 kwh/yr  @ $0.07/kwh)                                 300
                          Cooling Water
                              (45.8 x 106 liter/yr @ $0.0264/1000  1)                      1,210
                          Acetone
                              (210,650 kg/yr @  $0.60/kg)                              126,400


                           TOTAL ANNUAL OPERATING COSTS                    $ 394,410

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                            VH.   WATER EXTRACTION
A.     Process Description

       Water extraction is a solvent extraction process using a cheap, non-flammable
solvent.  Since TNT, RDX and tetryl are not very soluble,  fairly large volumes of water
are required to dissolve the explosives.  In addition, the water  is heated to increase the
solubility.  Nitrocellulose is so insoluble in water that this  process cannot  be  applied
to removing  it from sediment.  If  temperatures greater than 100C are desired, the
process must include a high  pressure chamber in which the extraction is carried  out.
The process is operated on a cycle  in which the water and contaminated sediment are
heated  together,  then  separated.   The extracted  sediment  proceeds  to  another
extraction stage  or  is discharged.   The  explosives containing water  is then cooled
causing the explosives precipitate  out  of solution.  The  water is  then reheated and
returned to the extraction chamber.

       The equipment in  which  the extractions are performed will be similar  to  that
used in acetone extraction except that the equipment must be  heated and must  be  able
to withstand the appropriate pressures  if  temperatures higher than the normal boiling
point of water are desired.

B.      Experimental Procedure

        Atmospheric  water extraction  experiments were  conducted in 250  ml round
bottom flasks equipped with water cooled  reflux  condensers  and  heated by  heating
mantles.  LAAP  Lagoon 9 sediment samples weighing approximately 10 g were heated
with 100 ml of water under reflux  for  one hour.  The extract was decanted off, and
the remaining sediment was air  dried and analyzed for TNT, RDX and tetryl.

        High  pressure  extractions  were   conducted  in   the apparatus  shown  in
Figure 16. The reactor consists  of  two pieces  of stainless steel pipe joined with  high
pressure flanges and sealed at each end with a welding cap.  The faces of the  flanges
have  been machined  to hold in place a piece of 50 mesh wire screen  which separates
the halves of the reactor.  A thermocouple  is inserted into one end of the tube.  The
opposite end has a pressure gage, a  pressure  relief valve, and a valve to allow pressure
release or drainage when desired.  The  thermocouple output, is monitored by  a strip
chart recorder and a temperature controller.  The temperature controller drives a 600
watt band heater which is placed  on the thermocouple half of the reactor.

        In the experiments, 10 g  samples  of  LAAP Lagoon 9 or Lagoon 11 sediment and
100 ml of water were placed in the  thermocouple half of the reactor.  The screen was
put on top of the flange, and the other half  of  the reactor was bolted on with the gage
and  valves upward.  The reactor  was then purged for several minutes  with nitrogen  to
prevent  oxidation of  the  explosives to ensure  that extraction is the  only  method  by
which explosives are removed. The controller was set, and the reactor was allowed  to
come  to  temperature and remain at temperature for  one hour.  When the experiment
was over, the heater  was shut off and  the reactor  turned upside down and  allowed  to
cool  for  several  hours.   This maneuver trapped  the sediment on the screen  while
allowing the water extract to drain through.  When the reactor was cool, the water and
crystallized  explosives  were  drained  into  a  container  of acetone  to  dissolve the
explosives.  The reactor was  taken apart,  and the sediment was removed and air dried.
The sediment was then analyzed for TNT, RDX and  tetryl. The water extracts  could
not  be analyzed for explosives because  the water in the solution would damage  the gas
chromatograph column used in this analysis.

                                         82

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00
                                                  Figure   16.     Water  Extraction  Apparatus

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C.      Results

        In the  atmospheric pressure experiments, the high level explosives  sediment
formed a scum over the top of the liquid as the sample was heated.  Boiling  broke up
the layer, and spattered the  scum  on the sides  of  the flask.   This  scum presumably
contained a significant fraction of the TNT which melted and floated  on the surface
of the liquid rather than dissolved  in the solution.

        Results of  the  water  extraction experiments are  presented in Table  40. Each
entry represents  the average  results of two experiments.  The  atmospheric extraction
shows  excellent explosives removal, however, this is probably the result of pouring off
the finer  portion of the sediment in the decanting  procedure  and  leaving  sandy soil.
More reliable results were obtained in the high pressure reactor where  rapid filtering
at the  treatment temperature  was possible.   Significant reduction  in the  sediment
explosives levels  was observed at both 150C and at 200C.  The extraction efficiency
was  quite high at 200C and  a  complete extraction  could  probably be accomplished in
only two stages at  this temperature.

D.      Conclusions

        Water extraction  is  an effective method of removing TNT, RDX and  tetryl
from sediment at 200C.  However, if TNT is present in excess, the amount that is not
dissolved  will melt  and float on the liquid.  A layer of  melted TNT floating  on  the
liquid  could  pose  serious  combustion  hazards.   If  this  is the case,  then  the  non-
flammability of water  which  was supposed to  be one of  the  main advantages  of  this
method is no longer important.  The requirements for a hot extraction process and for
high pressure to  achieve an efficient extraction temperature dictate that  specialized
equipment be designed.  Finally, the technology and equipment for this process have not
yet  been  developed.

E.      Cost Analysis

        It is difficult to arrive at  a  reliable  cost estimate for the  water extraction
process because  the  equipment required has not been developed.  There are several
factors inherent in this process  which have the  potential of driving equipment costs up.
Primary among these are the  operating conditions of the process.  The equipment must
be designed  for the generation  of high temperatures.  In addition, the equipment must
withstand high pressures.   Equipment  designed to  meet  these requirements is much
more costly  than equipment designed for operation at standard  conditions such as those
at which  the acetone extraction system is operated.  Therefore, it is  apparent that
capital costs for water extraction  will surpass those for  acetone extraction.

F.      Future Work

        Further  work  in  the  area  of  water  extraction   of explosives contaminated
sediment  is  not  recommended.   There are several  factors which make this process
                                         84

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                                              Table 40.    Water  Extraction
oo
01
Temperature
c
100
149
204
Explosives
Level
High
Low
Low
Percent Explosives Remaining
TNT RDX
1.0 4.8
50.5 6.3
2.4 <4.1
in Sediment
Tetryl
-
31.1
8.2
Original Explosives Levels in  Sediment
                  High Level              Low Level
TNT:              385,300 pg/g             39,200  pg/g
RDX:              80,000 pg/g             12,000  pg/g
Tetryl:             25,400 pg/g              3,800  pg/g

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unattractive  for  this application.   One of  the  most important  factors is the safety
uncertainty of the process.  As mentioned previously, a potential safety hazard exists
as a  result of  the  layer  of molten  TNT  in the heated  pressure  chamber.  Another
problem with this process  is the potentially  high equipment cost due to the extreme
operating  conditions.   Finally,  a problem exists in that the technology and equipment
have not been developed.  For the above reasons, water extraction does not compare
favorably  to  acetone extraction.
                                        86

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                  Vffi.  CONCLUSIONS AND RECOMMENDATIONS
        Laboratory scale experiments on various treatment methods for decontamina-
ting lagoon sediment  have been  conducted to determine  the effectiveness  of each
process. The  techniques  evaluated  were incineration, gamma  irradiation,  wet-air
oxidation, acetone extraction and water extraction.

        Incineration quickly and effectively destroyed explosives  in lagoon sediment.
TNT, RDX, tetryl and nitrocellulose are all oxidized to  environmentally acceptable
gases when combustion is complete.   Metals  in  the sediment could  be  a potential
problem.  There are two potential alternatives to the  metals problem depending on the
metal involved.   First operating temperatures and  dust emissions can be controlled  so
that very little of the metals are removed from  the sediment. The metal concentrations
in the  residual sediment  will,  of course, increase due to losses of organics.  The
resulting sediment may have to  be placed in a secure landfill  if final metal levels are
higher than allowed.  Another alternative is to deliberately vaporize any volatile metals
and collect  them in a baghouse.  If the sediment from this type  of operation  has less
than the  maximum allowable concentration  of metals,  it could  be  returned  to the
lagoon  thus saving landfill costs.   However, a penalty in fuel  costs  for  operating
conditions  could  vary from  lagoon  to lagoon  depending on the wastes found in the
sediments.   Incineration  is  recommended for  pilot-scale  study to optimize  system
parameters  for the burning of actual explosives contaminated lagoon  sediment.

        Gamma irradiation at a dose of  4.1 megarads degraded approximately 30%  of
the TNT and  RDX  in  sediment.   The  same  treatment  was  partially  effective for
nitrocellulose  in sediment; however,  this effectiveness could not be quantified  because
of interference with the analytical method. Gamma irradiation will require  high dosage
levels and  long retention times to affect complete decontamination of the explosives
in the  sediment.    A  large number  of unknowns  is  associated with this  process for
destruction of chemicals, therefore,  further studies of gamma irradiation for treatment
of highly contaminated explosives sediments  are not  recommended.

        Wet-air oxidation of sediments containing TNT, RDX and tetryl reduced these
explosives  to  below  the  detection  limits  at  all reaction  conditions.  Toxic  1,3,5-
trinitrobenzene and  1,3-dinitrobenzene  as well as bromoinated  nitrobenzenes were
observed in the aqueous effluent.  High temperatures and pressures  (250C/980 psig)
were  required  to degrade  99%  of   the  trinitrated benzene ring  structure.   Wet-air
oxidation of nitrocellulose  produced  95-96% reduction in nitrocellulose levels. Due  to
the potential  toxic by-products and  high costs, wet-air oxidation  is not recommended
for further  study.

