v>EPA
            United States
            Environmental Protection
            Agency
        Office of Water and
        Watte Management
        Washington. DC 20460
SW - 846
Revision A
August 8.1980
            Solid Waste
Test Methods
for Evaluating Solid Waste

Physical/Chemical Methods
                 Technical
                   U pdate

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                                                           SW- 846a
                                                        Technical
                                                          Update
The enclosed material,  SW-846.af  updates the manual "Test Methods for
Evaluating Solid Waste" (SW-846).   It is the first in a continuing
series of "Technical Updates" to  be issued as corrections, or additional
methodologies and procedures become available.

Insert these pages in your manual to replace like-numbered pages or
add as new pages where  appropriate.  The date of issue is printed in
the upper righthand corner.  Changes made on a page in that revision
(but not those made in  past revisions) are double-underlined.   For
easy and precise reference, the sequential number of each change is
given in a footnote.

The Office of Solid Waste  thanks  those in both the public and  private
sectors who have made suggestions for improvement of this manual.   We
encourage additional comments and suggestions,  which may be made by
telephone or in writing.   Conments should be sent to:

                     Manager, Waste Analysis Program
                     Office of Solid Waste
                     U.S. EPA (WH-565)
                     Washington,  D.C.  20460
                     (202-755-9187)

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U.S. Environmental Protection Agency

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                                              Revision  A   8/8/80     5.3-3

    seal, a thermove11 and  temperature regulating  device  ,  a

    heating device  (mantle, hot  plate, or  bath), and a specimen

    support system.  A typical resin  flask  set up  for  this  type

    test is shown in figure 1.

2.  The supporting  device and container  should not be

    affected by or  cause contamination of  the waste under test.

3.  The method of supporting the coupons will vary with

    the apparatus used for  conducting the  test but should be

    designed  to Insulate the coupons from  each other  physically

    and electrically and to insulate  the coupons from  any metallic

    container or other device used in the  test.  Some  common

    support materials include:   glass, fluorocarbon or coated metal.

4.  The shape and form of the coupon  support  should assure  free

    con'tact with the waste.

Test Procedure

1.  Assemble the test apparatus  as described  the "Equipment"

    section above.

2.  Fill the container with the  appropriate amount of  waste.

    (See #5 under the "Precautions and Comments" section.)

3.  Begin agitation at a rate sufficient to insure that

    the liquid is kept well mixed and homogeneous.

4.  Using the heating device bring the temperature of

    .the waste to 55° C (130° F).

5.  If the anticipated corrosion rate is moderate (i.e.,

    <.2S4 mmpy)*. the test should be run for at leat 200 hours to

    insure adequate weight loss  to permit accurate results  to be

    obtained.   If the corrosion rate is low (i.e., <.Q254 mmpy)**,
* Change #1
** Change #2

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                                                                       5.3-4
        then  the  test  duration  should  be  on  the  order  of  2000  hours.




        in  cases  where the  anticipated  corrosion rate  Is  completely




        unknown,  Initial  testing  should be performed using  a 200




        hour  duration.




    6.   In  order  to  accurately  determine  the  amount of  material




        lost  to corrosion,  the  coupons  have  to be  cleaned after




        immersion  and  prior  to  weighing.  The cleaning  procedure




        should remove  all products  of  corrosion  while  removing a




        minimum of sound metal.   Cleaning methods  can  be  divided




        into  three general  categories:  mechanical, chemical and




        electrolytic.




        Mechanical  cleaning includes  scrubbing,  scraping,  brushing




    and  ultrasonic procedures.  Scrubbing with a  bristle brush




    and  mild  abrasive  is the most popular of these methods; the




    others  are used  In  cases of heavy corrosion  as a first  step




    in removing heavily encrusted corrosion products prior  to



    scrubbing.  Care should be  taken to avoid removing  sound metal.




        Chemical  cleaning  implies  the  removal of material  from




    the  surface of the  coupon by  dissolution in  an appropriate



    solvent.  Solvents  such as  acetone, dichloromethane, and




    alcohol are used to remove  oil, grease or resinous  materials,




    and are used prior  to immersion to  remove the products  of corrosion.



    Solutions suitable  for removing corrosion from the  steel




    coupon are:




           Solution                     Soaking Time       Temperature



   20% NaOH + 200g/l zinc dust             5 min            Bo'iling




           or




Cone. HC1 + 50g/l SnCl2 + 20g/l SB-^s    Until clean           Cold

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                                                                     5.3-5
      Electrolytic  cleaning  should  be proceeded  by  scrubbing




 to  remove  loosely  adhering  corrosion products.   One  method of



 electrolytic  cleaning  that  can  be  employed  is:
      Solution




      Anode




      Cathode



      Cathode current density



      Inhibitor




      Temperature



      Exposure Period
50 g/1 H2S04




Carbon or lead




Steel coupon




20 amp/cm2 (129 amp/In2)




2 cc organic inhibitor/liter




74°C (165°F)




3 minutes
Kote: Precautions must be taken to insure good electrical




contact with the coupon, to avoid contamination of the cleaning




solution with easily reducible metal ions, and to insure




that inhibitor decomposition has not occurred.  Instead of




using a proprietary inhibitor, 0.5 g/1 or either diorthotolyl




thiourea or qulnolin ethlodide can be used.




