-------
                                 TABLE 2.
             QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS
                        OF HIGH-LEVEL SOILS/SEDIMENTS
                Approximate                         Volume of
            Concentration Range                  Methanol  Extract3
              500-10,000 ug/kg                         100 uL
            1,000-20,000 ug/kg                          50 uL
            5,000-100,000 ug/kg                         10 uL
           25,000-500,000 ug/kg               100 uL of 1/50 dilution
     Calculate appropriate  dilution  factor for concentrations  exceeding  this
table.

     aThe volume  of methanol added  to  5 mL  of  water being purged  should be
kept constant.  Therefore, add to the 5-mL syringe whatever volume of methanol
is necessary to maintain a volume of 100 uL added to the syringe.

     ^Dilute  an   aliquot  of the  methanol  extract  and  then take  100  uL  for
analysis.
                                  5030 -  14                      Revision 1
                                                                 December 1987

-------
                        FIGURE 1.
                    PURGING  CHAMBER
       OPTIONAL
       FOAM TRAP
Inch 0. 0. Exit
Exit tt Inch 0. 0.

14 mm 0. D.


Inlet 14 Inch 0. D.
                                Sample Inlet
                                2-Way Syringe Valve
                                17 cm. 20 Gauge Syringe Needle
                                6 mm 0. 0. Rubber Septum
   10 mm G»M* Frit
   Medium PorMity
                                                 U— 1/16 Inch 0  D
                                                       Stainless Stec:
                                                       13x Molecular
                                                       Sieve Purge
                                                       Gas Filter
                                                       Purge Gas
                                                       Flow Control
                        5030 -  15
                                Revision 1
                                December 1987

-------
                            FIGURE 2.
TRAP PACKING MATERIALS AND CONSTRUCTION FOR METHOD  8010
              Packing Procedure
Construction
Glass Wool 5 mm
Activated ]
Charcoal 7.7 cm
i
•
Grade 15
Silica Gel 7.7 cr
4
Tenax 7.7 cr
••
}% OV-1 1 cm
,
1
»
'
P
|
|
1
L'
I
i IKS
                         7f7/Foot
                         Resistance
                         Wire Wrapped
                         Solid
                         (Double Layer)
                             7n/Foot
                             Resistance
                             Wire Wrapped
                             Solid
                             (Single Layer)
                                       8cm
   Glass Wool  5 mm
            Compression
            Fitting Nut
            and Ferrules
             Thermocouple/
             Controller
             Sensor
                   Electronic
                   Temperature
                   Control and
                   Pyrometer
              Tubing 25 cm
              0.105 In. I.D.
              0.125 In. O.D.
              Stainless Steel
                     Trap Inlet
                             5030  -  16
                           Revision  1
                           December  1987

-------
                                  FIGURE 3.
TRAP PACKING  MATERIALS  AND CONSTRUCTION  FOR METHODS 8020 AND  8030
            Packing Proctdun
Construction
Glass Wool    5 mm
   Tenax   23 cm
3% OV-1   1 cm ^;

Glass Wool   5 mm
                Compression Fitting Nut
                and Farrules

                  14 Ft. ?n/Foot Rtsisunca
                  Wire Wrapped Solid
                                                             Thtrmocouplt/Controllar Stnsor
                                                                  Electronic
                                                                  Temperature
                                                                  Control and
                                                                  Pyrometer
                                                           Tubing 25 cm
                                                           0.105 In. I.D.
                                                           0.125 In. O.D.
                                                           Stainless Steel
                   Trap Inlet
                                  5030  -  17
                               Revision  1
                               December  1987

-------
                       FIGURE 4.
      PURGE-AND-TRAP  SYSTEM,  PURGE-SORB MODE,
          FOR  METHODS 8010,  8020, AND 8030
CARRIER GAS
FLOW CONTROL
PRESSURE
REGULATOR
LIQUID INJECTION PORTS

      COLUMN OVEN
                              OPTIONAL 4-PORT COLUMN
                              SELECTION VALVE
PURGE GAS
PLOW CONTROL
13X MOLECULAR
SIEVE FILTER
               CONFIRMATORY COLUMN

              TO DETECTOR
                                                ANALYTICAL COLUMN
                                       TRAP INLET
                                PURGING
                                DEVICE
             NOTE
             ALL LINES BETWEEN TRAP
             AND GC SHOULD BE HEATED
             TO80*C
                        5030 - 18
                          Revision  1
                          December  1987

-------
                             FIGURE 5.
               PURGE-AND-TRAP  SYSTEM, DESORB MODE,
                 FOR METHODS 8010, 8020,  AND 8030
CARRIER GAS
FLOW CONTROL
PRESSURE
REGULATOR
r- UOmO INJECTION PORTS

        COLUMN OVEN
                              OPTIONAL 4^ORT COLUMN
                              SELECTION VALVE
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
                  CONFIRMATORY COLUMN

                 TO DETECTOR
                                                ANALYTICAL COLUMN
                                       TRAP INLET
                                PURGING
                                DEVICE
                NOTE
                ALL LINES BETWEEN TRAP
                AND GC SHOULD BE HEATED
                TOWC.
                            5030  -  19
                                Revision 1
                                December 1987

-------
                           METHOD 5030
                         PURGE-AND-TRAP
                                                      O
 7.1
      Calibrate
      GC •yetem
    •nd prepare
      standard*
7.1.2
                                                   7.1.4
       Carry  out
    purga-and-trap
       analyeis
      AceemDle
 purga-end-trap
   davlca and
 condition trap
7.1.3
7.1.8j

        Calculate
       reaponae or
  calibration  factor*
    for each analyte
      (Hatnod  aOOO.
      Section  7.4)
 Connect  to gee
 chromatograph
                                                   7.1.61
       Calculate
    average RF  for
     each compound
7.1.3
 Prepare final
   eolutlona
       O
   O
                            5030  -  20
                Revision 1
                December 1987

-------
                     METHOD  5030
                     (Continued)
Uow-le»el to
toll/ccdimen
                      Medium-level
                        for coll/
                         sediment
                                                                                    In)ect
                                                                              —•  (••pie
                                                                              into chamber;
                                                                              pure*:  decorb
                                                                              trap into gas
                                                                              cnromatogreoh
                                         matnano1
                                        extract to
                                     reagent water
                                      for analysis
Prepare ••mole*
   •od 
-------
                                METHOD 6010

           INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCOPY
1.0 SCOPE AND APPLICATION

    1.1  Inductively  coupled  plasma-atomic emission  spectroscopy  (ICP)
determines trace  elements  including  metals  in  solution.  The method  is
applicable to  a large number  of  metals and  wastes.  All  matrices, including
ground water,  aqueous samples,  EP  extracts,  industrial wastes,  soils, sludges,
sediments, and other solid wastes,  require digestion prior to analysis.

    1.2  Elements for which Method  6010 is  applicable are listed in Table 1.
Detection limits, sensitivity,  and optimum ranges  of the metals will vary with
the matrices  and model  of spectrometer.  The data  shown  in Table  1  provide
concentration  ranges for clean  aqueous  samples.  Use  of  this method  is
restricted  to  spectroscopists who  are knowledgeable  in  the  correction  of
spectral, chemical,  and physical  interferences.

2.0 SUMMARY OF METHOD

    2.1  Prior  to  analysis,  samples must  be solubilized  or  digested  using
appropriate Sample Preparation  Methods  (e.g.  Methods 3005-3050).

    2.2  Method 6010 describes  the simultaneous, or sequential, multielemental
determination of elements by  ICP.  The method  measures  element-emitted light by
optical  spectrometry. Samples are  nebulized and  the resulting  aerosol  is
transported to the plasma torch.  Element-specific  atomic-line emission spectra
are produced by  a radio-frequency inductively coupled plasma. The spectra are
dispersed  by  a  grating  spectrometer,  and  the  intensities  of the  lines  are
monitored  by photomultiplier  tubes.  Background  correction is  required  for
trace element determination. Background must  be  measured  adjacent to analyte
lines on  samples during  analysis. The  position selected  for the background-
intensity measurement, on either  or  both sides of  the  analytical  line, will  be
determined by the complexity  of the  spectrum  adjacent  to the analyte line. The
position  used  must  be  free  of  spectral interference  and reflect  the same
change in  background  intensity as  occurs at  the analyte wavelength measured.
Background correction  is  not  required  in  cases  of  line broadening  where  a
background correction  measurement would  actually  degrade the  analytical
result.  The  possibility of additional interferences  named  in  Section  3.0
should also be  recognized and appropriate corrections made;  tests for their
presence are described in Step  8.5.

3.0 INTERFERENCES

    3.1  Spectral interferences are  caused by:   (1) overlap  of  a  spectral line
from  another  element;  (2) unresolved overlap of  molecular  band  spectra;  (3)
background contribution  from  continuous or  recombination  phenomena;  and  (4)
stray light from the line emission of high-concentration elements.
                                 6010  - 1                        Revision 1
                                                                December 1987
-------
                                 TABLE 1.
    RECOMMENDED WAVELENGTHS AND ESTIMATED INSTRUMENTAL  DETECTION  LIMITS
Detection
Element
Aluminum
Antimony
Arsenic
Barium
Beryl 1 i urn
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Selenium
Silver
Sodium
Strontium
Thallium
Vanadium
Zinc
Wavelength* (nm)
308.215
206.833
193.696
455.403
313.042
226.502
317.933
267.716
228.616
324.754
259.940
220.353
670.784
279.079
257.610
202.030
231.604
213.618
766.491
196.026
328.068
588.995
407.771
190.864
292.402
213.856
Estimated
Limitb (ug/L)
45
32
53
2
0.3
4
10
7
7
6
7
42
5
30
2
8
15
51
See note c
75
7
29
0.3
40
8
2
     aThe wavelengths listed are recommended because of their sensitivity and
overall acceptance. Other wavelengths may  be  substituted  if they can provide
the needed sensitivity and are  treated with the  same corrective techniques for
spectral interference (see Step 3.1). In time, other elements may be added as
more information becomes available  and as required.
           estimated  instrumental  detection limits  shown  are  taken  from
Reference  1  in Section  10.0  below.  They  are given  as  a  guide  for  an
instrumental  limit. The  actual  method detection  limits  are  sample dependent
and may vary as the sample matrix  varies.

     cHighly dependent on operating  conditions and plasma position.


                                 6010  - 2                         Revision 1
                                                                 December 1987
-------
Spectral  overlap can  be  compensated  for by computer-correcting the raw  data
after monitoring  and measuring  the  interfering  element. Unresolved  overlap
requires selection  of an  alternate  wavelength.  Background contribution  and
stray light can usually be  compensated for by a background correction adjacent
to the analyte line.

     Users  of simultaneous  multielement  instruments must verify the absence of
spectral interference from  an  element  in  a  sample  for which  there is  no
instrument detection channel.  Potential  spectral  interferences  for  the
recommended wavelengths are given in Table 2. The data in Table 2 are intended
as  rudimentary  guides  for  indicating potential  interferences;  for  this
purpose,  linear relations between concentration and intensity for the analytes
and the  interferents  can  be assumed.

         3.1.1  The  interference  is  expressed  as  analyte  concentration
    equivalents (i.e. false analyte concentrations) arising from  100  mg/L of
    the  interference element.  For example,  assume  that  As is to be determined
    (at   193.696 nm)  in  a sample  containing  approximately  10  mg/L of  Al.
    According to Table 2,  100  mg/L of Al would yield  a false signal for As
    equivalent to approximately  1.3 mg/L. Therefore, the presence of  10  mg/L
    of Al  would  result  in  a  false signal for  As  equivalent to approximately
    0.13 mg/L.  The  user  is cautioned  that  other instruments  may  exhibit
    somewhat different levels of  interference than those shown in Table 2. The
    interference  effects  must  be evaluated  for  each  individual  instrument
    since the intensities will  vary with operating conditions, power,  viewing
    height, argon flow rate, etc.

         3.1.2  The  dashes  in   Table  2  indicate  that  no  measurable
    interferences  were  observed  even  at higher  interferent  concentrations.
    Generally,  interferences  were  discernible if they  produced peaks,  or
    background shifts, corresponding  to  2 to 5% of the  peaks generated by the
    analyte concentrations.

         3.1.3  At present,  information  on the listed silver  and  potassium
    wavelengths is not available, but it  has  been reported  that second-order
    energy from the magnesium 383.231-nm wavelength interferes with the listed
    potassium line at 766.491 nm.

    3.2   Physical  interferences are  effects  associated  with  the sample
nebulization and transport  processes. Changes in viscosity and surface tension
can  cause  significant  inaccuracies, especially  in samples  containing  high
dissolved  solids or  high acid  concentrations.  If  physical  interferences  are
present,  they must  be reduced by  diluting the sample or by using a peristaltic
pump. Another problem  that  can occur with  high  dissolved  solids  is  salt
buildup  at the  tip  of  the nebulizer,  which   affects  aerosol  flow rate  and
causes instrumental  drift.  The  problem  can be  controlled by  wetting  the  argon
prior to nebulization, using a  tip  washer,  or diluting the sample. Also,  it
has  been  reported  that better control of  the  argon flow rate  improves
instrument performance;  this  is  accomplished with  the  use of  mass  flow
controllers.
                                6010 - 3                        Revision  1
                                                                December  1987
-------
                                  TABLE  2.
               ANALYTE CONCENTRATION EQUIVALENTS  ARISING  FROM
                     INTERFERENCE AT THE 100-mg/L LEVEL
1
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryl 1 i urn
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
U^wol onn t li
nave 1 cily IN
(nm) Al
308.215
206.833 0.47
193.696 1.3
455.403
313.042
226.502
317.933
267.716
228.616
324.754
259.940

Ca Cr
— —
-- 2.9
-- 0.44
— —
- -
— 	
-- 0.08
--
-- 0.03
--
__

Cu Fe
— —
-- 0.08
- -
— —
__
-- 0.03
-- 0.01
-- 0.003
-- 0.005
-- 0.003
__
Interferent
Mg Mn
-- 0.21
__
- -
	 —
- -
	 —
0.01 0.04
-- 0.04
	 	
--
-- 0.12
a,b
Ni Tl
	 —
-- 0.25
- -
	 —
-- 0.04
0.02
-- 0.03
__
0.03 0.15
-- 0.05
__

V
1.4
0.45
1.1
—
0.05
	
0.03
0.04
	
0.02
--
Lead       220.353  0.17
Magnesium  279.079    --  0.02  0.11    --  0.13     --  0.25     --   0.07   0.12
Manganese  257.610  0.005   --  0.01    --  0.002  0.002   	

Molybdenum 202.030  0.05    	  0.03
Nickel     231.604    	
Selenium   196.026  0.23    --    --    --  0.09
Sodium
Thallium
Vanadium
Zinc
588.995 -- 	 -
190.864 0.30
292.402 -- -- 0.05 -- 0.005
213.856 -- -- -- 0.14
-- 0.08
-- 0.02
-- 0.29
     aDashes indicate that no interference was observed even when interferents
were introduced at the following levels:

          Al - 1000 mg/L                      Mg - 1000 mg/L
          Ca - 1000 mg/L                      Mn -  200 mg/L
          Cr -  200 mg/L                      Tl -  200 mg/L
          Cu -  200 mg/L                      V -   200 mg/L
          Fe - 1000 mg/L

     &The  figures  recorded  as  analyte  concentrations  are not  the  actual
observed concentrations; to obtain those figures, add the listed concentration
to the interferent figure.

                                 6010 - 4                        Revision 1
                                                                 December 1987
-------
       3.3   Chemical  interferences include  molecular  compound formation,
ionization effects,  and  solute  vaporization effects.  Normally,  these effects
are not significant with  the  ICP technique. If observed, they can be minimized
by  careful  selection  of operating conditions  (incident  power,  observation
position,  and so forth),  by  buffering of  the  sample,  by matrix matching,  and
by  standard addition procedures.  Chemical  interferences are highly dependent
on matrix type and  the specific  analyte  element.

4.0  APPARATUS AND  MATERIALS

     4.1  Inductively coupled argon  plasma emission spectrometer:

         4.1.1   Computer-controlled  emission  spectrometer with  background
    correction.

         4.1.2  Radio frequency  generator.

         4.1.3  Argon gas supply - Welding grade or better.

    4.2   Operating  conditions  -  The  analyst  should  follow the instructions
provided by the instrument manufacturer. For operation with organic solvents,
use  of the  auxiliary  argon   inlet  is  recommended,  as  are solvent-resistant
tubing, increased  plasma  (coolant)  argon  flow,  decreased nebulizer flow,  and
increased  RF power to  obtain  stable  operation  and  precise  measurements.
Sensitivity,  instrumental detection limit, precision,  linear  dynamic range,
and interference effects must be  established for each individual analyte line
on  that particular  instrument.  All  measurements must be within the instrument
linear range where  coordination  factors  are valid. The analyst must (1) verify
that  the  instrument  configuration  and  operating  conditions satisfy  the
analytical  requirements  and (2) maintain quality  control data  confirming
instrument performance and analytical results.

5.0  REAGENTS

    5.1  Reagent grade chemicals  shall  be used in all  tests. Unless otherwise
indicated,   it  is  intended  that all   reagents   shall  conform  to  the
specifications of  the  Committee  on  Analytical  Reagents  of the  American
Chemical Society, where such  specifications are available. Other grades may be
used,  provided  it  is  first  ascertained  that  the  reagent  is  of sufficiently
high  purity  to  permit  its use  without lessening  the  accuracy  of  the
determination.

         5.1.1  Hydrochloric  acid (cone),  HC1.

         5.1.2  Hydrochloric  acid (1:1),  HC1. Add 500 ml concentrated HC1  to
    400 ml water and dilute to 1 liter.

         5.1.3  Nitric acid  (cone),  HNOs.

         5.1.4   Nitric  acid (1:1), HNOs.  Add  500 ml concentrated  HNOs  to
    400 ml water and dilute to 1 liter.


                                 6010 -  5                        Revision 1
                                                                December 1987
-------
    5.2  ASTM Type II Water (ASTM D1193-77 (1983)).  All  references to water in
the method refer to ASTM Type II unless otherwise specified.

    5.3   Standard stock  solutions  may be purchased  or prepared  from  ultra-
high purity grade chemicals or metals  (99.99 to  99.999% pure).  All  salts  must
be dried for 1 hour at 105°C, unless otherwise  specified.

     CAUTION:   Many metal salts are extremely toxic  if inhaled or swallowed.
                Wash hands thoroughly after handling.

Typical  stock  solution  preparation  procedures  follow.  Concentrations  are
calculated based  upon  the weight of pure metal added,  or with  the  use  of the
mole fraction and the weight of the metal salt  added.

Metal

          Concentration (ppm) = ^~-{n

Metal salts
           Concentration  (ppm) - BSl9!!t^l.i..laJrsct1oa

         5.3.1  Aluminum  solution,  stock,  1 mL = 100  ug Al:   Dissolve  0.10 g
    of  aluminum  metal,  weighed  accurately  to  at  least  four  significant
    figures,  in an  acid mixture  of  4 mL of (1:1) HC1  and 1 mL of concentrated
    HNOs  in  a  beaker.  Warm  gently to  effect  solution.  When solution  is
    complete,  transfer  quantitatively to  a  liter flask,  add  an additional
    10 mL of  (1:1) HC1 and dilute to 1,000 mL with water.

         5.3.2  Antimony  solution,  stock,  1 mL = 100  ug Sb:   Dissolve  0.27 g
    K(SbO)C4H40e  (mole fraction Sb = 0.3749),  weighed  accurately to at least
    four  significant figures,  in  water,  add  10  mL  (1:1)  HC1,  and  dilute to
    1,000 mL with water.

         5.3.3  Arsenic solution, stock,  1 mL =  100 ug  As:  Dissolve 0.13 g of
    As20s  (mole fraction  As  = 0.7574),  weighed  accurately  to  at  least  four
    significant figures,  in  100 mL  of water containing  0.4 g NaOH. Acidify the
    solution with 2  mL concentrated HNOs  an°l dilute to  1,000 mL with water

         5.3.4   Barium solution,  stock,  1 mL  =  100  ug Ba:    Dissolve  0.15 g
    Bad2  (mole fraction  Ba  = 0.6595),  dried at 250°C for  2  hours,  weighed
    accurately  to at least four  significant figures, in  10 mL water with  1 mL
     (1:1) HC1.  Add  10.0 mL (1:1) HC1 and  dilute to 1,000 mL with water.

         5.3.5   Beryllium solution, stock,  1  mL  =  100 ug  Be:   Do  not  dry.
    Dissolve  1.97 g  BeS04-4H20  (mole fraction Be = 0.0509), weighed accurately
    to  at  least four significant figures, in water,  add 10.0 mL concentrated
          and dilute to 1,000 mL with   water.
          5.3.6   Cadmium solution, stock,  1  mL  = 100 ug Cd:   Dissolve 0.11 g
    CdO   (mole  fraction Cd  =  0.8754),  weighed accurately  to at  least four
    significant  figures,  in  a minimum amount of  (1:1)  HNOs.  Heat to  increase
    rate  of dissolution. Add  10.0 mL concentrated  HNOs  ano< dilute to  1,000 mL
    with  water.
                                  6010 - 6                        Revision 1
                                                                 December 1987
-------
     5.3.7   Calcium solution,  stock, 1 ml  = 100 ug  Ca:   Suspend 0.25 g
       (mole Ca  fraction  =  0.4005),  dried at  180°C for  1  hour before
weighing,  weighed  accurately  to at  least   four  significant  figures,  in
water  and  dissolve cautiously with  a minimum amount  of  (1:1)  HN03.  Add
10.0 ml concentrated HNOs and dilute to 1,000 ml  with  water.

     5.3.8  Chromium solution, stock, 1 ml  = 100  ug Cr:   Dissolve  0.19 g
CrOs  (mole  fraction Cr  = 0.5200),  weighed accurately to  at least  four
significant  figures,  in water.  When  solution is  complete,  acidify  with
10 ml concentrated HN03 and dilute to 1,000  ml  with  water.

     5.3.9  Cobalt  solution, stock, 1 ml =  100 ug Co:  Dissolve   0.1000 g
of cobalt metal, weighed  accurately to  at least  four  significant  figures,
in a  minimum amount of  (1:1)  HN03.  Add 10.0 ml  (1:1)  HC1  and dilute  to
1,000 ml with water.

     5.3.10  Copper solution, stock, 1 ml  =  100 ug Cu: Dissolve  0.13  g CuO
(mole  fraction  Cu =  0.7989),  weighed  accurately to  at  least   four
significant  figures),  in a minimum  amount of  (1:1) HN03.  Add  10.0  ml
concentrated HN03 and dilute to 1,000 ml with water.

     5.3.11   Iron  solution, stock,  1 ml  =  100  ug Fe:   Dissolve 0.14 g
Fe203  (mole  fraction Fe  =  0.6994), weighed accurately to  at least  four
significant  figures,  in a warm  mixture of  20 ml (1:1)  HC1  and  2 ml  of
concentrated HN03.  Cool,  add an  additional  5.0  ml of concentrated  HN03,
and dilute to 1,000 ml with water.

     5.3.12  Lead  solution,  stock,  1 ml  =   100  ug  Pb:   Dissolve 0.16 g
Pb(N03)2 (mole fraction  Pb = 0.6256), weighed  accurately  to at  least  four
significant  figures,  in a minimum  amount of (1:1)  HN03.  Add 10 ml  (1:1)
HN03 and dilute to  1,000 ml with water.

     5.3.13  Lithium solution, stock, 1 mL  = 100  ug Li: Dissolve  0.5324 g
lithium  carbonate  (mole fraction Li  =  0.1878),  weighed accurately to  at
least  four  significant  figures,  in  a minimum  amount of  (1:1)  HC1  and
dilute to 1,000 mL with water.

     5.3.14  Magnesium solution, stock, 1  mL = 100 ug  Mg:  Dissolve 0.17 g
MgO  (mole fraction Mg  = 0.6030), weighed accurately to  at least  four
significant figures, in a minimum amount of (1:1) HN03. Add  10.0  mL  (1:1)
concentrated HMOs and dilute to 1,000 mL with water.

     5.3.15   Manganese solution,  stock,   1  mL  =  100 ug  Mn:    Dissolve
0.1000  g  of manganese  metal,  weighed  accurately to  at  least   four
significant  figures,  in  acid  mixture  (10  mL  concentrated HC1  and   1  mL
concentrated HNOs)  and dilute to 1,000 mL  with water.
     5.3.16   Molybdenum  solution,  stock,  1  mL =  100 ug  Mo:    Dissolve
0.20 g  (NH4)6Mo7024.4H20  (mole  fraction Mo = 0.5772), weighed  accurately
to at least four significant figures,  in water and  dilute  to 1,000 mL  with
water.
                             6010 - 7                        Revision  1
                                                             December  1987
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         5.3.17   Nickel  solution,  stock,  1 ml  =  100 ug Ni:  Dissolve  0.1000 g
    of nickel  metal,  weighed accurately to at least four significant figures,
    in 10.0 ml hot concentrated  HNO$,  cool, and  dilute to 1,000 ml with water.

         5.3.18   Phosphate solution,  stock, 1  mL = 100 ug P: Dissolve 0.4393 g
    anhydrous  KH^PO^  (mole fraction  P = 0.2276),  weighed accurately  to at
    least four significant figures,  in water.  Dilute to  1,000 ml.

         5.3.19   Potassium solution,  stock,  1 ml =  100  ug  K:  Dissolve 0.19 g
    KC1  (mole  fraction  K  = 0.5244)  dried at  110°C, weighed  accurately to at
    least four significant figures,  in water and dilute  to  1,000 ml.

         5.3.20    Selenium solution,  stock,  1 ml  =  100  ug Se:    Do  not dry.
    Dissolve 0.17 g H2$e03 (mole fraction Se =  0.6123),  weighed accurately to
    at least four significant  figures, in water  and dilute  to 1,000 ml.

         5.3.21   Silver solution, stock,  1 ml = 100 ug Ag:   Dissolve 0.16 g
    AgN03 (mole  fraction  Ag  =  0.6350),  weighed accurately to at  least four
    significant  figures,   in  water  and  10 ml  concentrated HN03.  Dilute to
    1,000 ml with water.

         5.3.22   Sodium solution, stock,  1 mL = 100 ug  Na:   Dissolve 0.25 g
    NaCl   (mole  fraction Na =  0.3934), weighed accurately to at  least four
    significant  figures,  in water. Add 10,0 ml concentrated HN03 and dilute to
    1,000 ml with water.

         5.3.23   Strontium  solution,  stock,  1  ml  =  100  ug  Sr:  Dissolve
    0.2415 g of  strontium nitrate  (Sr(N03)2)  (mole  fraction 0.4140), weighed
    accurately  to at  least  four  significant  figures, in  a 1-liter flask
    containing  10 ml  of  concentrated HC1   and 700 ml of water.  Dilute to
    1000 ml with water.

         5.3.24  Thallium solution,  stock,  1  ml = 100 ug Tl: Dissolve  0.13 g
    T1N03  (mole  fraction  Tl  =  0.7672),  weighed accurately to  at least  four
    significant figures, in water. Add 10.0 ml concentrated HN03 and dilute to
    1,000 ml with water.

         5.3.25   Vanadium solution,  stock,  1 ml   =    100  ug   V:  Dissolve
    0.23 g  NH403 (mole  fraction V =  0.4356), weighed  accurately  to at least
    four significant figures, in  a  minimum  amount  of concentrated HN03.  Heat
    to increase  rate of dissolution.  Add 10.0 ml concentrated HNOs and dilute
    to 1,000 mL with, water.

         5.3.26  Zinc solution,  stock, 1 mL = 100 ug Zn:   Dissolve 0.12 g ZnO
    (mole  fraction  Zn  = 0.8034),  weighed accurately  to at  least  four
    significant  figures,  in  a minimum  amount  of  dilute  HN03.   Add  10.0 mL
    concentrated HN03 and dilute to  1,000 mL  with water.

    5.4   Mixed  calibration  standard solutions -  Prepare mixed calibration
standard solutions by combining appropriate volumes of  the stock  solutions in
volumetric flasks  (see  Table  3).  Add 2 mL (1:1) HNOs and  10  mL of (1:1) HC1
and dilute to 100 mL with  water. Prior to preparing the mixed standards,  each
stock solution  should  be  analyzed  separately to  determine possible  spectral

                                 6010 - 8                       Revision  1
                                                                December  1987
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interference  or  the  presence  of  impurities.  Care  should  be  taken when
preparing the  mixed  standards  to ensure that the elements are compatible  and
stable together. Transfer the mixed  standard solutions  to  FEP  fluorocarbon  or
previously  unused  polyethylene  or  polypropylene bottles  for  storage.  Fresh
mixed  standards should be  prepared,  as  needed,  with  the  realization that
concentration  can  change on  aging.  Calibration standards must  be  initially
verified using  a  quality control sample  (see  Step  5.8) and monitored  weekly
for stability.  Some  typical calibration  standard  combinations are  listed  in
Table 3. All  mixtures  should then be scanned using a  sequential  spectrometer
to verify the absence of interelement spectral  interference in  the  recommended
mixed standard solutions.