        Acetone  extraction effectively  removed  TNT,  RDX  and  tetryl  from  lagoon
sediment.  Approximately 27% of the nitrocellulose was extracted.  While a  single stage
extraction  did not  completely remove  all explosives, solvent extraction is  usually
conducted as a multi-stage operation to  obtain complete extraction. The low recovery
of nitrocellulose  means it  will require more stages  than  will TNT, RDX and tetryl
sediment.  Additional acetone extraction experiments followed by a  somewhat larger
scale  demonstration are recommended as the  next steps  in the investigation  of this
process.
                                        87

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        Water extraction at high temperatures and pressures proved to be a moderately
effective  means of removing TNT, RDX and tetryl from sediment.  The heating, cooling
and high pressure environment required by this process will greatly  increase capital and
operating  costs over those required for acetone extraction.  In addition, the much lower
solubilities of the explosives in water, even at high  temperature, will require a larger
system  to contain the liquid  volume.   Finally,  the floating  of molten  TNT on the
surface of the water  could pose a  serious safety  hazard.  For these reasons, water
extraction is not recommended for further study.

        Of the five process tested, only incineration and acetone  extraction produced
effective  decontamination  of  explosives containing  sediments with  no  major  process
complications.   Incineration equipment is readily available, and pilot testing of this
process should  be  top priority.   Acetone extraction  has not  been  used  in  this
application, but existing solvent extraction equipment  should be usable without major
modifications.  Through the use of these  technologies,  it  is expected that  relatively
cost effective  decontamination of lagoon  sediments  can be accomplished  with only a
fairly small process development effort.
                                         88

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                                IX.   REFERENCES

 C-E Raymond (1980), "Bartlett-Snow," Bulletin 793.

Conway, R.A.  and  Ross,  R.D. (1980), Handbook  of  Industrial  Waste  Disposal,  Van
        Nostrand  Reinhold  Company,  New  York.

Dawson, G.W. (1978), "Appendix A to the  EPA Kepone Mitigation  Project Report:  The
        Feasibility of Mitigating Kepone  Contamination in the James  River  Basin,"
        BatteUe,  Pacific Northwest Laboratory.  NTIS, PB 286 085.

 Department  of  the  Army  and the  Air  Force (1967}, Military Explosives,  Technical
        Manual No.  9-1300-214, November  28, 1967.

EPA (1979), Process Design Manual - Sludge Treatment and  Disposal, Environmental
        Protection Agency, Cincinnati, Ohio, EPA  628/1-79-01L

IT-Enviroscience (1981),  "Evaluation of Catalyzed Wet Air Oxidation for Treating Army
        Lagoon Sediments,"  unpublished  report  submitted to Atlantic Reerch  Cor-
        poration.

Met-Pro Corporation (1980), Personal Visit, Harleyville, Pennsylvania.

Morris,  M.; Sivinski,  J.; Brandon, J.; Neuhausser,  K. and Wood, R. (1979), "A Summary
        of Recent Developments in  the  Sludge  Irradiation Program  at  Sandia  Lab-
        oratories," Sandia Laboratories, Albuquerque, New  Mexico.

Peterbilt (1980),  Personal Communication,  Landover,  Maryland.

Peters,  M.S.  and  Timmerhaus,  K.D. (1968),  Plant Design and  Economics for  Chemical
        Engineers, 2nd edition, McGraw-Hill Book Company, New  York.

Peters,  M.S.  and  Timmerhaus,  K.D. (1979),  Plant Design and  Economics for  Chemical
        Engineers, 3rd  edition,  McGraw-Hill Book Company, New  York.

Popper,  H.   ed.  (1970), Modern  Cost  Engineering  Techniques,   McGraw-Hill  Book
        Company, New  York.

Salemink, W. (1980),  Personal Communication, Letter, Assemblers Inc., West Liberty,
        Iowa.

Scurlock, A.D.; Lindsey, A.W.; Fields, T.  Jr. and Huber, D.R. (1975), "Incineration  in
        Hazardous   Waste    Management,"   Environmental    Protection  Agency,
        EPA/530/SW-141. NTIS,  PB 261 049.

Stribling, J.B. (1972), "Sludge  Incineration  By  Cyclone Furnace,"  Effluent and Water
        Treatment Journal, 12(8):  395-400.
                                            89

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Treybal, R.C. (1955),  Mass-Transfer Operations, McGraw-Hill Book Company, New York.

Wentsel,  R.S.; Sommerer, S. and  Kitchens, J.F.  (1982), "Engineering and Development
       Support of General Decon  Technology for the  DARCOM Installation Restoration
       Program.   Task  E:   Treatment  of Explosives Contaminated Lagoon Sediment
       - Phase I.  Literature Review and Evaluation," Atlantic Research Corporation.

Wentsel,  R.S.; Wilkinson, M.S.;  Hyde, R.G.; Harward, W.E.; Jones, W.E. and  Kitchens,
       J.F. (1979),  "Problem  Definition  Study  on 1,3-Dinitrobenzene,  1,3,5-Trinitro-
       benzene  and  Di-n-Propyl  Adipate,"  Contract No. DAMD17-77-C-7057,  U.S.
       Army Medical Research and  Development  Command, Fort Detrick,  Frederick,
       Maryland.
                                      90

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APPENDIX  A.  ANALYTICAL METHODS
               A-l

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                           Appendix  A

                        Analytical Methods

Analysis of High Levels of TNT and RDX in  Sediment - Quantitative

Determination of Nitrocellulose in Sediment - Quantitative

Lead and Cadmium  in  Water -  Quantitative
Chromium and  Zinc in Water - Semi-Quantitative

Lead and Cadmium  in  Sediment -  Quantative
Chromium and Zinc in Sediment - Semi-Quantitative

Analysis of Nitrate-N in Sediment - Semi-Quantative

Analysis of Nitrate-N in Water - Semi-Quantative

Analysis of Low Levels of TNT, RDX and Tetryl in Sediment -
SemirQuantative
                                A-2

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 ANALYSIS OF  HIGH  LEVELS OF  TNT  AND RDX IN SEDIMENT - QUANTITATIVE
                             ARC  METHOD NO. 1 for
                      DECON Technology DAAK11-80-C-0027
1.      APPLICATION

       Method used to determine the concentration of TNT and RDX in  sediment.

       A.   Tested  Concentration Range;  (pg/g dry sediment)

            TNT  -     126.0 to 2520.0  pg/g
            RDX  -   249.1 to  5340.0  ^g/g

       B.   Sensitivity;

            TNT  -     2.93  area units/ng based on 288 ng injection
            RDX -    0.42  area units/ng based on 304 ng injection

       C.   Detection Limit; (ug/g  dry  sediment)

            TNT    -  178.5 Vg/g
            RDX   -  490.1 Mg/g

       D.   Interferences;   None encountered during  analysis

       E.   Analysis Rate;  Each sample  requires 15 minutes  for extraction and  20
minutes for GC analysis.   With a GC autosampler, one  analyst can perform  30-40
extractions and  load  the autosampler vials  in an 8-hour day.

II.     CHEMISTRY:
                   Toluene, 2,4,6-trinitro-
       CAS RN    118-96-7
       Melting Point;   80.75C       Boiling  Point;   240C (explodes)
                   Hexahydro-1 ,3,5-trinitro-l ,3,5-triazine
       CAS RN    121-82-4
       Melting Point;   204C          Boiling Point;    not  available

       TNT - Use  caution in handling  TNT.  Potential explosive,  skin absorption
and toxic inhalation hazards  exist.

       RDX  -  Use caution  in handling RDX.  Potential explosive  and toxic  inhalation
hazards exist.
                                       A-3

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III.     APPARATUS
       A.   Instrumentation;

            Gas Chromatograph  -  Hewlett-Packard 5880A with flame  ionization
                detector, auto injector, computer controller  and integrator.

       B.   Parameters;

            Column  -  2% Dexsil 300  GC  on Anakrom Q packed in a 2  mm
                        I.D., 0.25  in. O.D.  by a  2 ft. column.
            Gas Flow - nitrogen - 32 ml/min at detector
            Temperature - injection port  210C
                           oven   140-230C
                           Detector    250C
            Temperature programming - 8C/min
            Injection volume - 4  yl
            Detector   -  flame  ionization detector
            Retention  times   -   TNT  -  2.0  minutes
                                 RDX -  3.4 minutes

       C.   Hardware/Glassware;

            1 ml pipets (1  for each standard;  1 per sample)
            10  ml pipets (1 for  solvent; 1 per  sample)
            culture tubes - 16 mm x 150 mm, teflon lined
               screw cap (2 per  sample)
            10  ml volumetric  flask (4)
            GC vials - teflon septum (1 per sample)
            centrifuge  (1)
            refrigerator (1)
            25   yl Hamilton syringe (1)
            50   yl Hamilton syringe (1)
            10   yl Hamilton syringe (1)
            aluminum  foil
             ASTM #10  sieve (1)

        D.   Chemicals;

            TNT "SARM"   -   #PA 364,  Lot #2714
             RDX  "SARM"   -   #PA 361, Lot #1101475-1
            TNT           -   recrystallizod (determinedto be equivalent
                                  purity as SARM)
             RDX           -   rccrystallizcd (determined to be  equivalent
                                  purity ns SARM)
             Acetone,  certified (Fisher Scientific)
                                       A-4

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IV.     STANDARDS:

       Concentrated stock solutions of RDX and TNT are prepared by weighing  out
the following amounts of SARM material  (or equivalent) into volumetric flasks and
bringing to volume  with acetone.