     Whatever treatment is employed to clean the coupons, its




effect in removing sound metal should be determined using a




blank (i.e., a coupon that has not been exposed to the waste).




The blank should be cleaned along with the test coupon and




its waste loss subtracted from that calculated for the test




coupons*




7.  After corroded specimens have been cleaned and dried,




    they are reweighed.   The weight loss is employed  as the




    principal measure of corrosion.  Use of weight loss as a

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                                             Revision A  8/8/80   5.3-6

    measure of corrosion required making the assumption that

    all weight loss has been due to generalized corrosion

    and not localized pitting.  In order to determine the

    corrosion rate for purpose of this requlation, the following

    formula is used:

          Corrosion Rate (mmpy) » (weight loss) (11.145)*
                                    (area) (time)==-

          where weight loss is In milligrams, area In square

          centimeters, time in hours, and corrosion rate in

          millimters per year (mmpy).
* Change #3

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                                                                        7.2-5
                                Table  7.2-1

                         APPROVED FILTER HOLDERS
Vacuum Filters
Manufacturer
Size
   Model No
  Comments
  Nalgene
500 ml
   Systems
  Millipore
 142  mm
    45-0045


p


Nuclepore
Millipore
ressure Filters
Nuclepore
Micro Filtration
47 mm
4 7 mm

142 mm
142 mm
410400
XX10 047 00

420800
302300
YT30 142 HW
Disposable plastic unit,
includes prefilter and
filter pads, and reservoir
Should only be used when
solution is to be analyzed
for inorganic constituents

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                                                   Revision  A   8/8/80   7.2-6

                                   Table  7.2-2

                            APPROVED  FILTRATION  MEDIA
Filter
Type
          Supplier
Filter To Be Used
For Aqueous Systems*
Filter To Be Used
For Organic Systems*

Coarse
Pref liter

Medium
Pref ilters
Fine
Pref ilters

Fine
Filters
(0.45um)




Gelman
Nuclepore
Millipore
Nuclepore
Millipore
Nuclepore
Millipore

Gelman

Pall
Nuclepore
Millipore
Selas
J_
210907
211707
AP25 042 00
AP25 127 50
211705
AP20 042 00
AP20 124 50
210903
211703
APIS Q42 OQttt
API 5 124 50
60173
60177
N704750tttt
NX14225
111107
112007
HAWP 047 00
HAWP 142 50
83485-02
83486-02
J_
210907
211707
AP25 042 00
AP25 127 00
211705
AP20 042 00
AP20 124 50
210903
211703
APIS 042 OfHtt
AP15 1?4 SO
60540
60544


181107
182007
FHLP 047 00
FHLP 142 00
83485-02
83486-02
t
tt
Change #4
Change #5
      ttt  Chenge #6
      tttt Change #7

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                                                                   8.01-4
3.  Stock standards - prepare stock standard solutions In




    methyl alcohol using assayed liquids or gas cylinders




    as appropriate.  Because of the toxicity of many of




    the compounds being analyzed, primary dilutions of these




    materials should be prepared in a hood .  A NIOSH/MESA




    approved toxic gas respirator should be used when




    the analyst handles high concentrations of such




    materials.



    a.  Place about 9.8 ml of methyl alcohol into a 10 ml




        ground glass stoppered volumetric flask. Allow




        about 10 minutes or until all alcohol wetted surfaces




        have dr
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                                             Revision A  8/8/80  8.01-5




    c.  Reveigh, dilute to volume, stopper, then nix by




        by inverting the flask several tines.  Transfer the




        standard solution to a 15 ml screw cap bottle with a




        teflon cap liner.




    d.  Calculate the concentration in mg/1 from the net




        gain in weight.




    e.  Store stock standards at A.OeC.* Prepare fresh standards




        weekly for the 4 compounds whose BP £ 30° C.  All other




        standards must be replaced with fresh standards each




        month.




Calibration




1.  Using stock standards, prepare secondary dilution standards




    in methyl alcohol that contains the compounds of interest,




    eitner singly or mixed together.




2.  Assemble necessary gas chromatographic apparatus and establish



    operating parameters equivalent to those indicated in the




    Procedure section.  By injecting secondary standards, adjust




    the sensitivity of the analytical system for each compound




    being analyzed so as detect _<_ 1 ug.




Quality Controls




1.  Before processing any samples, the analyst should dally



    demonstrate through the analysis of an organic-free water




    or solvent blank that the entire analytical system is



    interference free.



^.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected to




    validate the precision of the sampling technique.






*  Change #8

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                                                                  8.04-3
  4.   Gas  chromatograph  -  Analytical  system complete  with




      programmable  gas chromatograph  suitable  for  on-column




      injection  and  all  required  accessories,  including  FID  or




      HSD,  column supplies,  recorder  and  gases.  A data  system




      for  measuring  peak area  is  recommended.