    NOTE:   If  the  addition  of  silver to the  recommended  acid  combination
            results in  an  initial  precipitation,  add  15 ml of water and warm
            the flask  until  the  solution  clears.  Cool and dilute to  100  ml
            with water.  For this acid  combination,  the silver  concentration
            should be  limited  to 2  mg/L.  Silver under  these conditions  is
            stable in a tap-water matrix for 30 days.  Higher concentrations  of
            silver require additional HC1.


                                  TABLE 3.
                          MIXED STANDARD SOLUTIONS
           Solution                           Elements
             I                         Be,  Cd,  Mn,  Pb,  Se and Zn
            II                         Ba,  Co,  Cu,  Fe,  and V
           III                         As,  Mo
            IV                         Al,  Ca,  Cr,  K,  Na, Ni, Li,  and Sr
             V                         Ag (see  Note to  Step 5.4),
                                          Mg, Sb,  and  Tl
             VI                        P
    5.5   Two  types of blanks  are  required  for the analysis.  The  calibration
blank is  used  in  establishing  the  analytical  curve, and the reagent  blank  is
used to correct  for  possible contamination  resulting from varying  amounts  of
the acids used in the sample processing.

         5.5.1    The  calibration   blank is  prepared  by  diluting  2  mL  of
    (1:1)  HNOs and  10 mL  of  (1:1)  HC1 to   100  mL with  water.  Prepare  a
    sufficient quantity to flush the system  between standards and samples.

         5.5.2   The  reagent blank  must  contain all the  reagents  and  in the
    same volumes  as used  in  the processing of  the  samples. The reagent   blank
                                 6010 - 9                        Revision  1
                                                                 December  1987
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    must be carried through the complete procedure and contain  the  same acid
    concentration  in the  final  solution  as the sample  solution used  for
    analysis.

    5.6  The instrument  check standard  is prepared by the analyst by combining
compatible  elements at  concentrations equivalent to  the  midpoint of  their
respective calibration curves (see  Step 8.6.2.1 for use).

    5.7   The  interference check solution  is  prepared  to  contain  known
concentrations of  interfering elements  that will  provide an adequate  test of
the correction  factors.  Spike the sample  with  the  elements of  interest at
approximate concentrations  of  10 times the instrumental  detection limits. In
the absence of measurable analyte,  overcorrection could go undetected because
a negative value could be reported as  zero. If the particular instrument will
display overcorrection as a negative number,  this spiking  procedure will  not
be necessary.

    5.8  The quality control sample should  be  prepared  in the same acid matrix
as the calibration standards at 10  times the  instrumental detection limits and
in accordance with the instructions provided  by the supplier.

6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

    6.1   See  the  introductory  material in  Chapter Three,  Inorganic Analytes,
Steps 3.1 through 3.3.

7.0  PROCEDURE

    7.1   Preliminary treatment of  all  matrices is always necessary because of
the  complexity  and  variability  of  sample matrices.  Solubilization  and
digestion  procedures are   presented  in Sample  Preparation  Methods (Methods
3005-3050).

    7.2  Set up the instrument with proper  operating parameters established in
Step 4.2.  The instrument must be  allowed  to become  thermally  stable before
beginning  (usually requiring  at  least  30  minutes  of  operation prior to
calibration).

    7.3   Profile  and  calibrate the  instrument  according  to  the  instrument
manufacturer's  recommended  procedures,  using the typical  mixed  calibration
standard  solutions  described in  Step  5.4.  Flush the  system with  the
calibration  blank  (Step   5.5.1)  between each   standard.  (Use  the  average
intensity of  multiple exposures  for both standardization and sample analysis
to reduce random error.)

    7.4   Before  beginning the   sample  run,  reanalyze  the highest  mixed
calibration standard  as if it  were a  sample.  Concentration values obtained
should  not  deviate from  the actual values  by  more than 5%  (or the  established
control limits, whichever is lower).  If they  do,  follow the recommendations of
the instrument manufacturer to correct  for  this  condition.

    7.5   Flush the  system  with  the calibration  blank  solution  for at least
1  minute  (Step 5.5.1) before  the  analysis of each sample  (see  Note to  Step

                                 6010 - 10                       Revision  1
                                                                December  1987
-------
7.3). Analyze  the instrument  check  standard (Step  5.6)  and the  calibration
blank (Step 5.5.1) after each 10 samples.

    7.6  Calculations:   If dilutions were performed, the  appropriate  factors
must be applied to sample  values. All results should  be  reported  in  ug/L  with
up to three significant figures.

8.0  QUALITY CONTROL

    8.1  All quality control data should  be  maintained and available for  easy
reference or inspection.

    8.2   Dilute  and  reanalyze samples  that are  more  concentrated than  the
linear calibration  limit  or use an  alternate,  less sensitive line  for which
quality control data is already established.

    8.3  Employ  a minimum of one reagent blank per  sample batch  to  determine
if contamination or any memory effects are occurring.

    8.4  Analyze  one  replicate sample for every 20  samples  or  per analytical
batch, whichever  is more  frequent.   A replicate  sample is a  sample  brought
through the whole sample preparation and analytical process.

    8.5   It is recommended  that  whenever a new  or unusual sample  matrix is
encountered, a  series  of  tests be performed prior  to reporting  concentration
data for analyte  elements. These tests,  as outlined  in Steps 8.5.1 and 8.5.2,
will ensure  the  analyst that neither positive nor  negative  interferences are
operating  on  any of  the analyte  elements to  distort  the accuracy of the
reported values.

         8.5.1  Serial  dilution:  If  the analyte  concentration  is  sufficiently
    high  (minimally,  a factor  of  10 above  the  instrumental detection  limit
    after dilution), an analysis  of  a 1:4 dilution  should  agree  within ± 10%
    of the original determination.  If not, a chemical or  physical  interference
    effect should be suspected.

         8.5.2  Matrix  spike addition:  An analyte spike  added to  a portion of
    a prepared  sample,  or its  dilution, should be recovered to within 75% to
    125% of the known value. The spike addition should produce a minimum level
    of 10 times  and  a  maximum of 100 times  the  instrumental  detection limit.
    If the spike is not recovered within the specified limits,  a matrix effect
    should be suspected.

    CAUTION:  If  spectral  overlap is  suspected, use  of  computerized
              compensation,  an alternate wavelength, or  comparison  with  an
              alternate method is recommended.

    8.6  Check the  instrument  standardization by  analyzing appropriate check
standards as follows.

         8.6.1  Check instrument calibration  using a calibration blank and two
    appropriate standards.


                                 6010 - 11                      Revision  1
                                                                December  1987
-------
         8.6.2  Verify  calibration  every  10  samples and at  the end  of  the
    analytical  run,  using a  calibration  blank  (Step  5.5.1)  and a  check
    standard (Step  5.6).

              8.6.2.1   The results of the  check  standard  are  to agree  within
         10% of the expected  value;  if not, terminate the  analysis,  correct
         the problem,  and  recalibrate the instrument.

              8.6.2.2    The results  of the  calibration  blank are to  agree
         within three  standard  deviations  of the  mean  blank  value. If  not,
         repeat the analysis two  more  times  and average the  results.  If  the
         average is not  within three  standard  deviations of  the  background
         mean, terminate the analysis, correct  the  problem, recalibrate,  and
         reanalyze  the previous  10 samples.

         8.6.3  Verify the  interelement and  background  correction  factors at
    the beginning  and end  of  an analytical run or  twice  during every  8-hour
    work  shift, whichever  is more  frequent. Do this  by   analyzing  the
    interference check sample  (Step 5.7).  Results  should be within +  20% of
    the true value  obtained in  Step 8.6.2.1.

         8.6.4  Spiked replicate samples  are to be  analyzed  at a frequency of
    20%.

              8.6.4.1   The  relative  percent  difference  between  replicate
         determinations  is to  be calculated as follows:

                              D. - D,
                      RPO' TnrnnjTZ *  "»
          where:

               RPD  = relative  percent  difference.
                DI  = first sample  value.
                D2  = second sample value  (replicate).

          (A  control  limit  of  + 20% for RPD shall  be  used  for sample values
          greater  than 10 times the  instrument detection  limit.)

              8.6.4.2  The spiked replicate  sample recovery is  to  be  within
         ± 20% of  the  actual  value.

9.0  METHOD PERFORMANCE

    9.1   In  an EPA round-robin  Phase  1  study,  seven laboratories applied the
ICP  technique  to  acid-distilled water  matrices  that  had  been  spiked  with
various metal  concentrates. Table 4 lists  the  true values,  the mean reported
values, and the mean percent relative  standard deviations.

    9.2   In a  single  laboratory evaluation, seven wastes were  analyzed for 22
elements  by  this  method.  The  mean  percent relative  standard  deviation  from
triplicate analyses for all elements and wastes  was 9  + 2%. The mean percent
recovery  of  spiked  elements  for all  wastes was 93  + 6%.  Spike levels ranged

                                6010  - 12                       Revision 1
                                                                December 1987
-------
from  100  ug/L to  100  mg/L. The  wastes  included  sludges and  industrial
wastewaters.

10.0  REFERENCES

1.   Winge,  R.K.;  Peterson,  V.J.;  Fassel,  V.A.  Inductively Coupled Plasma-
     Atomic Emission Spectroscopv:  Prominent  Lines  (final  report, March 1977 -
     February  1978);   EPA-600/4-79-017,  Environmental  Research  Laboratory,
     Athens, GA, March 1979; Ames Laboratory:  Ames  IA.

2.   Test  Methods:  Methods for Organic  Chemical  Analysis  of  Municipal  and
     Industrial Wastewater;  U.S.  Environmental  Protection  agency.  Office of
     Research  and  Development.  Environmental  Monitoring  and  Support
     Laboratory. ORD Publication Offices of Center for  Environmental  Research
     Information:  Cincinnati, OH, 1982;  EPA-600/4-82-057.

3.   Patel, B.K.;  Raab, G.A.; et al. Report on  a Single Laboratory  Evaluation
     of  Inductively  Coupled Optical Emission  Method 6010;  EPA  Contract  No.
     68-03-3050, December 1984.

4.   Sampling  and  Analysis  Methods  for  Hazardous  Waste  Combustion;  U.S.
     Environmental  Protection Agency;  Air  and Energy Engineering  Research
     Laboratory, Office  of  Research and  Development: Research Triangle Park,
     NC, 1986; Prepared by Arthur D. Little,  Inc.

5.   Bowmand, P.W.J.M. Line Coincidence Tables  for Inductively Coupled Plasma
     Atomic Emission Spectrometry,  2nd  ed.; Pergamon:  1984.

6.   Rohrbough, W.G.; et  al. Reagent  Chemicals.  American  Chemical Society
     Specifications,  7th  ed.; American  Chemical  Society: Washington,  DC, 1986.

7.   1985 Annual Book  of ASTM Standards.  Vol.  11.01; "Standard Specification
     for Reagent Water";  ASTM: Philadelphia,  PA, 1985; D1193-77.
                                 6010  -  13                       Revision 1
                                                                December 1987
-------
                             TABLE 4.
                 ICP PRECISION AND ACCURACY DATAa
Sample No.
Ele-
ment
Be
Mn
V
As
Cr
Cu
Fe
Al
Cd
Co
Ni
Pb
Zn
Sec
True
Value
(ug/L)
750
350
750
200
150
250
600
700
50
700
250
250
200
40
1
Mean Re-
ported Mean
Value SDb
(ug/L) (%)
733
345
749
208
149
235
594
696
48
512
245
236
201
32
6.2
2.7
1.8
7.5
3.8
5.1
3.0
5.6
12
10
5.8
16
5.6
21.9
Sample No.
Mean Re-
True ported
Value Value
(ug/L) (ug/L)
20
15
70
22
10
11
20
60
2.5
20
30
24
16
6
20
15
69
19
10
11
19
62
2.9
20
28
30
19
8.5
2
Mean
SDb
9.8
6.7
2.9
23
18
40
15
33
16
4.1
11
32
45
42
Sample No.
True
Value
(ug/L)
180
100
170
60
50
70
180
160
14
120
60
80
80
10
Mean Re-
ported
Value
(ug/L)
176
99
169
63
50
67
178
161
13
108
55
80
82
8.5
3
Mean
SDb
5.2
3.3
1.1
17
3.3
7.9
6.0
13
16
21
14
14
9.4
8.3
*Not all elements were analyzed by all laboratories.

b$D = standard deviation.

cResults for Se are from two laboratories.
                            6010 - 14                       Revision 1
                                                            December 1987
-------
                                        METHOD 6010
              INDUCTIVELY  COUPLED  ATOMIC  EMISSION  SPECTROSCOPY
7 1 Prepare sample
using Method 3006,
 3010, 3020, 3040.
   or 30SO as
   appropriate
  7 2 Set  up and
    stabilize
   instrument
  7 3 Profile and
    calibrate
   instrument
 7 6 Flash system
and analyze saaple
 7 5 Analyze check
   standard and
 calibration blank
   after each 10
     samples
   7 4 Reanalyze
   highest mixed
   calibration
    standard
   7 6 Calculate
  concentratione
                         7.4 Adjust
                        instrument per
                        manufacturer*•
                        recommendations
      Stop
                                   6010  -  15
             Revision  1
             December  1987
-------
                                  METHOD  6020

                INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
1.0  SCOPE AND APPLICATION

      1.1  Inductively coupled plasma-mass  spectrometry  (ICP-MS) is a technique
which is  applicable  to ptg/L  concentrations  of a large number  of  elements in
water and wastes  after appropriate sample preparation  steps  are  taken [1,2].
When dissolved  constituents  are required,  samples must be  filtered  and acid-
preserved prior to analysis.   No further digestion is  required  prior to analysis
for dissolved  elements.   Acid-digestion prior to filtration and  analysis is
required for groundwater, aqueous  samples,  industrial  wastes, soils, sludges,
sediments, and other solid wastes  for which total  (acid-leachable) elements are
required.

      1.2  Elements for which Method 6020 has  shown acceptable performance  in a
multi-laboratory study are listed in TABLE 1.  Acceptability of the method for
an element was  based  upon the multi-laboratory performance  compared with that of
either furnace  atomic absorption  spectroscopy or  inductively coupled plasma-
atomic emission spectroscopy.   Other elements may be added  to Table  1 as more
information becomes available. Multi-laboratory performance data for  the listed
elements (and others) are provided  in Section 9.   Instrument detection limits,
sensitivities,  and linear ranges for these elements will  vary with the matrices,
instrumentation, and operating conditions.

      1.3    Use of  this method   is  restricted  to   spectroscopists who  are
knowledgeable in the recognition and the correction of spectral, chemical, and
physical interferences in ICP-MS.

      1.4   An  appropriate   internal  standard  is required  for each  analyte
determined by ICP-MS.  Recommended  internal standards are  6Li, 45Sc,  89Y,  103Rh,
1l5In,  159Tb,  165Ho,  and 209Bi.  The lithium  internal standard  should  have an
enriched abundance of 6Li, so that  interference from lithium native to  the sample
is minimized.   Other elements may need to be  used as  internal  standards when
samples contain significant  amounts of the recommended internal  standards.


2.0  SUMMARY OF METHOD

      2.1 Prior to analysis,  samples which require total  values must be digested
using appropriate sample preparation methods  (such  as Methods 3005  - 3051).

      2.2  Method 6020 describes the multi-elemental  determination of analytes
by ICP-MS.  The method measures ions produced by a radio-frequency inductively
coupled plasma.  Analyte species originating  in a liquid are nebulized and the
resulting aerosol  transported by  argon gas  into  the plasma  torch.   The ions
produced are entrained in the plasma gas and  introduced,  by means  of a water-


                                    6020-1                         Revision  0
                                                                  November  1992
-------
cooled interface,  into a quadrupole mass spectrometer.   The ions produced in the
plasma are sorted according to their mass-to-charge ratios and quantified with
a  channel  electron  multiplier.    Interferences  must  be  assessed and  valid
corrections applied  or  the data  flagged  to indicate problems.   Interference
correction must  include  compensation  for  background  ions contributed  by the
plasma gas, reagents, and constituents of the sample matrix.


3.0  INTERFERENCES

      3.1  Isobaric elemental  interferences in  ICP-MS are caused by isotopes of
different elements forming atomic ions with  the same nominal mass-to-charge ratio
(m/z). A  data  system must be  used  to correct for these  interferences.   This
involves determining the signal for another isotope of the interfering element
and subtracting the appropriate signal from the analyte isotope signal.  Since
commercial ICP-MS  instruments  nominally provide  unit resolution  at 10% of the
peak height, very  high ion currents at adjacent masses can also contribute to ion
signals at the mass of interest. Although this type of interference  is uncommon,
it is not easily corrected, and samples exhibiting a significant problem of this
type could require resolution  improvement,  matrix separation,  or use of another
method.

      3.2  Isobaric molecular and doubly-charged ion interferences  in ICP-MS are
caused by  ions consisting of more than one atom or charge, respectively.  Most
isobaric  interferences   that   could  affect  ICP-MS determinations have  been
identified in the literature  [3,4].   Examples  include  ArCl+ ions on the  75As
signal and MoO+  on the  cadmium isotopes.   Since the 35C1  natural  abundance of
75.8  percent  is   3.13 times  the  37C1  abundance  of 24.2 percent,  the choride
corrections can be calculated as follows (where the 38Ar37Cl+ contribution at m/z
75 is a negligible 0.06 percent of the 40Ar35Cl+  signal):

      corrected arsenic  signal = (m/z  75  signal)  - (3.13)  (m/z  77  signal)  +
      (2.53) (m/z 82  signal),  (where the  final  term adjusts for any selenium
      contribution at 77 m/z),

Similarly,

      corrected cadmium  signal =  (m/z 114  signal)  -  (0.027)(m/z 118 signal)  -
      (1.63)(m/z  108  signal),  (where last 2 terms adjust for any  tin or MoO+
      contributions at m/z 114).

The above equations are based upon the constancy of the  isotopic ratios for the
interfering species.  Corrections that presume a constant fraction of a molecular
ion relative to the "parent" ion  have  not  been found [5] to  be reliable, e.g.,
oxide levels can vary.  If a correction for an oxide ion is based upon  the ratio
of  parent-to-oxide ion   intensities,  the  correction must be  adjusted for the
degree of  oxide formation by the  use  of an appropriate oxide  internal standard
previously demonstrated  to  form a  similar level  of  oxide as the  interferant.
                                    6020-2                        Revision  0
                                                                  November 1992
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This type of correction has  been  reported  [5]  for  oxide-ion  corrections using
ThO+/Th+  for the determination  of rare earth elements.

      3.3 Physical interferences are associated with the sample nebulization and
transport processes as well as with ion-transmission efficiencies.  Nebulization
and transport processes  can be affected if a matrix  component causes a change in
surface  tension or viscosity.    Changes  in  matrix   composition  can  cause
significant signal  suppression or  enhancement [6].  Dissolved solids can deposit
on the  nebulizer  tip of a pneumatic nebulizer and on  the  interface  skimmers
(reducing the orifice size  and the instrument performance).  Total solid levels
below 0.2% (2,000 mg/L)  have  been  recommended [7] to minimize solid deposition.
An internal  standard can be used to correct for  physical  interferences, if it is
carefully matched to the analyte so that the two elements are similarly affected
by matrix changes  [8].  When the intensity level of  an internal standard  is less
than 30  percent or  greater  than  120  percent  of  the  intensity of the first
standard used during calibration,  the sample must  be reanalyzed after a fivefold
(1+4) dilution has been performed.

      3.4   Memory interferences  can occur  when  there  are large concentration
differences between samples or standards which are analyzed  sequentially.  Sample
deposition on the sampler  and skimmer cones, spray  chamber design, and the type
of nebulizer affect the extent of the memory interferences which are observed.
The rinse period between samples  must  be  long  enough  to eliminate significant
memory interference.


4.0  APPARATUS AND MATERIALS

      4.1  Inductively coupled plasma-mass spectrometer:

            4.1.1   A system capable of  providing  resolution,  better  than or
      equal  to  1 amu  at  10%  peak height is required.   The  system  must  have a
      mass range  from at least  6 to  240  amu  and a  data system  that  allows
      corrections for isobaric interferences and the application  of the internal
      standard technique.  Use of  a mass-flow controller for the nebulizer argon
      and a peristaltic pump for  the sample solution  are recommended.

            4.1.2  Argon gas supply:  high-purity grade (99.99%).


5.0  REAGENTS

      5.1  Acids used in the  preparation of  standards and for sample processing
must be of high purity.   Redistilled acids are  recommended because of the high
sensitivity of ICP-MS.  Nitric acid at less than 2 per cent  (v/v)  is required for
ICP-MS to minimize damage to the  interface and to minimize isobaric molecular-ion
interferences with  the  analytes.   Many  more molecular-ion  interferences  are
observed  on the analytes when hydrochloric  and sulfuric acids  are used [3,4].
Concentrations of antimony and  silver  above 300  jug/L  require  1% (v/v)  HC1  for


                                    6020-3                        Revision  0
                                                                  November  1992
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stability.  If HC1 is added as a stabilizer, then corrections for the chloride
molecular-ion interferences must be applied to all data generated.

      5.2   Reagent  water:    Reagent  water  will  be  interference  free.   All
references  to water  in  the  method  refer to  reagent water  unless otherwise
specified.  Refer to Chapter One for a definition of reagent water.

      5.3  Standard stock solutions may be purchased or prepared  from ultra-high
purity grade  chemicals  or metals (99.99 to 99.999%  pure).   See Method 6010A,
Section 5.3,  for instructions on preparing standard solutions from  solids.

            5.3.1  Bismuth internal  standard  solution,  stock,  1  mL = 100 jug Bi:
      Dissolve 0.1115 g  Bi203 in  a  minimum amount of  dilute  HN03.   Add  10  ml
      cone. HN03 and dilute to 1,000 ml with reagent water.

            5.3.2  Holmium internal  standard  solution,  stock,  1  ml = 100 p.g Ho:
      Dissolve 0.1757 g  Ho2(C03)2-5H20 in  10 ml  reagent  water  and  10 mL  HN03.
      After dissolution  is complete, warm the solution to degas.   Add  10  ml
      cone. HN03 and dilute to 1,000 ml with reagent water.

            5.3.3  Indium internal standard solution,  stock, 1  ml =  100 /zg In:
      Dissolve 0.1000 g  indium  metal  in 10 ml cone. HN03.   Dilute  to  1,000  ml
      with reagent water.

            5.3.4  Lithium internal  standard  solution,  stock, 1  ml = 100 jug 6Li:
      Dissolve 0.6312 g 95-atom-% 6Li, Li2C03  in 10 ml of reagent water and  10  ml
      HN03.   After  dissolution  is complete,  warm the  solution  to degas.  Add
      10 ml cone. HN03 and dilute to 1,000 ml with reagent water.

            5.3.5  Rhodium internal  standard  solution,  stock,  1  ml = 100 ;ug Rh:
      Dissolve 0.3593 g  ammonium hexachlororhodate  (III)  (NH4)3RhCle in  10  ml
      reagent water.  Add  100 ml cone.  HC1 and dilute  to 1,000  ml with  reagent
      water.

            5.3.6  Scandium internal  standard  solution, stock, 1 ml = 100 jug Sc:
      Dissolve 0.15343 g Sc203 in 10  ml  (1+1)  hot HN03.  Add 5 ml cone. HN03 and
      dilute  to  1,000 mL with reagent water.

            5.3.7  Terbium internal standard solution,  stock,  1  ml = 100 jug Tb:
      Dissolve 0.1828 g Tb2(C03)3-5H20 in 10 ml (1+1) HN03.  After dissolution  is
      complete,  warm the  solution to  degas.   Add  5  ml  cone.  HN03  and dilute  to
      1,000 ml with  reagent water.

            5.3.8  Yttrium internal standard  solution, stock, 1 ml  = 100  /ug  Y:
      Dissolve 0.2316 g  Y2(C03)3.3H20 in 10 ml (1+1) HN03.   Add  5 ml cone. HN03
      and  dilute to  1,000 ml  with reagent  water.
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            5.3.9  Titanium solution,  stock, 1 ml = 100 /ug  Ti: Dissolve 0.4133 g
      (NH4)2TiF6  in reagent water.  Add 2 drops cone. HF and dilute to 1,000 ml
      with reagent water.

            5.3.10   Molybdenum solution,  stock,  1 ml =  100 jug  Mo:   Dissolve
      0.2043 g (NH4)2Mo04 in reagent  water.   Dilute  to  1,000  ml with reagent
      water.

      5.4   Mixed calibration standard solutions  --  Dilute the  stock-standard
solutions  to  levels  in  the  linear  range  for  the  instrument  in  a  solvent
consisting of 1  percent  (v/v) HN03 in reagent water.  The calibration standard
solutions  must  contain  a suitable concentration  of an  appropriate internal
standard for each analyte.   Generally,  an  internal  standard should be no more
than 50 amu removed  from the analyte.  Recommended internal standards include
6Li,  45Sc, 89Y,  103Rh,  115In, 159Te, f69Ho, and 209Bi.   Prior to  preparing the mixed
standards, each stock solution must be analyzed separately  to determine possible
spectral interferences or the presence of impurities.  Care must be taken when
preparing  the  mixed  standards  that   the elements  are compatible  and stable.
Transfer the mixed standard solutions to freshly acid-cleaned FEP fluorocarbon
bottles for storage.   Fresh mixed standards must  be  prepared as needed with the
realization that concentrations can change on aging.  Calibration  standards must
be initially  verified using  a  quality control  sample  (see Section  5.8)  and
monitored weekly for  stability.

      5.5   Blanks: Three types of blanks are  required for the analysis.   The
calibration blank is  used in  establishing  the calibration curve.  The reagent
blank is used to monitor for possible contamination resulting  from the sample
preparation procedure.  The rinse blank is  used to  flush the system between all
samples and standards.

            5.5.1  The  calibration  blank consists  of 1  percent  HN03 (v/v) in
      reagent water along with the selected concentrations  of internal standards
      such that  there is an  appropriate  internal  standard element for each of
      the analytes.

            5.5.2  The reagent blank  must contain all the reagents in the same
      volumes as used in processing  the  samples.   The reagent  blank must be
      carried  through  the  complete  procedure   and contain  the  same  acid
      concentration  in  the  final  solution  as the  sample  solutions  used  for
      analysis.

            5.5.3  The  rinse blank consists  of  1 to 2 percent  HN03 (v/v) in
      reagent water.   Prepare a sufficient quantity  to flush the  system between
      standards  and samples.

      5.6  The  instrument check  standard is prepared by the analyst by combining
compatible  elements   at  concentrations equivalent  to the  midpoint  of  their
respective calibration ranges.
                                    6020-5                        Revision  0
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      5.7  The  interference check solution(s)  (ICS) is prepared to contain known
concentrations of  interfering  elements  that will  demonstrate the magnitude of
interferences and provide an adequate test of any  corrections.  Chloride in the
ICS  provides  a means  to evaluate  software corrections  for chloride-related
interferences such as 35C1160+  on  51V+ and 40Ar36Cl+ on 76As+.  Iron is used to
demonstrate adequate  resolution  of the spectrometer  for  the determination of
manganese.  Molybdenum serves to indicate oxide effects on cadmium isotopes.  The
other components are present to evaluate the ability of the measurement system
to correct for various molecular-ion  isobaric interferences.  The ICS is used to
verify that  the  interference  levels  are  corrected by the  data system within
quality control limits.

            5.7.1  The final concentrations of elements  in ICS A  and ICS AB are
      shown  in Table  2. These  solutions  must  be  prepared  from ultra-pure
      reagents.  They can be obtained commercially or  prepared by the following
      procedure.

                   5.7.1.1   Mixed  ICS  solution  I may  be prepared  by adding
            13.903 g A1(N03)3-9H20,  2.498 g CaC03  (dried at 180 C for 1  h before
            weighing), 1.000 g Fe,  1.658 g MgO, 2.305 g Na2C03, and 1.767 g K2C03
            to 25  ml of  reagent water.  Slowly  add 40 ml  of  (1+1)  HN03.  After
            dissolution  is  complete, warm  the solution  to  degas.   Cool  and
            dilute to 1,000 ml with  reagent water.

                   5.7.1.2   Mixed  ICS  solution II may  be  prepared by slowly
            adding 7.444 g 85 % H3P04,  6.373 g 96% H2S04,  40.024  g  37% HC1, and
            10.664 g citric  acid C607H8  to 100 ml of reagent water.  Dilute to
            1,000  ml with reagent water.

                   5.7.1.3  Mixed ICS  solution III may be prepared by adding 5 ml
            each of 100 /Ltg/ml  arsenic stock solution, chromium stock solution,
            copper  stock solution,  manganese  stock  solution,  selenium stock
            solution, silver stock solution, and zinc stock solution, 10 ml each
            of  100 jug/ml  cobalt  stock  solution,  nickel   stock  solution,  and
            vanadium  stock  solution, and 2.5 ml  of  100  jug/ml  cadmium stock
            solution.  Dilute  to 100 ml with 2% HN03.

                   5.7.1.4  Working ICS  Solutions

                         5.7.1.4.1   ICS A  may  be prepared  by adding 50 ml of
                   mixed  ICS solution  I  (5.7.1.1),  10 ml  each  of  100  /iQ/ml
                   titanium stock solution (5.3.9)  and molybdenum stock  solution
                   (5.3.10),  and  25  ml  of  mixed  ICS  solution  II  (5.7.1.2).
                   Dilute to  100 ml with reagent water.  ICS  solution A must be
                   prepared  fresh weekly.