       RDX

       534.1  mg  in 10 ml    =    53,411  mg/1 (I)
       498.3  mg  in 50 ml    =     9,965  mg/1 (II)
       111.9  mg  in 25 ml    =     4,474  mg/1 (III)

       TNT

       561.5  mg  in 10 ml    =    56,150  mg/1 (I)
       360.0  mg  in 50 ml    =     7,200  mg/1 (II)
       32.5 mg in  100 ml    =       325  mg/1 (III)


These volumetrics are wrapped in  aluminum foil and  stored in  a refrigerator until
needed.   Storage  time should  not exceed  one  month.

       A.   Calibration Standards

            Working standards are prepared by diluting the concentrated stock
solutions according  to the following scheme in acetone.

            RDX

       5 ml of n to 10  ml  =    4,983 mg/1 (A)
       2.5  ml of I  to 100  ml  =  1,335 mg/1 (B)
       1 ml of II to 10  ml    -    997 mg/1 (C)
       new stock             =    206 mg/1 (D)
       new stock             =    153.9 mg/1 (E)
       1 ml of C to  10  ml    =     99.7 mg/1 (F)
       5 ml of E to 10  ml    =     76   mg/1 (G)
       5 ml of F to 10 ml     =     38   mg/1 (H)

            TNT   '
       5 ml of II to 10  ml  =    3,600 mg/1 (A)
       1 ml of II to 5 ml   =    1,440 mg/1 (B)
       1 ml of II to 10  ml  =      720 mg/1 (C)
                                   325 mg/1 (D)
       5 ml of III  to 10 ml  =      162 mg/1 (E)
       1 ml of C to  10  ml  =       72 mg/1 (F)
       5 ml of F to 10  ml   =       3G mg/1 (G)
       5 ml of G to 10 ml   =       18  mg/1 (H)

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Working  standards should  be  freshly prepared at least every 2 days.
                                                  
       B.    Control  Spikes;

             The concentrated stock solutions were used for spiking the sediment
samples.   The dried sediment samples are spiked with  the  TNT or RDX by
pipeting  known amounts of the control stock solutions  U5  yl to  1  ml)  onto  the
sediment in a culture tube with a  microliter syringe or 1 ml pipct.  Spike should
be double expected TNT or RDX concentration or 2 to 10  times detection limit.
The  sediment is allowed to dry  in  the dark  and extracted and analyzed as in procedure.

             Perform extraction, calibration, and analysis.

             The following spiking  procedure was implemented to determine pre-
cision, accuracy and  detection limit for TNT and RDX  in sediment:   Four sets of
duplicate dried sediment  samples weighing 2.00 + 0.02  g each were spiked as
follows:


           Sample set A   50 yl of RDX Stock II     =    249.1 yg/g  RDX
                          25 yl of TNT Stock II     =    126.0 yg/g  TNT

           Sample set B   20 yl of RDX Stock I     =    534.0 yg/g  RDX
                          70 yl of TNT Stock II     =    252.0 yg/g  TNT

           Sample set C   50 yl of RDX Stock I     =   1335.3 yg/g  RDX
                          20 yl of TNT Stock I      =    561.5 yg/g  TNT

           Sample set D   0.5 ml of RDX Stock II    =   2491  yg/g  RDX
                          50 yl of TNT Stock I      =   1404  yg/g  TNT

           Sample set E   1.0 ml of RDX Stock II    =   4982  yg/g  RDX
                          0.7 ml of TNT Stock II    =   2520  yg/g  TNT


Four sets of  duplicate 2.00 g  + 0.02 g of unspiked sediment samples  served as
blanks.

V.      PROCEDURE:

       The sediment  samples  are air dried in  the dark by spreading on individual
labeled   pieces of aluminum  foil.  Once the  samples are dried, each  sample  is
sieved through an A.S.T.M. No. 10 sieve.

       Each  dried sieved  sample is  thoroughly mixed.  Duplicate 2.0 g  samples
are taken for analysis.  Each  subsamplc  is weighed  and  placed into a  new  culture
tube with a teflon-lined screw cap.
                                       A-6

-------
       Ten ml of acetone  are  pipeted  into the tube.  The tube contents are shaken
well and allowed to settle  after which  they are centrifuged.  The  supernatant
is  removed  with  a  clean  10  ml  pipct  and placed in  a second culture  tube.   The
contents of the tube arc shaken to thoroughly mix  the  sample.  The mixed  extract
is  pipetted into a teflon  septum sealed  GC  vial.
        Samples are ready  for GC analysis
        Inject 4 pi of sample extract onto GC column in duplicate and
           record peak area
        Calibration, inject  working calibration  solutions singly at beginning
          and conclusion  of each analytical run:   Plot peak area in nano-
          grams injected  of each standard to obtain working curve.

VI.      CALCULATIONS;

        Peak area of working standards  used to  prepare  a calibration curve from
which  apparent  concentrations can  be determined.

        The concentration in the original sediment  is calculated by the following
formula:


                       C(S)  =   C(e) x  v(e)
                                    w(s)
where       C(s)    =   concentration in the original  sediment
            C(e)    =   concentration in extract
            w(s)    =   weight of dry sediment
            V(e)    =   volume of extract

The  concentration  is corrected for extraction efficiency by  the following formula:


                        C(cs)  =      +  b
                        where   C(cs)   =   corrected concentration in
                                            dry sediment
                                bi      =   slope  of the regression line
                                            for found vs.  target  for
                                            spiked samples
                                bo      =   intercept  of the  regression
                                            line for found  vs. target for
                                            spiked samples
                                        A-7

-------
VII.    REFERENCE:


       Lindner, V. (1980), "Explosives and  Propellents," Kirk-Othmer  Encyclopedia
Chemical Technology, 3rd edition, John Wiley and  Sons, NY,  9, 561-671.

-------
                    DETERMINATION OF NITROCELLULOSE
                         IN SEDIMENT - QUANTITATIVE
                                 ARC Method No. 2

L       APPLICATION:

        Method used to determine the concentration  of nitrocellulose in sediment.

        A,    Tested Concentration Range:   (yg/g sediment)

             4.4  to 110.2  yg/g

        B.    Sensitivity:

             0.23 absorbance units/yg  (nitrite-nitrogen) based on a 0.5  yg sample.

        C.    Detection Limit:   (yg/g sediment)

             17.17 yg/g

        D.    Interferences:  Organic nitrates  and  nitrite and  inorganic nitrates and
nitrites in  high concentrations.

        E.    Analysis  Rate:  Extraction, conversion and  evaporation require 8  hours
(about 2 hours of "labor).    Analysis requires 30 minutes for  6  samples.   Total time
required for  analysis  is 1.5 days.

2.       CHEMISTRY:

        (CsH702(ON02)3N    Nitrocellulose, Cellulose Trinitrate
        CAS.RN:       9004-70-0
        Melting Point:  Decomposes* at 125C

Nitrocellulose used in propellants  has  a  nitrogen content ranging  from  12.6  to  13.596.
Care  should  be taken  in  handling  this explosive, especially  in the dry  state.

This method  for  analysis of nitrocellulose  in  sediment involves  the  following steps:

             removal  of  interfering  species by extraction with  methanol'

             extraction of the nitrocellulose  with acetone

             treatment with NaOH  and  evaporation  to convert  nitrocellulose
             to nitrate/nitrite

             conversion  of nitrate to  nitrite  by treatment with a Hach
             Nitri  Ver VI  Reagent

             analysis  for nitrite by  EPA Method 354.1
                                         A-9

-------
As no  "standard sediment" has been  approved and since the method is not adaptable
to the analysis of "standard  distilled water," a sample of sediment was obtained
from a pond  near  Atlantic Research,   dried  and   sieved.   This material was
employed as  a "provisional standard sediment."

3.     APPARATUS:

       A.   Instrumentation:

             Hach DR/2 Spectrophotometer with absorbance scale

       B.   Parameters:

             Wavelength - 540  nm

       C.   Glassware/Hardware:

             16x125  mm culture  tubes  with screw  caps (teflon liners)  (112)
             25 ml  volumetric flasks (6)
             125 ml Erlenmeyer  flasks  (7)
             Hach 25  ml sample cells  (2 - matched)
             pipets- 1 ml
             pipets- 5  ml
             pipets- 10 ml

       D.   Chemicals:

             Acetone,  ACS certified (Fisher  Scientific)
             Methanol, ACS certified (Fisher Scientific)
             NaOH, reagent grade
             Nitrocellulose,  provisional SARM  PA  365, Lot No.  36181
             Hach  Nitri Ver  VI Reagent Powder Pillows
             Nitrogen
             Water, Nitrite  Free Distilled
             Sodium Nitrite,  ACS  certified (Fisher Scientific)
             Buffer Color Reagent
                  HC1, Reagent Grade
                  Sulfanilamide, Baker Analyzed
                  N-U-Napthyl)  Ethylene Diamine  Dihydrochloride
                  Sodium Acetate, Baker  Analyzed

 4.      STANDARDS

        A 100 mg/1  (nitrite-nitrogen) stock solution (NI)  is prepared by wieighing
 out  0.493 g  of sodium  nitrite and diluting to 1000  ml with nitrite-nitrate free
 distilled water.