  5.   Supelcoport 80/100 mesh  coated  with  1% SP-1240  DA  in




      1.8  meter  long  2 mm  ID glass  column  (Column  1)  or  Chromosorb




      V-AWDMCS 80/100 mesh coated with  5%  OV-17  packed in a  1.8




      meter long X mm ID glass column (Column  2).




  6.   Syringes - 5 ml glass hypodermic with Luerlok tip  (2each).




  7.   Micro syringe - 10,  25,  100 ul.




  8.   2-way syringe valve with Luer ends (3 each).




  9.   Syringe - 5 ml gas tight with shut-off valve.




10.   Bottle - 15 ml screw-cap, with teflon cap  liner.




11.  Kuderna-Danish apparatus (K-D) [Kontes K-570000 or equivalent]




     with 3 ball Snyder column.




12.  Water bath - heated with concentric ring cover capable




     of temperature control (+ 2°C).   The bath should be used




     in a hood.




13.  Chromatographic column - 10mm ID by 100mm  length with




     teflon stopcock.




14.  Reaction vial  - 20  ml with  teflon  - lined cap.




 Reagents




 1.  2 - propanol - pesticide  quality or equivalent




 2.  Stock standards - prepare stock  standard  solutions  at




     a concentration of  1.0  ug/ul by  dissolving  0.100 grams

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                                            Revision A  8/8/80  8.04-




 of  assayed  reference  material  in  pesticide  quality  2-propanol




 and  diluting  to  volume  in  a  100 ml  ground glass  stopped




 volumetric  flask.   The  stock solution  is transferred to




 ground glass  stoppered  reagent bottles,  stored In a refrigera-




 tor,  end  checked frequently  for signs  of degradation or




 evaporation,  especially  just prior  to  preparing  working  stan-




 dards from  then.




 3.   PFB derivative  reagents:




     a.  Hexane and  toluene - pesticide quality or equivalent




     b.    Sodium  sulfate  -  (ACS) granular, anhydrous  (purified




          by heating at 400°C for  4  hours in a shallow tray).




     c.    Potassium  carbonate - (ACS) powdered.




     d.    Silica  gel - (ACS)  100/200 mesh, grade  923; activated




          at 130°C and stored in a desslcator.




     e.    Pentafluorobenzyl bromide - 97% minimum purity.



     f.    1,4,7,10,13,16-Hexaoxacylooctadecene (18




          crown  6) - 98% minimum  purity.



     E.  Preparation of derlvitiztng reagent!  Add 1 ml pentafluro-




        benzil bromide and 1 gm of the 18 crown  6 ether to a 50 ml




        volumetric flask and dilute to volume with 2-propanol.




        Prepare  fresh weekly.*




Calibration



1.  Dsing stock  standards, prepare secondary dilution standards



    in 2-propanol that contain  the compounds of  interest, either



    singly or mixed together.



2.  Assemble necessary gas chromatographlc  apparatus and



    establish operating parameters equivalent to  those in the




* Change  #9

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                                                                 8.04-5
      "procedure section."  By injecting secondary standards

      adjust the sensitivity limit and the linear range of the

      analytical system for each compound being analyzed for to

      a sensitivity of £ 1 ug (2X background).
Quality Control

1.  Before processing any samples the analyst should demon-

    strate through the analysis of an organic - free water

    or solvent blank that the entire analytical system is

    interference free.

2.  Standard quality assurance practices should be used with

    this method.  Field replicates should be collected to vali-

    date the precision of the sampling technique.  Laboratory

    replicates should be analyzed to validate the accuracy of

    the analysis.  Where doubt exists over the identification

    of a peak on the gas chromatogram confirmatory techniques

    such as mass spectroscopy should be used.

3.  The analyst should maintain constant surveillance of both

    the performance of the analytical system and the effective-

    ness of this method in dealing with each sample matrix by

    spiking each sample with known amounts of the compounds

    the waste is being analyzed for and using these spiked

    samples readjust the sensitivity of the instrument such

    that 1 ug/gm of sample can be readily detected (see Quality

    Control).

          Flame lonization Gas Chromatography Procedure

1.  Assemble gas chromatograph with column 1 and Flame lonization

    Detector (apparatus section).

2.  .Set nitrogen carrier gas at 30 ml/min flow rate.

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                                                               8.04-6
 3.   Set  column temperature at 80°C at injection and program




     to  immediately  rise at 8°C/min to 150°C.




  Derivatizatlon and Electron  Capture  Gas  Chromatography  Procedure




 1.   Pipet  a  1.0 ml  aliquot of the  2-propanol  solution  of  standard




     or sample  extract  into a  glass reaction vial.   Add 1.0  ml




     derivatization  reagent.   This  is  a  sufficient  amount  of




     reagent  to  derivatize  a solution  whose total phenolic




     content  does not exceed 0.3 mg/ml.




 2.   Add  about  3  mg  of  potassium carbonate to  the solution and




     shake  gently.




 3.   Cap  the  mixture  and heat  for 4  hours at 80°C in  a hot




     water  bath.




 4.   Remove the  solution from  the hot  water bath and  allow it




     to cool.