                         5.7.1.4.2   ICS  AB  may  be  prepared by adding 50 ml of
                   mixed  ICS solution  I  (5.7.1.1),  10 ml  each  of  100  jug/ml
                   titanium stock solution (5.3.9)  and molybdenum stock  solution

                                     6020-6                         Revision  0
                                                                   November 1992
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                  (5.3.10), 25 ml of mixed ICS solution II (5.7.1.2),  and 2 ml
                  of Mixed ICS solution  III  (5.7.1.3).   Dilute  to  100 ml with
                  reagent water.   ICS solution AB must be  prepared fresh weekly.

      5.8  The quality control sample  is the initial calibration verification
solution, which must  be  prepared in the same acid matrix as the  calibration
standards.  This solution must be an independent standard near the midpoint of
the  linear  range  at  a  concentration  other than  that  used  for  instrument
calibration.  An independent standard is defined as a standard composed of the
analytes from a  source different from those used  in the standards for instrument
calibration.
6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Sample  collection  procedures  should  address  the  considerations
described in Chapter Nine of this Manual.

      6.2  See the introductory material in Chapter Three,  Inorganic Analytes,
Sections  3.1.3  for  information on  sample  handling  and  preservation.   Only
polyethylene or Teflon containers are recommended for use in Method 6020.


7.0   PROCEDURE

      7.1  Solubilization and digestion procedures are presented in the Sample
Preparation Methods (e.g. Methods 3005 - 3050).

      7.2   Initiate appropriate  operating  configuration  of  the   instrument
computer.

      7.3  Set up the instrument with the proper operating  parameters.

      7.4   Operating  conditions:    In  general,  the analyst should  follow the
instructions  provided  by  the  instrument manufacturer.    The  following  is  a
suggested listing of operating conditions which may be useful.

                   Perkin-Elmer  Sciex
                       Elan  500         VG Plasmaquad
Plasma Gas (1pm)           12                   13
Aux. Gas (1pm)            1.2                 0.65
Neb. Gas (1pm)           0.95                 0.69
Forward power (kW)        1.2                 1.30
Reflected power (W)       < 5                  <  5
Sampling Height            18                   12
  (mm above load coil)

     Note:  Addition of nitrogen to  the  plasma  argon  has been      reported to
decrease many molecular interferences [9].


                                    6020-7                        Revision 0
                                                                  November 1992
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    Allow at least 30 minutes for the instrument to equilibrate before analyzing
any samples.  This must be verified  by  analyzing a tuning solution (such as 100
jug/L Li, Co, In,  and Tl) at least four times with relative standard deviations
of less than 10% for the analytes contained in the tuning solution.

      Note:  Precautions must be taken to protect the  channel electron multiplier
from high  ion currents.   The channel electron multiplier suffers from fatigue
after being exposed to high ion  currents.   This fatigue can  last from several
seconds to hours depending on the extent of  exposure.  During this time period,
response factors  are  constantly  changing,  which invalidates  the calibration
curve, causes instability, and invalidates sample analyses.

      7.5  Conduct mass calibration  and resolution checks in the mass regions of
interest.  The mass calibration and  resolution parameters are required criteria
which must be met prior to any  samples  being analyzed.   If the mass calibration
exceeds a difference of more than 0.1 amu from the actual value, then the mass
calibration must be adjusted to the  correct values.   The  resolution must also be
verified to be less than 1.0 amu full width at 10 percent peak height.

      7.6  Calibrate the instrument for  the analytes of interest for the isotopes
shown in Table  3 using the calibration  blank and at least  a single standard
according to the manufacturer's recommended procedure.  Flush the system with the
rinse blank  (5.5.3) between  each standard  solution.   Use the  average  of the
multiple integrations for both standardization and sample analysis.

      7.7  Some elements  (such  as Hg, W, and Mo) require  extended  flushing times
which need to be determined for each instrumental system.

      7.8   All  masses  which  could  affect data  quality  should be monitored to
determine potential effects from matrix components on  the analyte peaks.  These
masses must be monitored  either simultaneously in a separate scan  or at the same
time quantification occurs.

      7.9    Immediately  after  the calibration  has   been  established,  the
calibration must be verified and documented for every analyte  by the analysis of
the initial calibration verification solution  (Section 5.8).  When measurements
exceed ± 10% of the accepted  value the  analysis must be  terminated, the problem
corrected,  the  instrument recalibrated,  and  the calibration  reverified.   Any
samples analyzed  under an out-of-control calibration must be reanalyzed.

      7.10  Flush the system with the rinse  blank solution  (5.5.3) for at least
30 seconds before the analysis  of each  sample  (see Section  7.7).   Aspirate each
sample for at least 30 seconds before collecting data.  Analyze  the instrument
check standard  (Section  5.6)  and  the  calibration  blank (Section 5.5.1)  at  a
frequency  of at least once every  10 analytical samples.

      7.11   Dilute and reanalyze samples that  are  more concentrated than the
linear range for  an analyte (or species needed for a correction)  or measure an
alternate  less-abundant  isotope.


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                                                                  November  1992
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      7.12  Calculations:  The quantitative values shall  be reported  in units of
micrograms per  liter (ng/l) for  aqueous  samples and milligrams  per kilogram
(mg/kg)  for  solid  samples.   If  dilutions  were  performed,  the  appropriate
corrections must be applied to the sample values.

            7.12.1  Results  for solids must be reported on  a dry-weight basis as
      fol1ows:

                  (1) A  separate  determination  of  percent  solids  must  be
                      performed.

                  (2) The  concentrations  determined  in  the  digest are  to be
                      reported on  the basis  of  the  dry weight of the sample.

                                                       f y U
                  Concentration (dry weight) (mg/kg) =  r.   *
                                                       W X o

                      Where,

                  C = Digest Concentration (mg/L)
                  V = Final  volume in liters  after sample preparation
                  W = Weight in kg of wet sample

                     =  % Solids
                           100

      Calculations  should  include  appropriate  interference  corrections (see
      Section  3.2  for  examples),   internal  standard  normalization,  and  the
      summation of signals at 206, 207,  and 208 m/z for lead  to compensate for
      any differences in the abundances of these isotopes between samples and
      standards.
8.0  QUALITY CONTROL

      8.1  All quality  control  data  should  be maintained and be available for
easy reference or inspection.

      8.2   Instrument Detection Limits (IDL's) (in M9/L)  can  be estimated by
multiplying by three the  average  of  the standard  deviations obtained on three
nonconsecutive days from  the  analysis  of  a  standard  solution (each analyte in
reagent water)  at a concentration 3x-25x IDL, with seven consecutive measurements
per day.   Each measurement  must be  performed as though  it were  a separate
analytical sample  (i.e., each  measurement must be followed by a rinse  and/or any
other procedure normally  performed between  the analysis  of separate samples).
IDL's must be determined at least every  three months and  kept with  the  instrument
log book.  Refer to Chapter One for additional guidance.
                                    6020-9                        Revision  0
                                                                  November 1992
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      8.3  The  intensities of all internal  standards must be monitored for every
analysis.  When the intensity  of any  internal standard fails to fall between 30
and  120  percent of  the intensity of  that internal  standard in  the  initial
calibration standard, the following procedure is followed.  The sample must be
diluted fivefold (1+4) and reanalyzed with the addition of appropriate amounts
of  internal  standard.   This  procedure must  be  repeated until  the  internal
standard intensities fall within the prescribed window. The intensity levels of
the internal  standards for the calibration  blank (Section 5.5.1) and instrument
check standard  (Section  5.6)  must  agree within ±  20  percent  of the intensity
level of the internal standard of the original  calibration blank solution.  If
they do not agree,  terminate the analysis,  correct  the  problem, recalibrate, and
reanalyze the affected samples.

      8.4  To obtain analyte data of known quality, it is necessary to measure
more than the  analytes  of interest  in  order to determine whether interference
corrections are necessary.   If the concentrations  of interference sources (such
as C, Cl,  Mo,  Zr,  W) are below the levels  that show  an  effect  on the analyte
level, uncorrected equations may be used provided all QC criteria are met.  Note
that monitoring the interference sources does not necessarily require monitoring
the interferant itself,  but that a molecular species may be monitored  to indicate
the  presence of the interferent.  When  corrected equations  are  used,  all  QC
criteria must  also  be  met.   Extensive QC  for   interference corrections  are
required at all times.  The monitored masses must include those elements whose
hydrogen, oxygen,  hydroxyl,  chlorine, nitrogen, carbon and  sulfur molecular ions
could impact  the analytes of interest.  Unsuspected interferences  may be detected
by adding pure major matrix  components  to  a sample to  observe  any  impact on the
analyte  signals.   When  an interference  source  is  present, the sample elements
impacted must be flagged to  indicate  (a) the percentage interference correction
applied to the  data or (b) an uncorrected interference by virtue of the elemental
equation used  for quantitation.   The isotope proportions  for  an  element  or
molecular-ion cluster provide information useful   for quality assurance.

      NOTE:  Only  isobaric elemental, molecular, and doubly charged interference
corrections which  use  established  isotopic response ratios  or parent-to-oxide
ratios (provided an oxide internal standard  is used as described  in Section 3.2)
are  acceptable corrections for  use in Method 6020.

      8.5  Serial  dilution:   If  the analyte concentration is within the linear
dynamic range of the  instrument and sufficiently high (minimally, a factor of 100
above the instrumental detection limit), an  analysis of a  fivefold dilution must
agree within ±  10% of the original determination.   If not,  an interference effect
must be suspected.  One  serial dilution must be analyzed for each  twenty samples
or less  of each matrix  in a batch.

      8.6  Matrix spike addition:    An  analyte spike added to  a portion  of  a
prepared sample, or its  dilution, should be recovered to within 75 to 125 percent
of the known  value.  The spike addition should produce a minimum  signal level of
10 times and a maximum  of  100 times  the instrumental  detection  limit.  If the
spike is not recovered  within the  specified limits, a matrix effect should be
suspected.   The  use of  a  standard-addition  analysis procedure  can usually

                                    6020-10                       Revision  0
                                                                  November 1992
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compensate for this effect.  See Section 8.5.3 of Method 6010 for information on
standard additions.

      8.7  A Laboratory Control Sample (LCS) should be analyzed for each analyte
using the  same sample preparations,  analytical  methods and  QA/QC  procedures
employed for the test samples.  One LCS  should  be  prepared and analyzed for each
sample batch at a frequency of one LCS for each 20 samples or less.

      8.8  Check the  instrument standardization by analyzing appropriate quality
control  solutions as follows:

            8.8.1    Check  instrument  calibration using  a calibration  blank
      (Section  5.5.1)  and  the  initial  calibration  verification  solution
      (Sections 5.8 and 7.9).

            8.8.2   Verify  calibration at  a  frequency of every  10  analytical
      samples  with  the   instrument  check  standard  (Section  5.6)  and  the
      calibration blank (Section 5.5.1).   These  solutions must also be analyzed
      for  each  analyte  at the  beginning of  the  analysis  and after  the last
      sample.

            8.8.3  The results  of the initial  calibration verification solution
      and the instrument  check standard must  agree within ± 10% of the expected
      value.    If  not,  terminate  the  analysis,  correct  the  problem,  and
      recalibrate the instrument.  Any sample analyzed under an out-of-control
      calibration must be reanalyzed at no additional  cost to the government.

            8.8.4   The results of the calibration blank  must be less  than  3
      times the current  IDL  for each element.   If this is not  the  case,  the
      reason for the out-of-control condition must be found and corrected,  and
      affected samples must be reanalyzed.

      8.9    Verify  the  magnitude  of elemental   and  molecular-ion  isobaric
interferences  and the adequacy of  any   corrections  at the  beginning  of  an
analytical run or once every 12 hours, whichever  is more frequent.   Do this by
analyzing the interference check solutions A and AB

      8.10   Analyze one duplicate sample for  every  matrix  in  a  batch at  a
frequency of one matrix duplicate for every 20 samples.
                                    6020-11                        Revision  0
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            8.10.1   The relative percent  difference (RPD)  between  duplicate
      determinations must be calculated as follows:
                                ID,  - D2  |
                   RPD =      	     x 100
                               (D, + D2)/2

            where:

            RPD = relative percent difference.
            D,  = first sample value.
            D2  = second sample value (duplicate)

      A control  limit of 20%  RPD should  not  be exceeded for  analyte values
      greater than 100 times  the instrumental detection limit.  If this  limit is
      exceeded, the reason for the  out-of-control  situation  must be found and
      corrected, and  any  samples  analyzed  during the out-of-control  condition
      must be reanalyzed.


9.0  METHOD PERFORMANCE

      9.1  In an EPA multi-laboratory study, 10 laboratories applied the
ICP-MS technique  to both aqueous and  solid samples.  TABLE  5  summarizes the
method performance data for aqueous  samples.  Performance data for solid samples
is provided in TABLE 6.


10.0  REFERENCES

1. Horlick, G., et  al., Spectrochim. Acta  40B, 1555  (1985).

2. Gray, A.L.,  Spectrochim.  Acta  40B,  1525 (1985); 41B,  151  (1986).

3. Tan, S.H.,  and Horlick, G., Appl. Spectrosc.  40,  445  (1986).

4. Vaughan, M.A., and  Horlick, G.,  Appl. Spectrosc.  40,  434  (1986).

5.  Lichte, F.E., et al., Anal. Chem. 59,  1150 (1987).

6. Beauchemin,  D.,  et  al., Spectrochim. Acta  42B,  467  (1987).

7. Houk, R.S.,  Anal.  Chem. 58, 97A  (1986).

8. Thompson, J.J.,  and Houk,  R.S.,  Appl. Spectrosc.  41,  801  (1987).

9. Evans,  E.H.,  and Ebdon, L., J. Anal. At. Spectrom.  4,  299 (1989).
                                    6020-12                        Revision  0
                                                                   November 1992
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TABLE 1. ELEMENTS APPROVED FOR ICP-MS DETERMINATION
            Element
  CAS* #
Estimated Detection
   Limit (M9/L)
            Aluminum
            Antimony
            Arsenic
            Barium
            Beryllium
            Cadmium
            Chromium
            Cobalt
            Copper
            Lead
            Manganese
            Nickel
            Silver
            Thallium
            Zinc
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-3
7440-48-4
7440-50-8
7439-92-1
7439-96-5
7440-02-0
7440-22-4
7440-28-0
7440-66-6
        0.1
        0.02
        0.4
        0.02
        0.1
        0.07
        0.02
        0.01
        0.03
        0.02
        0.04
        0.03
        0.04
        0.05
        0.08
                                    6020-13
                           Revision 0
                           November 1992
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TABLE 2.  RECOMMENDED INTERFERENCE CHECK SAMPLE COMPONENTS AND CONCENTRATIONS.
   Interference                          Solution A              Solution AB
    component                  Concentration  (mg/L)         Concentration  (mg/L
Al
Ca
Fe
Mg
Na
P
K
S
C
Cl
Mo
Ti
As
Cd
Cr
Co
Cu
Mn
Ni
Ag
Zn
500.0
500.0
500.0
500.0
500.0
500.0
500.0
500.0
1000.0
3600.0
10.0
10.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
500.0
500.0
500.0
500.0
500.0
500.0
500.0
500.0
1000.0
3600.0
10.0
10.0
0.100
0.050
0.100
0.200
0.100
0.100
0.200
0.100
0.100
                                    6020-14                        Revision 0
                                                                   November 1992
-------
TABLE 3.  RECOMMENDED ISOTOPES FOR SELECTED ELEMENTS
Mass                                           Element of interest


27                                                   Aluminum
121, 123                                             Antimony
75                                                   Arsenic
138, 137, 136, 135, 134                              Barium
9                                                    Beryllium
209                                                  Bismuth (IS)
114, 112, 111, 110, 113, 116, 106                    Cadmium
42, 43, 44, 46, 48                                   Calcium (I)
35, 37, (77, 82)a                                    Chlorine (I)
52, 53, 50, 54                                       Chromium
59                                                   Cobalt
63, 65                                               Copper
165                                                  Holmium (IS)
115, 113                                             Indium (IS)
56, 54, 57, 58                                       Iron (I)
139                                                  Lanthanum (I)
208, 207, 206, 204                                   Lead
6b, 7                                                Lithium (IS)
24, 25, 26                                           Magnesium (I)
55                                                   Manganese
98, 96, 92, 97, 94, (108)a                           Molybdenum (I)
58, 60, 62, 61, 64                                   Nickel
39                                                   Potassium (I)
103                                                  Rhodium (IS)
45                                                   Scandium (IS)
107, 109                                             Silver
23                                                   Sodium (I)
159                                                  Terbium (IS)
205, 203                                             Thallium
120, 118                                             Tin (I)
89                                                   Yttrium (IS)
64, 66, 68, 67, 70                                   Zinc

       NOTE:  Method 6020 is recommended for only  those analytes listed in Table
1.   Other  elements  are  included in  this table  because  they  are potential
interferents (labeled I) in the determination of recommended analytes, or because
they are commonly used internal  standards (labeled  IS).   Isotopes  are listed in
descending order of natural abundance.  The most generally useful isotopes are
underlined and  in  boldface,  although certain matrices may  require  the  use of
alternative isotopes. a These masses are also useful for interference correction
(Section 3.2).  b Internal  standard must be enriched in the 6Li isotope.  This
minimizes interference from indigenous lithium.
                                    6020-15                        Revision  0
                                                                  November 1992
-------
TABLE 4.  SPIKING LEVELS FOR ICP-MS ANALYSIS  (M9/L)
             Element
  No spike required.
Water
Soil
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lead
Manganese
Nickel
Silver
Thall ium
Vanadium
Zinc
500
100
100
200
50
50
50
100
50
50
50
100
50
50
100
100
*
100
100
200
50
50
50
100
50
50
50
100
50
50
100
100
                                    6020-16
                                       Revision  0
                                       November 1992
-------
 'ABLE  5.
 SOLUTIONS
ICP-MS MULTI-LABORATORY  PRECISION AND  ACCURACY DATA  FOR AQUEOUS
ilement
Comparability8
Range
%RSD
Range
Nb Sc
\luminum
\ntimony
Arsenic
Sari urn
Beryllium
ladmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
        95  -  100
           d
        97  -  114
        91  -  99
       103  -  107
        98  -  102
        99  -  107
        95  -  105
       101  -  104
        85  -  101
        91  -  900
        71  -  137
        98  -  102
        95  -  101
        98  -  101
       101  -  114
       102  -  107
       104  -  105
        82  -  104
        88  -  97
       107  -  142
        93  -  102
11
5.0
7.1
4.3
8.6
4.6
5.7
13
8.2
6.1
11
11
10
8.8
6.1
9.9
15
5.2
24
9.7
23
6.8
- 14
- 7.6
- 48
- 9.0
- 14
- 7.2
- 23
- 27
- 8.5
- 27
- 150
- 23
- 15
- 15
- 6.7
- 19
- 25
- 7.7
- 43
- 12
- 68
- 17
14 - 14
16 - 16
12 - 14
16 - 16
13 - 14
18 - 20
17 - 18
16 - 18
18 - 18
17 - 18
10 - 12
17 - 18
16 - 16
18 - 18
18 - 18
11 - 12
12 - 12
13 - 16
 9 - 10
18 - 18
 8 - 13
16 - 18
4
3
4
5
3
3
5
4
3
5
5
6
5
4
2
5
3
2
5
3
3
5
a Comparability refers to the percent agreement of mean ICP-MS values to those
of  the reference  technique.   b  N  is  the  range of  the  number  of  ICP-MS
measurements where  the analyte values exceed the limit of quantitation  (3.3 times
the average IDL value).      c S is the number of samples with results greater
than the  limit of quantitation.   d No comparability values  are  provided for
antimony  because  of  evidence  that  the  reference  data  is  affected  by  an
interference.
                                    6020-17
                                                      Revision  0
                                                      November 1992
-------
TABLE 6.   ICP-MS MULTI-LABORATORY PRECISION AND ACCURACY DATA FOR SOLID MATRICES
Element
Comparability8
Range
%RSD
Range Nb
Sc
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
                   83 - 101
                      d
                   79 - 102
                  100 - 102
                   50 - 87
                   93 - 100
                   95 - 109
                   77 - 98
                   43 - 102
                   90 - 109
                   87 - 99
                   90 - 104
                   89 - 111
                   80 - 108
                   87 - 117
                   97 - 137
                     81
                   43 - 112
                  100 - 146
                     91
                   83 - 147
                   84 - 124
 11 - 39
 12 - 21
 12 - 23
4.3 - 17
 19 - 34
6.2 - 25
4.1 - 27
 11 - 32
 15 - 30
9.0 - 25
6.7 - 21
5.9 - 28
7.6 - 37
 11 - 40
9.2 - 29
 11 - 62
   39
 12 - 33
 14 - 77
   33
 20 - 70
 14 - 42
13 - 14
15 - 16
16 - 16
15 - 16
12 - 14
19 - 20
15 - 17
17 - 18
17 - 18
18 - 18
12 - 12
15 - 18
15 - 16
16 - 18
16 - 18
10 - 12
  12
15 - 15
 8 - 10
  18
 6 - 14
18 - 18
7
2
7
7
5
5
7
7
6
7
7
7
7
7
7
5
1
3
5
1
7
7
  Comparability refers to the percent
                                 b
                                      agreement of mean ICP-MS values to those
of  the reference  technique.   D  N  is  the  range of  the  number  of  ICP-MS
measurements where the analyte values exceed the limit of quantitation (3.3 times
the average IDL value).      c S is the number of samples with results greater
than the  limit  of quantitation.   d No comparability values  are  provided  for
antimony  because  of  evidence  that  the  reference  data  is  affected  by  an
interference.
                                    6020-18
                                                                  Revision  0
                                                                  November 1992
-------
                                                  METHOD 6020
                             INDUCTIVELY COUPLED PLASMA  MASS  SPECTROMETRY
                                      C   Start    J
7 1 Analyse
by Method
7000 or
Method 6010


7.1 U..
M.thod 3040
                                 Y..
  7.1 U>.
Method 300S
 or  Method
  3015
                                         I* sample
                                       oil*.greases
                                          »axea?
                                                                            the xnitruaant
                      I* NiO
                    •oidifi.d,
                   pr«-filt«r«d?
                       I*
                      •ampl*
                    analyzed by
                    FLAA/ICP or
                      CFAA?
  7  1 U..
Method 3020
 or  Method
   3015
                                                        instrument per
•qu«ou* or
  •olxd?
                                                                           date quality ae
                                                                                               reco«aendations
                                      configuration
                                                                            concentration
                                     calibration and
                                                      6020-19
                                                                                             Revision   0
                                                                                             November 1992
-------
                                METHOD 7000

                         ATOMIC ABSORPTION METHODS
1.0 SCOPE AND APPLICATION

    1.1  Metals in  solution  may be  readily determined by  atomic absorption
spectroscopy. The  method is simple, rapid, and applicable to a large number of
metals  in  drinking,  surface, and  saline  waters and  domestic  and industrial
wastes.  While drinking water  free  of particulate  matter  may  be  analyzed
directly, ground water,  other aqueous  samples, EP extracts, industrial wastes,
soils, sludges, sediments, and  other  solid  wastes  require  digestion  prior to
analysis.

    1.2  Detection limits, sensitivity,  and  optimum ranges  of the metals will
vary with the matrices and models of  atomic  absorption  spectrophotometers. The
data  shown  in Table  1  provide  some  indication  of  the  detection  limits
obtainable by direct  aspiration and  by  furnace  techniques.  For clean aqueous
samples, the detection  limits shown  in  the  table  by direct  aspiration may be
extended downward with  scale expansion  and  upward  by  using  a  less sensitive
wavelength  or  by  rotating  the  burner  head.  Detection  limits by  direct
aspiration may  also be  extended through  concentration of the  sample and/or
through  solvent extraction  techniques.  For  certain  samples,  lower
concentrations  may also be  determined using  the furnace  techniques.  The
detection limits given in Table  1 are  somewhat dependent on equipment  (such as
the type  of  spectrophotometer and  furnace  accessory,  the  energy source, the
degree  of electrical  expansion  of the  output  signal),  and  are  greatly
dependent  on  sample  matrix. When  using furnace  techniques,  however,  the
analyst  should  be cautioned  as  to  possible chemical  reactions  occurring at
elevated temperatures  which may  result in either suppression or enhancement of
the  analysis  element.  To ensure  valid data   with  furnace techniques, the
analyst  must examine  each matrix  for interference effects  (see  Step 3.2.1)
and,  if  detected, treat  them accordingly,  using  either successive dilution,
matrix modification, or method of standard additions  (see Step 8.7).

    1.3  Where direct-aspiration atomic absorption  techniques  do not provide
adequate sensitivity,  reference  is  made  to specialized  procedures  (in addition
to the  furnace  procedure)  such  as  the gaseous-hydride method for arsenic and
selenium and the cold-vapor technique  for mercury.

2.0 SUMMARY OF METHOD

    2.1  Although  methods  have  been  reported for  the analysis  of  solids by
atomic absorption spectroscopy, the  technique generally is  limited to metals
in solution or solubilized through  some  form of  sample  processing.

    2.2  Preliminary treatment of waste  water,  ground water,  EP extracts, and
industrial waste is  always necessary  because of  the  complexity and variability
of sample  matrix.  Solids,  slurries,  and suspended  material  must be subjected
to a solubilization process  before analysis. This process may vary because of
the metals to  be determined and  the nature of  the  sample being  analyzed.


                                 7000  -  1                        Revision 1
                                                                December 1987
-------
Solubilization  and digestion  procedures  are presented  in  Step 3.2  (Sample
Preparation Methods).

    2.3  In direct-aspiration atomic  absorption  spectroscopy,  a sample  is
aspirated and atomized in a flame.  A light beam from a hollow cathode lamp or
an  electrodeless  discharge  lamp  is  directed through the  flame  into a
monochromator, and onto a detector  that measures the amount of absorbed light.
Absorption depends upon  the presence of  free unexcited  ground-state  atoms in
the flame. Because the wavelength of the light beam is characteristic of only
the metal  being  determined,   the  light  energy  absorbed by  the  flame  is  a
measure of the  concentration  of  that metal  in the  sample.  This  principle is
the basis of atomic absorption spectroscopy.

    2.4  When  using  the furnace  technique  in  conjunction  with  an  atomic
absorption spectrophotometer,  a representative aliquot  of a sample  is placed
in  the graphite  tube  in  the furnace,  evaporated  to dryness, charred,  and
atomized. As a greater percentage of available analyte atoms is vaporized and
dissociated  for  absorption in the tube  rather  than  the flame,  the  use  of
smaller  sample  volumes or detection of  lower concentrations of elements  is
possible.  The principle  is  essentially  the  same  as  with  direct  aspiration
atomic  absorption,  except that a  furnace,  rather than  a  flame,  is  used  to
atomize the sample. Radiation  from  a given excited element  is passed through
the vapor containing ground-state atoms of that element. The intensity of the
transmitted radiation  decreases  in proportion to  the amount of the ground-
state  element in the  vapor. The metal  atoms  to  be  measured  are placed in the
beam  of radiation  by  increasing  the temperature of  the   furnace,  thereby
causing the injected specimen to be volatilized. A monochromator isolates the
characteristic  radiation  from  the  hollow cathode  lamp  or  electrodeless
discharge lamp,  and  a photosensitive  device  measures  the  attenuated
transmitted radiation.

3.0 INTERFERENCES

    3.1  Direct aspiration

          3.1.1  The  most  troublesome  type  of  interference  in  atomic
     absorption  spectrophotometry  is usually termed "chemical"  and  is caused
     by  lack  of  absorption  of atoms  bound  in  molecular combination  in the
     flame. This  phenomenon can occur  when the  flame  is not sufficiently hot
     to dissociate the molecule,  as in  the case  of  phosphate  interference with
     magnesium,  or when  the  dissociated atom  is  immediately oxidized  to  a
     compound  that will  not  dissociate further  at  the temperature  of the
     flame. The  addition  of lanthanum will overcome phosphate interference in
     magnesium,  calcium,  and  barium  determinations. Similarly,  silica
     interference  in  the  determination of manganese can be  eliminated by the
     addition of calcium.

          3.1.2  Chemical  interferences may  also  be eliminated by separating
     the metal  from the interfering material. Although  complexing  agents are
     employed primarily  to increase the  sensitivity of the  analysis, they may
     also be used to eliminate or reduce  interferences.
                                 7000 - 2                       Revision 1
                                                                December 1987
-------
      3.1.3  The presence  of high  dissolved  solids in  the sample  may
 result  in  an  interference from  nonatomic  absorbance  such  as  light
 scattering.  If  background correction  is  not available,  a  nonabsorbing
 wavelength should be checked. Preferably,  samples containing high solids
 should be extracted.

      3.1.4  lonization interferences  occur when  the flame temperature is
 sufficiently high to generate the  removal  of an  electron from  a neutral
 atom,  giving a positively  charged ion.  This  type of  interference  can
 generally  be controlled  by  the  addition, to  both standard and sample
 solutions, of a  large  excess (1,000 mg/L) of an easily ionized element
 such as K, Na,  Li  or Cs.