        A.   Calibration:

             Calibration  standards arc  prepared from the stock  solution  as  follows:
                                        A-10

-------
Calibration
Standard
1
2
3
4
Method of
Preparation
1 ml of NI to
1000 ml
50 ml of 1 to
100 ml
20 ml of 1 to
100 ml
. 10 ml of 1 to
Final Concentration
mg/1 nitrite-N
0.100
0.050
0.020
0.010
                                  100  ml

These  standards  are  run with each analysis.

        B.    Control Spikes:

             The following  stock  solutions of nitrocellulose  are prepared in  acetone.
Stock No.
I
II

III

Method of
Preparation
44.1 mg NC to
100 ml
1 ml of I to
10 ml
1 ml of I to
50 ml
Final Concentration
mg/1 NC
- 441
44.1

8.82

Soil  samples of 2.00 + 0.05 grams are weighed out and placed in 6 different culture
tubes.   The sediment "is spiked  with  the  following  target  solutions:
Blank
Tube A
Tube B
Tube C
Tube D
Tube E
Volume
of Spike
0
0.5 ml
2.0 ml
1.0 ml
0.5 ml
1.0 ml
Stock Solution
Cone., mg/1
0
441
44.1
44.1
44.1
8.82
Target Cone, in
Dry Sed., ug/g
0
110.2
44.1
22.0
11.02
4.41
                                          A-ll

-------
5.       PROCEDURE:

        Add 6 ml  of methanol to the sediment  in  the culture tube, replace cap,
shake well and centrifuge for 5-6 minutes, decant the methanol  and discard.
Repeat  the extraction scheme with 6 additional ml of methanol.   Extract  the
sediment, add 3 ml of acetone to the culture tube.   Shake well, centrifuge,
pipet off the  acetone and place in a clean culture tube.   Repeat the extraction
scheme 3 times and combine the extracts.  Add 3  ml of 1.0 N  NaOH and  evaporate
at 30C under a stream  of  nitrogen to a  final  volume of  less  than 3  ml.

        Quantitatively transfer the sample into  a 25 ml  volumetric  flask and
bring up to volume with  nitrite  free  distilled water.  Shake well and transfer to
125 ml  Erlenmeyer  flask.  Add contents of 1  Hach  Nitri Ver VI  Reagent  Pillow
and  swirl sample.

        Prepare buffer color reagent, adding 105  ml cone. HC1, 5.0  g sulfanilamide,
0.5 g N-(l-Napthyl) ethylene-diamine  dihydrochloride and 136 g sodium acetate
to 250  ml nitrite  free distilled water in a 500  ml volumetric flask.

        Stir until  dissolved and bring to volume  with  nitrite free distilled water.
Reagent is stable  for several weeks if  stored in the dark.

        Add 2  ml of buffer  color reagent  to  solution  in  Erlenmeyer flask.   Swirl
flask contents and allow  color to develop  for 15 minutes.   Place sample in 25  ml
sample  cell and blank in a  second cell.   Zero machine  on blank  before  each
sample.   Read absorbance of sample at 540 nm.   Dilute  as necessary to maintain
absorbance readings between 0.2  and 0.8.   Read absorbance of calibration  standards,
plot calibration curves of mg/1 Nitrite-N  versus absorbance.

6.      CALCULATIONS:

        The nitrite-nitrogen  concentration  is read off the calibration curve.   The
nitrocellulose concentration  is calculated assuming 13.0%  nitrogen and taking
into account  the  dilution factor.
                  Ug nitrocellulose = nitrite-N   (yg/ml)   x
                   g sediment

                   LOO g nitrocellulose  x 25 ml  x  10
                     0.13 g  N                2  g
                                        A-12

-------
7.     REFERENCES:

       "EPA Methods  for Chemical Analysis of  Water and Wastes,"  March, 1979,
EPA-600/4-79-020.

       ".Water  Analysis Handbook," (1979),   Hach Chemical Company, Loveland,
CO., 12338-08.

       Lindner, W. (1980),  "Explosives  and  Propellants," Kirk-Othmer Encyclopedia  of
Chemical Technology, 3rd edition, John Wiley and Sons,  NY, 9, 561-671.
                                      A-13

-------
                   LEAD AND CADMIUM IN  WATER -  QUANTITATIVE

                 CHROMIUM AND ZINC  IN WATER - SEMI QUANTITATIVE
                               ARC  METHOD H
                               DECON TECHNOLOGY

                               DAAK11-80-C-0027


I.     APPLICATION;

       Method used to determine lead and  cadmium in  water (quantitative) and chromium
and zinc in water (semiquantitative).

       A.   Concentration Range Tested;

            Lead      -    0.25 to  5.0
            Cadmium   -    0.05 to  1.0
            Chromium  -    0.25 to  5.0  ug/ml
            Zinc      -    .0.05 to  1.0

       B.   Sensitivity;  Not applicable.

       C:   Detection Limit;

            Lead      -    0.250 yg/ml
            Cadmium   -    0.050 ug/ml
            Chromium  -    0.277 yg/ml
            Zinc      -    0.177 yg/ml

       D.   Interferences;  None observed during analysis.

       E.   Analysis Time;  Analysis of a set of six samples  can  be accomplished
in 30 minutes per metal (including  preparation  of standards  and  standard  curve.)

II.    CHEMISTRY;

       Lead:     CAS Registry No.   - 7439-92-1
                 Melting Point  -   327.4C      Atomic Weight  -   207.2

       Lead exhibits acute human toxic  effects  for blood levels  above
0.05 mg %.

       Cadmium:  CAS Registry No.   - 7440-43-9
                 Melting Point  -  321C         Atomic Weight  -   112.40

       Cadmium and its salts are highly toxic by inhalation  and  ingestion.

       Chromium: CAS Registry No..  - 7^40-47-3
                 Melting Point  -  1900C        Atomic Weight  -   51.996
                                       A-14

-------
       Chromium(VI) salts have irritant effects' on skin and respiratory pas-
sages and are highly  toxic  if. ingested.   Chromium (III) compounds show  little
or no toxic effects.

       Zinc:     CAS  Registry No.   -  7440-66-6
                 Melting Point  -  419.5C      Atomic Weight  -  65.38

       Zinc salts have irritant  effects  on  skin and  respiratory passages and
are highly toxic  if  ingested.


III.   APPARATUS;

       A.   Instrumentation;

            Van'an Atomic Absorption  Spectrophotometer AA-775
            Varian hollow cathode  lamps
            Cadmium #56-100008-00
            Lead  #56-100029-00
            Chromium  #56-100012-00
            Brass (combination Copper -  Lead - Zinc)  #56-100192-00

       B.   Parameters;

            Lamp  Current              Cadmium       3.5m Amp
                                      Lead         5.0 m Amp
                                      Chromium      7.0 m Amp
                                      Zinc         5.0 m Amp

            Fuel                       Air-acetylene flame

            Wavelength
            Spectral  Band Pass
       C.    Hardware/Glassware;

            16 x 150mm  culture  tubes with teflon lined screw  caps
            1, 5 and 10  ml  disposable pipets

       D.    Chemicals;

            Cadmium (certified Atomic Absorption, Reference  Standard  1,000
                    ppm  -  Fisher Scientific Co.)

            Lead (certified Atomic Absorption,  Reference Standard  1,000
                    ppm  -  Fisher Scientific Co.)
                                      A-15
Cadmium
Lead
Chromium
Zinc
Cadmium
Lead
Chromium
Zinc
228.8 nm
283.3 nm
357.9 nm
213.9 nm
0.5 nm
0.5 nm
0.2 nm
1.0 nm

-------
            Chromium  (Dilut-It   Chromium Standard,  1  g Cr + as K2Cr04
                      J.T.  Baker Chemical  Co.)

            Zinc (certified Atomic Absorption Reference Standard 1,000
                      ppm - Fisher Scientific Co.)
IV.     STANDARDS;
schemes.
            Calibration Standards;

            The working standards were prepared according to the following
            Lead Standard = 1,000 yg/ml (I)

            1  ml of I diluted to 10 ml    =     100
            2 ml of II diluted to 10 ml    =      20
            1  ml of II diluted to 10 ml    =      10
            1  ml of IV diluted to 10 ml           1
            5 ml of V diluted to 10 ml    =     0.5
            2.5 ml of  V diluted to 10 ml  =     0.25
pg/ml
yg/ml
yg/ml
yg/ml
yg/ml
 pg/ml
      (II)
      (III)
      (IV)
      (V)
      (VI)
       (VII)
            Cadmium Standard = 1,000 yg/ml (I)

            1 ml of I diluted to 10 ml    =     100 ug/ml  (II)
            1 ml of II diluted to 10 ml   =      10 wg/ml  (III)
            3 ml of III diluted to 10 ml  =       3 pg/ml  (IV)
            2 ml of III diluted to 10 ml  =       2 yg/ml  (V)
            1 ml of III diluted to 10 ml  =       1 yg/ml  (VI)
            1 ml of VI diluted to 10 ml   =     0.1 yg/ml  (VII)
            5 ml of VII diluted to 10 ml  =     0.05 yg/ml  (VIII)
            Chromium Standards = 1000 yg/ml (I)

            1 ml of I diluted to 10 ml
            2 ml of II diluted to 10 ml
            1 ml of II diluted to 10 ml
            1 ml of IV diluted to 10 ml
            5 ml of V diluted to 10 ml
            5 ml of VI diluted to 10 ml
100
 20
 10
  1
0.5
0.25
yg/ml
yg/ml
yg/ml
yg/ml
ug/ml
      (II)
      (III)
      (IV)
      (V)
      (VI)
       (VII)
             Zinc  Standard  =  1000  ug/ml  (I)
             1  ml  of I  diluted  to  10  ml
             1  ml  of I  diluted  to  10  ml
             1.5 ml  of  III  diluted to 10
             1.0 ml  of  III  diluted to 10
             0.5 ml  of  III  diluted to 10
             1  ml  of VI diluted to 10 ml
ml =
ml =
ml =
100 ug/ml (II)
10 yg/ml (III)
1.5 yg/ml (IV)
1.0 ug/ml (V)
0.5 ug/ml (VI)
0.05 ug/ml (VII)
                                    A-16

-------
       B.   Control Spikes

            Lead and cadmium were spiked together into  corresponding  test
tubes and brought up to a volume of 15 ml  with distilled water.