 5.   Add  10 ml hexane to the reaction  vial and shake  vigorously




     for  one  minute.  Add 3.0 ml of  distilled deionized water




     to the reaction vial and shake  for two minutes.




 6.  Decant organic layer into a concentrator tube and cap with



     a glass  stopper.




7.  Pack a 10mm ID chromatographlc column with 4.0 grams  of



    activated silica gel.  After settling the  silica gel  by




    tapping the column, add about two grams  of anhydrous  sodium




    sulfate to the top.



8.  Pre-elute the column with  6 ml hexane.   Discard the eluate




    and  Just  prior to exposure of  the sulfate  layer to  air




    pipet onto the column 2.0  ml of the  hexane solution that



    contains  the derivatlzed sample or standard.  Elute the

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                                                              8.04-7






     column with 10.0 ml of hexane (Fraction 1) and discard




     this fraction.  Elute the column, in order with 10.0 ml




     15% toluene in hexane (Fraction 2), 10.0 ml 40% toluene




     in hexane (Fraction 3), 10.0 ml 75% toluene in hexane




     (Fraction 4), and 10.0 ml 15% 2-propanol in toluene (Fraction




     5).  Elution patterns for the phenolic derivatives are




     shown in Table 8.04-2 Fractions nay be combined as desired




     depending upon the specific phenols of interest or level




     of interferences.   Collect the fractions in appropriate




     sized K-D apparatus and concentrate each fraction to 10 al.




 9.   Assemble gas chromatograph with column 2 and HSD (apparatus




     sect ion).



10.   Using 5% methane/95% argon as the carrier gas adjust flow to




     30 ml/min.




11.   Set column  temperature at 200°C.




12.   Inject  2-5ml of the appropriate fraction using the solvent  -




     flush technique.   Smaller (1.0 ml)  volumes  can be  injected




     if automatic devices are  employed.   Record  volume  injected



     to the  nearest 0.05 ml and the resulting peak size In  area




     units.   If  the peak area  exceeds  the linear range  of the




     system  dilute the  extract and reanalyze.



      Calibrate  the system immediately  prior  to  conducting  any




 analyses and recheck  as in Quality Control  for  each  type of




 waste.  Calibration should be done no  less  frequently  than  at




 the  beginning and end  of  each session.

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                                                              8.04-8




Calculations




1.  If a response for the contaminant being analyzed for is




    greater than 2X background is noted, then the waste does




    not meet the criteria for delisting of being fundamentally




    different than the listed waste.  If a response is not noted,




    then prior to concluding that the sample does not contain




    the specific contaminant, the analyst must demonstrate, using




    spiked samples, that the instrument sensitivity is ^ 1 ug/gm.




2.  When duplicate and spiked samples are analyzed, all data




    obtained should be reported.




3.  If one desires to determine the actual concentration of




    the compound in the waste, the method of standard addition




    should be used.

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                                             Revision A  8/8/80  8.06-8




    d.   Just prior to exposure of the sodium sulfate layer to




        the air add 40 ml hexane and continue the elutlon at




        the rate of 2 ml/minute.  This eluate is Traction 1.




        Concentrate the fraction by standard K-D technque.  No




        solvent exchange is necessary.  After concentration and




        cooling, transfer to a* 10 ml volumetric flask, dilute to




        10 ml and analyze by gas chromatography.




    e.   Next elute the Florisil with 100 ml of 5 percent ethyl




        ether/95% hexane (v/v) and concentrate as in step d.




        [Fraction 2] .




    f.   Next, elute with 100 ml of 15% ethyl ether/85% hexane




        (v/v) and concentrate Fraction 3 as in step d.




    g.   Elute with 100 ml of 50% ethyl ether/50% hexane (v/v),




        and concentrate, Fraction 4 as in step d.




    h.   Finally, elute with 100 ml of ethyl ether, and concen-




        trate, Fraction 5 as in step d.




Gas Chromatography




1.  Assemble gas chromatograph with either Column 1 or 2 (see




    Apparatus) .




Column  1 (Supelcoport 100/120 with l.S%  SP 2250 + 1.95% SP 2401)




    a.   Set carrier gas at 60 ml/minute  flow rate.




    b.   Column temperatures will vary from 180°C to 220°C depending




        on the compound.




Column  2 (Supelcoport 100/120 with 3Z OV-1)




    a.   Set carrier gas at 60 ml/min flow rate.




    b.   Column temperature will vary from 200CC to 220°C depending




        on the compound.
* Change #10

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                                                                    8.06-9
2.  Calibrate the system at the beginning and end of an analytical




    session by spiking aliquots of the extract with calibration




    standards.




3.  Inject 2-5 ul of the sample extract or appropriate Florisil




    eluate using the solvent-flush technique.  Smaller (1.0 ul)




    volumes can be injected if automatic devices are employed.




    Recorc the volume injected to the nearest 0.05 ul, and the




    resulting peak size, in area units.




4.  If a response for the contaminant being analyzed for is greater




    than 2x background, then the waste does not meet the criteria




    for delisting of being fundamentally different than the




    listed waste.  If a response is not noted, then prior to




    concluding that the sample does not contain the specific




    contaminant, the analyst must demonstrate, using the spiked




    samples, that the method sensitivity is £ 1 ug of compound




    per gm of sample.