      3.1.5  Spectral  interference can occur when an absorbing wavelength
 of an element present in the sample but not being determined falls within
 the width of the absorption line of the element  of  interest. The results
 of  the  determination will then  be erroneously high,  due  to  the
 contribution of the interfering element to the atomic absorption signal.
 Interference can also occur when resonant energy from another element in
 a multielement lamp, or from a metal impurity in the lamp cathode,  falls
 within the bandpass of the slit setting when that other metal  is present
 in  the  sample.  This  type of interference may   sometimes be reduced by
 narrowing the slit width.

      3.1.6  Samples  and  standards should  be monitored for  viscosity
 differences that may alter the aspiration  rate.

      3.1.7  All  metals  are  not  equally  stable in  the  digestate,
 especially  if  it  contains  only  nitric acid,  not  nitric  acid  and
 hydrochloric acid.   The digestate should be analyzed as soon as possible,
 with preference given to Sn,  Sb,  Mo,  Ba, and Ag.

3.2  Furnace procedure

     3.2.1  Although the  problem  of  oxide formation is  greatly  reduced
with furnace procedures because atomization occurs in an inert atmosphere,
the technique is still subject to chemical  interferences. The composition
of the sample matrix can have a major effect on the  analysis. It is those
effects  which must  be determined  and  taken  into  consideration in  the
analysis of each different matrix encountered. To help verify the absence
of matrix  or chemical  interference,  the  serial   dilution  technique   (see
Step  8.6)  may  be  used.  Those samples which indicate the  presence of
interference should be treated in  one  or more  of the  following ways:

      1.  Successively  dilute  and  reanalyze  the  samples to  eliminate
          interferences.

      2.  Modify the  sample  matrix  either  to remove interferences  or to
          stabilize the  analyte.  Examples  are  the  addition  of ammonium
          nitrate to remove alkali chlorides and   the addition of ammonium
          phosphate to  retain cadmium.   The mixing  of hydrogen  with  the
          inert  purge  gas  has   also  been  used to suppress   chemical


                             7000  -  3                        Revision  1
                                                            December  1987
-------
          interference.  The hydrogen  acts as a reducing agent and aids in
          molecular dissociation.

      3.   Analyze  the  sample by  method  of  standard  additions  while
          noticing the  precautions and  limitations  of its  use  (see Step
          8.7.2).

     3.2.2  Gases  generated  in the  furnace during  atomization  may have
molecular absorption  bands encompassing the  analytical  wavelength. When
this  occurs,  use  either  background correction  or choose  an  alternate
wavelength.  Background  correction may  also  compensate  for nonspecific
broad-band absorption interference.

     3.2.3  Continuum background correction  cannot  correct  for  all types
of  background  interference.  When  the background interference  cannot be
compensated for,  chemically remove  the analyte or  use an  alternate  form of
background correction, e.g., Zeeman background correction.
                                                                      can
                                                                       er
                                                                     Care
     3.2.4  Interference  from  a  smoke-producing  sample  matrix  c;
sometimes  be  reduced  by extending  the  charring  time at  a  high
temperature or utilizing  an ashing cycle  in  the presence of air.   Ca
must be taken,  however, to prevent  loss  of  the analyte.

     3.2.5  Samples containing large amounts  of  organic materials should
be  oxidized by  conventional  acid  digestion  before  being placed  in  the
furnace. In this  way,  broad-band  absorption will  be minimized.

     3.2.6  Anion  interference studies  in   the graphite furnace indicate
that,  under  conditions  other  than  isothermal,  the  nitrate  anion  is
preferred.  Therefore,  nitric acid is  preferable  for any  digestion  or
solubilization  step.   If  another  acid  in  addition to  nitric acid  is
required, a minimum  amount should  be used.  This applies  particularly to
hydrochloric and, to  a lesser  extent, to sulfuric and phosphoric acids.

     3.2.7  Carbide formation  resulting from  the chemical  environment of
the furnace has been  observed.  Molybdenum may  be  cited as an example. When
carbides form, the metal is released very  slowly from the resulting metal
carbide  as  atomization continues.  Molybdenum may  require 30 seconds  or
more  atomization  time before the signal  returns  to  baseline  levels.
Carbide  formation  is  greatly  reduced  and  the sensitivity increased with
the  use of pyrolytically  coated  graphite.  Elements   that  readily form
carbides are noted with the symbol  (p)  in Table 1.

     3.2.8  For comments on spectral interference, see Step 3.1.5.

     3.2.9  Cross-contamination  and  contamination of  the sample  can  be
major sources of error  because of  the extreme sensitivities achieved with
the furnace. The sample preparation work area should be kept  scrupulously
clean.  All  glassware  should be  cleaned as directed  in Step  4.8.   Pipet
tips are a  frequent source  of contamination. If  suspected, they should be
acid soaked with  1:5  nitric acid and  rinsed thoroughly with tap and Type
II water. The  use  of  a better grade  of pipet tip can greatly reduce this
problem.  Special  attention should be given to reagent  blanks  in both

                             7000 - 4                        Revision 1
                                                            December 1987
-------
    analysis and in  the  correction  of analytical  results. Lastly, pyrolytic
    graphite,  because  of  the  production  process  and  handling,  can become
    contaminated.  As  many as  five to  ten high-temperature  burns  may  be
    required to clean the  tube before use.

4.0 APPARATUS AND MATERIALS

    4.1  Atomic  absorption  spectrophotometer  -  Single- or  dual-channel,
single-  or double-beam  instrument  having   a  grating  monochromator,
photomultiplier  detector,  adjustable  slits, a  wavelength range  of 190  to
800 nm, and provisions  for interfacing with a strip-chart recorder.

    4.2  Burner  -   The burner  recommended by  the  particular  instrument
manufacturer should be  used. For certain  elements the  nitrous oxide burner is
required.

    4.3  Hollow  cathode  lamps  -  Single-element  lamps  are  preferred but
multielement lamps  may  be  used.  Electrodeless discharge lamps  may  also be used
when available.

    4.4  Graphite  furnace  -  Any  furnace  device  capable of  reaching the
specified temperatures  is  satisfactory.

    4.5  Strip-chart recorder  -  A  recorder is recommended  for furnace work so
that there will be  a permanent record and that any  problems with  the  analysis
such  as drift,  incomplete atomization,   losses  during  charring,  changes  in
sensitivity, peak shape, etc., can be easily recognized.

    4.6  Pipets - Microliter,  with  disposable tips.  Sizes  can range from 5 to
100 uL as  required. Pipet tips should  be  checked as  a  possible source  of
contamination prior to  their use.

    4.7  Pressure-reducing valves - The supplies  of fuel  and oxidant should be
maintained at pressures somewhat higher than the  controlled operating  pressure
of the instrument by suitable valves.

    4.8  Glassware  - All  glassware, polypropylene,  or  Teflon  containers,
including sample  bottles,  should  be  washed  in  the  following sequence:
detergent, tap water,  1:1  nitric acid, tap  water,  1:1 hydrochloric acid, tap
water, and Type II  water.  (Chromic acid should not be used  as  a  cleaning agent
for glassware if chromium  is to  be  included  in the  analytical scheme.)  If it
can be documented through  an active  analytical  quality  control  program using
spiked samples  and  reagent blanks that certain steps in the cleaning procedure
are not  required for routine samples, those steps may be  eliminated  from the
procedure.

5.0 REAGENTS

    5.1  Reagent grade  chemicals shall be  used in all  tests. Unless otherwise
indicated,  it  is  intended  that  all  reagents  shall  conform   to  the
specifications  of  the Committee  on  Analytical   Reagents of the American
Chemical Society, where such specifications are available.  Other grades may be
used,   provided  it  is first ascertained that the  reagent  is  of  sufficiently

                                7000 - 5                       Revision 1
                                                               December 1987
-------
high  purity  to  permit  its  use without  lessening the  accuracy  of  the
determination.

    5.2  ASTM Type II Water (ASTM D1193-77 (1983)). All references to water in
the method refer to ASTM Type II  unless  otherwise specified.

    5.3  Nitric acid (concentrated),  HN03.   Use a spectrograde acid certified
for AA use. Prepare a 1:1 dilution with water by adding the concentrated acid
to an equal volume of water.

    5.4  Hydrochloric acid (1:1), HC1.   Use a spectrograde acid certified for
AA use. Prepare a  1:1 dilution with  water  by adding  the concentrated acid to
an equal  volume of water.

    5.5  Fuel  and oxidant  -  Commercial   grade  acetylene is  generally
acceptable.  Air may  be  supplied  from a compressed  air line,  a  laboratory
compressor, or  a  cylinder of  compressed air. Nitrous  oxide  is also required
for  certain  determinations. Standard,  commercially  available  argon  and
nitrogen are required for furnace work.

    5.6  Stock  standard metal  solutions  - Stock  standard solutions  are
prepared  from  high  purity  metals,  oxides,  or nonhygroscopic  salts  using
water  and  redistilled nitric  or hydrochloric  acids.  (See individual  methods
for specific instructions.)  Sulfuric or phosphoric acids  should be avoided as
they  produce  an  adverse  effect on  many elements.  The  stock solutions  are
prepared at  concentrations  of 1,000  mg of  the  metal  per liter. Commercially
available  standard solutions may  also  be  used. Where  the  sample  viscosity,
surface tension,  and  components  cannot be accurately matched with standards,
the method of standard addition  (MSA) may be used  (see  Step 8.7).

    5.7  Calibration standards -  For those  instruments  which  do  not read out
directly  in  concentration,   a calibration  curve  is  prepared to  cover the
appropriate  concentration  range.  Usually,  this  means  the  preparation of
standards which produce an absorbance of 0.0 to  0.7.  Calibration standards are
prepared by  diluting the stock  metal  solutions at the time  of analysis. For
best results, calibration standards should be prepared  fresh each time a batch
of  samples  is  analyzed.  Prepare a blank  and  at least three calibration
standards  in  graduated  amounts in  the  appropriate range of the linear part of
the curve. The calibration standards  should  be prepared using  the same type of
acid or combination  of  acids and at  the same concentration as will result in
the samples following processing.  Beginning with the blank and working toward
the highest  standard, aspirate the solutions and  record the  readings. Repeat
the operation with both the calibration standards  and  the  samples a sufficient
number of times  to  secure   a  reliable average  reading for each solution.
Calibration standards for furnace procedures should  be prepared as described
on the individual sheets for that metal.

6.0 SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

    6.1  See the introductory material  in Chapter  Three,  Metallic Analytes.
                                 7000 - 6                        Revision  1
                                                                 December  1987
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7.0 PROCEDURE

    7.1  Preliminary treatment of waste water,  ground water,  EP extracts,  and
industrial  waste is always necessary  because of the complexity and variability
of sample matrices. Solids,  slurries, and suspended material must be subjected
to a solubilization process before analysis.  This process may vary because of
the metals  to  be  determined and  the  nature of  the sample  being  analyzed.
Solubilization and digestion  procedures are presented  in Chapter Three,  Step
3.2,  Sample Preparation Methods.

    7.2  Direct aspiration (flame)  procedure

         7.2.1  Differences  between   the various  makes   and models  of
    satisfactory atomic absorption spectrophotometers prevent the formulation
    of detailed instructions applicable  to  every  instrument. The  analyst
    should follow  the  manufacturer's operating  instructions  for a particular
    instrument. In general, after  choosing the  proper  lamp for the analysis,
    allow the lamp to warm up for  a minimum of 15 minutes, unless operated in
    a double-beam mode. During this period, align the instrument, position the
    monochromator  at the  correct  wavelength,  select  the proper monochromator
    slit  width,  and  adjust the  current  according to the  manufacturer's
    recommendation. Subsequently,  light  the  flame and  regulate the  flow of
    fuel  and  oxidant.  Adjust  the burner and nebulizer  flow  rate for maximum
    percent absorption and stability. Balance the photometer. Run a series of
    standards of the element  under analysis.  Construct a calibration curve by
    plotting the concentrations of the standards against absorbances. Set the
    curve  corrector  of a  direct  reading  instrument to read  out  the proper
    concentration.  Aspirate  the   samples  and  determine the  concentrations
    either directly or from the calibration curve. Standards must be run each
    time a sample or series of samples  is run.

    7.3  Furnace procedure

         7.3.1  Furnace  devices  (flameless  atomization)  are  a  most useful
    means  of  extending  detection  limits.  Because of differences  between
    various  makes and  models  of  satisfactory  instruments,  no  detailed
    operating  instructions  can  be  given  for  each  instrument.  Instead,  the
    analyst should follow  the instructions provided  by  the manufacturer of a
    particular instrument.

         7.3.2  Background correction is  important  when  using  flameless
    atomization, especially below 350 nm. Certain samples, when atomized,  may
    absorb or scatter  light from the lamp.  This can be caused by the presence
    of gaseous molecular species,  salt  particles,  or  smoke  in  the sample beam.
    If no correction is made,  sample  absorbance  will  be  greater  than it should
    be, and the analytical result  will be  erroneously high. Zeeman background
    correction is effective in overcoming composition or structured background
    interferences.  It  is  particularly  useful  when  analyzing  for As  in  the
    presence of Al  and when analyzing for Se  in  the presence of  Fe.

         7.3.3  Memory effects  occur when the analyte  is  not   totally
    volatilized during atomization. This  condition depends  on  several factors:
    volatility of the  element  and its  chemical   form,  whether  pyrolytic

                                 7000 -  7                        Revision 1
                                                                December 1987
-------
graphite  is used,  the  rate  of  atomization,  and  furnace  design.  This
situation is detected  through  blank burns.  The tube should be cleaned by
operating  the furnace at  full  power for  the required  time  period,  as
needed, at regular intervals during the series of  determinations.

     7.3.4  Inject  a  measured  microliter  aliquot of  sample  into the
furnace  and atomize.  If  the  concentration  found  is  greater  than the
highest standard, the sample should be diluted in  the same acid matrix and
reanalyzed. The  use  of multiple  injections  can improve accuracy and help
detect furnace pipetting errors.

     7.3.5  To verify the  absence  of interference,  follow the  serial
dilution procedure given in Step 8.6.

     7.3.6  A  check  standard  should  be  run  after approximately every 10
sample  injections.  Standards  are  run in part  to monitor  the  life and
performance of the  graphite tube. Lack of reproducibility or significant
change  in  the  signal for the  standard indicates  that  the tube  should be
replaced. Tube life  depends on  sample matrix  and  atomization temperature.
A  conservative  estimate would  be  that  a tube  will  last  at  least 50
firings. A  pyrolytic coating  will extend that estimated  life by a  factor
of three.

7.4  Calculation

     7.4.1  For  determination of metal  concentration by  direct  aspiration
and  furnace:   Read  the metal  value  in ug/L from  the calibration curve or
directly from  the read-out system of the instrument.

     7.4.2  If dilution of sample was required:


      ug/L metal in  sample =


where:

     A = ug/L  of metal in diluted aliquot from calibration curve.
     B = Acid  blank  matrix used  for dilution,  mL.
     C = Sample  aliquot, mL.


     7.4.3  For  solid samples, report all concentrations as ug/kg based on
wet  weight. Hence:


     ug metal/kg sample = A x V
                            VI
where:

     A = ug/L  of metal in processed sample from calibration curve.
     V = Final volume of the processed sample, mL.
     W = Weight  of sample, grams.
                             7000 - 8                        Revision 1
                                                             December 1987
-------
         7.4.4  Different injection volumes must  not  be used for samples and
    standards.  Instead,  the  sample  should  be  diluted  and  the  same size
    injection volume  be  used for both  samples  and  standards.  If dilution of
    the sample was required:


         ug/L of metal in sample = Z (_C_±_B)
                                         C

    where:

         Z = ug/L of metal read from calibration curve or read-out system.
         B = Acid blank matrix used for dilution ml.
         C = Sample aliquot, ml.

8.0 QUALITY CONTROL

    8.1  All quality control data should  be maintained  and  available  for easy
reference or inspection.

    8.2  A  calibration curve must be  prepared  each  day with  a  minimum of  a
reagent blank and three standards, verified by use of  at least  a  reagent blank
and one  check standard at  or  near the mid-range. Checks  throughout the day
must be within 20% of original  curve.

    8.3  If  20  or more  samples per  day  are analyzed,  the working  standard
curve must  be verified by running an  additional standard at or  near  the mid-
range every 10 samples.  Checks  must  be within  +  20% of true value.

    8.4  At  least  one spiked matrix  and  one replicate  sample  should  be run
every 20 samples or per analytical batch, whichever is  greater.   At  least one
spiked replicate  sample  should also  be run with each  matrix  type to  verify
precision of the method.

    8.5  Where  the  sample  matrix is so  complex that  viscosity,  surface
tension,  and components  cannot  be  accurately matched with  standards,  the
method of standard addition may be used (see Step 8.7  below).

    8.6  Serial  dilution  - Withdraw from the sample two equal aliquots.  To one
of the aliquots add a known  amount of  analyte and dilute both  aliquots  to the
same  predetermined  volume.  (The dilution volume  should  be  based  on  the
analysis  of the  undiluted  sample.  Preferably,  the  dilution  should  be 1:4,
while keeping in  mind that the diluted value should  be at least 5 times the
instrument detection limit.  Under no circumstances should the dilution be less
than  1:1.)   The diluted  aliquots should then  be analyzed,  and  the  unspiked
results,  multiplied by the dilution  factor,  should be  compared  to the  original
determination. Agreement of  the results  (within  10%)  indicates the absence of
interference. Comparison  of the actual signal  from the spike with the  expected
response  from  the  analyte  in  an aqueous  standard  should  help confirm the
finding from the dilution analysis.

    8.7  Method  of  standard  additions  -  The  standard  addition  technique
involves  adding known amounts  of standard  to one or more aliquots of the
processed sample solution. This technique compensates  for a sample constituent

                                 7000  - 9                        Revision 1
                                                                 December 1987
-------
that  enhances  or  depresses  the  analyte  signal,  thus  producing a  different
slope from that of the calibration standards.  It will  not correct for additive
interferences which cause a baseline shift.

         8.7.1  In  the  simplest  version of  this  technique is  the  single
    addition method,  in  which  two identical  aliquots  of  the  sample  solution,
    each of  volume  Vx,  are taken. To the first (labeled A) is  added  a  known
    volume  Vs  of  a  standard  analyte  solution  of  concentration  Cs.  To  the
    second aliquot (labeled B)  is added the  same volume Vs of the solvent.  The
    analytical  signals of  A and  B  are  measured and corrected for  nonanalyte
    signals. The unknown sample concentration  Cx is  calculated:

                 SBVsCs
         cx =   (SA-SB)VX

    where S/\  and  SB are the  analytical  signals  (corrected for the  blank)  of
    solutions A and B, respectively. Vs  and Cs should  be  chosen  so  that  SA is
    roughly twice SB  on  the average, avoiding excess  dilution of the  sample.
    If a separation or concentration step is used,  the additions  are best made
    first and carried through the entire procedure.

         8.7.2  Improved  results  can  be  obtained by employing  a   series  of
    standard  additions.  Equal  volumes  of the  sample are added to a  series of
    standard  solutions  containing  different known  quantities  of the  test
    analyte,  all diluted to the same volume. For example,  addition 1 should be
    prepared  so that  the resulting concentration  is  approximately  50  percent
    of the expected sample absorbance.  Additions 2 and 3 should be prepared so
    that  the concentrations  are  approximately  100  and  150  percent  of  the
    expected  sample absorbances, respectively. The absorbance of each solution
    is determined and  then  plotted on  the vertical axis of  a  graph, with the
    concentrations of the known standards 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  the  right
    side,  but in  the  opposite direction from the ordinate.  An example  of a
    plot so obtained is  shown  in Figure  1.

         8.7.3  For the  results of this  technique to  be  valid,  the following
    limitations must be  taken  into consideration:

         1.  The  absorbance  plot of  sample  and standards must be  linear over
    the  concentration range  of concern. For best  results,  the slope of the
    plot should be  nearly the same as  the slope  of the standard curve. If the
    slope  is significantly  different  (greater than  20%),  caution  should be
    exercised.

         2.  The  effect  of  the interference should not  vary as the ratio of
    analyte  concentration to  sample  matrix changes,  and the standard addition
    should respond  in a  similar manner as the analyte.

         3.  The  determination  must  be free of  spectral  interference  and
    corrected for nonspecific  background  interference.


                                 7000  -  10                       Revision 1
                                                                 December 1987
-------
    8.8  All quality  control  measures descibed  in  Chapter One  should be
followed.

9.0  METHOD PERFORMANCE

    9.1  See individual methods.

10.0 REFERENCES

1.   Methods for  Chemical  Analysis of  Water and Wastes;  U.S.  Environmental
     Protection  Agency. Office  of Research and Development.  Environmental
     Monitoring and Support Laboratory.  ORD Publication Offices of Center for
     Environmental  Research  Information:    Cincinnati,  OH,  1983;  EPA-
     600/4-79-020.

2.   Rohrbough,  W.6.;  et  al.  Reagent  Chemicals, American  Chemical  Society
     Specifications. 7th ed.; American Chemical  Society: Washington, DC, 1986.

3.   1985 Annual  Book  of ASTM  Standards.  Vol.  11.01; "Standard Specification
     for Reagent Water"; ASTM:  Philadelphia,  PA,  1985; Dl193-77.
                                 7000  -  11                       Revision 1
                                                                December 1987
-------
                            TABLE 1.
              ATOMIC ABSORPTION CONCENTRATION RANGES
Metal
                    Direct Aspiration
Detection Limit  Sensitivity
     (mg/L)         (mg/L)
Furnace Procedurea»c
    Detection Limit
         (ug/L)
Aluminum
Antimony
Arsenic"
Barium
Beryl 1 i urn
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Mercury0"
Molybdenum(p)
Nickel
Osmium
Potassium
Selenium^
Silver
Sodium
Strontium
Thallium
Tin
Vanadium(p)
Zinc
0.1
0.2
0.002
0.1
0.005
0.005
0.01
0.05
0.05
0.02
0.03
0.1
0.002
0.001
0.01
0.0002
0.1
0.04
0.03
0.01
0.002
0.01
0.002
0.03
0.1
0.8
0.2
0.005
1
0.5
--
0.4
0.025
0.025
0.08
0.25
0.2
0.1
0.12
0.5
0.04
0.007
0.05
0.4
0.15
1
0.04

0.06
0.015
0.15
0.5
4
0.8
0.02

3
1
--
0.2
0.1
--
1
1
--
--
1
--
--
— —
1
--
--

2
--
--
--
1
--
4
"
NOTE:  The  symbol  (p)  indicates the  use  of pyrolytic graphite  with  the
       furnace procedure.

a For furnace sensitivity values, consult instrument operating manual.

b Gaseous hydride method.

c The  listed  furnace  values  are those  expected  when  using  a  20-uL
  injection and  normal  gas  flow,  except  in  the  cases  of  arsenic  and
  selenium, where gas interrupt is used.
  Cold vapor technique.
                            7000 - 12
                                              Revision 1
                                              December 1987
-------
                             FIGURE  1.
                     STANDARD ADDITION
                          PLOT
                                                              Concentration
Cone, of
Sample
AddnO
No Addn
Addn 1
Addn of 50%
of Expected
Amount
Addn 2      Addn 3
Addn of 100% Addn of 150%
of  Expected   of Expected
Amount      Amount
                           7000 -  13
                                               Revision 1
                                               December 1987
-------
                           METHOD  7000
                   ATOMIC ABSORPTION METHODS
                       7. 1
                                OO
                             preliminary
                        treatment through
                        eolubl llzat Ion  and
                       dlgaatlon procedure*
                            (Chapter 3.
                           Section 3.2)
7.2. i
  Chooaa end
prepare noliox
 cathode lamp
                                                  7.3.1
       Follow
      operating
   instruction*
fro* Inatrunent
   Manufacturer
7.2.1
   Ad)uat  and
align aqutP«ant
7.2. 1
   Light flame
  and regulate
7.2.1
 Run atandarda
    o
                                                     In)act  and
                                                    •tomlze  part
                                                     of  (ample
                            0
                            7000  -  14
               Revision  1
               December  1987
-------
                            METHOD 7000
                            (Continued)
    O
7.Z.I
      Construct
  • celloration
 curve end  »et
curve corrector
7.8.1
    Aspirate
7.4
   Determine
 concentration
O
                         O
7.3.4

Dilute sample




                   >^ Concentration
                        "Beater then
                         highest
                        standard?
7.3.SI   verify
of int«rf«r«nc«
  using serial
    dilution
   (•ee •.«)
                                                   7.3.61
                        Run • check
                         •tendcrd
                        (     Stoo       1
                             7000  - 15
                                    Revision 1
                                    December 1987
-------
                                 METHOD 7060A

                ARSENIC (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
 .0  SCOPE AND APPLICATION

      1.1   Method  7060  is  an  atomic  absorption  procedure  approved  for
 etermining the concentration of arsenic in wastes, mobility procedure extracts,
 ;oils,  and  ground water.   All  samples  must be  subjected  to  an  appropriate
 issolution step prior to analysis.


 !.0  SUMMARY OF METHOD

      2.1   Prior to analysis  by  Method 7060, samples must be prepared in order
 ,o convert  organic forms of arsenic  to  inorganic forms, to  minimize organic
 nterferences, and to convert  the  sample  to a  suitable solution for analysis.
 'he sample preparation procedure varies depending on  the sample matrix.  Aqueous
 ;amples are subjected to the acid digestion  procedure described  in this method.
 >ludge samples are prepared using the procedure described in Method 3050.

      2.2  Following the appropriate dissolution of the sample, a representative
 liquot of the digestate is spiked  with a  nickel nitrate solution and is placed
 anually or by means of  an automatic sampler into a graphite tube furnace.  The
 sample  aliquot is  then slowly  evaporated  to dryness,  charred  (ashed),  and
 itemized.  The absorption of hollow cathode  or EDL radiation during atomization
 tfill  be proportional  to  the arsenic concentration.  Other modifiers may be used
 'n  place  of  nickel  nitrate   if   the analyst  documents  the  chemical  and
 :oncentration used.

      2.3   The typical  detection limit for water samples using this method is
 1 ug/L.  This detection limit may  not be achievable when analyzing waste samples.


 3.0  INTERFERENCES

      3.1   Elemental arsenic  and many of its compounds are volatile; therefore,
 samples may be subject  to  losses of arsenic during  sample  preparation.   Spike
 samples  and  relevant  standard  reference  materials  should  be processed  to
 determine if the chosen dissolution method  is appropriate.

      3.2   Likewise,  caution  must  be  employed  during  the  selection  of
temperature and  times  for  the dry and char (ash)  cycles.   A  nickel  nitrate
solution  must  be  added  to  all   digestates  prior  to  analysis  to  minimize
volatilization losses during drying and ashing.

      3.3   In addition  to the  normal  interferences experienced during graphite
furnace analysis,  arsenic analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix  components  during atomization.   Arsenic
analysis  is  particularly  susceptible  to  these  problems because  of its  low
analytical wavelength (193.7 nmj.   Simultaneous  background  correction must be
employed  to  avoid erroneously high results.  Aluminum is  a  severe  positive

                                   7060A -  1                      Revision 1
                                                                  November 1992
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Interferent  in  the analysis  of arsenic,  especially  using D2  arc  backgroun
correction.  Zeeman background correction is very useful in this situation.

      3.4   If the analyte  is  not  completely  volatilized  and  removed from th
furnace during atomization,  memory effects will occur.   If this situation i
detected by means of blank  burns,  the  tube should  be  cleaned  by operating th
furnace at full power at regular intervals in the analytical  scheme.


4.0  APPARATUS AND MATERIALS

      4.1   Griffin beaker or equivalent:  250 ml.

      4.2   Class A Volumetric flasks:  10-mL.

      4.3   Atomic absorption spectrophotometer:  Single or dual  channel, single
or  double-beam instrument  having  a  grating monochromator,  photo-multiplie
detector, adjustable slits,  a wavelength range of 190  to 800 nm,  and provision:
for  simultaneous  background  correction  and  interfacing  with  a  strip-char
recorder.

      4.4   Arsenic hollow cathode lamp, or electrodeless  discharge lamp (EDL):
EDLs provide better sensitivity for arsenic analysis.

      4.5   Graphite furnace:  Any graphite furnace device with  the appropriate
temperature and timing controls.

      4.6   Data  systems  recorder:   A  recorder is   strongly  recommended for
furnace work so that there will be  a permanent record  and so that any problems
with the analysis  such as drift, incomplete atomization, losses  during charring,
changes in sensitivity, etc., can easily be recognized.

      4.7   Pipets:  Microliter with disposable  tips.   Sizes can range from
5 to 1,000 uL, as required.


5.0  REAGENTS

      5.1   Reagent water:  Water  should be monitored  for impurities.
All references to water will  refer  to  reagent water.

      5.2   Concentrated nitric acid: Acid should be analyzed to determine levels
of impurities.  If a method blank using the acid is 
-------
grade) or equivalent in 100 mL of reagent water containing 4 g NaOH.  Acidify the
solution with 20 ml concentrated HN03 and dilute to 1 liter (1 ml = 1 mg As).