                              Lead Concentration

            Test Tube 1.   3.75 ml of V      = 0.25  yg/ml
            Test Tube 2.   0.75 ml of IV     = 0.5   yg/ml
            Test Tube 3.   1.5 ml of IV      -1.0   ug/ml
            Test Tube 4.   3.75 ml of IV     = 2.5   yg/ml
            Test Tube 5.   7.5 ml of IV      = 5.0
            Test Tube 6.   Blank
                            Cadmium Concentration

            Test Tube 1.    0.75 ml  of VI      =   0.05
            Test Tube 2.    1.5 ml  of VI       =0.1   ug/ml
            Test Tube 3.    3.0 ml  of VI       -   0.2   pg/ml
            Test Tube 4.    0.75 ml  of III     =   0.5   gg/ml
            Test Tube 5.    1.5 ml  of III      =   1.0   yg/ml
            Test Tube 6.    Blank


            Zinc and chromium standards were  spiked toegther  into corres-
ponding test tubes and brought up  to a volume of 15 ml  with distilled water.


                            Chromium Concentration

            Test Tube 1.    3.75 ml  of V       =   0.25  ug/ml
            Test Tube 2.    0.75 ml  of IV      =   0.5   yg/ml
            Test Tube 3.    1.5 ml  of IV       =1.0   yg/ml
            Test Tube 4.    3.75 ml  of IV      =   2.5   yg/ml
            Test Tube 5.    7.5 ml  of IV       =   5.0   yg/ml
            Test Tube 6.    Blank

                                Zinc Concentration

            Test Tube 1.    0.75 ml  of V       =   0.05  ug/ml
            Test Tube 2.    1.5mlofV       =   0.1   ug/ml
            Test Tube 3.    3.0 ml  of V       =   0.2   ng/ml
            Test Tube 4.    0.75 ml  of III     =   0.5   yg/ml
            Test Tube 5.    1.5 ml  of IIT     =   1.0   ug/ml
            Test Tube 6.    Blank
                                      A-17

-------
V.     PROCEDURE;

       The samples to be analyzed are aspirated into the flame for analysis.
Distilled water is aspirated between samples  to ensure no cross contamination.
Each sample is run in duplicate.   Standards  are run daily to construct a
calibration curve  which is input  into the AA  so that the sample concentra-
tions are read out directly in ppm.

VI.    CALCULATIONS;

       The apparent concentration of the metal  is  read directly from the
AA and multiplied  by the appropriate dilution factor, if any.   The actual
concentration is read from the target versus  found line.

VII.   REFERENCES;

       Windholz, M. (1976), "The  Merck Index,"  9th edition,  Merck Company,
       Inc., Rahway, New Jersey.

       Varian Techtrcn Pty, Ltd.  (1979), "Analytical Methods for flame
       spectroscopy," Springvale, Australia,  Publication No. 85-100009-00.
                                      A-18

-------
              LEAD  AND CADMIUM  IN  SEDIMENT. - QUANTITATIVE

            CHROMIUM  AND ZINC  IN SEDIMENT  -SEMIQUANTITATIVE

                                ARC METHOD  #5

                              DECON TECHNOLOGY

                                DAAK11-80-C-0027
 1.      APPLICATION;

        The method  is applicable to the analysis  of lead, cadmium, chromium and
 zinc in soil.

        A.   Tested  concentration range;

B.
C.

Lead
Cadmium -
Chromium -
Zinc
Sensitivity; not
Detection Limit
Lead
Cadmium -
Chromium -
Zinc
3.125 yg/g to 31.25 yg/g
0.625 ug/g to 12.5 ug/g
2.5 yg/g to 50.0 yg/g
2.0 ug/g to 40.0 Mg/g
applicable

7.07 yg/g
2.53 yg/g
7.21 yg/g
4.54 yg/g
        D.    Interference;  None observed  during operation.

        E.    Analysis Time;  Extraction  and  filtering of 6 samples can be accomplished
in approximately  2  1/2 hours.   Analysis of  the samples on the  instrument can be
accomplished in about 20 minutes.

II.      CHEMISTRY

        Lead:     CAS Registry No.  - 7439-92-1
                 Melting  Point  -  327.4C      Atomic Weight  -  207.2

        Lead exhibits acute human toxic effects  for blood levels above 0.05  mg %.

        Cadmium: CAS Registry No.  - 7440-43-9
                 Melting  Point  -  321C       Atomic Weight  -  112.40

        Cadmium  and its salts are highly toxic by inhalation and ingestion.

        Chromium: CAS Registry No.  - 7440-47-3
                 Melting  Point  -  1900C       Atomic Weight  -  51.996

        Chromium(VI) salts  have  irritant effects on skin nnd respiratory passages and
are highly toxic if ingested.  Chromium  (III)  compounds show  little or no toxic
effects.

                                      A-19

-------
       Zinc:      CAS  Registry No.  -  7440-66-6
                 Melting Point  -  419.5C       Atomic Weight  -  65.38

       Zinc salts have  irritant effects on  skin and respiratory passages and are
highly toxic if  ingested.

III.     APPARATUS;

       A.   Instrumentation;

            Varian Atomic  Absorption Spectrophotometer  AA-775
            Varian Hollow Cathode Lamps
            Cadmium #56-100008-00
            Lead #56-100029-00
            Chromium  #56-100012-00
            Brass (combination copper  - lead - zinc)  #56-100192-00
       B.    AA  Parameters
             I.    Lamp  Current   -
                     Cadmium
                     Lead
                     Chromium
                     Zinc
             2.

             3.
Fuel - Air-acetylene flame
Wavelength
             4.    Spectral Band  Pass-
        C.    Hardware/Glassware
Cadmium
Lead
Chromium
Zinc

Cadmium
Lead
Chromium
Zinc
               3.5 millilamps
               5.0 millilamps
               7.0 millilamps
               5.0 millilamps
228.8  nm
283.3  nm
357.9  nm
213.9  nm

0.5  nm
0.5  nm
0.2  rim
1.0  nm
             16 x 150 mm culture  tubes with Teflon lined screw caps
             25 ml volumetrics
             50 ml graduated cylinders
             glass funnels
             15 cm  filter paper for quantitative analysis
               weight of ash below 0.1 milligram
             H2O water bath
             Thermolyne heating plate
             25 mm x  150 mm test tubes 
             25 ml flasks
             1,  5  and 10 ml disposable pipets
                                       A-20

-------
       D.    Chemicals;

             Nitric acid - Reagent  A.C.S. (Fisher  Scientific Company)
             Cadmium Certified  Atomic  Absorption Reference
               Standard 1000 ppm (Fischer  Scientific  Company)
             Lead Certified  Atomic Absorption Reference  Standard
               1000 ppm  (Fisher Scientific Company)
             Dilut-It Chromium Standard, 1  g Cr6+ as I^CrCXi
               (J.T. Baker Chemical Company)
             Zinc  Certified Atomic Absorption  Reference Standard
               1000 ppm  (Fisher Scientific Company)
IV.     STANDARDS;
        A.    Calibration Standards;

             Lead Standard = 1000 ug/ml (I)

             1  ml of I diluted to 10  ml      =    100  pg/ml (II)
             2  ml of II diluted  to 10  ml     =      20  ug/ml (III)
             1  ml of II diluted  to 10  ml     =      10  yg/ml (IV)
             1  ml of IV diluted to 10 ml     =       1  Pg/ml (V)
             5  ml of V diluted  to 10  ml     =    0.5  ug/ml (VI)
             2.5 ml  of IV diluted to  10  ml   =    0.25 yg/ml (VH)

            Cadmium  Standard  = 1000 ug/ml (I)

            1 ml of I diluted to 10 ml     =     100 ug/ml (II)
            1 ml of II diluted to 10  ml     =     10 ug/ml (III)
            3 ml of III diluted  to 10  ml    =       3 ug/ml (IV)
            2 ml of III diluted  to 10  ml    =       2 ug/ml (V)
            1 ml of III diluted  to 10  ml            1 ug/ml (VI)
            1 ml of VI diluted to 10  ml    =     0.1 ug/ml (VII)
            5 ml of VII diluted to 10  ml    =     0.05  ug/ml (VIII)

            Chromium  Standard  = 1000 ug/ml (I)

            1 ml of I diluted to 10 ml     =     100 ug/ml (II)
            2 mi of II diluted to 10  ml     =     20 ug/ml (III)
            1 ml of II diluted to 10  ml     =     10 ug/ml (IV)
            1 ml of IV diluted to 10  ml    =       1 ug/ml (V)
            5 ml of V diluted to  10  ml     =     0.5 ug/ml (VI)
            5 ml of VI diluted to 10  ml     =     0.25  ug/ml (VII)

            Zinc Standard =  1000 ug/ml (1)