5.  If the peak area measurement is prevented by the presence of




    interferences, further cleanup is required.

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                                                                    8.08-6
    preparation and measurement steps.  Where doubt exists over




    the Identification of a peak on the chromatogram, confirmatory




    techniques such as mass spectroscopy should be used.




Cleanup and Separation



     Cleanup procedures are used to extend the sensitivity of a




method by minimizing or eliminating interferences that mask or




otherwise disfigure the gas chromatographic response to the




pesticides and PCB's.  The Florisil column allows for a select



fractlonatlon of the compounds and will eliminate polar materials.




Elemental sulfur interferes with the electron capture gas chro-




matography of certain pesticides but can be removed by the



techniques described below.




Florisil Column Cleanup:



1.  Add a weight of Florisil, (nominally 21g,) predetermined by



    calibration to a chromatographic column.  Settle the Florisil




    by tapping the column.  Add sodium sulfate to the top of the




    Florisil to form a layer 1-2 cm deep.  Add 60 ml of hexane to



    wet and rinse the sodium sulfate and Florisil.  Just prior to




    exposure of the sodium sulfate to air, stop the elution of the




    hexane by closing the stopcock on the chromatography column.




    Discard the eluate.



2.  Adjust the sample extract volume to 10 ml and transfer it from




    the K-D concentrator tube to the Florisil column.  Rinse the



    tube twice with 1-2 ml hexane, adding each rinse to the column.




3.  Place a 500 ml K-D flask and clean concentrator tube under the




    chromatography column.  Drain the column Into the flask until




    the sodium sulfate layer is nearly exposed.   Elute the column

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                                              Revision  A   8/8/80    8.08-5




    with  200 ml  of  6%  ethyl  ether  in  hexane  (Fraction  1)  using a




    drip  rate  of  about  5 ml/min.   Remove  the  K-D  flask and  set




    aside  for  later  concentration.




4.  Elute  the  column again,  using  200 ml  of  15% ethyl  ether  in




    hexane  (Fraction 2), into a second K-D flask.  Perform  the




    third  elution using 200  ml of  50% ethyl  ether/hexane  (V/V).*




    (Fraction  3).   The  elution patterns for  the pesticides  and




    PCB's  are  shown  in  Table 8.08-2.




5.  Concentrate  the  eluates  by standard K-D  techniques, substi-




    tuting  hexane for  the glassware rinses and using the water




    hath at about 85CC.  Adjust final volume  to 10 ml  with hexane.




    Analyze by gas  chromatography.




6.  Elemental  sulfur will usually  elute entirely  in Fraction 1.




    To remove  sulfur interference  from this  fraction or the




    original extract, pipet  1.00 ml of the concentrated extract




    into a  clean concentrator tube or Teflon-sealed vial.   Add 1-3




    drops of mercury and seal.  Agitate the contents of the vial




    for 15-30  seconds.   Place the vial in an upright position on




    a reciprocal laboratory shaker for 2 hours.  Analyze by gas




    chromatography.




Gas Chromatography




     Table 8.08.1 summarizes some recommended gas chromatographic




column materials, operating conditions for the instrument, and




some estimated retention times.   Examples of  the separations




achieved by these columns are shown in Figures 8.08-1 through
* Change

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                                                                8.49-6
Method of  Standard  Additions


     In this method,  equal volumes of sample are added


to a delonized  distilled  water blank and to three stan-


dards containing  different known amounts of the test

element.   The final volume of the blank and of the stan-


dards must be the  same  so that the interfering substance


is present in the  same  amount.  The absorbance of each

solution is determined  and then plotted on the vertical


axis of a  graph with  the  concentrations of the standard


plotted on the  horizontal axis.  When the resulting line

is extrapolated back  to  zero absorbance, the point of


interception of the abscissa is the concentration of the


unknown.   The abscissa  on the left of the ordinate is

scaled the same as  on right  side, but in the opposite


direction  from  the  ordinate.   An example of a plot so


obtained is shown  below:








Zero
Absorbance ^X*
Lx^
1 Cone, of
Sample
9
O
c
A
h_
8
A
<
X"


/
^r

^*

.x*^
^^^
^/^
/

\


r i







, i










Concentration
i
Addn 0 Addn 1 Addn 2 Addn 5
No Addn Addn of 50% Addn of 100% Addn of 150%
                         of Expected   of Expected  of Expected
                         Amount      Amount     Amount
                       Figure 8.49-1
            PLOT OF METHOD OF STANDARD ADDITIONS

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                                             Revision A  8/8/80  8.49-




Note:  For this method to be valid, the plot must be linear.




The slope of this line should not differ by more than 20%




from the slope of the standard solutions.  The effect of the




assumed interference must not change as the proportion of




sample to standard changes.




Solids, Sludges and Slurries




     Solids, sludges and slurries may be analyzed by these




methods by weighing out suitable portions and digesting as




described for each metal.  The material is then filtered




through a 0.45 micron filter while washing down the sides of




the beaker and rinsing the filter with distilled deionlzed




water.  The filtrate is then made up to a suitable volume




and analyzed in the ususal manner.  Results can be related




back to the original sample weight and reported as mg/kg.