      5.5   Nickel nitrate solution  (5%):  Dissolve 24.780 g of ACS reagent grade
Ni(N03)26H20 or equivalent in reagent water and  dilute to  100 ml.

      5.6   Nickel nitrate solution  (1%):  Dilute 20 ml of  the 5%  nickel nitrate
to 100 ml with reagent water.

      5.7   Arsenic working standards:  Prepare  dilutions  of  the  stock solution
to be  used as calibration  standards at the time of the  analysis.   Withdraw
appropriate aliquots of the stock solution,  add  concentrated HN03, 30% H202, and
5% nickel  nitrate  solution.   Amounts  added should be representative  of the
concentrations found in the samples.  Dilute to 100 ml with reagent water.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All  samples  must have  been  collected using  a  sampling  plan that
addresses the considerations discussed  in Chapter Nine of this manual.

      6.2   All sample containers must be  prewashed with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Special  containers   (e.g.,  containers  used  for  volatile  organic
analysis) may  have to be  used  if  very volatile  arsenic  compounds  are  to be
analyzed.

      6.4   Aqueous samples must be  acidified to a pH of <2 with nitric acid and
refrigerated prior to analysis.

      6.5   Although waste samples do not need to be refrigerated sample handling
and storage must comply with the  minimum requirements established in  Chapter One.


7.0  PROCEDURE

      7.1   Sample preparation:  Aqueous samples  should be prepared in the manner
described in  Paragraphs  7.1.1-7.1.3.  Sludge-type  samples  should  be prepared
according to Method 3050A.   The  applicability of a sample-preparation technique
to a new  matrix  type must be demonstrated  by analyzing spiked  samples and/or
relevant standard reference materials.

            7.1.1    Transfer  a  known volume of well-mixed  sample  to a 250-mL
      Griffin  beaker or  equivalent;  add  2  mL  of 30%  H202 and  sufficient
      concentrated HN03 to result in an acid concentration of 1% (v/v).  Heat,
      until digestion is complete, at 95°C or until  the volume is slightly less
      than 50 mL.

            7.1.2   Cool and bring back to 50 mL with reagent water.
                                   7060A  -  3                       Revision 1
                                                                  November 1992
-------
            7.1.3   Pipet 5 ml of this digested  solution into a 10-mL volumetric
      flask, add 1  mL  of  the 1% nickel  nitrate solution, and dilute  to  10 ml
      with  reagent  water.    The sample is  now ready  for  injection  into  the
      furnace.

      7.2   The 193.7-nm wavelength line and a background correction system are
required.  Follow the manufacturer's suggestions for all other spectrophotometer
parameters.

      7.3   Furnace parameters suggested by the manufacturer should be employed
as  guidelines.     Because   temperature-sensing   mechanisms   and  temperature
controllers can  vary between  instruments  or  with time,  the validity of  the
furnace parameters  must be periodically confirmed by systematically altering the
furnace parameters  while analyzing a standard.   In this manner,  losses of analyte
due to overly high temperature settings or losses in sensitivity due to  less than
optimum settings can be minimized.  Similar verification of furnace parameters
may be required for complex sample matrices.

      7.4   Inject a measured microliter aliquot of sample into the furnace and
atomize.   If the concentration  found is greater than the highest standard,  the
sample should  be diluted  in  the same acid matrix and  reanalyzed.   The use of
multiple  injections can  improve  accuracy and  help  detect  furnace  pipetting
errors.
8.0  QUALITY CONTROL

      8.1  Refer to section 8.0 of Method 7000.


9.0  METHOD PERFORMANCE

      9.1   Precision and accuracy data  are available in Method 206.2  of Methods
for Chemical Analysis of Water and Wastes.

      9.2  The optimal concentration range for aqueous samples using this method
is  5-100  ug/L.   Concentration  ranges  for non-aqueous  samples  will  vary with
matrix type.

      9.3   The data  shown  in  Table  1  were  obtained from records of state and
contractor laboratories.   The  data are intended to  show the precision of the
combined sample preparation and analysis method.


10.0  REFERENCES

1.    Methods  for Chemical  Analysis of  Water and  Wastes,   EPA-600/4-82-055,
December 1982, Method 206.2.

2.    Gaskill, A., Compilation and Evaluation of RCRA Method  Performance Data,
Work Assignment No. 2,  EPA  Contract  No. 68-01-7075,  September 1986.
                                   7060A - 4                       Revision  1
                                                                   November 1992
-------
                       TABLE 1. METHOD PERFORMANCE DATA
iample                       Preparation                Laboratory
.atrix                         Method                   Replicates
Contaminated soil                3050                  2.0, 1.8 ug/g
)ily  soil                        3050                  3.3, 3.8 ug/g
JBS SRM 1646 Estuarine sediment 3050                  8.1, 8.33 ug/ga
[mission control  dust           3050                  430, 350 ug/g

 Bias of -30 and  -28% from expected, respectively.
                                  7060A  - 5                       Revision 1
                                                                  November 1992
-------
                              METHOD  7060A
        ARSENIC  (ATOMIC ABSORPTION,  FURNACE TECHNIQUE)
        Aqueous

7.1


.1 Iran
•aapla
beaker , add
and

• fer
to
H,0.
cone HNO, ,
heat






                                        7 1  Prepare
                                          •aaple*
                                       according to
                                       M«thod 3050
  712 Cool
 and bring to
  voluae with
 r»ag*nt vatvr
  7.13 Pip.t
 •olution into
  fU.k, add
nick«l nitrata,
    dilut.
7 2  S.t up
initrum«nt
 operating
 paraa>t«r
                        7  3  '
                   Piriodically
                      verify
                      furnac*
                    p»r«m«t«r»
                    7 4 Inj.ct
                    aliquot of
                    •*mpl« into
                     furnae*,
                      atoaii*
                   7 4 Raeord A>
                   concentration
                                         7  4 Dilute
                                         •aapl* and
                                         reanalyze
                       Stop
                        7060A  -  6
                                            Revision  1
                                            November 1992
-------
                                METHOD 7061

                ARSENIC (ATOMIC ABSORPTION.  GASEOUS  HYDRIDE)
1.0  SCOPE AND APPLICATION

     1.1  Method 7061  is  an atomic  absorption  procedure  for determining the
concentration of  arsenic  in wastes, mobility  procedure  extracts,  soils, and
ground water.   Method 7061 is approved only  for  sample  matrices that do not
contain  high concentrations  of  chromium,  copper,  mercury,  nickel,  silver,
cobalt,  and molybdenum.    All  samples must  be subjected  to  an  appropriate
dissolution  step  prior to analysis.   Spiked samples and  relevant  standard
reference materials are employed to  determine the  applicability  of the method
to a given waste.

2.0  SUMMARY OF METHOD

     2.1  Samples are prepared according to  the  nitric/sulfuric  acid  digestion
procedure  described  in this  method (Step  7.1).    Next,  the arsenic in the
digestate is reduced  to the trivalent  form  with tin chloride.    The  trivalent
arsenic is then converted  to a volatile hydride  using hydrogen produced from a
zinc/hydrochloric acid reaction.

     2.2  The volatile hydride is  swept into an argon-hydrogen  flame  located
in the optical  path of an  atomic absorption  spectrophotometer.   The  resulting
absorption of the lamp radiation  is proportional to the arsenic  concentration.

     2.3  The typical  detection limit for  this method is 0.002 mg/L.

3.0  INTERFERENCES

     3.1  High  concentrations  of chromium, cobalt,  copper,   mercury,
molybdenum, nickel,  and silver can  cause analytical  interferences.

     3.2  Traces of nitric  acid left following  the sample work-up can result
in analytical interferences.  Nitric acid  must be distilled  off  by heating the
sample until fumes of sulfer trioxide ($03)  are  observed.

     3.3  Elemental  arsenic and many of its  compounds are  volatile; therefore,
certain samples may be subject to  losses of  arsenic during sample preparation.

4.0  APPARATUS AND MATERIALS

     4.1  Beaker - 100-mL.

     4.2  Electric hot plate.

     4.3  A  commercially  available  zinc  slurry/hydride generator  or  a
generator constructed from the following materials  (see Figure 1):

          4.3.1  Medicine  dropper  - Capable  of fitting into a size "0" rubber
     stopper and delivering 1.5 mL.

                                  7061  - 1                       Revision 1
                                                                 December 1987
-------
          4.3.2  Pear-shaped reaction  flask  -  50-mL, with  two 14/20  necks
     (Scientific Glass  JM-5835  or equivalent).

          4.3.3  Gas inlet-outlet tube  -  Constructed  from  a  micro  cold-finger
     condenser (JM-3325)  by cutting the  portion below  the  14/20 ground-glass
     joint.

          4.3.4  Magnetic  stirrer - To homogenize the zinc slurry.

          4.3.5  Polyethylene  drying  tube  -  10-cm,  filled with  glass  to
     prevent particulate matter from entering the burner.

          4.3.6  Flow meter - Capable of  measuring 1 liter/min.

     4.4  Atomic  absorption  spectrophotometer -  Single or  dual   channel,
single-  or double-beam  instrument having a grating  monochromator,  photo-
multiplier detector, adjustable slits, a wavelength  range  of 190 to 800  nm,
and provisions for interfacing  with a strip-chart recorder.

     4.5  Burner -  Recommended  by  the  particular  instrument  manufacturer  for
the argon-hydrogen flame.

     4.6  Arsenic hollow  cathode lamp or  arsenic electrodeless discharge lamp.

     4.7  Strip-chart recorder.

5.0  REAGENTS

     5.1  Reagent grade chemicals shall be used  in all tests. Unless otherwise
indicated,   it  is  intended  that  all  reagents  shall   conform  to  the
specifications  of  the  Committee  on  Analytical  Reagents  of  the  American
Chemical Society, where such specifications are  available. Other grades may be
used,  provided it  is  first  ascertained  that the reagent is  of sufficiently
high   purity  to  permit  its  use  without  lessening the  accuracy of  the
determination.

     5.2  ASTM Type  II Water  (ASTM D1193-77 (1983)).  All  references to water
in the method refer to ASTM Type II unless otherwise  specified.

     5.3  Nitric  acid  (concentrated),   HN03.   Acid should  be analyzed  to
determine  levels  of impurities.  If a  method blank  is  <  MDL,  the  acid can be
used.

     5.4  Sulfuric  acid  (concentrated),  H2S04.    Acid  should be  analyzed  to
determine  levels  of impurities.  If a  method blank  is  <  MDL,  the  acid can be
used.

     5.5  Hydrochloric acid  (concentrated),  HC1.  Acid  should  be  analyzed to
determine  levels  of impurities.  If a  method blank  is  <  MDL,  the  acid can be
used.
                                  7061  - 2                      Revision 1
                                                                December 1987
-------
     5.6  Diluent - Add 100 ml 18N H2S04 and 400  mL  concentrated  HC1  to 400 ml
water and dilute to a final volume of 1  liter with water.

     5.7  Potassium iodide solution - Dissolve 20 g  KI  in  100  ml  water.

     5.8  Stannous  chloride solution   -  Dissolve  100  g  SnCl2  in  100 ml
concentrated HC1.

     5.9  Arsenic solutions

          5.9.1  Arsenic  standard solution  (1,000  mg/L)  -  Either procure  a
     certified  aqueous standard from a  supplier  and  verify  by comparison  with
     a  second  standard,  or  dissolve  1.320  g  of  arsenic  trioxide  AS203 in
     100 ml  of water containing  4  g NaOH.   Acidify the  solution  with 20 ml
     concentrated HN03 and dilute to 1 liter.

          5.9.2  Intermediate arsenic  solution  -  Pipet  1  ml  stock  arsenic
     solution  into  a 100-mL  volumetric  flask  and  bring to volume with water
     containing 1.5 ml concentrated HNOa/liter (1 mL =  10  ug As).

          5.9.3  Standard arsenic solution  -  Pipet  10  ml  intermediate  arsenic
     solution  into  a 100-mL  volumetric  flask  and  bring to volume with water
     containing 1.5 mL concentrated HN03/liter (1 mL =  1 ug  As).

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All  samples must  have  been  collected using a  sampling plan  that
addresses the considerations discussed in Chapter Nine  of  this manual.

     6.2  All sample  containers must be  prewashed with detergents, acids,  and
water.  Plastic and glass containers are both suitable.

     6.3  Special  containers  (e.g.  containers used for volatile organic
analysis) may  have  to be  used  if very  volatile arsenic  compounds are to be
analyzed.

     6.4  Aqueous samples must be acidified to a  pH  of  < 2 with nitric  acid.

     6.5  Nonaqueous samples  shall  be  refrigerated, when possible,  and
analyzed as soon as possible.

7.0  PROCEDURE

     7.1  Place a  50-mL  aliquot of digested  sample (or,  in  the  case of
analysis of  EP extracts, 50  mL)  of the material to be analyzed in a 100-mL
beaker.   Add  10  mL  concentrated  HN03  and  12 mL  18N  HgSO^    Evaporate  the
sample in the hood on an electric hot plate until white $03  fumes are observed
(a volume of  about  20 mL).   Do not let the  sample  char.  If  charring  occurs,
immediately  turn  off the  heat,  cool,  and  add  an  additional 3 mL  of HN03.
Continue to  add additional  HN03 in order to maintain  an  excess  (as  evidenced
                                  7061 - 3
Revision 1
December 1987
-------
by the  formation  of brown fumes).   Do not  let  the solution darken, because
arsenic may be reduced  and lost.   When the sample remains colorless or straw
yellow  during  evolution of $63  fumes,  the digestion is  complete.   Cool  the
sample,  add about  25  ml  water,  and again  evaporate  until  $63  fumes  are
produced in order to  expel oxides  of nitrogen.   Cool.  Transfer the digested
sample to a 100-mL volumetric flask.  Add  40 ml  of  concentrated HC1  and bring
to volume with water.

     7.2  Prepare  working  standards from  the  standard arsenic  solution.
Transfer 0, 0.5,  1.0,  1.5,  2.0, and  2.5  ml  of standard to  100-mL  volumetric
flasks  and  bring to volume with diluent.   These concentrations will be 0,  5,
10, 15, 20, and 25 ug As/liter.

     7.3  If EP  extracts are being  analyzed or  if  a matrix interference  is
encountered, take the  15-,  20-, and  25-mg/liter  standards and  quantitatively
transfer  25 ml  of each of  these standards into  separate  50-mL  volumetric
flasks.  Add 10 ml of the prepared sample to  each flask.   Bring  to volume  with
water containing 1.5 ml HCl/liter.

     7.4  Add  10 ml of  prepared  sample to  a  50-mL volumetric flask.   Bring  to
volume  with water  containing  1.5  mL  HCl/liter.   This  is  the zero  addition
aliquot.

NOTE:   The  absorbance  from  the  zero  addition  aliquot will   be  one-fifth  that
        produced  by the prepared  sample.   The  absorbance  from  the spiked
        samples will  be one-half  that produced by  the standards  plus the
        contribution from  one-fifth of  the  prepared sample.   Keeping these
        absorbances  in  mind will  assist  in  judging  the  correct dilutions  to
        produce optimum  absorbance.

     7.5  Transfer  a  25-mL portion of the digested sample or standard to the
reaction vessel  and  add 1  mL KI solution.  Add  0.5 mL SnCl2 solution.  Allow
at least 10 minutes for the metal to be reduced to its lowest oxidation  state.
Attach  the  reaction vessel  to  the special gas  inlet-outlet glassware.   Fill
the medicine dropper with 1.50 mL zinc slurry that has been  kept in  suspension
with the magnetic stirrer.   Firmly insert  the  stopper containing  the medicine
dropper into  the  side  neck of  the reaction  vessel.    Squeeze  the bulb  to
introduce  the  zinc  slurry into the sample  or  standard  solution.    The metal
hydride will produce a  peak almost immediately.   After the recorder  pen  begins
to return to the base line, the reaction vessel  can  be removed.

     CAUTION;  Arsine  is very  toxic.   Precautions  must be  taken to  avoid
               inhaling arsine gas.

     7.6  Use  the  193.7-nm  wavelength  and background correction  for the
analysis of arsenic.

     7.7  Follow the  manufacturer's  instructions  for  operating  an argon-
hydrogen flame.   The argon-hydrogen flame is colorless;  therefore,  it may  be
useful  to  aspirate  a low concentration of sodium to  ensure  that  ignition has
occurred.
                                  7061 - 4                       Revision 1
                                                                 December 1987
-------
     7.8  If  the  method  of  standard  additions was  employed,  plot  the
absorbances  of  spiked  samples  and  blank  vs.  the  concentrations.   The
extrapolated value will be one-fifth the  concentration  of the  original  sample.
If the  plot does not result  in a  straight  line,  a nonlinear interference is
present.  This  problem can sometimes  be  overcome  by  dilution or addition of
other reagents if  there  is  some  knowledge about the waste.   If the method of
standard additions was not required, then the concentration can  be part of the
calibration curve.

8.0  QUALITY CONTROL

     8.1  All quality control  data should be maintained and available  for easy
reference or inspection.

     8.2  Calibration curves  must  be composed  of  a minimum of a calibration
blank and three  standards.  A calibration curve should be  made  for every hour
of continuous sample analysis.

     8.3  Dilute samples  if  they  are  more concentrated than the   highest
standard or if they fall  on the plateau of a calibration curve.

     8.4  Employ a minimum of one reagent blank per sample batch to determine
if contamination or any memory effects are occurring.

     8.5  Verify calibration  with  an  independently  prepared  quality  control
reference sample every 10 samples.

     8.6  Run one matrix spiked replicate or one replicate  sample for  every 20
samples  or  per  analytical  batch,  whichever  is more  frequent.   A replicate
sample is a sample brought through  the whole sample  preparation  and analytical
process.

     8.7  The method of  standard additions  shall  be used   for the analysis of
all EP  extracts,  on all  analyses submitted  as  part of a  delisting petition,
and whenever a new sample matrix  is  being analyzed.

     8.8   See  Section 8.0  of Method 7000  for  additional  quality  control
requirements.

9.0  METHOD PERFORMANCE

     9.1  Precision and accuracy  data are available  in  Method  206.3 of Methods
for Chemical Analysis of Water and Wastes.

10.0 REFERENCES

1.   Methods  For Chemical  Analysis  of  Water  and  Wastes, EPA-600/4-82-055,
     December 1982, Method 206.3.
                                  7061  -  5                       Revision 1
                                                                December 1987
-------
2.   Rohrbough,  W.G.;  et  al.  Reagent Chemicals.  American Chemical  Society
     Specifications. 7th ed.; American Chemical Society: Washington, DC,  1986.

3.   1985 Annual  Book of ASTM Standards. Vol.  11.01;  "Standard Specification
     for Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
                                  7061  - 6                       Revision 1
                                                                 December 1987
-------
                                      Figure  1.

Zinc slurry hydride generator apparatus set-up and AAS sample introduction system.
                          Argon
                  Flow Mtter
         JM-3325
       M«dicint
       Dropptr in
       Szt "0"
       Rubbtr
       Stopptr
                                               r—i
JM-5835
                             (Auxiliary Air)


                              Argon (Nebufiztr Air)
                                       7061 - 7
                                                                          Revision 1
                                                                          December 1987
-------
                                          METHOD 7O61

                         ARSENIC  (ATOMIC  ABSORPTION. GASEOUS HrORIOE)
 7. 1  |

       Pl«c«
    •llquot of
digested sample
    In beaker
 7. 1
        When
      digestion
   Is complete.
cool sample: add
 Tyoe II Mater:
evaporate:  cool
      Add cone.
HNOj and HtSO-t:
    evaporate
     sample
                           Turn off heat.
                           cool,  and add
 7.1
     ' Transfer
digested sample
 to flask:  add
   cone. HC1:
Bring to volume
                                                     7.3
       Prepare
     »  Morklng
     standards:
    transfer to
  flasks:  orlng
    to  volume
Continue adding
     HNOj
Are EP eitrects
enalyzed.  or is
 there metrlx
   Interfer-
     ence?
                                                                            7.3
 Teke standards and
transfer part of eecn
 to separate flasks:
 add prepared sample
   to eacn flask;
  bring to volume
                                                       \^
                                             7061  - 8
                             Revision 1
                             December 1987
-------
                                            METHOD  7061

                                    (ATOMIC ABSORPTION. GASEOUS HYORIOE)
                                             (ContInuad)
          Add
   prepereo ••mole
   to flask/  bring
      to volume:
     u*c •• blank
     Introduce
   tine «lurry
   Into sample
   or standard
    solution
    7.S
          Transfer
        » portion
       ot digested
        samole or
       standard to
   reaction vessel
                                                        7.6
        Use
      t93.7-nm
    wavelength
and Background
correction for
    analysis
    7.3
        Add Kl
    solution:  add
    Snd.2 solution
                                                        7.7
        TO
      operate
argon hydrogen
 flame,  folio*
manufacturer*a
  instructions
    7.5
   Reduce metal to
     its lowest
   oxidation state
 7.S
    Attacn reaction
     vessel to qes
    glassware:  fill
medicine droooer wltn
  tine slurry;  Insert
 into reaction vessel
                                                                                  7.8
                                                                                        Plot
                          aosoroances of
                         talked samples.
                           olank vs the
                          concentrations
      Have
 concentration
   Be part of
  calibration
     curve
                                                      f     Stoo       )
                                              7061  -  9
                          Revision 1
                          December 1987
-------
                                 METHOD 7062

         ANTIMONY AND ARSENIC (ATOMIC ABSORPTION,  GASEOUS  BOROHYDRIDE)


1.0  SCOPE AND APPLICATION

      1.1  Method 7062 is an atomic absorption  procedure for determining 1 /jg/l
to 400/yg/L concentrations of antimony and arsenic in wastes, mobility procedure
extracts, soils, and ground water.   Method 7062 is  approved for sample matrices
that contain  up to 4000 mg/L concentrations of cobalt,  copper,  iron, mercury, and
nickel.   A  solid sample can contain up to 40% by weight  of the interferents
before exceeding 4000 mg/L in a digested sample.  All samples including aqueous
matrices must be subjected to an appropriate dissolution step  prior to analysis.
Spiked samples and relevant  standard reference materials are used to determine
the applicability of the method to a given waste.


2.0  SUMMARY OF METHOD

      2.1  Samples are prepared according to the nitric  acid digestion procedure
described  in   Method   3010  for    aqueous  and   extract  samples   and   the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace  AA  option)   for  sediments,  soils, and  sludges.   Excess  peroxide is
removed  by  evaporating   samples to  near dryness  at  the end of  the digestion
followed by degassing the samples upon addition  of urea.  L-cystine is then added
as a masking  agent.   Next, the antimony and arsenic in  the digest are reduced to
the trivalent forms with potassium iodide.  The trivalent antimony and arsenic
are then converted to volatile hydrides using hydrogen produced from the reaction
of the  acidified sample with sodium borohydride  in  a  continuous-flow hydride
generator.

      2.2  The  volatile  hydrides are swept into an air-acetylene flame heated
quartz  absorption  cell   located  in  the optical  path  of an  atomic  absorption
spectrophotometer.    The  resulting  absorption  of  the  lamp  radiation  is
proportional  to the arsenic  or antimony concentration.

      2.3  The typical detection limit for this method is 1.0 jjg/l.


3.0  INTERFERENCES

      3.1   Very  high (>4000  mg/L)  concentrations of cobalt,  copper,  iron,
mercury, and  nickel  can  cause analytical interferences through precipitation as
reduced metals and associated blockage of transfer lines and fittings.

      3.2  Traces of peroxides left following the sample work-up can result in
analytical interferences.  Peroxides must  be removed by evaporating each sample
to near dryness followed by reaction with  urea  and  allowing sufficient time for
degassing before analysis (see Sections 7.1 and 7.2).

                                    7062-1                        Revision 0
                                                                  November  1992
-------
4.0  APPARATUS AND MATERIALS

      4.1  Electric hot  plate:   Large enough to hold at least  several  100 mL
Pyrex digestion beakers.

      4.2   A  continuous-flow hydride  generator:    A commercially  available
continuous-flow  sodium  borohydride/HCl  hydride  generator  or  a  generator
constructed similarly  to  that shown in Figure 1 (P. S. Analytical or equivalent).

            4.2.1  Peristaltic Pump:  A four-channel, variable-speed peristaltic
      pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
      or equivalent).   Pump speed and tubing diameters should  be  adjusted to
      provide  the  following  flow rates:    sample/blank  flow  = 4.2  mL/min;
      borohydride flow =2.1 mL/min;  and potassium iodide flow = 0.5 mL/min.

            4.2.2  Sampling Valve (optional):     A sampling valve (found in the
      P. S.  Analytical  Hydride  Generation  System or equivalent)  that  allows
      switching between samples and blanks (rinse solution) without introduction
      of air into the system will provide more signal stability.

            4.2.3  Transfer Tubing and Connectors:  Transfer tubing  (1 mm I.D.),
      mixing T's, and connectors  are  made of teflon and are of compatible sizes
      to  form tight,  leak-proof connections  (Latchat,  Technicon,  etc.  flow
      injection apparatus accessories or equivalent).

            4.2.4  Mixing Coil:   A 20-turn coil made by wrapping transfer tubing
      around a 1-cm diameter  by  5-cm long plastic or glass rod (see Figure 1).

            4.2.5  Mixing Coil Heater:  A 250-mL Erlenmeyer  flask  containing 100
      mL of water heated to boiling on a dedicated one-beaker hotplate (Corning
      PC-35 or equivalent).  The  mixing  coil in 4.2.4  is  immersed  in the boiling
      water  to speed  kinetics of the hydride  forming  reactions and increase
      solubility of interfering  reduced metal precipitates.

            4.2.6   Gas-Liquid Separator:   A glass   apparatus  for collecting
      liquid  and gaseous  products  (P.T. Analytical   accessory  or  equivalent)
      which allows the  liquid fraction  to drain to waste and gaseous products
      above the liquid to be swept by  a regulated carrier gas (argon)  out of the
      cell for analysis.   To avoid  undue carrier gas dilution,  the gas volume
      above the liquid should not exceed 20 mL.   See  Figure  1 for an acceptable
      separator  shape.

            4.2.7  Condensor:   Moisture picked  up by the  carrier  gas must be
      removed  before  encountering the hot absorbance cell.   The moist carrier
      gas with the hydrides is dried  by  passing the gasses through a small  (< 25
      mL) volume condenser coil  (Ace Glass Model 6020-02 or  equivalent) that is
      cooled to 5°C by a water chiller (Neslab  RTE-110 or equivalent).   Cool tap-
      water  in place of  a  chiller is  acceptable.


                                     7062-2                        Revision 0
                                                                  November 1992
-------
           4.2.8  Flow Meter:  A meter capable of regulating up to 1 L/min of
     argon carrier gas is recommended.

     4.3  Absorbance Cell:   A 17 cm or longer quartz tube T-cell  (windowless is
trongly suggested) is recommended,  as  shown in Figure 1 (Varian Model VGA-76
ccessory or equivalent).  The cell  is held in place  by a holder  that positions
he  cell  about  1  cm over  a conventional AA air-acetylene burner head.   In
peration, the cell is heated  to around 900°C by an air-acetylene flame.

     4.4  Atomic absorption  spectrophotometer:  Single or dual channel,  single-
r  double-beam  instrument   having  a  grating  monochromator,  photomultiplier
etector, adjustable slits, a wavelength range of 190 to 800 nm,  and provisions
or  interfacing with a strip-chart recorder.

     4.5  Burner: As recommended by the particular instrument manufacturer for
n air-acetylene flame.  An appropriate mounting bracket attached to the burner
hat suspends the quartz absorbance cell between 1  and 2 cm above the burner slot
s required.

     4.6   Antimony  and  arsenic hollow cathode  lamps or antimony and  arsenic
lectrodeless discharge lamps and  power supply.  Super-charged  hollow-cathode
amps or EDL lamps are recommended for maximum sensitivity.

     4.7    Strip-chart  recorder   (optional):         Connect   to  output  of
pectrophotometer.


i.O  REAGENTS

     5.1   Reagent water:   Water must be  monitored  for impurities.   Refer to
:hapter 1 for definition of  Reagent water.

     5.2  Concentrated nitric acid (HN03):  Acid  must be analyzed to determine
evels of impurities.  If a  method blank  is  
-------
                                  QUARTZ  CELL


                                  ft ft  OURNER
                                                                        TO
                                                                     CHILLER
    '•DISCONNECTED
     OUR INO S«/Sn
    .  nriALYSis
                                                                OAS/LIQUIO
                                                                 SEPARATOR
                                                                    —» DRAIN
                          20 TURN COIL
                            (TEFLON)
                            HOTPLATE-
                            VALUE
                           (BLANK)
Figure 1.  Continuous-flow sodium borohydride/hydride generator apparatus  set-
up and an AAS sample  introduction system.
                                     7062-4
                                                                   Revision 0
                                                                   November 1992
-------
      5.5  Diluent solution:  A 3% HC1  solution in reagent water must be prepared
as a diluent solution if excessive levels  of  analytes or  interfering metals are
found in the undiluted samples.

      5.6  Urea (H2NCONH2):  A 5.00-g portion of reagent grade urea must be added
to  a  25-mL  aliquot of  each sample  for  removal  of  excess  peroxide  through
degassing  (see Section 7.2).