            1 ml of  I  diluted to 10  ml      =    100 ug/ml (II)
            1 ml of  I  diluted to 10  ml      =     10 ug/ml (III)
            1.5 ml of  III diluted to 10 ml   =    1.5 ug/ml (IV)
            1.0 ml of  III diluted to 10 ml   =    1.0 ug/ml (V)
            0.5 ml of  III diluted to 10 ml   =    0.5 ug/ml (VI)
            1 ml of  VI diluted to 10  ml     =   0.05 ug/ml (VII)
                                      A-21

-------
       B.   Control Spikes;

            Lead and cadmium standards  were spiked together into corresponding
test tubes containing 2.00 + .005 gram sediment samples.
            Test Tube 1.
            Test Tube 2.
            Test Tube 3.
            Test Tube 4.
            Test Tube 5.
            Test Tube 6.
            Test Tube 1.
            Test Tube 2.
            Test Tube 3.
            Test Tube 4.
            Test Tube 5.
            Test Tube 6.
   Lead Concentrations

0.625  ml of IV  =     3.125  yg/g
1.25  ml of IV   =     6.25   yg/g
2.5  ml of IV    =     12.5   ug/g
0.625  ml of H   =     31.25  ug/g
125 ml of II    *     62.50  yg/g
Blank
 Cadmium  Concentration
1.25 ml of VI
2.5  ml of VI
0.5  ml of HI
1.25 ml of III
2.5  ml of III
Blank
0.625 yg/g
1.25   yg/g
2.5    yg/g
6.25   yg/g
12.5   yg/g
             Chromium and zinc standards were spiked  together into corresponding
test tubes  containing 2.00  +  .005  gram sediment samples.

                             Chromium Concentration
Test Tube 1.
Test Tube 2.
Test Tube 3.
Test Tube 4.
Test Tube 5.
Test Tube 6.
.625 ml of IV
1.25 ml of IV
2.5 ml of IV
.525 ml of II
1.25 ml of II
Blank
=



=

2.5 yg/g
5.0 yg/g
10.0 yg/g
25 yg/g
50 yg/g

Zinc Concentration
Test Tube 1.
Test Tube 2.
Test Tube 3.
Test Tube 4.
Test Tube 5.
Test Tube 6.
.4 ml of III
.8 ml of III
2 ml of III
.4 ml of II
.8 ml of II
Blank

=

=
=

2.0 yg/g
4.0 yg/g
10.0 yg/g
20.0 yg/g
40.0 yg/g

                                       A-22

-------
V.      PROCEDURE

        Two g + .005 g sediment samples are  digested in 20 ml  of  1:1  nitric  acid/
distilled water Tor  2  hours on  a  hot  water bath.   The extract  fronn the digestion
is filtered, diluted  to 20  ml with distilled water  and then poured into  a flask for
analysis.  Additional  dilutions  are. made of samples that  are   outside  the optimum
working range for the AA.   The samples are aspirated into the  AA for analysis.
The aspirator is rinsed  with  distilled water between analyses to  prevent cross
contamination.   The  standards  are  run  before  the samples and the curve input
into the AA so  that  the sampled concentrations are read out directly  in ppm.

\L      CALCULATIONS;

        The apparent concentration of the metal  in  the solution  is read directly
from the  AA.  The  concentration in  the sediment is calculated by:

       ug/g sediment = pg/ml from  A A x 20  ml x any additional dilution  factor
                                          2 g

The actual concentration  is  read from  the target versus found  line.

YD.-     REFERENCES:

        Windholz, M.  (1976),  'The Merck  Index," 9th edition,  Merck  Company, Inc.
        R'ahway, New Jersey.

        Varian Techtron Pty. Ltd. (1979), "Analytical Methods for Flame Spectro-
        scopy,"  Springvale, Australia, Publication  No. 85-100009-00.
                                        A-23

-------
         ANALYSIS OF NITRATE-N IN SEDIMENT - SEMIQUANTITATIVE
                                 ARC Method  #6
                      DECON  Technology DAAK11-80-C-0027

I.      APPLICATION

       Method used to determine the concentration of nitrate-N  in soils and
sediment.

       A.   Tested Concentration Range (yg/g  dry sediment)

            Nitrate-N - 1.0 to 20.0  yg/g

       B.   Sensitivity;

            50  mV/yg

       C.   Detection Limit: (yg/g  dry  sediment)

            Nitrate-N  - 2.056  Mg/g

       D.   Interferences;  none encountered during analysis

       E.   Analysis Rate; Each sample requires 20 minutes for  extraction and about
3 minutes to test;  A  set of six samples can be analyzed in 40 minutes.

II.     CHEMISTRY

       Nitrate usually occurs in soils and sediment as a salt  and is a common
plant nutrient.

III.     APPARATUS

       A.   Instrumentation;

            Orion  93-07 nitrate specific ion electrode
            Orion  91-05 combination pH gel  filled electrode
            Orion  399A pH/mV meter
            Mettler H5AR Analytical Balance

       B.   Hardware/Glassware;

             volumetric flask  -  1000  ml (1)
             volumetric flask  -  100  ml (1)
             volumetric flasks  - 10 ml (4)
             beakers   -  100 ml (6)
             pipet - 10 ml (6)
             pipet - 1 ml  (3)
             pipet - 2__ml  (2)
            quart dark reapent bottle (1)
                                      A-24

-------
       C.    Chemicals;

             Potassium Nitrate, analytical reagent grade, (Mallinckordt, Inc.).

             Silver  Sulfate, Certified  ACS, (Fisher Scientific Co.)

             Aluminum Sulfate, Certified  ACS, (Fisher Scientific Co.)

             Boric Acid, Photographic/Technical,  (Eastman  Kodak Co.)

             Sulfamic Acid, Certified (Fisher Scientific  Co.)

IV.     STANDARDS

       A.    Extracting Solution  (I)

             16.66 g Aluminum Sulfate
             1.24 g Boric Acid
             4.67 g Silver  Sulfate
             2.43 g Sulfamic Acid

             Diluted to 1 liter with distilled water

       B.    Calibration  Standards;

             Calibration  standards are prepared according to the following scheme:

             1.44 g Potassium  Nitrate/100  ml = 2000  ppm  (II)
             1 ml II diluted to 10  ml = 200  ppm  (III)
             1 ml in diluted to 10 ml = 20 ppm  (IV)
             1 ml IV diluted to 10 ml = 2 ppm (V)
             1 ml V diluted to 10 ml =  .2 ppm (VI)

             Standards IH through VI prepared  from n daily.   Calibration standards
were  all  diluted  with extracting  solution I, spiking standards were diluted with
distilled  water.

       C.    Control Spikes;

             Prepared standards were added to dried,  preweighed sediment samples
weighing 2.000 10.005 g  according  to  the  following scheme:

             (a)   1  ml of  VI to  give  target  of 1 y g/g
             (b)   2  ml of  VI to  give  target  of 2 u g/g
             (c)   4  ml of  VI to  give  target  of 4 u g/g
             (d)   1  ml of  V to give target of  10 ug/g
             (e)   1 ml of III to  give  target of 100 ug/g
             (f)   Blank

             The sediment  was allowed  to  dry  before  extraction and analysis.  Or.e
set of spiked controls  is run.
                                      A-25

-------
V.      PROCEDURE

       A  calibration curve is plotted daily  using standards III  through  VI which
were mixed with extracting solution.

       Each  2  gram sediment sample is dispersed in 10 ml of extracting solution.
After 20 minutes, mV readings are taken using the nitrate specific  ion electrode
and the reference portion of the combination pH electrode with the pH/mV meter.
Between samples,  the electrodes are rinsed  with  distilled  water and blotted dry.

VI.     CALCULATIONS

       From the calibration  plot, concentrations are determined in  ug/ml for the
sample dispersions and are converted to yg/g of  sediment  by  multiplying by:

             10 ml dilution
             2.00 g sample

Vn.    REFERENCES:

       Orion Research, Inc.  (1978) "Methods Manual,  93 series electrodes", Form
       93  MM/8740, Cambridge, Massachusetts.

       Sawyer,  C.N. and  McCarty, P.L. (1978), Chemicals  for  Environmental
       Engineering, 3rd Edition,  McGraw-Hill Book Company, New  York.
                                       A-26

-------
          ANALYSIS OF  NITRATE - N  IN  WATER  -  SEMIQUANTITATIVE
                                 ARC Method #7  ..
                      DECON Technology DAAK11-80-C-0027

I.     APPLICATION

       A.   Tested  Concentration Range;

            Nitrate-N  -  0.2 to 4.0.ug/ml

       B.   Sensitivity;

            50  mV/vg

       C.   Deteciion Limit;

            Nitrate-N  -  0.243 ug/ml

       D.   Interferences; none encountered during  analysis.

       E.   Analysis Rate; Samples require  about 5 minutes  to  prepare and  test.

D.     CHEMISTRY

       The  nitrate ion, NO3~,  often occurs in natural waters as a result of  aerobic
oxidation of amrr.onia-N.  It  was determined that drinking waters with a high nitrate
content caused methemoglooinemia in  infants.   EPA therefore proposed that  nitr&te-N
levels should not exceed 10  mg/1 in public water supplies.

IE.     APPARATUS
       A.   Instrumentation;

            Orion 93-07 nitrate  specific  ion electrode
            Orion 91-05 combination pH  gel filled electrode
            Orion 399A pH/mV meter
            Mettler H5AR  Analytical Balance

       B.   Hardware/Glassware;

            100 ml  volumetric flasks
            100 ml  beakers
            10 ml disposable pipets
            1 ml disposable pipets
            1 quart dark reagent bottles

       C.   Chemicals;

            Potassium  Nitrate, analytical reagent grade  (Mallinckrodt, Inc.)
                                       A-27

-------
             Ammonium sulfate, t:Baker Analyzed" reagent grade (J.T. Baker
             Chemical  Co.)