Samples Containing oils,  greases, or waxes*




     Samples of listed and non-listed wastes may contain sub-




stantial amounts of organic materials.  These organics can be




in the form of oils, greases, or waxes. The general HN03 diges




tion, as given in this manual, will not be vigorous enough to



remove organics when analyzing for metals.  In order to overcome




this deficiency, the metals analysis may be performed in




groups, whea organics are present.




     The first group:  (Direct Aspiration Method)



          Ba, Cd, Cr, Pb, and Ag




     The second group:  (Wet Digestion Method)




          AS, Hg, (Se), Cd, Cr,  Ag, (Pb), and (Ba)








* Change # 15

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                                              Revision  A   8/8/80   8.49-E

Scope

     Elements of the first group can  be  determined  directly  by

by dissolving the organic portion of  the waste in an apporpriate

organic solvent and proceeding with atomic absorption  using  a

direct aspiration technique.  To determine the elements of the

second group the waste is subjected to a wet  digestion procedure,

followed by subsequent analysis as specified  in this manual.

     There is some overlap between these two  groups of metals

and the analyst may chose either method for determining those

elements common to both groups.

     To analyze for metals in oil,  grease,  or wax containing

wastes, the following methods apply:

I.   Analysis of wastes containing oil, grease, or wax of the
    ==      elemets ba,  ca, cr, pt>,  and Ag.

    A.   Reagents

        1.  Cyclohexane                 ultra  high purity grade

        2.  Mthylisobutylketone

        3.  p-Xylene

    B.   Procedure

        1.  Weigh out  a  100 gm representative  sample  of  the waste

           or  extract.   Separate  the  phases,  if more than  one

           phase is  present,  and  weigh eacn phase.

        2.  The  metals  in  the  organioc  phase can be determined

           by  diluting  with  a solvent  (specified  in  the reagents

           section  or  other  appropriate solvent)  and preceding

           with  atomic  absorption by direct aspiration  as  given

           in  this manual.  Record metal  concentrations  taking

           any  dilutions  into account.

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                                             Revision A  8/8/80  8.49-°

        3. Metals in the aqueous phase are determined by the pro-

           cedures in this manual.  (Sections 8.50 thru 8.60)

        4. Report concentrations for the metals as the weighted

           average for both the organic and aqueous phases.

II.   Analysis of oil, grease or wax containing wastes for the
          "e"Iemenfs~'A8';Hg, (Se)t C3T, Cr, Ag, (Pb), ana (Ba) ~~~

     A. Reagents

        1. Concentrated Nitric Acid          ultra high purity

        2. Concentrated Sulfuric Acid

        3. Hydrogen Peroxide (30%)

        4. Cnecentrated Hydrochloric Acid    "               "

     B. Apparatus

        Digestion flask, 250 ml flat bottom boiling flask with

        S 24/40 joint, 300 mm Allihin condenser filled to 50 mm

        with Rashing rings and glass beads, and heating mantle.

        Kjeldahl flask 300 ml, ground glass stoppered.

     C. Procedure

        1. weigh out a 100 gm representative sample of the waste

           or extract.  Separate the phases, if more than one is

           present, and weigh each phase.

        2. Weigh 2.0 gms of the organic phase into the digestion

           or Kjeldahl flask.  Add 10 ml T^SO^ and a 6 mm glass

           bead.  Swirl flask to mix the contents.

        3. If using a Kjeldahl flask approximately 3/4 of the neck

           of the flask should be cooled by air by directing an

           air stream against the neck of the flask.   If using

           the flask and condenser apparatus, connect the Allihin

           condenser and circulate cooling water.

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                                      Revision  A   8/8/80   8.49-10




4. Heat  flask  gently  and  continue  heating  until  dense




   white  fumes  appear.  While  boiling,  cousiously  add




   1 nl  HN(>3 dropwise to  oxidize  the  organic material.




   This  may be  done through  the condenser.  When the




   HN03  has boiled off and dense white  fumes reappear




   repeat the  treatment with an additional  1 ml  of HN(>3.




   Continue the addition  of  HNOg in 1 ml inceraents




   until  the digestion, mixture is  no  darker than a




   straw  color, indicating that almost  all  the organic




   matter has  been oxidized.




5. Cool  the flask slightly and add 0.5  ml  (dropwise) of




   H202-  Heat  until  dense white fumes  appear, and while



   boiling coutlously add 1 ml of  ENO^  dropwise.  When the




   HH03  has boiled off and dense white  fumes reappear




   repeat the  treatment with H202  and HN03 until the



   digestion mixture  is colorless, at which time the




   organic material will  be completely  oxidized.  Four




   treatments will usually suffice.  The total amount of




   H202 used should be noted.




6. When oxidation is  complete,  allow the flask to cool,




   wash down the mouth, neck/condenser with a small



   volume of distilled water (5 ml) and mix the  contents.