      5.7  L-cystine (C6H12N204S2):  A  1.00-g portion of reagent grade L-cystine
must be  added  to  a  25-mL aliquot of  each  sample for masking the  effects of
suppressing transition metals (see Section 7.2).

      5.8  20% Potassium iodide (KI):   A 20%  KI  solution  (20 g reagent-grade KI
dissolved  and  brought to  volume  in 100 ml reagent water) must be prepared for
reduction  of antimony and arsenic  to their +3 valence states.

      5.9  4% Sodium borohydride (NaBHJ:  A 4%  sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water) must  be prepared  for  conversion of  the antimony and  arsenic  to their
hydrides.

      5.10 Analyte solutions:

            5.10.1  Antimony and arsenic stock standard solution (1,000 mg/L):
      Either  procure  certified  aqueous   standards  from   a  supplier  (Spex,
      Inorganic Ventures, or equivalent) and  verify by comparison with a second
      standard, or dissolve  1.197  g  of antimony trioxide Sb203 and  1.320 g of
      arsenic  trioxide  As203  in  100  ml of reagent water containing  4  g NaOH.
      Acidify the solution with 20 ml concentrated HN03 and dilute  to 1  liter.

            5.10.2   Intermediate  antimony and  arsenic  solution:   Pipet  1 ml
      stock antimony  and  arsenic solution into a  100-mL  volumetric flask and
      bring  to  volume  with  reagent  water  containing  1.5  ml  concentrated
      HN03/liter (1 ml = 10 jjg each of Sb  and As).

            5.10.3   Standard  antimony and  arsenic  solution:    Pipet   10 ml
      intermediate antimony and arsenic solution into a 100-mL volumetric flask
      and  bring  to volume with  reagent water containing  1.5  ml concentrated
      HN03/liter (1 ml = 1 /yg each of Sb and  As).


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   All samples must  have been collected  using  a  sampling  plan  that
addresses  the considerations discussed in  Chapter Nine of this manual.

      6.2  All  sample containers must be prewashed with detergents,  acids, and
reagent water.   Plastic and glass  containers are both suitable.

                                    7062-5                        Revision 0
                                                                  November  1992
-------
      6.3   Special  containers  (e.g.,  containers  used  for volatile  organic
analysis) may have  to be used if very volatile antimony and arsenic compounds are
suspected to be present in the samples.

      6.4  Aqueous samples must be acidified to a pH of <2  with nitric acid.

      6.5  Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.


7.0  PROCEDURE

      7.1  Place a 100-mL portion  of  an aqueous  sample or extract or 1.000 g of
a dried solid sample in a 250-mL digestion beaker.   Digest  aqueous samples and
extracts according to Method 3010.   Digest  solid samples according to Method 3050
(furnace AA option) with the following modifications:  add 5 ml of concentrated
hydrochloric  acid  just prior to  the  final volume  reduction  stage to  aid in
antimony recovery; the  final volume reduction should be to less than 5 ml but not
to dryness  to adequately remove  excess  hydrogen peroxide   (see  note).   After
dilution to volume, further dilution with diluent may be necessary if analytes
are known to exceed 400 jjg/l or if interferents are expected  to exceed 5000 mg/L
in the digest.

Note:  For  solid  digestions,  the  volume reduction  stage  is  critical  to obtain
accurate  data,  especially for  arsenic.   Close  monitoring  of each  sample is
necessary when this critical stage is  reached.

      7.2  Prepare samples for hydride  analysis by adding 5.00  g  urea,  1.00 g L-
cystine, and 20 mL concentrated HC1 to a  25-mL aliquot of digested sample in a
50-mL volumetric flask.  Heat in a water bath  until the L-cystine has dissolved
and  effervescence  has  subsided   (At  least  30  minutes   is  suggested.    If
effervescense is still  seen, repeat step 7.1 with more volume  reduction.).  Bring
flask to volume with reagent water before  analyzing.  A 1:1 dilution correction
must be made  in the  final concentration calculations.

      7.3   Prepare working  standards  from the  standard antimony  and arsenic
solution.   Transfer 0, 0.5, 1.0,  1.5, 2.0,  and 2.5 mL of  standard  to 100-mL
volumetric  flasks  and  bring to volume  with diluent.  These concentrations will
be 0, 5,  10,  15, 20, and  25/yg Sb and As/liter.

      7.4   If EP  extracts  (Method  1310)  are being  analyzed  for arsenic,  the
method  of  standard  additions must  be  used.    Spike  appropriate amounts of
intermediate  or standard  antimony and  arsenic solution to three 25 mL aliquots
of each  unknown.   Spiking volumes should be  kept less  than 0.250 mL to avoid
excessive spiking  dilution errors.

      7.5   Set up  instrumentation  and hydride  generation  apparatus  and  fill
reagent containers.  The sample  and blank  flows should be  set around 4.2 mL/min,
the borohydride flow around 2.1 mL/min, and the potassium iodide  flow around 0.5
mL/min.  The argon carrier gas flow is adjusted to about 200 mL/min. For the AA,

                                     7062-6                        Revision  0
                                                                  November 1992
-------
use the 217.6-nm wavelength and 0.7-nm slit width without background correction
if analyzing for antimony.   Use the  193.7-nm wavelength  and 0.7-nm slit width
without background correction for the analysis of arsenic.   Begin all flows and
allow 10 minutes for warm-up.

      7.6  Place sample feed  line into a prepared sample solution and start pump
to begin  hydride  generation.   Wait  for  a maximum steady-state signal  on the
strip-chart recorder  or output meter.   Switch to  blank sample and  watch for
signal to decline to baseline before  switching to the next sample and beginning
the next analysis.  Run standards first  (low to high),  then unknowns.  Include
appropriate QA/QC solutions,  as required.   Prepare calibration curves and convert
absorbances to concentration.  See following analytical  flowchart.

        CAUTION:  The  hydrides  of  antimony  and  arsenic  are  very  toxic.
                  Precautions must be taken to avoid inhaling the gas.

      7.7  If the method of  standard additions was employed, plot the measured
concentration  of  the  spiked samples  and unspiked  sample  versus  the  spiked
concentrations.  The spiked  concentration axis intercept will be the method of
standard additions  concentration.   If the plot does not result  in a straight
line,  a  nonlinear  interference  is  present.   This  problem can  sometimes  be
overcome by dilution or addition of  other reagents  if there is some knowledge
about the waste.   If the method of standard additions  was not required, then the
concentration is determined  from a standard calibration  curve.


8.0  QUALITY CONTROL

      8.1  See section 8.0 of Method 7000.
9.0  METHOD PERFORMANCE

      9.1  The relative standard deviations  obtained by a single laboratory for
7 replicates of a contaminated soil were 18%  for antimony at  9.1  ug/L in solution
and 4.6% for arsenic at 68 ug/L in solution.


10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of  Water  and Wastes,  EPA-600/4-82-055,
      December 1982, Method 206.3.

2.    "Evaluation of Hydride Atomic Absorption  Methods  for Antimony,  Arsenic,
      Selenium, and Tin",  an  EMSL-LV internal report under Contract 68-03-3249,
      Job Order  70.16,  prepared  for T.  A.  Hinners by D.  E.  Dobb, and  J.  D.
      Lindner of Lockheed Engineering and Sciences Co.,  and L.  V.  Beach of the
      Varian Corporation.
                                    7062-7                        Revision 0
                                                                  November 1992
-------
                                 METHOD  7062
ANTIMONY  AND  ARSENIC  (ATOMIC  ABSORPTION, GASEOUS  BOROHYDRIDE)
     7 1 Ui«  Method
      30SO (furnace
      AA option) to
      digest  1  0 g
         sample
         7  1-7  4
       Digest with
         H,0. as
      described in
       Method 3050
         7  5  Add
      concentrated
           HC1
      7 6 Do  final
         v o 1 ume
      reduction and
      dilution, ai
        described
       7 1 Further
       dilute with
         diluent
                            7 1 Use
                          Method 3010
                         to digest  100
                           ml sample
  7.2  Add to
 aliquot urea,
L-cyatine, HC1;
heat H,0 bath;
bring  to volume
  7 3  Prepare
standards from
standard stock
solution* of Sb
    and As
                                7 4 Spike 3
                               tliquots with
                                 working
                                standard Se
                                solution
7.5-7.6 Analyis
  the sample
 using hybrid
  generation
   apparatus
                               7  7 Determine
                              Sb  and As cone
                               from standard
                               calibration
                                  curve
                          7 4 Use the
                           method of
                           standard
                         additions on
                        extracts,  only
                        7 5-7 6 Analyze
                          the sample
                         using hybrid
                          generation
                           apparatus
 7 7  Determine
   Sb and As
concentrations
  from linear
     plot
                                  Stop
                                   7062-8
                                             Revision 0
                                             November  1992
-------
                                 METHOD 7080A

                 BARIUM (ATOMIC  ABSORPTION,  DIRECT ASPIRATION)


1.0  SCOPE AND APPLICATION

      1.1   See Section 1.0 of Method 7000.


2.0  SUMMARY OF METHOD

      2.1   See Section 2.0 of Method 7000.


3.0  INTERFERENCES

      3.1   See Section 3.0 of Method 7000 if interferences are suspected.

      3.2   High hollow cathode  current settings and a narrow spectral band pass
must  be  used,  because  both  barium  and  calcium  emit  strongly  at  barium's
analytical wavelength.

      3.3   Barium  undergoes  significant   ionization  in  the  nitrous  oxide/
acetylene flame, resulting in a significant decrease in sensitivity.  All
samples and standards must contain a ionization suppressant.  Type of
suppressant and concentration must be documented.


4.0  APPARATUS AND MATERIALS

      4.1   For basic apparatus, see Section 4.0 of Method 7000.

      4.2   Instrument parameters (general):

            4.2.1  Barium hollow cathode lamp.
            4.2.2  Wavelength:  553.6 nm.
            4.2.3  Fuel:  Acetylene.
            4.2.4  Oxidant:  Nitrous oxide.
            4.2.5  Type of flame:  Fuel rich.
            4.2.6  Background correction:  Not required.


5.0  REAGENTS

      5.1   See Section 5.0 of Method 7000.

      5.2   Preparation of standards:

            5.2.1    Stock  solution:    Dissolve  1.7787  g  barium  chloride
      (BaCl22H20)  analytical reagent  grade in reagent water  and  dilute to 1
                                   7080A -  1                       Revision 1
                                                                  November  1992
-------
      liter (1000 mg/L).   Alternatively,  procure a certified  standard  from a
      supplier and verify by comparison with a second standard.

            5.2.2    Prepare  dilutions of  the  stock solution  to be used  as
      calibration standards at the time of analysis.  The calibration standards
      should  be  prepared   using   the  same  type  of acid   and   at  the  same
      concentration  as  will   result  in  the  sample  to  be  analyzed  after
      processing.  All   calibration   standards and  samples  should contain the
      ionization suppressant.   KC1 is detailed in Section 5.2.3.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See Chapter Three, Section 3.1.3, Sample Handling and Preservation.


7.0   PROCEDURE

      7.1   Sample preparation: The procedures for preparation of the  sample are
given in Chapter Three, Section 3.2.

      7.2   See Method 7000, Section 7.2, Direct Aspiration.


8.0  QUALITY CONTROL

      8.1   See Section 8.0 of Method  7000.


9.0  METHOD PERFORMANCE

      9.1   The performance characteristics  for an aqueous sample free of inter-
ferences are:

      Optimum concentration range:   1-20 mg/L with a wavelength of 553.6 nm.
      Sensitivity:  0.4 mg/L.
      Detection limit:  0.1 mg/L.

      9.2   In a single laboratory, analysis  of a mixed industrial-domestic waste
effluent, digested with Method 3010,  at concentrations of 0.4 and 2 mg Ba/L gave
standard deviations  of +0.043 and +0.13,  respectively.   Recoveries at these
levels were 94% and 113%, respectively.


10.0  REFERENCES

1.    Methods  for Chemical Analysis  of  Water  and  Wastes,  EPA-600/4-82-055,
December 1982, Method  208.1.
                                   7080A - 2                      Revision  1
                                                                  November 1991
-------
                   METHOD 7080A
BARIUM (ATOMIC ABSORPTION,  DIRECT ASPIRATION)
                    Start
                  5 0 Prapara
                   •tandarda
                7 1 For sample
                preparation «ee
               Chapter 3, Section
                     3 2
                7 2 Analyze using
                 Method 7000
                  Section 7 2
                    Stop
                  7080A  -  3
Revision  1
November 1992
-------
                                 METHOD 7131A

                CADMIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)


1.0  SCOPE AND APPLICATION

      1.1   See Section 1.0 of Method 7000.


2.0  SUMMARY OF METHOD

      2.1   See Section 2.0 of Method 7000.


3.0  INTERFERENCES

      3.1   See Section 3.0 of Method 7000 if interferences are suspected.

      3.2   In addition to the normal  interferences experienced during graphite
furnace analysis,  cadmium  analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Simultaneous
background correction is required to avoid erroneously high results.

      3.3   Excess  chloride  may  cause premature  volatilization  of  cadmium.
Ammonium  phosphate used  as  a  matrix modifier  minimizes  this  loss.   Other
modifiers may be used as long as it is documented with the type of suppressant
and concentration.

      3.4   Many  plastic  pipet  tips  (yellow) contain cadmium.   Use "cadmium-
free" tips.


4.0  APPARATUS AND MATERIALS

      4.1   For basic apparatus, see Section 4.0 of Method 7000.

      4.2   Instrument parameters (general):

            4.2.1   Drying time and temp:  30 sec at 125°C.

            4.2.2   Ashing time and temp:  30 sec at 500°C.

            4.2.3   Atomizing time and temp:  10 sec at 1900°C.

            4.2.4   Purge gas:  Argon.

            4.2.5   Wavelength:  228.8 nm.

            4.2.6   Background correction:  Required.

            4.2.7   Other  operating parameters should be set  as specified by the
      particular  instrument manufacturer.


                                   7131A  - 1                       Revision 1
                                                                  November 1992
-------
      NOTE:  The above concentration values and instrument conditions are for a
            Perkin-Elmer HGA-2100,  based  on  the  use  of  a 20-uL  injection,
            continuous-flow purge gas, and nonpyrolytic  graphite.  Smaller sizes
            of furnace devices or  those  employing  faster rates  of atomization
            can be operated  using  lower atomization temperatures  for shorter
            time periods than the above-recommended settings.


5.0  REAGENTS

      5.1   See Section 5.0 of Method 7000.

      5.2   Preparation of standards:

            5.2.1     Stock  solution:    Dissolve  1.000  g  of  cadmium  metal
      (analytical reagent grade)  in 20 ml of 1:1 HN03 and  dilute to 1 liter with
      reagent  water.    Alternatively,   procure  a  certified  standard from  a
      supplier and verify by comparison with a second standard.

            5.2.2   Prepare dilutions of the stock cadmium solution to be used
      as calibration  standards  at the  time  of analysis.   To each 100  mi of
      standard and sample alike add 2.0 ml of the ammonium phosphate solution.
      The calibration standards should be prepared to contain 0.5% (v/v) HN03.

            5.2.3     Ammonium phosphate  solution   (40%):    Dissolve  40 g  of
      ammonium phosphate,  (NH4)2HP04 (analytical reagent grade), in reagent water
      and dilute to 100 ml.
6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See Chapter Three,  Section 3.1.3, Sample Handling and Preservation.


7.0  PROCEDURE

      7.1   Sample preparation:  The procedures  for preparation of the sample are
given in Chapter Three, Section 3.2.

      7.2   See Method 7000,  Paragraph 7.3,  Furnace Procedure.  The calculation
is given in Method 7000, Paragraph 7.4.


8.0  QUALITY CONTROL

      8.1   See Section 8.0 of Method 7000  .


9.0  METHOD PERFORMANCE

      9.1   Precision and accuracy data are  available in Method 213.2 of Methods
for Chemical Analysis of Water and Wastes.
                                   7131A -  2                      Revision 1
                                                                  November 1992
-------
      9.2   The performance characteristics for an aqueous sample  free of inter-
ferences are:

      Optimum concentration range:  0.5-10 ug/L.
      Detection limit:  0.1 ug/L.

      9.3   The data shown  in Table  1 were obtained  from records of state and
contractor laboratories.   The data are  intended to  show  the  precision  of the
combined sample preparation and analysis method.


10.0  REFERENCES

1.    Methods  for Chemical Analysis of  Water  and  Wastes,  EPA-600/4-82-055,
December 1982, Method 213.2.

2.    Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No.  68-01-7075, September 1986.
                                   7131A  - 3                       Revision 1
                                                                  November 1992
-------
                       TABLE 1. METHOD PERFORMANCE DATA
Sample                      Preparation             Laboratory
Matrix                        Method                Replicates
Lagoon soil                     3050           0.10, 0.095 ug/g

NBS SRM 1646 Estuarine sediment 3050                  0.35 ug/ga

Solvent extract of oily waste   3030            1.39, 1.09 ug/L



"Bias of -3% from expected value.
                                   7131A - 4                       Revision 1
                                                                   November 1992
-------
                    METHOD  7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE  TECHNIQUE)
                     Start
                   5  0 Pr«p»r«
                   >tandard*
                 7 1  For sample
                 preparation see
               Chapter 3,  Section
                      3 2
                7 2 Analyze using
                  Method 7QOO
                   Section 7 3
                     Stop
                    7131A - 5
Revision  1
November 1992
-------
                                METHOD 7196

                    CHROMIUM. HEXAVALENT (COLORIMETRIC)
1.0  SCOPE AND APPLICATION

     1.1  Method  7196  is  used to  determine  the concentration  of dissolved
hexavalent  chromium  [Cr(VI)]   in  Extraction  Procedure  (EP)  toxicity charac-
teristic extracts and  ground  waters.   This method may  also  be applicable to
certain domestic  and  industrial  wastes,  provided  that  no  interfering
substances are present  (see Step 3.1 below).

     1.2  Method 7196 may be used to analyze samples  containing  from 0.5 to
50 mg of Cr(VI) per liter.

2.0  SUMMARY OF METHOD

     2.1  Dissolved hexavalent chromium,  in the  absence  of  interfering amounts
of  substances  such  as molybdenum,  vanadium,  and mercury, may be determined
colorimetrically by reaction with diphenylcarbazide  in acid solution.  A red-
violet  color  of  unknown  composition is  produced.    The reaction  is  very
sensitive, the  absorbancy  index  per gram atom of chromium being  about 40,000
at  540  nm.   Addition  of an excess of diphenylcarbazide yields  the red-violet
product, and its absorbance is measured  photometrically  at  540  nm.

3.0  INTERFERENCES

     3.1  The  chromium  reaction  with diphenylcarbazide is usually free from
interferences.    However,  certain  substances may  interfere   if the  chromium
concentration is relatively low.   Hexavalent molybdenum  and mercury salts also
react  to  form  color  with  the reagent;  however, the  red-violet  intensities
produced  are  much  lower  than those  for chromium  at   the   specified  pH.
Concentrations of up to  200 mg/L of molybdenum  and  mercury can be tolerated.
Vanadium  interferes strongly, but  concentrations  up  to 10  times  that of
chromium will not cause trouble.

     3.2  Iron  in concentrations greater  than  1 mg/L  may produce  a yellow
color,  but the ferric iron  color is not strong and difficulty  is  not normally
encountered  if  the  absorbance  is measured photometrically at the  appropriate
wavelength.

4.0  APPARATUS AND MATERIALS

     4.1  Colorimetric equipment -  One of the  following  is  required:  Either a
spectrophotometer,  for  use at  540  nm,  providing a light path  of  1  cm or
longer, or a  filter photometer,  providing  a light  path  of 1  cm or longer and
equipped  with  a greenish-yellow filter   having  maximum   transmittance  near
540 nm.
                                  7196 -  1                       Revision 1
                                                                December 1987
-------
5.0  REAGENTS

     5.1  Reagent grade chemicals  shall  be  used  in all tests. Unless otherwise
indicated,  it  is  intended  that  all   reagents  shall  conform  to  the
specifications  of the  Committee  on Analytical  Reagents  of the  American
Chemical Society, where such specifications  are  available. Other grades may be
used, provided  it  is  first  ascertained that  the reagent  is  of sufficiently
high  purity to  permit  its  use without lessening  the accuracy of  the
determination.

     5.2  ASTM Type II Water  (ASTM  D1193-77 (1983)). All  references to water
in the method refer to ASTM Type II  unless  otherwise specified.

     5.3  Potassium dichromate  stock  solution  -  Dissolve  141.4 mg  of dried
potassium dichromate,  K2Cr20y,  in water and dilute  to 1 liter  (1  ml = 50 ug
Cr).

     5.4  Potassium dichromate  standard solution  -  Dilute  10.00 ml potassium
dichromate stock solution to 100 ml  (1 ml  = 5  ug Cr) .
     5.5  Sulfuric  acid  ((10%)  (v/v)),  ^SO/j.    Dilute  10 ml  of distilled
reagent grade or spectrograde quality H2S04 to  100  ml with water.

     5.6  Diphenylcarbazide solution  -  Dissolve  250 mg 1,5-diphenylcarbazide
in 50 ml acetone.  Store in a brown bottle.  Discard when the solution becomes
discolored.
     5.7  Acetone,  CHsCOCHs.   Avoid  or  redistill  material  that  comes in
containers with metal or metal -lined caps.

6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

     6.1  All  samples must  have  been collected  using  a  sampling  plan  that
addresses the considerations discussed in Chapter Nine of  this manual.

     6.2  Since  the  stability  of  Cr(VI)  in  EP extracts  is  not completely
understood  at  this time,  the  analysis  should be  carried  out as  soon as
possible.

     6.3  To retard the chemical activity  of hexavalent chromium, the samples
and extracts should be stored at 4°C until  analyzed.  The  maximum holding  time
prior to analysis is 24 hours.

7.0  PROCEDURE

    7.1  Color development and measurement - Transfer 95 mL of the extract to
be tested to a 100-mL volumetric flask.   Add  2.0 mL diphenylcarbazide solution
and mix.   Add H2S04 solution to give a pH of  2 +  0.5,  dilute to 100 mL  with
water, and let  stand  5 to  10  minutes  for  full  color development.  Transfer an
appropriate portion of the solution to a  1-cm  absorption cell and measure its
absorbance  at 540  nm.   Use  water as a  reference.   Correct  the absorbance
reading of the sample by subtracting the  absorbance of a blank carried through
the method (see Note below).   An aliquot  of the sample containing all reagents

                                  7196 -  2                       Revision  1
                                                                 December  1987
-------
except  diphenyl  semicarbazide  should  be  prepared and  used  to  correct  the
sample for turbidity (i.e.  a  turbidity blank).  From the corrected absorbance,
determine the mg/L  of chromium present by reference to the calibration curve.

NOTE: If the solution is turbid after dilution to  100 ml  in  Step 7.1,  above,
      take  an  absorbance  reading before  adding  the  carbazide  reagent  and
      correct  the  absorbance  reading  of the  final  colored  solution  by
      subtracting the absorbance measured previously.

    7.2  Preparation of  calibration curve

         7.2.1   To  compensate for possible slight losses  of  chromium  during
    digestion  or  other operations  of the  analysis,  treat  the  chromium
    standards  by the same  procedure as  the sample.   Accordingly, pipet  a
    chromium  standard  solution  in  measured volumes  into 250-mL  beakers  or
    conical flasks   to  generate standard concentrations   ranging  from  10  to
    200 ug/L Cr(VI)  when diluted to the  appropriate volume.

         7.2.2   Develop the color  of  the standards  as for the  samples.
    Transfer a suitable  portion of each colored solution to a 1-cm absorption
    cell  and measure the  absorbance at 540  nm.   As reference,  use  water.
    Correct  the absorbance  readings  of the  standards  by  subtracting  the
    absorbance of  a reagent blank carried  through the  method.   Construct  a
    calibration curve by plotting corrected absorbance values against mg/L of
    Cr(VI).

    7.3  Verification

         7.3.1   For  every  sample matrix analyzed, verification is required to
    ensure  that neither a  reducing  condition  nor chemical  interference  is
    affecting  color  development.   This  must  be  accomplished  by  analyzing  a
    second 10-mL aliquot of the  pH-adjusted  filtrate that  has been spiked with
    Cr(VI).  The amount of spike  added  should  double the concentration found
    in the original  aliquot.   The  increase  must be  > 30 ug  Cr(VI)/L. To verify
    the absence of an interference, the  spike recovery must be between 85% and
    115%.

         7.3.2   If  addition  of  the spike extends the concentration beyond the
    calibration  curve,   the  analysis solution should  be  diluted  with  blank
    solution and the calculated  results  adjusted  accordingly.

         7.3.3   If the result  of  verification  indicates  a  suppressive
    interference, the sample should be diluted and  reanalyzed.

         7.3.4   If the interference  persists  after  sample dilution,  an
    alternative method  (Method  7195, Coprecipitation,  or  Method  7197,
    Chelation/Extraction) should be used.

    7.4  Acidic  extracts  that  yield  recoveries  of less  than  85%  should  be
retested to  determine  if  the low spike recovery  is  due to the  presence  of
residual  reducing   agent.    This  determination  shall  be performed  by  first
making  an  aliquot  of  the  extract  alkaline  (pH  8.0-8.5) using  IN sodium
hydroxide and then respiking and analyzing.  If a  spike recovery of 85-115% is

                                  7196 -  3                       Revision 1
                                                                December 1987
-------
obtained in the alkaline aliquot of an acidic extract that initially was found
to  contain less  than 5  mg/L  Cr(VI),  one  can conclude  that the  analytical
method has been verified.

    7.5  Analyze all  EP  extracts,  all  samples  analyzed  as part  of a delisting
petition, and all  samples  that  suffer from  matrix  interferences  by the method
of standard additions (see Method 7000, Step 8.7).

8.0  QUALITY CONTROL

    8.1  All quality  control data  should  be maintained  and available for easy
reference or inspection.

    8.2  Dilute  samples  if  they  are more concentrated than  the  highest
standard or if they fall on the plateau of a calibration curve.

    8.3  Employ  a minimum of  one blank per  sample batch  to  determine  if
contamination or any memory effects are occurring.

    8.4  Verify calibration with an independently prepared QC reference sample
every 15 samples.

    8.5  Run one  matrix spike  replicate  or  one replicate sample  for every 10
samples.   A replicate  sample  is  a  sample  brought  through the  whole sample
preparation and analytical process.

    8.6  The method of  standard additions (see Method 7000, Step 8.7) shall be
used for the analysis of all EP extracts, on all analyses  submitted as part of
a delisting petition, and  whenever  a  new  sample matrix is  being analyzed.

9.0  METHOD PERFORMANCE

    9.1  The data shown  in  Table   1  were obtained  from  records  of state and
contractor  laboratories.   The  data are intended to  show  the  precision of the
combined sample preparation and analysis  method.

10.0 REFERENCES

1.   Methods  for  Chemical Analysis  of  Water and  Wastes,  EPA-600/4-82-055,
     December 1982, Methods 218.4  and 218.5.

2.   Gaskill, A.,  Compilation  and  Evaluation of RCRA Method Performance Data,
     Work Assignment  No. 2, EPA Contract  No. 68-01-7075,  September  1986.

3.   Rohrbough,  W.G.;  et al.  Reagent  Chemicals,  American  Chemical  Society
     Specifications.  7th ed.; American  Chemical Society:  Washington, DC, 1986.