IV.     STANDARDS

       A.    Ionic Strength Adjuster (I);

             26.42  g ammonium sulfate diluted  to 100 ml with distilled  water

       B.    Calibration Standards;

             1.444  g Potassium nitrate/100  ml distilled  water = 2000 ppm (II)
             1 ml II diluted to 10 ml = 200 ppm  (III)
             1 ml ID diluted  to 10  ml = 20  ppm  (IV)
             1 ml IV diluted  to 10  ml = 2 ppm (V)
             1 ml V diluted to 10 ml = .2 ppm (VI)

             Standards  ni  through VI are prepared daily from II.

       C.    Control Spikes;

             Prepared standards were diluted with distilled water  according  to  the
following scheme:
             (a)   25 ml  of  VI undiluted to give target of  0.2
             (b)   5 ml of V diluted to 25 ml  to give target of 0.4 yg/ml
             (c)   10 ml  ofV diluted to 25 ml  to give target of 0.8 yg/ml
             (d)   25 ml  of  V undiluted to give target  of 2.0 yg/ml
             (e)   5 ml of IV diluted to 25 ml  to give target  of 4.0 ug/ml

             One  set of spiked controls were run.

V.      PROCEDURE

        A calibration curve  is plotted daily using standards III through VI.  Prior  to
testing, all  samples and standards have 0.5 ml  Ionic Strength  Adjuster added to
25  ml of sample  to provide  a constant background.

        Millivolt readings are taken  of  each  sample and standard using the nitrate
specific ion  electrode and the reference portion of the  combination pH  electrode
with  the  pH/mV meter.   Between samples the electrodes are rinsed with distilled
water and blotted dry.

VI.      CALCULATIONS

        From the  calibration plot, concentrations are determined directly in  ug/ml.

VH.     REFERENCE

        Orion Research, Inc. (1978) "Methods Manual, 93 series electrodes," form
        93 MM/8740, Cambridge,  Massachusetts.
                                         A-28

-------
Sawyer, C.N. and McCarty, P.L.  (1978), Chemistry for  Environmental
Engineering, 3rd  Edition, McGraw-Hill  Book Company,  New York.
                              A-29

-------
           ANALYSIS OF LOW LEVELS OF TNT, RDX AND  TETRYL  IN
                           SEDIMENT - SEMIQUANTITATIVE
                                 ARC Method #12  '


. I.      APPLICATION:

        Method used to determine the concentration of TNT,  RDX and tetryl  in
 sediment.
                   *
        A.   Tested Concentration Range;  (yg/g dry sediment)

             TNT      0.502 to 10.05 ug/g
             RDX      0.540 to 10.80 pg/g
             Tetryl     0.495 to 9.90  pg/g

        B.   Sensitivity;

             TNT      7.8 cm  based  on a  0.196  yg  injection
             RDX      5.6 cm  based  on a  0.194  yg  injection
             Tetryl     5.7 cm  based  on a  0.155  yg  injection

        C.   Detection Limit; (pg/g dry sediment)

             TNT      1.5551 yg/g
           '  RDX      1.4039 yg/g
             Tetryl     0.2965 yg/g

        D.   Interferences;   No interferences were observed with  TNT, RDX and
 tetryL

        E.   Analysis  Rate;  Six samples can be  extracted in  20-30 minutes.   With
 an  LC autosamplcr, one analyst can extract and  perform  duplicate analyses on
 approximately 18 samples in an  8-hour day, including standards.

 H.     CHEMISTRY;
                       Toluene, 2,4,6-trinitro-
        CAS RN        118-96-7
        Melting Point:  80.75C              Boiling Point;  24()C (explodes)

        C3H6N6 6     Hexahydro-1,3 ,5-trinitro-l,3 ,5-triazine
        CAS RN        121-82-4
        Melting Point:  204CC               Boiling Point;  not  available
                       Tetryl;  Aniline,  M-methyl-N-2,4,6-tetranitro
        CAS RN        479-45-8
        Melting Point:  131C                Boiling Point;  187C (explodes)
                                          A-30

-------
Hazards. Use caution in handling TNT, RDX and  tetryl, explosive and toxic  hazards
exist.

ID.     APPARATUS:

     ~   A,   Instrumentation;

            HPLC  - Perkin-Elmer  "601  Liquid Chromatograph with Perkin-
            Elmer  UV Spectrophotometer
            LC-55  variable wavelength detector
            Waters Radial Compression  Unit
            Cole-Parmer Recorder

        B.   Parameters;

            Column - Waters 8"Cig 10 fi reverse phase radial compression
                       column
            Mobile  Phase - isocratic;  4596  methanol/5596  water @  3.0 ml/min
            At  other methanol  concentrations,  interfering, peaks  present
            problems, particularly  with  RDX.
            Detector - 230 nm
            Injection Volume  -  175 pi  for all samples
            Retention Times  of Compounds:

                 TNT       10.5 min
                 RDX       4.0 min
         .        Tetryl     8.0 min

        C.   Hardware/Glassware;

            Gelman suction  filter  apparatus (1)
            Aqueous 0.45 //m membrane filters (1 for  each solvent run)
            Volumetric flask  -  100 ml (4)
            Volumetric flask  -  50  ml  (1)
            Culture tubes - 16  mm x  150  mm,  teflon  lined screw cap (6)
            Pipets - 1  ml (10)
            Pipets - 10  ml  (6)
            Pasteur Pipets  (12)
            Aluminum  foil
            Refrigerator
            Centrifuge
            1 ml LC sample  bottles with teflon lined  caps (12)
                                         A-31

-------
       D.   Chemicals;

            TNT "SARM"    -     PA  364,  Lot  #2714
            RDX  "SARM"   -     PA  361, Lot #1101475-1
            Tetryl "SARM"  -     PA  608,  Lot  #2714
            Acetone, HPLC (Fisher Scientific)
            Methanol, HPLC (Fisher Scientific)
            Distilled water

IV.     STANDARDS:

       A.   Calibration Standards;

            Concentrated  individual stock standards of  TNT, RDX and  tetryl are
prepared by weighing out  the following amounts of SARM material into volumetric
flasks and bringing them to volume  with  HPLC grade  methanol:

            TNT       33.5  mg in 100 ml   =    335   mg/1 (I)
            RDX       27.75 mg  in 100  ml  =    277.5  mg/1 (II)
            Tetryl     6.65  mg in 50 ml    =    133 mg/1  (in)

The concentrated individual stock  solutions  are  mixed  and diluted with HPLC  grade
methanol according to the following scheme to produce  the  calibration standards:

            Standard Solution  A

            TNT       1  ml I  to  100 ml     =    3.35  mg/1
            RDX       1  ml II to  100  ml    =    2.775  mg/1
            Tetryl     2  ml III to 100 ml   =    2.66  mg/1

            Standard Solution  B                                                \

            TNT       0.5  ml I to  10 ml    =    16.75  mg/1
            RDX       0.5  ml II  to 10 ml   =    13.88  mg/1
            Tetryl     1.0 ml  III  to 10 ml   =    13.30  mg/1

            Standard Solution  C

            TNT       0.5  ml I to  15 ml    =    11.16  mg/1
            RDX     .  0.6  ml II  to 15 ml   =    11.10  mg/1
            Tetryl     1.0 ml  III  to 15 ml   =    8.86  mg/1
                                        A-32

-------
             Standard Solution D

             TNT       1  ml Standard Solution C  to  10' ml
             RDX       1  ml Standard Solution C  to  10 ml
             Tetryl     1  ml Standard Solution C  to  10 ml

             Standard Solution E

             TNT       i  ml Standard Solution C  to  25  ml
             RDX       1  ml Standard Solution C  to  25  ml
             Tetryl     1  ml Standard Solution C  to  25  ml

             Standard Solution F
                         1.12  mg/1
                         1.11 mg/1
                         0.886  mg/1
                         0.446  mg/1
                         0.444  mg/1
                         0.354  mg/1
            TNT       1  ml Standard Solution B  to 100 ml
            RDX       1  ml Standard Solution B  to 100 ml
            Tetryl     1  ml Standard Solution B  to 100 ml
                         0.168 mg/1
                         0.139 mg/1
                         0.133 mg/1
Working standards should  be freshly prepared at least every 2 days.