   Continue heating to the appearence of dense white




   fumes•



7. Cool and dilute to a total volume of 25 ml.    Precede




   with determination of metals as given in this manual.

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                                             Revision A  8/8/80  8.49-11




        Note: If a percipitate forms add 2ml of concentrated HCL




              before diluting to remove the precipitate.  If




              the precipitate pesists filter or centrifuge the




              solution to remove the precipitate, and precede to




              determine As, Se, Hg, Cr, and Cd.  Ba, Pb, and Ag




              may be determined either by the direct aspiration




              method or by digestion of a smaller sample.




        8. Metals in the aqueous phase, if an aqueous phase was




           present, are determined by the procedures in this




           manual, sections 8.50 thru 8.60.




        9. Report concentration for metals as the weighted average




           for both organic and aqueous phases.









Conclusion



     The details of the following approved methods are examples




of acceptable techniques.  Dilutions and concentrations may




have to be varied to suit the instrument being used.  It is




important not to overwhelm the instrument with very high




concentrations above the optimum recommended range.  Contami-




nation can result which is difficult to remove.  At the same




time, many dilutions introduce error which can be avoided by



some knowledge of the waste beforehand.  If nothing is known,




caution is advised.



     For additional information the applicable sections of




"Methods for Chemical Analysis of Water and Wastes", EPA




600/4-79-020 (Appendix II of this manual) may be consulted.

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                                             Revision A   8/8/80   8.60-7




                       Graphite Furnace*




Comment s:




1.  It has been reported that the addition of cyanogen iodide




    in this procedure does not Interfere in the silver




    determination.




2.  Samples should be analyzed immediately after collection.




Procedure




1.  Standards are prepared by making dilutions to cover the




    range 1 - 25ug Ag/llter as described in the direct




    aspiration method.




2.  Samples are prepared, standard additions made and analyses




    are performed as in the direct aspiration method.




Instrument Operation




    Wavelength:  328.1 nanometers




    Optimum Concentration Range:   1-25 ug/liter.



    Lower detection limit:   0.2 ug/liter




    Purge gas:  Argon




    Drying time and temp: 30 sec - 125°C




    Ashing time and temp: 30 sec - 400°C




    Atomizing time and temp: 10 sec - 2700°C




    The conditions listed above are based on a 20 ul




    injection; continuous flow purge gas and non-pyrolytic




    graphite on a Perkin Elmer model HGA 2100  furnace.




    Other equipment will have different requirements.  Follow



    the manufacturer's manual.






* Change  #12                                              ~~

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                                                                   8.82-1
                           Method 8.82




                        BEADSPACE  METHOD




Scope and Application



     This method provides  a procedure  for  the  extraction of




volatile organic compounds In pastes and solids.  The  static




headspace technique is a simple method which allows large




numbers of samples to be analyzed  in a relatively short period




of time.  Because of the large variability and complicated




matrices of waste samples  in the solid and paste forms,




detection limits for this method may vary widely among samples.




The method works best for compounds with boiling points less



than 125CC.  Due to their  low solubility, low molecular




weight compounds can or.ly be detected at high concentrations




or at reduced pressure.




     The sensitivity of chis method will depend on the equili-




bria of the various compounds between the vapor and dissolved




phases .



                  Static Headspace Technique




Summary of Method




     The waste is collected in sealed glass containers and




allowed to equilibrate at 90°C.   A sample of the headspace




gas is withdrawn with a gas tight syringe for analysis by the




appropriate gas chromatographic  method.




Apparatus



1.  Gas-tight syringe - 5-cc.



2.  Head space standard solutions - Prepare two standard solu-




    tions of the compounds being determined at the 50-ng/ul and

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                                             Revision  A  8/R/80  8.82-2




    250-ng/ul concentrations.  Standard solutions should be prepared




    using tnethanol, methane, or other appropriate solvent.  The




    standard solutions should be stored at less than 0°C, then




    allowed to warn to room temperature before dosing.  Fresh




    standards should be prepared weekly.  Procedures for preparing




    standards are outlined in the Purge and Trap Procedure of this




    manual (Method 8.83).




3.  Vials, 125 ml "Hypo-Vials" (Pierce Chemical Co., #12995), or




    equivalent.




4.  Septa, "Tuf-Bond" (Pierce 012720), or equivalent.




5.  Seals, aluminum, (Pierce #13214), or equivalent.




6.  Crimper, hand, (Pierce #13212), or equivalent.




Procedure*




1.  Place 10.0-g each of the well-mixed waste sample into three




    separate 125-ml septum seal vials.




2.  Dose one sample vial through the septum with 200-ul of the




    50-ng/ul standard methanol solution.  Label this 1 *ppm spike.




3.  Dose a separate (empty) 125 ml septum seal vial with 200 ul of




    the 50 ng/ul standard methanol solution. Label this 1 ppm standard.



4.  Place the sample, 1 ppm spike, and the 1 ppm standard vials




    into a 90°C water bath for 1 hour. Store the remaining sample




    vial at 4.0°C for possible future analysis.