4.   1985  Annual  Book of  ASTM  Standards. Vol.  11.01; "Standard Specification
     for Reagent Water"; ASTM:  Philadelphia, PA, 1985; D1193-77.
                                  7196 - 4                       Revision 1
                                                                 December 1987
-------
                                  TABLE 1.
                           METHOD PERFORMANCE DATA
       Sample                      Preparation             Laboratory
       Matrix                        Method                Replicates


Wastewater treatment sludge         Not known            0.096, 0.107 ug/g

Sediment from chemical
  storage area                        3060                   115, 117 ug/g
                                  7196 - 5                       Revision 1
                                                                 December 1987
-------
            METHOD 7195
HCXAVALCNT CHROMIUM (COLOfUMETRIC)
       7. J
      For color development
       transfer internet, to
           MasK:  add
        dtphenyleerDecide
         solution;  ml*
          7. 1 I

                Add
         H.SOt solution:
            dilute:  1st
               stsnd
       7.1
       Measure snd correct
       •osoroance reading:
       determine chronium
            present
         7.2.1
                Treet
              chromium
            standards  by
          (•me procedure
             es sample
         7.2.ll
         	1  Plpet
              chromium
              standard
           solution  into
              beakers
           7196 -  6
Revision 1
December 1987
-------
                                            METHOD 7196

                                HEXAVALENT CHROMIUM  (COLORIMETflIC)
                                             (Continued)
7.2.2
   0«velop color of
  standards:  measure
 •nd correct reading;
construct calibration
        curve
7.3.1
    Analyze • 2nd
   •llauot or PM-
  adjusted filtrate
  solked with Cr (vi)
  for verification
      Oo«c spike
   extend concentr.
     beyond cell-
       oration
        curve
      Dilute
     analysis
 solution
blank solution
     Does result
     indicate •
     suppresslvc
      interfei—
        ence?
Dilute semole
end reanalyze
                              Interference
                             Use alternative
                                 iiethod
                                                        7.3
                                                      le a spike
                                                     recovery at
                                                       85-115X
                                                      obtained?
                          Analytical
                      method verified
                       -waste Is not
                          hezerdous
  Analyze
 by method
of standard
additions
                        (      Stop      J
                                               7196  -  7
                                                     Revision  1
                                                     December  1987
-------
                                METHOD 7430

               LITHIUM (ATOMIC ABSORPTION.  DIRECT ASPIRATION)


1.0  SCOPE AND APPLICATION

     1.1  See Section 1.0 of Method 7000.

2.0  SUMMARY OF METHOD

     2.1  See Section 2.0 of Method 7000.

3.0  INTERFERENCES

     3.1  See Section 3.0 of Method 7000 if interferences are  suspected.

4.0  APPARATUS AND MATERIALS

     4.1  For basic apparatus, see Section 4.0 of Method 7000.

     4.2  Instrument parameters (general):

          4.2.1  Lithium hollow cathode lamp.

          4.2.2  Wavelength:  670.8 nm.

          4.2.3  Fuel:  Acetylene.

          4.2.4  Oxidant:  Air.

          4.2.5  Type of flame:  Oxidizing (fuel  lean).

          4.2.6  Background Correction:  Not required.

5.0  REAGENTS

     5.1  See Section 5.0 of Method 7000.

     5.2  Preparation of standards

          5.2.1   Stock  solution:  (1.0  mL = 1.0  mg   Li). Dissolve 5.324  g
     lithium carbonate,  Li2C03, in  a  minimum  volume of 1:1 HC1 and  dilute  to
     1 liter  with  water. Alternatively, procure  a  certified  standard from  a
     supplier and verify by comparison with a  second standard.

          5.2.2   Prepare dilutions  of  the  stock  solution  to  be  used  as
     calibration standards at the  time of analysis.   The calibration  standards
     should be  prepared  using the  same  type  of acid as  the  samples used  to
     prepare the samples and cover the range of expected concentrations  in the
     samples.
                                 7430 - 1                         Revision  0
                                                                 December  1987
-------
6.0  SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

     6.1  See Chapter Three, Step 3.1.3,  Sample Handling  and  Preservation.

7.0  PROCEDURE

     7.1   Sample  preparation - The procedures  for  preparation of the  sample
are given in Chapter Three, Step 3.2.

    7.2  See Method 7000, Step 7.2,  Direct Aspiration.

8.0  QUALITY CONTROL

    8.1  See Section 8.0 of Method 7000.

9.0  METHOD PERFORMANCE

    9.1  The  performance  characteristics  for an  aqueous  sample  free  of
interferences are:

     Optimum concentration range:  0.1-2 mg/L at a  wavelength of 670.8 nm.
     Sensitivity: 0.04 mg/L.
     Detection limit: 0.002 mg/L.

10.0  REFERENCES

1.   Standard Methods for  the Examination of Water and  Wastewater,  16th  ed.;
     Greenberg,  A.E.;  Trussell,  R.R.;  Clesceri, L.S.,  Eds.; American  Water
     Works  Association,  Water  Pollution  Control  Federation, American  Public
     Health Association:  Washington,  DC, 1985.
                                 7430 - 2                        Revision 0
                                                                 December 1987
-------
                    METHOD 7430
LITHIUM  (ATOMIC ASORPTION,  DIRECT ASIRATION)
                      C   ""*  )
                       6.3 Pr.p*r.
                        it.id.rd.
                      7.1
 pr«p*r.tio»,
Ck.pt.r -  -
                          for ».ipl«
                           tio>, >••
                           3. St.p 3.3
                     7.2 An.lTl. »lif
                     M.tkod 7000. St.p
                           7.3
                    7430 -  3
                                      Revision  0
                                      December  1987
-------
                                 METHOD 7470A

             MERCURY  IN  LIQUID WASTE  (MANUAL  COLD-VAPOR TECHNIQUE)
1.0   SCOPE AND APPLICATION

      1.1   Method 7470 is a cold-vapor atomic absorption procedure approved for
determining the concentration of mercury in mobility-procedure extracts, aqueous
wastes, and ground waters.  (Method 7470  can  also be used for analyzing certain
solid  and  sludge-type wastes;  however,  Method  7471  is usually the  method of
choice for these waste types.)  All  samples must be subjected to an appropriate
dissolution step prior to analysis.


2.0   SUMMARY OF METHOD

      2.1   Prior to analysis,  the liquid samples must be prepared according to
the procedure discussed in this method.

      2.2   Method 7470,  a cold-vapor atomic absorption technique, is based on
the absorption of radiation at 253.7-nm by mercury vapor. The mercury  is reduced
to the elemental state and aerated from solution in  a closed  system. The mercury
vapor passes through a cell positioned in the light  path of an atomic absorption
spectrophotometer.  Absorbance  (peak height) is measured as a  function  of mercury
concentration.

      2.3   The typical detection limit for this method is 0.0002 mg/L.


3.0   INTERFERENCES

      3.1   Potassium permanganate is added to eliminate possible interference
from sulfide.  Concentrations as high as 20 mg/L of  sulfide as sodium  sulfide do
not interfere with the recovery of added  inorganic mercury from reagent water.

      3.2   Copper has also been  reported to  interfere; however, copper concen-
trations as  high  as  10 mg/L had  no effect on recovery of mercury from spiked
samples.

      3.3   Seawaters, brines,  and industrial  effluents high in chlorides require
additional permanganate (as much as 25 mL) because, during the oxidation step,
chlorides are converted to free chlorine,  which  also absorbs radiation of 253.7
nm.  Care must therefore be taken  to  ensure that free chlorine is absent before
the mercury  is  reduced  and swept  into the cell.   This may  be  accomplished by
using an excess of hydroxylamine sulfate reagent (25 mL).   In addition, the dead
air space in the BOD  bottle must be purged before adding stannous sulfate.  Both
inorganic and  organic mercury  spikes have been quantitatively  recovered from
seawater by using this technique.

      3.4   Certain volatile organic materials that  absorb at  this wavelength may
also cause interference.   A preliminary run without  reagents  should determine if
this type of interference is present.

                                   7470A  - 1                       Revision 1
                                                                  November  1992
-------
4.0   APPARATUS AND MATERIALS

      4.1   Atomic  absorption  spectrophotometer  or equivalent:   Any  atomic
absorption unit with  an open sample  presentation  area  in which to  mount  the
absorption cell is suitable.  Instrument settings recommended by the particular
manufacturer should  be followed.   Instruments  designed specifically  for  the
measurement of mercury using the cold-vapor technique are commercially available
and may be substituted for the atomic absorption spectrophotometer.

      4.2   Mercury hollow cathode lamp or electrodeless discharge lamp.

      4.3   Recorder:  Any multirange variable-speed recorder that is compatible
with the UV detection  system is suitable.

      4.4   Absorption cell:  Standard spectrophotometer cells 10 cm long with
quartz end windows may be used.  Suitable cells may be constructed from Plexiglas
tubing,  1  in.  O.D.  x 4.5  in.    The ends  are ground  perpendicular  to  the
longitudinal axis, and quartz windows (1 in.  diameter x 1/16  in. thickness) are
cemented in place.  The cell  is strapped to a burner for support and aligned in
the light beam by  use of two 2-in.  x 2-in. cards.   One-in.-diameter holes  are cut
in the middle of each  card.  The cards are then placed over each end  of the cell.
The cell is then positioned and adjusted vertically and horizontally to give the
maximum transmittance.

      4.5   Air pump:   Any peristaltic pump  capable of delivering 1 liter  air/min
may be used.  A Masterflex pump with  electronic  speed control has been found to
be satisfactory.

      4.6   Flowmeter:  Capable of measuring an air flow of  1 liter/min.

      4.7   Aeration tubing: A straight glass frit with a coarse porosity. Tygon
tubing  is  used  for  passage  of  the mercury  vapor from  the sample bottle to the
absorption cell and return.

      4.8   Drying tube:  6-in.  x 3/4-in.-diameter tube containing  20 g  of mag-
nesium perchlorate or  a small reading lamp with 60-W bulb which may be  used to
prevent condensation of moisture  inside the cell.  The  lamp  should be positioned
to shine on the absorption  cell so that the air temperature in the cell  is about
10°C above ambient.

      4.9   The cold-vapor generator  is assembled as shown in Figure 1.

            4.9.1   The apparatus shown in  Figure  1  is a closed system.   An open
      system, where the mercury vapor is passed through the  absorption cell only
      once, may be  used instead of the closed system.

            4.9.2   Because mercury vapor is toxic,  precaution must be  taken to
      avoid its inhalation.  Therefore, a bypass has been included  in the system
      either to vent the mercury  vapor into an exhaust hood or to pass the vapor
      through  some  absorbing medium,  such  as:
                                   7470A - 2                      Revision 1
                                                                  November 1992
-------
            1.  Equal volumes of 0.1 M KMn04 and 10% H2S04; or

            2.  0.25% Iodine in a 3% KI solution.

      A  specially  treated  charcoal  that  will  adsorb  mercury  vapor  is  also
      available from  Barnebey  and Cheney,  East 8th Avenue  and  North Cassidy
      Street,  Columbus,  Ohio 43219, Cat. #580-13 or #580-22.

      4.10  Hot plate or  equivalent  -  Adjustable and capable of maintaining a
temperature of 90-95°C.

      4.11  Graduated cylinder or equivalent.


5.0   REAGENTS

      5.1   Reagent  Water:   Reagent water  will  be  interference  free.   All
references to  water in this  method will  refer to reagent water unless otherwise
specified.

      5.2   Sulfuric acid (H2S04),  concentrated:  Reagent  grade.

      5.3   Sulfuric acid, 0.5  N:   Dilute  14.0 ml of  concentrated sulfuric acid
to 1.0 liter.

      5.4   Nitric  acid  (HN03),  concentrated:    Reagent grade of  low mercury
content.  If a high reagent blank is obtained, it may be necessary  to distill the
nitric acid.

      5.5   Stannous  sulfate:   Add 25 g  stannous sulfate to 250 ml  of 0.5 N
H2S04.   This mixture is  a suspension and should be stirred continuously during
use.  (Stannous chloride may be used in place of  stannous sulfate.)

      5.6   Sodium chloride-hydroxylamine  sulfate solution:   Dissolve 12  g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to
100 ml.   (Hydroxylamine hydrochloride may be   used  in  place of hydroxylamine
sulfate.)

      5.7   Potassium permanganate, mercury-free, 5% solution  (w/v):  Dissolve
5 g of potassium permanganate in 100 ml of reagent water.

      5.8   Potassium persulfate,  5% solution (w/v):   Dissolve 5  g of potassium
persulfate  in 100 ml of reagent water.

      5.9   Stock mercury solution:  Dissolve 0.1354 g of mercuric chloride in
75 mL of reagent water.  Add  10 ml of concentrated HN03 and adjust the volume to
100.0 ml  (1 ml = 1 mg Hg).  Stock solutions may also be purchased.

      5.10  Mercury working  standard:   Make successive dilutions of the stock
mercury  solution to  obtain  a working standard  containing 0.1 g  per  ml.  This
working  standard  and the dilutions  of the  stock mercury solution  should be
prepared  fresh daily.  Acidity of the working standard should be maintained at


                                   7470A -  3                      Revision 1
                                                                  November  1992
-------
0.15% nitric acid.  This acid  should  be  added  to  the  flask,  as needed, before
addition of the aliquot.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All samples  must  have been  collected  using a sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual.

      6.2   All sample containers must be prewashed with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Aqueous  samples  must  be  acidified to  a  pH  <2  with HN03.   The
suggested maximum holding times for mercury is 28 days.

      6.4   Nonaqueous samples  shall be refrigerated, when possible, and analyzed
as soon as possible.


7.0   PROCEDURE

      7.1   Sample preparation:  Transfer  100 mL,  or  an   aliquot diluted  to
100 mL, containing <1.0 g of mercury,  to a 300-mL BOD  bottle or equivalent.  Add
5 mL of H2S04  and  2.5  mL  of concentrated  HN03, mixing after each addition.  Add
15 mL of potassium permanganate solution  to each sample  bottle.  Sewage samples
may require additional permanganate.   Ensure that equal  amounts of permanganate
are  added  to  standards  and blanks.   Shake and  add  additional   portions  of
potassium permanganate solution, if necessary, until  the purple color persists
for at least 15 min.  Add 8 mL of potassium persulfate to each bottle and heat
for  2  hr in  a  water bath maintained at 95°C.   Cool  and  add 6  mL  of sodium
chloride-hydroxylamine sulfate  to reduce  the excess permanganate.   After a delay
of at least 30 sec, add 5 mL of stannous  sulfate, immediately  attach the bottle
to the aeration apparatus,  and continue as described in Paragraph 7.3.

      7.2   Standard preparation: Transfer 0-,  0.5-, 1.0-, 2.0-, 5.0-,  and 10.0-
mL aliquots of the mercury  working standard,  containing  0-1.0  ug of mercury, to
a series of 300-mL BOD bottles.  Add enough reagent water to each bottle to make
a total volume of 100 mL. Mix  thoroughly  and add 5 mL of concentrated H2S04 and
2.5 mL of concentrated HN03 to  each bottle.  Add 15 mL of KMn04 solution  to each
bottle and allow to stand at  least 15  min.  Add  8 mL of  potassium  persulfate to
each bottle and heat for 2 hr in a water  bath maintained at 95°C.  Cool  and add
6 mL of sodium chloride-hydroxylamine  sulfate solution to  reduce the excess
permanganate.  When the solution has  been decolorized,  wait 30 sec, add 5 mL of
the  stannous  sulfate  solution, immediately attach the  bottle to  the  aeration
apparatus, and continue  as described  in  Paragraph 7.3.

      7.3   Analysis:   At  this  point the sample  is allowed  to  stand quietly
without  manual  agitation.    The circulating  pump,  which  has previously been
adjusted  to  a  rate  of  1  liter/min, is  allowed  to  run  continuously.   The
absorbance will  increase and reach a maximum  within  30 sec.  As soon as the
recorder pen levels off (approximately 1 min), open the bypass  valve and  continue
the aeration until the absorbance returns to its minimum value.  Close the bypass


                                   7470A  - 4                      Revision 1
                                                                  November 1992
-------
valve,  remove  the  stopper  and  frit  from  the  BOD  bottle,  and  continue  the
aeration. Because of instrument variation refer to the manufacturers recommended
operating conditions when using this method.

      7.4   Construct a calibration curve by plotting the absorbances of stan-
dards versus micrograms of mercury.   Determine  the peak height of the unknown
from the chart and read the mercury value from the standard curve.

      7.5   Calculate  metal   concentrations  (1)  by  the  method  of  standard
additions, or  (2)  from  a  calibration curve.   All  dilution  or concentration
factors must be taken into  account.  Concentrations reported for multiphased or
wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).


8.0   QUALITY CONTROL

      8.1  Refer to section 8.0 of Method 7000.
9.0   METHOD PERFORMANCE

      9.1   Precision and accuracy data are available in Method  245.1 of Methods
for Chemical Analysis of Water and Wastes.


10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of  Water  and  Wastes,  EPA-600/4-82-055,
December 1982, Method 245.1.
                                   7470A  -  5                       Revision 1
                                                                  November 1992
-------
                        METHOD 7470A
MERCURY IN  LIQUID  WASTE  (MANUAL  COLD-VAPOR TECHNIQUE)
                      C
Sample Preparation
1
7 1 Tram far
aliquot to
bottle, add
H.SO, and
HNO. , and mix
I
7.1 Add KMnO.
and ahaka
/ la aample ^V
f from
N. sewage? /
JNo
7 1 Add
potamum
peraul fate, heat
for 2 hra , cool

7.1 Add sodium
chloride -
hydroxy lamina
sulfate.wait 30
eec
1
7 1 Add
s tannous
>ulf ate, attach
to aeration
apparatus
Yes


7 1 Adc
permanc
if neci






7 3
analya
circu
pur
contim




! more
|anata
issary

For
is run
ating
up
loualy

7 4 Construct
calibration
curve , determine
peak height and
Hg value


1
7 . 2 Transfer
aliquot of the
Hg working
standard to
bottle

7 2 Add reagent
concentrated
H.SO, and HNO.

7.2 Add KMnO, ,
potassium
persul fate, heat
for 2 hrs and
cool

7 2 Add sodium
chl oride -
hydroxylamine
sulfate.wait 30
sec
1
7 2 Add
s tannous
sulfate .attach
to aeration
apparatus

                        7 S Analyze
                          sample
                       7 6 Routinely
                          analyze
                        duplicates,
                          spiked
                          samples
                       7 7 Calculate
                           metal
                       concentrations
                         7470A -  6
Revision 1
November  1992
-------
                                 METHOD 7471A

      MERCURY  IN  SOLID OR  SEMISOLID WASTE  (MANUAL COLD-VAPOR TECHNIQUE)


1.0   SCOPE AND APPLICATION

      1.1   Method 7471  is  approved  for measuring total mercury  (organic and
inorganic) in soils,  sediments,  bottom deposits, and sludge-type materials. All
samples must be subjected to an  appropriate dissolution step prior to analysis.
If this dissolution procedure is not sufficient to dissolve  a  specific matrix
type or sample, then this method is not applicable for that matrix.


2.0   SUMMARY OF METHOD

      2.1   Prior to analysis, the  solid or semi-solid samples must be prepared
according to the procedures discussed in this method.

      2.2   Method 7471,  a cold-vapor atomic  absorption method, is based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor.  The mercury
is reduced to the elemental  state and aerated  from solution in a closed system.
The mercury vapor  passes through a cell positioned in the light path of an atomic
absorption spectrophotometer.  Absorbance (peak height) is measured as a function
of mercury concentration.

      2.3   The typical  detection limit for this method is  0.0002 mg/L.


3.0   INTERFERENCES

      3.1   Potassium permanganate  is added to eliminate possible interference
from sulfide.  Concentrations as high as 20 mg/Kg of sulfide, as sodium sulfide,
do not interfere with the recovery  of added inorganic mercury in reagent water.

      3.2   Copper has also been reported  to  interfere; however, copper concen-
trations as high  as  10 mg/Kg had no effect on recovery  of  mercury from spiked
samples.

      3.3   Brines and industrial effluents high in chlorides require additional
permanganate (as much  as 25 mL) because,  during the oxidation step, chlorides are
converted to free chlorine, which also absorbs radiation of 253 nm.   Care must
therefore be taken to ensure that free chlorine  is absent before the mercury is
reduced and swept into the cell.  This may be  accomplished by using an excess of
hydroxylamine sulfate reagent (25 ml).   In addition,  the dead air space in the
BOD bottle must be purged before adding stannous sulfate.

      3.4   Certain volatile organic materials that absorb at this wavelength may
also cause interference.  A preliminary run without reagents should determine if
this type of interference is present.
                                   7471A  -  1                       Revision 1
                                                                  November 1992
-------
4.0   APPARATUS AND MATERIALS

      4.1   Atomic  absorption  spectrophotometer  or equivalent:   Any  atomic
absorption unit with  an open sample  presentation  area  in which to  mount the
absorption cell is suitable.  Instrument  settings recommended by the particular
manufacturer should  be followed.   Instruments  designed  specifically  for the
measurement of mercury using the cold-vapor technique are commercially available
and may be substituted for the atomic absorption spectrophotometer.

      4.2   Mercury hollow cathode lamp or electrodeless discharge lamp.

      4.3   Recorder:  Any multirange variable-speed recorder that is compatible
with the UV detection system is suitable.

      4.4   Absorption cell:  Standard spectrophotometer cells 10 cm long with
quartz end windows may be used.  Suitable cells may be constructed from Plexiglas
tubing,  1 in.  O.D.   x  4.5  in.    The ends  are ground  perpendicular  to the
longitudinal axis, and quartz windows (1  in.  diameter x 1/16  in. thickness) are
cemented in place.  The cell  is  strapped  to a burner for support and aligned in
the light beam by  use of two 2-in.  x 2-in. cards.   One-in.-diameter holes  are cut
in the middle of each card.  The cards are then placed over each end  of the cell.
The cell is then positioned and adjusted vertically and horizontally to give the
maximum transmittance.

      4.5   Air pump:  Any peristaltic pump capable  of delivering 1  L/min  air may
be used.  A Masterflex pump with electronic  speed control has been found to be
satisfactory.

      4.6   Flowmeter:  Capable of measuring an air flow of  1 L/min.

      4.7   Aeration tubing:  A straight glass frit with a coarse porosity. Tygon
tubing  is  used  for passage of  the mercury  vapor from  the sample bottle to the
absorption cell and return.

      4.8   Drying  tube:   6-in.  x 3/4-in.-diameter tube containing 20  g  of
magnesium  perchlorate or a small reading lamp with  60-W bulb which may  be used
to  prevent condensation  of moisture  inside the  cell.    The lamp  should  be
positioned to  shine  on  the  absorption cell  so that the  air temperature in the
cell is about  10°C above ambient.

      4.9   The cold-vapor generator  is assembled as shown in Figure 1.

            4.9.1   The apparatus  shown in  Figure 1  is  a  closed system.   An open
      system, where the mercury vapor  is passed through the absorption cell only
      once, may be used instead of the closed system.

            4.9.2   Because mercury vapor is  toxic,  precaution  must be taken to
      avoid its inhalation.   Therefore, a bypass has been included  in the system
      either to   vent the mercury vapor  into  an exhaust hood or  to pass the
      vapor through  some absorbing medium, such as:

            1.    equal volumes of 0.1 M KMn04 and  10% H2S04,  or
            2.    0.25% iodine in  a 3% KI  solution.


                                   7471A  -  2                        Revision 1
                                                                   November 1992
-------
      A  specially  treated  charcoal  that will  adsorb mercury  vapor  is  also
      available  from  Barneby and  Cheney,  East 8th  Avenue  and  North  Cassidy
      Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.

      4.10  Hot plate  or  equivalent  -  Adjustable  and  capable  of maintaining a
temperature of 90-95°C.

      4.11  Graduated cylinder or equivalent.


5.0   REAGENTS

      5.1   Reagent Water:    Reagent  water  will  be  interference  free.   All
references  to  water in this  method refer  to  reagent water  unless  otherwise
specified.

      5.2   Aqua regia: Prepare immediately  before use by  carefully adding three
volumes of concentrated HC1 to one volume of concentrated HN03.

      5.3   Sulfuric acid, 0.5 N:   Dilute 14.0 ml of concentrated sulfuric acid
to 1 liter.

      5.4   Stannous sulfate:   Add 25 g  stannous  sulfate  to  250 ml of 0.5 N
sulfuric acid.  This mixture is  a  suspension  and should be stirred continuously
during use.  A 10%  solution of stannous chloride can  be substituted for stannous
sulfate.

      5.5   Sodium chloride-hydroxylamine sulfate solution:   Dissolve  12 g of
sodium chloride and 12  g of hydroxylamine sulfate in  reagent water and dilute to
100 mL.   Hydroxylamine hydrochloride  may be  used  in place  of hydroxylamine
sulfate.

      5.6   Potassium permanganate, mercury-free,  5% solution (w/v):  Dissolve
5 g of potassium permanganate in 100 ml of reagent water.

      5.7   Mercury stock solution:  Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent water.   Add  10 ml of concentrated  nitric  acid and adjust the
volume to 100.0 ml (1.0 mL = 1.0 mg Hg).

      5.8   Mercury working standard:   Make  successive dilutions of  the stock
mercury solution to obtain a working standard  containing 0.1  ug/mL. This working
standard and the dilution of the  stock mercury solutions should  be prepared fresh
daily.  Acidity  of the working  standard should be  maintained at 0.15% nitric
acid.    This  acid should be added  to  the flask, as needed, before  adding the
aliquot.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All samples must  have been  collected  using  a sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual.
                                   7471A  - 3                       Revision 1
                                                                  November 1992
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      6.2   All sample containers must  be prewashed with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Non-aqueous  samples  shall  be  refrigerated,  when possible,  and
analyzed as soon as possible."


7.0   PROCEDURE

      7.1   Sample preparation:   Weigh  triplicate  0.2-g  portions  of untreated
sample and place in the bottom of a BOD bottle.  Add 5 ml of reagent water and
5 ml of aqua regia.  Heat 2 min  in a water bath at 95°C.   Cool; then add 50 ml
reagent water and 15 ml potassium permanganate solution to each sample bottle.
Mix thoroughly and place in the water bath for 30 min at 95°C.   Cool and add 6
ml of sodium chloride-hydroxylamine sulfate  to  reduce the excess permanganate.

      CAUTION:    Do this  addition   under  a hood,   as C12  could  be evolved.
                  Add  55   ml  of  reagent   water.    Treating   each  bottle
                  individually,  add  5  ml  of stannous  sulfate  and immediately
                  attach the  bottle to the  aeration  apparatus.    Continue as
                  described under step 7.4.

      7.2   An alternate digestion procedure employing  an autoclave may also be
used.  In this method, 5 ml of concentrated  H2S04 and 2 ml of concentrated  HN03
are added to the 0.2 g of sample.  Add 5 ml of saturated KMn04 solution  and cover
the bottle with a piece of  aluminum  foil.  The samples are  autoclaved at  121°C
and 15 Ib for 15 min.  Cool, dilute to a volume of 100 ml with reagent water, and
add 6 ml of sodium chloride-hydroxylamine sulfate solution to reduce the excess
permanganate.  Purge the dead air space  and continue as described under  step  7.4.
Refer to the caution statement in section 7.1 for the proper protocol  in reducing
the excess permanganate solution  and adding stannous sulfate.

      7.3   Standard preparation: Transfer 0.0-, 0.5-,  1.0-, 2.0-,  5.0-, and 10-
ml_ aliquots of the mercury working standard,  containing 0-1.0 ug of mercury, to
a series of 300-mL BOD bottles or equivalent.   Add  enough reagent water to  each
bottle to make a total volume of  10 mL.  Add 5 ml of aqua regia and heat 2 min
in a water bath at 95°C.  Allow the  sample to cool; add 50 ml reagent water and
15 ml of  KMn04 solution  to each bottle  and  return   to  the water bath for 30
min.  Cool  and add 6 ml of sodium  chloride-hydroxylamine  sulfate solution to
reduce the  excess  permanganate.  Add  50 ml of reagent water.   Treating  each
bottle individually, add 5  mL of  stannous sulfate solution,  immediately attach
the bottle to the aeration  apparatus, and continue as described in
Step 7.4.

      7.4   Analysis:   At  this point,  the sample  is  allowed  to  stand quietly
without  manual  agitation.    The  circulating  pump,  which has  previously  been
adjusted to a rate of 1 L/min, is allowed to  run continuously.  The absorbance,
as exhibited either on the spectrophotometer or the recorder, will increase and
reach  maximum  within  30   sec.    As  soon  as  the  recorder   pen  levels  off
(approximately 1 min), open the bypass valve and continue  the aeration  until the
absorbance  returns to  its  minimum value.   Close the  bypass valve,  remove the
fritted tubing from the BOD bottle,  and continue the aeration.
                                   7471A - 4                      Revision  1
                                                                  November 1992
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      7.5   Duplicates, spiked samples,  and check standards should be routinely
analyzed.

      7.6   Calculate  metal  concentrations:    (1)  by  the  method  of  standard
additions, (2) from a calibration curve, or (3) directly from the instrument's
concentration read-out. All dilution or  concentration factors must be taken into
account.   Concentrations  reported  for multiphased  or  wet  samples  must  be
appropriately qualified (e.g., 5 ug/g dry weight).


8.0   QUALITY CONTROL

      8.1  Refer to section 8.0 of Method 7000.
9.0   METHOD PERFORMANCE

      9.1   Precision and accuracy data are available in Method 245.5 of Methods
for Chemical Analysis of Water and Wastes.

      9.2   The data shown  in Table  1 were  obtained from records of state and
contractor  laboratories.   The  data  are  intended to  show  the  precision  of the
combined sample preparation and analysis method.