       B.   Control Spikes;

            .Concentrated stock solutions of TNT, RDX  and tetryl are prepared
by weighing out the following amounts of SARM  material into 100  ml volumetric
flasks and  bringing them  to  volume with HPLC grade methanol.
             TNT       2L6 mg in 100  ml    =
             RDX       33.5  mg  in 100 ml    =
             Tetryl     330.2  mg in 100 ml   =
           216 mg/1 (a)
           335  mg/1 (b)
          3302  mg/1 (c)
The concentrated stock solutions are then diluted  with  HPLC grade methanol  as  follows:
             1 ml  of I to 10 ml
   TNT      i mi  Of n to 10  ml

             1 ml  of I to 10 ml
   RDX      1 ml  of II to 10  ml

             1 ml  of n to 100  ml
   Tetryl    1 ml  of III  to  10  ml
21.6  mg/1  (d)
2.16  mg/1  (e)

33.5  mg/1 (f)
3.35  mg/1 (g)

33.02 mg/1 (h)
3.30  mg/1 (i)
These volumetrics are wrapped  in aluminum foil and  stored in a refrigerator until
needed.  Storage time should not exceed one  month.
                                          A-33

-------
            To spike the sediments, six  1 + 0.05 gram  samples cf dry sediment
are weighed out.  Each sample  is placed in  a  culture tube with teflon lined screw
cap.   The spiked samples are prepared as follows:


            L    TNT       0.3 ml of d    =    10.05 yg
                  RDX      0.5 ml of f    =    10.80 ug
                  Tetryl     0.3 ml of h    =    9.90  yg

            2.    TNT       0.15  ml of d   =    5.03  yg
                  RDX      0.25 ml of  f   =    5.40  yg
                  Tetryl     L5  ml of i     =    4.95  yg

            3.    TNT       0.6 ml of e    =    2.01 yg
                  RDX      LO  ml of g    =    2.16 yg
                  Tetryl     0.6 ml of i    =    L98 yg

            4.    TNT      0.3 ml of e    =    LOO yg
                  RDX      0.5 ml of g   =    1.08 yg
                  Tetryl     0.3 ml of i    =    0.99 yg

            5.    TNT      0.15  ml of e   =    0.50  yg
                  RDX      0.25 ml of  g   =    0.54  yg
                  Tetryl     0.15  ml of i   =    0.50  yg

            6.    Blank

The spikes are covered with aluminum foil and refrigerated until  analysis.  These
control spike  samples are used  to determine precision, accuracy and detection
limits for  TNT, RDX and  tetryl in sediment.

V.      PROCEDURE:

        The spiked sediment samples are evaporated to  dryness under a stream
of  nitrogen.   Once the sediment is dry,  2 ml  of  acetone  are  added to the culture
tube.  The tube  is capped and shaken to  extract the explosives from the  sediment.
The tubes are then centrifuged for 5  minutes. The acetone is carefully drawn
off the sediment  with a pasteur pipet  and  placed in LC  vials  for analysis.

        The samples are ready for LC  analysis .

        Inject 175 yl of methanol standard singly  before each  run.

        Inject 175 yl of each sample, unknown and spikes, in duplicate.

        In order  to keep the  peaks on  the scale of the  recorder,  the  detector and/or
recorder  sensitivity must be adjusted  to  the appropriate range.
                                        A-34

-------
VI.      CALCULATIONS:

        Plot peak height of standard (mm) versus  nanograms of material injected
on the column [fil injected x concentration of standard (ug/L  x 10~6)3  to obtain
standard curve.   Obtain  apparent  concentrations of unknown  by reading  the nano-
grams in the sample off the standard curve.   The  actual concentration  for analytes
in the samples are then  determined from  the  target versus found line.

VII.     REFERENCE :
       Lindner, V. (1980), "Explosives and  Propellents," Kirk-Othmer Encyclopedia
of Chemical Technology, 3rd edition, John Wiley and Sons, NY,  , 561-671.
                                         A-35

-------
APPENDIX  B.  WET CHEMISTRY METHODS
                B-l

-------
                                    Appendix B


 A.      p_H

        Twenty grams of  the dried sediment were  mixed with 20 ml of distilled water
 and placed on a shaker for an  hour.  The  mixture  was then allowed to settle for half
 an hour and  the  pH was  taken using an Orion 399A pH/mV  meter.

 B.      Chloride

        An additional 20  ml of distilled water were added to the pH  samples  to give
 a final  weight ratio of 1:2.  The mixtures were again placed on the shaker for an hour.
 MgSC>4  was added to  flocculate the sediment which was then centrifuged.  Measured
 amounts of the extract were  diluted to 50 ml  and sodium  bicarbonate and  K2CrO4
 indicator were added.  The samples  were finally titrated with .0025 N AgNOs to the
 appearance of  the reddish-brown precipitate indicating the endpoint.

 C.      Percent Moisture

        A 5 gram portion  of the sediment was added to a tared  crucible and dried in
 an oven (100-105C) to constant weight.  The crucible  was then cooled  in a dessicator
 and reweighed.  The  percent moisture  was calculated  from the following  formula:


        % moisture = 100  x weight before drying - weight after drying
                                    weight before drying

 D.      Percent Volatiles

        The weight lost by a dry sediment on heating to 550C provides a general idea
of the amount  of organic  matter in the sediment.   The previously oven dried sample
 from  the percent moisture analysis was heated in a muffle  furnace at 250C for  30
 minutes.  The  sample was then cooled  in a  dessicator and  reweighed.   The percent
volatiles was calculated by the following  formula:

        % volatiles  = 100 x weight of dried sample - weight after ignition
                                        wieght of dried sample

E.      Chemical Oxygen  Demand

        The Standard  Methods  (1979)  procedure  for chemical  oxygen demand (COD) in
Section  508 was followed.  Weighed samples  were diluted to 20 ml with distilled water
and prepared with mercuric sulfate, potassium dichromate  and  concentrated sulfuric
acid  '  fixed    with silver  sulfate.  The samples were refluxed for 2  hours, diluted and
titrated with ferrous ammonium sulfate and ferroin indicator.  A  blank and a standard
were run  with  each set of samples.
                                      B-2

-------
F.     Biochemical Oxygen Demand (BOD)

       The  procedure followed for BOD  is  listed  in  Section  507 of  the  Standard
Methods (1979). Dilutionsof 1,2 and3 grams of sediment  were made  with standard BOD
diluent and initial dissolved oxygen readings  were taken  after 15  minutes. The samples
were  incubated  at  20C   for  5  days.    At  the  end  of the incubation period,
dissolved oxygen readings were taken with a calibrated YSI Dissolved Oxygen Meter and
the soluble BOD calculated.

G.     Gas  Analyses

       Gas  samples were collected in 22 liter plastic air sampling bags (Plastic Film
Eng.).  The  gases analyzed were N2, O2, CO2 and CO.

       The  analyses  were performed in a Varian 3700  gas chromatograph.   The gas
chromatograph parameters were:

       Detector:             Thermal conductivity

       Column:             Altech "CTR" coaxial/molecular seive/
                            porapak column

       Gas  Flow:            35 cc/min

       Temperature:

             injection port:  210C
             oven:            60C isothermal
             detector:       200C

       Retention Time:

             CO2            0.25  min

             CO             2.72  min (and 0.16  min)

             N2             1.55  min (and  0.16 min)

             O2             L10 min (and 0.16  min)
                                      B-3

-------
APPENDIX C. RAW DATA FROM INCINERATION AND



      ACETONE EXTRACTION EXPERIMENTS
                   C-l

-------
     Table  C-I .  Sediment  Weights for Incineration Experiments
Sample
Weight Before  (g)
Weight After (  g)
Lagoon 9
300, 5 minutes
300, 30 minutes
300, 60 minutes
500, 5 minutes
500, 30 minutes
500, 60 minutes
700, 5 minutes
700, 30 minutes
700, 60 minutes
900, 5 minutes
900, 30 minutes
900, 60 minutes
Lagoon 11
200, 5 minutes
200, 30 minutes
200, 60 minutes
300, 5 minutes
300, 30 minutes
300, 60 minutes
500, 5 minutes
500, 30 minutes
500, 60 minutes
700, 5 minutes
700, 30 minutes
700, 60 minutes

4.442
4.112
3.989
4.120
4.164
4.299
4.112
3.999
3.987
3.905
4.010
4.022

4.072
4.129
4.031
4.070
4.077
4.102
4.149
4.155
4.682
4.005
4.031
4.039

3.471
3.212
3.127
3.027
2.484
3.079
3.016
2.429
2.426
2.357
2.937
2.397

3.795
3.916
3.804
3.846
3.769
3.795
3.733
3.710
4.260
3.563
3.597
3.585
                               C-2

-------
                           Table C-2.  Acetone Extraction of TNT/RDX/Tetryl Contaminated Sediment -

                                      Raw Data
O
i
CO
Run No.
1
2
3
4
5
ft
7
8
9
10
II
12
13
14
15
16
17
18
Temperature
(C)
25
25
25
25
25
25
50
50
50
50
50
50
75
75
75
75
75
75
Time
(in)
15
15
30
36
60
60
15
15
30
30
60
60
15
15
30
30
60
60
Weight
Pefore

10.04
10.06
10.08
10.00
10.00
10.02
10.10
10.15
10.12
10.00
10.00
10.00
10.15
10.00
10.15
10.01
10.19
10.02
Weight
After

-------
                             Table  C-3.   Acetone Extraction of Nitrocellulose - Raw Data
o
lun Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
IS
Ifi
17
18
Temperature
(C)
25
25
25
25
25
25
50
50
50
50
50
50
75
75
75
75
75
75
Time
(min)
15
15
30
30
60
60
15
15
30
30
60
60
15
15
30
30
60
60
Weight
Before
(g)
10.05
10.07
10.00
10.07
10.01
10.05
10.01
10.06
10.01
10.04
10.02
10.02
10.01
10.03
10.03
10.01
10.01
10.03
Weight
After
(g)
9.20
9.59
9.10
8.80
9.33
9.62
9.15
9.60
8.78
9.45
9.13
9.61
8.84
9.24
9.30
8.66
8.11
9.04
Volume Solvent
Solvent Recovered Nitrocellulose Acetone Nil
(ml) O'g/g) lvel (ug
95
117
115
117
105
120
110
115
120
117
95
113
105
95
110
105
90
117
38,900
31,800
17,800
44,700
54.700
62,700
47.000
55.200
32,000
29,900
44.800
64,600
11,700
15,400
-
12,000
15,100
20,600
2,340
1.832
1,832
1.393
2,271
1,956
3.161
2,024
3,409
4.681
2.463
1 ,956
7,327
5,627
5.683
4.681
5.052
4,422

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