5.  While maintaining the vials at 90°C withdraw 2 ml of the




    headspace gas with a gas tight syringe and analyze by injecting




    into a GC,  operating under the appropriate conditions for the GC




    measurement used. Analyze all three samples in exactly the same




    manner.






* Change #13

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                                              Revision  A   8/8/80   8.82-!

6.  Analyze the  I ppm  standard and adjust  instrument sensitivi-

    ty to give a responce of at least  2x the  background.  Record

    retention time and peak area.

7.  Analyze  the 1 ppm spiked sample in the same manner.  Record

    RT and peak  area.

8.  Analyze the  undosed sample as in item  7.

9.  If a positive responce is noted for the undosed sample, then

    the waste has not  been demonstrated to be free of  the

    contaminat of interest and is thus not fundamentally  different

    than the listed waste.  If no response is noted, reinject

    the 1 ppm standard to verify the required sensitivity.




Note;  Standard quality assurance protocols should be employed,

including blanks, duplicates,  and dosed samples, as described

in Section 10.


                          Bibliography

1.   "Interim Methods for the  Sampling and Analyses of  Priority
     Pollutants In Sediments and Pish Tissue," U.S. Environmental
     Protection Agency, Environmental Monitoring and Support
     Laboratory,  Cincinnati,  Ohio 45268 [19801.

2.   "Master Scheme for the Analysis  of Organic  Compounds in
     Water,  Part  I:   State-of-the-Art Review of  Analytical
     Operations," U.S.  Environmental  Protection  Agency,
     Environmental Research Laboratory, Athens,  Georgia 30605.

3.   "An EPA Manual for Organic  Analysis Using Gas  Chromatography -
     Mass Spectrometry,"  W.L.  Budde  and J.W.  Eichelberger, U.S.
     Environmental Protection  Agency,  Environmental Monitoring
     Support Laboratory,  Cincinnati,  Ohio,  1979, EPA/600/8-79/006,
     Order Number PB-297164.

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                                                                 8.83-1
                          Method 8.83




                     PURGE AND TRAP METHOD






Scope and Application




     This method covers a procedure for the extraction of pur-




geable organic compounds from aqueous liquids and free flowing




paste samples prior to gas chromatographlc analysis.




     The success of the extraction depends on partitioning




the compounds between the sample phase and gaseous headspace




phases.  This partitioning is a function of temperature,




interfacial area, the volatility of the species being analyzed




for, its solubility in the liquid being purged, and the




volatility of the waste matrix.  For highly volatile matrices,




direct Injection preceded by dilution, if necessary, should be




used.  For pastes, dilution of the sample until It becomes free




flowing is used to insure adequate interfacial area.  The




success of this method also depends on the level of interferences




in the sample; results may vary due to the large variability




and complicated matri'ces of solid waste samples.



Summary of Method



     An inert gas is bubbled through the sample contained in




a specially-designed purging chamber.   This purging transfers




the volatile compounds from the liquid phase to the vapor




phase.  The gaseous effluent is then swept through a short




sorbent tube where the organic compounds are trapped.   After




purging is completed,  the trap is heated and backflushed to

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                                                   Revision A   8/8/80  8.84-7

                    EXTRACTION CONDITIONS cont. (4)
Compound
Tetrachloroethene
Tetrachlorophenol
Toluene
Toluened iamine
Toluene diisocyanate( s )
Toxaphene
Trichloroethane
Trichloroethene(s)
Trichlorofluoromethane
Trichlorophenol(s)
2 ,4,5-TPCSilvex)
Trichloropropane
Vinyl chloride
Vinylidene chloride
1
Xylene
Extraction pH
NA
12
NA
> 11
NA*
5-9 or > 11
NA
NA
NA
12
<7 or > 11
NA
NA
NA
NA
Extraction
Solvent
NA
Methylene Chloride
NA
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
NA
NA
Methylene Chloride
Ethyl Ether or
Methylene Chloride
.NA
NA
NA
NA
* Change #
U.S Environmental Protoction Agency
Reason V, Library
230 South Dearborn  Street
Chicago, Illinois  60604

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                                                                  8.85-1
                           Method 8.85

                        SONICATION METHOD


Scope and Application

     This method covers a procedure for the extraction of non-

volatile and semi-volatile organic compounds from solids.  The

sonicatlon produces solid disruption to ensure Intimate contact

of the sample matrix with the extraction solvent.!

Summary of Method

     A weighed- sample of the solid waste is ground, mixed with

the extraction medium, then dispersed into the solvent using

sonication.  The resulting solution may then be cleaned up further

or analyzed directly using the appropriate technique (Methods

8.24 through 8.25).

Apparatus

1.  Apparatus for Grinding.*t

    The necessity for grinding and the choice of grinding

    apparatus will depend on the physical and chemical charac-

    teristics of the solid waste material in question.  Any of
1 The high energy vibrations produced by this method may produce
  artifacts and may drive off some semi-volatile compounds.

* Grinding is only necessary If the waste cannot either pass
  through a 1-mm standard seive or be extracted through a 1-mm
  diameter hole.

t Specific equipment listed in this method are for descriptive
  purposes only.  Equivalent equipment is available from other
  manufactures and laboratory supply companies.

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