10.0  REFERENCES

1.    Methods  for Chemical  Analysis of  Water  and  Wastes,  EPA-600/4-82-055,
December 1982, Method 245.5.

2.    Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No.  68-01-7075, September 1986.
                                   7471A  -  5                       Revision 1
                                                                  November 1992
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                      TABLE 1. METHOD PERFORMANCE DATA
Sample                         Preparation           Laboratory
Matrix                           Method              Replicates
Emission control dust          Not known              12,  12  ug/g

Wastewater treatment sludge    Not known          0.4, 0.28  ug/g
                                  7471A - 6                       Revision 1
                                                                  November 1992
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                                    METHOD 7471A
MERCURY  IN  SOLID  OR  SEMISOLID  WASTE  (MANUAL COLD-VAPOR  TECHNIQUE)
                                  C    Start    j
                    Sample Preparation
            7  1 Weigh
           triplicate
           sample*,add
          reagent water
         and aqua regia
            7  1  Heat,
            cool,add
          reagent  water
            and  KMnO,
         7.1 Heat,cool,
           add sodium
            chloride-
          hydroxylamine
             •ulfate
         7 1 Add  reagent
         water,stannous
         sulfate,  attach
           to aeration
            apparatua
         Standard Preparation
  7 2 Add  to
    •ample
 concentrated
   H,50, and
     HNO,
    7.2  Add
 KMnO..cover,
heat and cool,
  dilute with
 reagent water
7 2 Add  sodium
   chloride-
 hydroxylamine
 •ulfate.purge
dead air apace
    7  4  For
 analysis run
  circulating
     pump
 continuously
                                   7  5 Construct
                                   calibration
                                  curve;determine
                                  peak height and
                                     Hg value
                                    7 6 Analyze
                                     samples
                                   7  7 Routinely
                                     analyze
                                   duplicates,
                                     spiked
                                     samples
                                   7  8 Calculate
                                      metal
                                  concentrations
                                  C   st(>P     J
                                                           7 3 Transfer
                                                            aliquots of
                                                            Hg working
                                                           standards to
                                                              bottles
    7  3  Add
 reagent water
 to volume,add
  aqua regia,
 heat  and cool
    7  3  Add
 reagent water
   and KMnO,
   solution,
 heat  and cool
7 . 3 Add  sodium
   chloride -
 hydroxylamine
  sulfate and
 reagent water
    7.3  Add
   stannous
sulfate.attach
  to aeration
   apparatus
                                      7471A -  7
                                              Revision  1
                                              November 1992
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                                 METHOD 7741A

                 SELENIUM  (ATOMIC  ABSORPTION.  GASEOUS HYDRIDE)
1.0   SCOPE AND APPLICATION

      1.1   Method 7741 is an atomic absorption procedure that is approved for
determining the concentration of selenium in wastes, mobility-procedure extracts,
soils, and ground water, provided that the sample matrix does not contain high
concentrations of chromium, copper, mercury, silver,  cobalt,  or molybdenum.  All
samples must be subjected to  an  appropriate dissolution step prior to analysis.
Spiked  samples  and  relevant  standard reference  materials  are employed  to
determine applicability of the  method  to  a given waste.   If interferences are
present the analyst should consider using Method 7740.


2.0   SUMMARY OF METHOD

      2.1   Samples are prepared according to the nitric/sulfuric  acid digestion
procedure described  in this  method.   Next,  the selenium in  the digestate is
reduced to Se(IV) with  tin chloride.  The Se(IV) is then converted to a volatile
hydride  with  hydrogen produced  from  a  zinc/HCl   or sodium borohydrate/HCl
reaction.

      2.2   The volatile hydride is swept into an argon-hydrogen flame located
in the  optical  path  of an atomic  absorption  spectrophotometer;  the resulting
absorbance is proportional to the selenium concentration.

      2.3   The typical detection limit for this method is 0.002 mg/L.


3.0   INTERFERENCES

      3.1   High concentrations  of chromium, cobalt, copper, mercury, molybdenum,
nickel, and silver can cause analytical interferences.

      3.2   Traces of  nitric acid left following the sample work-up can result
in analytical  interferences.  Nitric  acid must be distilled off the sample by
heating the sample until fumes  of S03 are observed.

      3.3   Elemental selenium and many of its compounds are volatile; therefore,
certain samples may be  subject to  losses of selenium during sample preparation.


4.0   APPARATUS AND MATERIALS

      4.1   100-mL beaker.

      4.2   Electric  hot plate or  equivalent -  Adjustable  and  capable  of
maintaining a temperature of 90-95°C.
                                   7741A -  1                       Revision 1
                                                                  November 1992
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      4.3   A commercially available zinc slurry hydride generator or a generator
constructed from the following material (see Figure 1):

            4.3.1    Medicine  dropper:   Fitted into a  size  "0"  rubber stopper
      capable of delivering 1.5 ml.

            4.3.2    Reaction  flask:  50-mL,  pear-shaped,  with  two 14/20 necks
      (Scientific Glass, JM-5835).

            4.3.3   Gas  inlet-outlet tube:  Constructed  from a micro cold-finger
      condenser  (JM-3325) by  cutting the  portion  below the  14/20  ground-glass
      joint.

            4.3.4   Magnetic stirrer:  To homogenize the zinc slurry.

            4.3.5   Polyethylene drying tube:  10-cm, filled with glass wool to
      prevent particulate matter from entering the burner.

            4.3.6    Flow meter:  Capable of measuring 1 liter/min.

      4.4   Atomic absorption  spectrophotometer: Single or dual channel, single-
or double-beam instrument with  a grating monochromator, photomultipl ier detector,
adjustable  slits,  a wavelength   range  of  190-800 nm,  and   provisions  for
interfacing with a strip-chart recorder and simultaneous background correction.

      4.5   Burner:  Recommended by the particular instrument manufacturer for
the argon-hydrogen flame.

      4.6   Selenium hollow cathode lamp or electrodeless discharge  lamp.

      4.7   Strip-chart recorder  (optional).


5.0   REAGENTS

      5.1   Reagent  water:  Water  should be monitored for impurities.  Reagent
water will be interference  free.    All references to water will refer  to reagent
water.

      5.2   Concentrated nitric  acid:    Acid  should be  analyzed  to determine
levels of impurities. If a method blank made with  the acid is 
-------
      5.5   Diluent:  Add 100 ml 18 N H2S04 and 400 ml concentrated HC1 to 400
ml reagent water and dilute to a final volume of 1 liter with reagent water.

      5.6   Potassium iodide solution:  Dissolve 20 g KI in 100 ml reagent water.

      5.7   Stannous chloride  solution:    Dissolve 100 g  SnCl2  in  100  ml of
concentrated HC1.

      5.8   Selenium  standard  stock  solution:    1,000 mg/L  solution may be
purchased, or prepared as follows:  Dissolve 0.3453 g of selenious acid (assay
94.6% of H2Se03) in reagent  water.   Add to a 200-mL volumetric flask and bring
to volume (1 ml = 1 mg Se).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All samples  must have been  collected using a  sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual.

      6.2   All sample containers must be prewashed with detergents,  acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Special  containers   (e.g.,  containers used  for volatile  organic
analysis) may  have to  be used if  very volatile selenium compounds  are  to be
analyzed.

      6.4   Aqueous samples must be acidified to a pH of <2 with nitric acid.

      6.5   Nonaqueous samples shall be refrigerated, when possible,  and analyzed
as soon as possible.


7.0   PROCEDURE

      7.1   Sample preparation:

            7.1.1   To  a 50-mL aliquot  of digested sample  (or, in the case of
      extracts, a 50-mL sample)   add  10 mL of  concentrated HN03   and  12 mL of
      18 N H2S04.   Evaporate the sample on a hot plate  until  white S03 fumes are
      observed  (a  volume of  about  20  mL).  Do not let  it char.   If it chars,
      stop the digestion, cool,  and add additional  HN03.  Maintain  an excess of
      HN03 (evidence of brown fumes) and  do not let the solution darken because
      selenium may be  reduced and  lost.   When the sample remains colorless or
      straw yellow during evolution of S03 fumes,  the  digestion is  complete.

            Caution: Venting reaction vessels should be done with
            caution and only under a fume hood or well ventilated
            area.

            7.1.2   Cool the sample,  add about  25 mL  reagent water,  and again
      evaporate to S03  fumes just to expel oxides of nitrogen.   Cool.  Add 40 mL
      concentrated HC1  and bring to a volume of 100 mL with reagent water.

                                   7741A  - 3                       Revision 1
                                                                  November  1992
-------
      7.2   Prepare working standards from the  standard  stock  solutions.   The
following procedures provide standards in the optimum range.

            7.2.1   To  prepare  a working stock solution, pipet  1  ml standard
      stock solution (see Paragraph 5.8) into a 1-liter volumetric flask.  Bring
      to volume with  reagent water  containing 1.5 ml concentrated HN03/liter.
      The  concentration  of this solution is 1 mg Se/L (1 ml = 1 ug Se).

            7.2.2   Prepare six working standards by transferring 0, 0.5,  1.0,
      1.5, 2.0, and 2.5 ml of the working stock solution (see Paragraph 7.2.1)
      into  100-mL  volumetric  flasks.    Bring to  volume with  diluent.   The
      concentrations of these working standards are  0, 5,  10, 15, 20, and 25 ug
      Se/L.

      7.3   Standard additions:

            7.3.1     Take  the   15-,  20-, and 25-ug  standards and  transfer
      quantitatively 25 ml  from each  into separate 50-mL  volumetric  flasks.  Add
      10 ml of the prepared sample to each.   Bring to volume with reagent water
      containing 1.5 mL HNOg/liter.

            7.3.2   Add 10  ml  of prepared sample  to a 50-mL volumetric flask.
      Bring to volume with reagent water containing  1.5  mL HN03/liter.  This is
      the blank.

      7.4   Follow  the  manufacturer's  instructions  for  operating  an  argon-
hydrogen  flame.   The  argon-hydrogen flame is  colorless;  therefore,  it may be
useful to  aspirate  a  low concentration of sodium to  ensure  that ignition has
occurred.

      7,5   The 196.0-nm wavelength  shall  be  used  for  the  analysis of selenium.

      7.6   Transfer  a 25-mL portion of the digested sample or standard to the
reaction vessel.  Add  0.5 mL SnCl2 solution.   Allow at least 10 min for the metal
to be reduced to its lowest oxidation state.   Attach the  reaction vessel to the
special  gas  inlet-outlet  glassware.   Fill  the medicine  dropper with  1.50 mL
sodium borohydrate  or zinc slurry  that  has  been kept  in  suspension with the
magnetic stirrer.  Firmly insert the  stopper containing the medicine  dropper into
the side  neck  of  the  reaction  vessel.   Squeeze the bulb to introduce the zinc
slurry or  sodium  borohydrate into the sample or standard solution.  The metal
hydride will produce  a peak almost  immediately.  When the recorder  pen  returns
partway to the  base line, remove the reaction  vessel.


8.0   QUALITY  CONTROL

      8.1  Refer to section 8.0  of Method 7000.
                                   7741A - 4                       Revision  1
                                                                   November 1992
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9.0   METHOD PERFORMANCE

      9.1   Precision and accuracy data are available in Method 270.3 of Methods
for Chemical Analysis of Water and Wastes.


10.0  REFERENCES

1.    Methods  for Chemical  Analysis  of  Water and  Wastes,  EPA-600/4-82-055,
December 1982, Method 270.3.
                                   7741A - 5                      Revision  1
                                                                  November 1992
-------
                        METHOD  7741A
  SELENIUM (ATOMIC ABSORPTION,  GASEOUS  HYDRIDE)
C
                             surt
          Standard Preparation
         Sample Preparation
  7 2.1 Pipet
     • took
 solution into
 flack;  bring
   to vo 1 uae
7.2.2 Prepare 6
  Sm working
standard*  from
•tock;  bring to
    volume
7 3 1 Transfer
  3 standard
 portions,add
sample,bring to
    v o1ume
   7.3.2  To
 prepare  blank
add sample to a
flask and bring
   to volume
  7.4 Follow
 instruction*
 for operating
argon-hydrogen
     flan*
 7 5 Use  196.0
 nm wavelength
                           7.1 1 Add
                         concentrated
                        H.SO, and HNO.
                         to sample and
                           evaporate
  7 1.1  Stop
digestion,cool,
   add HNO.
 7 6 Transfer
digested  sampli
  to reaction
  vessel,add
     SnCl,
                          712 Cool
                          sample,add
                        reagent water,
                        evaporate,cool
                           7.1.2 Add
                         concentrated
                         HC1 and bring
                           to volume
                          7  6 Allow to
                          stand,attach
                            vessel to
                          glassware,add
                            Zn slurry
                          7  D Record Se
                          concentration
     Stop
                                     J
                           7741A -  6
                                            Revision  1
                                            November 1992
-------
                                  METHOD 7742

               SELENIUM (ATOMIC  ABSORPTION,  GASEOUS  BOROHYDRIDE)
1.0  SCOPE AND APPLICATION

      1.1  Method 7742 is an atomic absorption  procedure for determining 3 jjg/L
to 750 jjg/L concentrations of selenium in wastes, mobility procedure extracts,
soils,  and  ground water.   Method 7742  is  approved for  sample  matrices  that
contain up  to  1000 mg/L concentrations of cobalt,  copper,  iron,  mercury, and
nickel. A solid sample can contain up to 10% by weight of the interferents before
exceeding 1000 mg/L in a digested sample.  All samples including aqueous matrices
must be subjected to an  appropriate dissolution step prior to analysis.  Spiked
samples and relevant standard reference materials are employed to determine the
applicability of the method to a given waste.


2.0  SUMMARY OF METHOD

      2.1  Samples are prepared according to the nitric  acid digestion procedure
described   in   Method   3010   for  aqueous  and  extract  samples   and   the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace  AA option)  for  sediments,  soils,  and  sludges.   Excess  peroxide is
removed by  evaporating   samples  to near-dryness at  the  end of  the  digestion
followed by dilution to  volume and degassing  the  samples upon addition of urea.
The selenium  is  converted to the +4 oxidation  state during  digestion in  HC1.
After a 1:10 dilution, selenium is then converted to its volatile hydride using
hydrogen  produced  from the  reaction of  the  acidified  sample  with  sodium
borohydride in a continuous-flow hydride generator.

      2.2   The volatile hydride  is  swept  into  an  air-acetylene  flame heated
quartz  absorption  cell   located  in the optical  path of  an  atomic absorption
spectrophotometer.    The  resulting  absorption  of  the  lamp  radiation  is
proportional to the selenium concentration.

      2.3  The typical detection limit for this method is 3 jug/L.


3.0  INTERFERENCES

      3.1   Very  high (>1000  mg/L)  concentrations  of cobalt,  copper,  iron,
mercury, and,  nickel can  cause analytical  interferences  through precipitation as
reduced metals and associated blockage of transfer lines and fittings.

      3.2  Traces of peroxides left following the sample work-up can result in
analytical interferences.  Peroxides must be removed by evaporating each sample
to  near-dryness  followed  by  reacting  each   sample  with  urea  and  allowing
sufficient time for degassing before analysis  (see Sections 7.1 and 7.2).
                                    7742-1                        Revision 0
                                                                  November 1992
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4.0  APPARATUS AND MATERIALS

      4.1  Electric  hot  plate:   Large enough to hold at  least  several  100 mL
Pyrex digestion beakers.

      4.2   A  continuous-flow hydride  generator:    A commercially  available
continuous-flow  sodium  borohydride/HCl  hydride  generator  or  a  generator
constructed similarly to  that shown in Figure  1 (P. S.  Analytical or equivalent).

            4.2.1  Peristaltic Pump:  A four-channel,  variable-speed peristaltic
      pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
      or equivalent).  Pump speed and tubing diameters should  be  adjusted to
      provide  the  following  flow  rates:    sample/blank  flow  =  4.2  mL/min;
      borohydride flow = 2.1 mL/min.

            4.2.2  Sampling Valve (optional):    A  sampling valve (found in the
      P. S.  Analytical  Hydride  Generation  System or equivalent)  that  allows
      switching between samples and blanks (rinse solution) without introduction
      of air into the system will provide more signal stability.

            4.2.3  Transfer Tubing and Connectors:  Transfer tubing  (1 mm I.D.),
      mixing T's, and connectors  are made of  teflon and are of compatible sizes
      to  form tight,  leak-proof connections  (Latchat,  Technicon,  etc.  flow
      injection apparatus accessories or equivalent).

            4.2.4  Mixing Coil:  A 20-turn coil made by wrapping transfer tubing
      around a 1-cm diameter by 5-cm long plastic or glass rod (see Figure 1).

            4.2.5  Mixing Coil Heater:  A 250-mL Erlenmeyer flask containing 100
      mL of water heated  to boiling  on  a dedicated  one-beaker hotplate (Corning
      PC-35 or equivalent).  The  mixing  coil  in 4.2.4  is  immersed  in the boiling
      water  to  speed kinetics of the  hydride forming reactions  and increase
      solubility of  interfering reduced metal precipitates.

            4.2.6   Gas-Liquid Separator:    A glass   apparatus  for collecting
      liquid  and  gaseous products  (P.  S. Analytical  accessory  or equivalent)
      which allows the liquid  fraction  to drain to waste  and gaseous products
      above the liquid to be swept by a regulated carrier gas (argon)  out of the
      cell for analysis.   To avoid  undue carrier gas dilution,  the gas volume
      above the liquid should not exceed 20 mL.   See  Figure  1 for an acceptable
      separator shape.

            4.2.7  Condenser:   Moisture picked  up by the  carrier  gas must be
      removed before  encountering the  hot absorbance cell.   The moist carrier
      gas with the hydrides is dried by  passing the gasses  through a small  (< 25
      mL) volume condenser coil  (Ace Glass Model  6020-02 or  equivalent) that is
      cooled to 5°C by a water chiller (Neslab RTE-110 or equivalent).  Cool tap-
      water  in place  of  a chiller is acceptable.
                                    7742-2                        Revision 0
                                                                  November 1992
-------
            4.2.8  Flow Meter:  A meter capable of regulating up to 1 L/min of
      argon carrier gas is recommended.

      4.3  Absorbance Cell:  A 17-cm or longer quartz  tube T-cell (windowless is
strongly suggested)  is recommended,  as  shown  in  Figure  1  (Varian  Model  VGA-76
accessory or equivalent).   The cell  is held  in place  by a holder that positions
the  cell  about 1  cm over a  conventional  AA air-acetylene  burner head.   In
operation, the cell is heated to around 900°C by  an air-acetylene  flame.

      4.4   Atomic absorption  spectrophotometer:  Single-  or  dual-  channel,
single- or double-beam instrument having a grating  monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for interfacing with a strip-chart recorder.

      4.5  Burner:  As recommended by the particular instrument manufacturer for
an air-acetylene flame.  An appropriate  mounting  bracket attached to the burner
that suspends the quartz absorbance cell between 1 and 2 cm above the burner slot
is required.

      4.6  Selenium hollow cathode lamp or selenium electrode!ess discharge lamp
and  power  supply.    Super-charged  hollow-cathode  lamps  or   EDL  lamps  are
recommended for maximum sensitivity.

      4.7     Strip-chart   recorder   (optional):       Connect   to   output  of
spectrophotometer.


5.0  REAGENTS

      5.1  Reagent water :   Water must  be monitored  for impurities.   Refer to
Chapter 1 for definition of Reagent water.

      5.2  Concentrated nitric acid  (HN03):  Acid must be analyzed to determine
levels of impurities.  If a method blank is 
-------
                              QUARTZ  CELL

                              A A  OURHER
•DISCONNECTS
 DURING S*XSn
  ntlALVSIS
                                                                    TO
                                                                 CHILLER
                                                            0AS/LIQUID
                                                             SEPARATOR
                                                                —» DRAIN
                      20  TURN  COIL
                       (TEFLON)
                       HOTPLATE
                        VALUE
                       (BLANK)
Figure 1.  Continuous-flow sodium borohydride/hydride generator apparatus setup
and an AAS sample  introduction  system
                                     7742-4
Revision 0
November 1992
-------
      5.7  4% Sodium Borohydride  (NaBH4):  A 4 % sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water) must be prepared for conversion of the selenium to its hydride.

      5.8  Selenium solutions:

            5.8.1   Selenium  standard stock  solution   (1,000  mg/L):   Either
      procure  certified  aqueous  standards  from  a  supplier  (Spex,  Inorganic
      Ventures, or equivalent) and verify by comparison  with a second standard,
      or dissolve 0.3453 g of selenious  acid  (assay 96.6% of H2Se03) in 200 ml
      of reagent water (1 ml = 1 mg Se).

            5.8.2   Selenium  working  stock solution:    Pipet  1 ml  selenium
      standard stock solution into  a  1  L volumetric  flask  and  bring to volume
      with  reagent water  containing  1.5  ml concentrated  HN03/liter.    The
      concentration of this solution is  1 mg Se/L (1 mL = 1 jjg Se).


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All samples must  have been  collected  using a  sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual.

      6.2  All sample containers must be prewashed with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Special  containers   (e.g.,  containers used for volatile  organic
analysis) may have to be  used  if  very  volatile  selenium  compounds are suspected
to be present  in the samples.

      6.4  Aqueous samples must be acidified to a pH of <2 with nitric acid.

      6.5  Nonaqueous  samples  shall be refrigerated, when possible, and analyzed
as soon as possible.


7.0  PROCEDURE

      7.1  Place a 100-mL portion of an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-mL digestion beaker.  Digest aqueous samples and
extracts according to Method 3010.  Digest solid samples according to Method 3050
(furnace AA option) with  the following modifications:  add 5 mL of concentrated
hydrochloric  acid  just prior to  the final  volume  reduction  stage to  aid  in
conversion of selenium to  its  plus four state; the final  volume reduction should
be to less  than  5 mL but not to  dryness to adequately  remove  excess hydrogen
peroxide (see note).  After dilution to volume, further dilution  with diluent may
be necessary  if the analyte is known to  exceed 750 /yg/L or if interferents are
expected to exceed 1000 mg/L in the digestate.
                                    7742-5                        Revision 0
                                                                  November  1992
-------
NotetFor solid digestions, the volume reduction stage is critical to obtain
     accurate data.  Close monitoring of each sample is necessary when this
     critical stage in the digestion is reached.

      7.2  Prepare samples for hydride analysis by adding 1.00 g urea, and 20 ml
concentrated HC1 to a 5.00 ml aliquot of digested sample in a 50-mL volumetric
flask.  Heat in a water bath  to  dissolve salts and reduce selenium (at least 30
minutes  is  suggested).    Bring flask  to volume  with  reagent  water  before
analyzing.    A  ten-fold  dilution   correction  must  be  made   in  the  final
concentration calculations.

      7.3  Prepare working standards from  the standard stock selenium solution.
Transfer 0,  0.5,  1.0,  1.5, 2.0, and 2.5  ml  of standard to  100-mL volumetric
flasks and bring to volume with diluent.  These concentrations will be 0, 5, 10,
15, 20, and 25 /AJ Se/L.

      7.4   If  EP extracts (Method  1310)  are being  analyzed  for  selenium,  the
method of standard additions must be  used.   Spike appropriate  amounts of working
standard selenium  solution to  three 25 ml aliquots of  each  unknown.   Spiking
volumes should  be  kept  less  than 0.250  ml to avoid  excessive spiking dilution
errors.

      7.5   Set up  instrumentation  and  hydride generation apparatus  and fill
reagent containers.  The sample  and blank flows should be set  around 4.2 mL/min,
and the  borohydride flow  around 2.1 mL/min.   The  argon carrier gas  flow is
adjusted to about 200 mL/min.   For the AA,  use the 196.0-nm wavelength and 2.0-nm
slit width without background correction.   Begin all flows and allow 10 minutes
for warm-up.

      7.6  Place sample feed  line into a prepared sample solution  and start pump
to  begin  hydride generation.   Wait  for a maximum  steady-state  signal  on the
strip-chart recorder.  Switch to blank sample and watch for  signal to decline to
baseline before  switching to the next  sample and  beginning the  next analysis.
Run standards  first (low to  high),   then  unknowns.   Include  appropriate QA/QC
solutions,  as required.   Prepare calibration curves and convert  absorbances to
concentration.  See following analytical  flowchart.

        CAUTION:  The  hydride of selenium is  very toxic.   Precautions must be
                  taken to avoid inhaling the gas.

      7.7   If the method  of standard additions was employed,  plot the measured
concentration  of the  spiked samples  and unspiked  sample versus  the  spiked
concentrations.  The spiked concentration axis  intercept will be the method of
standard  additions  concentration.   If the plot does  not result  in a straight
line,  a  nonlinear  interference is  present.    This  problem   can sometimes be
overcome by dilution or addition of other reagents  if there  is  some knowledge
about the waste.  If the method  of standard additions was not  required, then the
concentration  is determined from a  standard calibration curve.
                                    7742-6                        Revision 0
                                                                  November 1992
-------
8.0  QUALITY CONTROL

      8.1  Refer to Section 8.0 of Method 7000.


9.0  METHOD PERFORMANCE

      9.1  The relative standard deviation obtained by a single laboratory for
7 replicates of a contaminated soil was 18% for selenium at 8.2  ug/L in solution.


10.0  REFERENCES

1.    Methods  for  Chemical Analysis  of  Water and Wastes,  EPA-600/4-82-055,
      December 1982, Method 206.3.

2.    "Evaluation of Hydride Atomic Absorption Methods  for Antimony,  Arsenic,
      Selenium, and Tin",  an EMSL-LV internal report under Contract 68-03-3249,
      Job Order  70.16,  prepared for  T.  A.  Hinners by  D.  E.  Dobb, and  J.  D.
      Lindner of Lockheed Engineering  and Sciences Co.,  and L. V. Beach of the
      Varian Corporation.
                                    7742-7                        Revision 0
                                                                  November 1992
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                          METHOD  7742
SELENIUM  (ATOMIC ABSORPTION,  GASEOUS BOROHYDRIDE)
7.1 Use Method
 3050  (furnace
 AA option) to
 digest 1.0 9
    •ample
    7.1-7.4
  Digest with
    H.O. a*
 described in
  Method 30SO
    7.5 Add
 concentrated
     HC1
 7.6 Do final
   volume
 reduction and
 dilution, a*
   described
                            7.1 Use
                          Method 3010
                         to digest 100
                           ml sample
 7 2 Add urea
and cone HC1 to
aliquot;heat in
H,0 bath; bring
   to volume
  7 3  Prepare
    working
standards from
standard stock
  Se solution
                          7 4 Spike 3
                         aliquoIs  with
                            working
                          standard Se
                           solution
                        7 5-7 6  Analyze
                          the samp1e
                         using hybrid
                          generation
                           apparatus
                         7 7 Determine
                         Sa cone   from
                           s tandard
                          calibration
                             curve
                          7 4 Use  the
                           method  of
                           standard
                         additions on
                        extracts,  only
                        7 5-7 6 Analyze
                          the sample
                         using hybrid
                          generation
                           apparatus
                         7 7 Determine
                              Se
                         concentration
                          from linear
                             plot
                             Stc
                            7742-8
                                           Revision 0
                                           November  1992
-------
                                METHOD 7760

               SILVER (ATOMIC ABSORPTION.  DIRECT ASPIRATION)
1.0  SCOPE AND APPLICATION

    1.1   Method  7760  is  an  atomic  absorption procedure  approved  for
determining the  concentration  of silver  (CAS  Registry Number  7440-22-4)  in
wastes, mobility procedure extracts, soils, and ground water. All samples must
be subjected to an appropriate  dissolution step prior to analysis.

2.0  SUMMARY OF METHOD

    2.1  Prior to analysis by Method 7760, samples must be prepared for direct
aspiration.  The method of sample  preparation will vary according to the sample
matrix.  Aqueous  samples  are  subjected to  the  acid-digestion procedure
described in this method.

    2.2  Following the appropriate dissolution of the sample, a representative
aliquot is aspirated into an air/acetylene flame.  The resulting absorption of
hollow  cathode  radiation will  be proportional  to the  silver concentration.
Background correction must be employed for all analyses.

    2.3  The  typical  detection  limit  for this  method  is 0.01  mg/L;  typical
sensitivity is 0.06 mg/L.

3.0  INTERFERENCES

    3.1  Background correction  is required because nonspecific absorption and
light scattering may occur at the analytical wavelength.

    3.2  Silver nitrate solutions are light-sensitive and have the tendency to
plate out on  container walls.  Thus  silver standards should be stored in brown
bottles.

    3.3  Silver  chloride is insoluble;  therefore,  hydrochloric acid should be
avoided unless the silver is already in solution as a chloride complex.

    3.4  Samples  and  standards  should  be monitored for viscosity differences
that may alter the aspiration rate.

4.0  APPARATUS AND MATERIALS

    4.1   Atomic absorption  spectrophotometer:   Single-  or  dual-channel,
single-  or  double-beam  instrument  with  a  grating  monochromator,
photomultiplier  detector,  adjustable  slits,  and provisions  for background
correction.

    4.2  Silver hollow cathode  lamp.

    4.3  Strip-chart recorder (optional).


                                 7760 - 1                        Revision 1
                                                                December 1987
-------
5.0  REAGENTS

    5.1  Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated,  it  is  intended  that  all  reagents   shall  conform  to  the
specifications  of the  Committee  on Analytical  Reagents  of the  American
Chemical Society, where such specifications  are available.  Other grades may be
used,  provided  it  is  first  ascertained  that the reagent  is  of sufficiently
high  purity to  permit  its  use  without   lessening the accuracy  of  the
determination.

    5.2  ASTM Type II Water (ASTM D1193-77  (1983)). All references to water in
the method refer to ASTM Type II unless  otherwise  specified.

    5.3  Nitric Acid (concentrated),  HN03.

    5.4  Ammonium Hydroxide (concentrated),  NH40H.

    5.5  Silver Stock Standard Solution  (1,000 mg/L),  AgNOa. Dissolve 0.7874 g
anhydrous  silver  nitrate in water.  Add  5  ml HN03  and  bring  to  volume  in a
500-mL  volumetric  flask  (1  ml  = 1  mg Ag).  Alternatively, procure a certified
aqueous  standard  from a  supplier  and  verify  by  comparison with  a second
standard.

    5.6   Silver working standards  -  These  standards  should be prepared from
silver  stock solution  to  be  used  as calibration  standards  at the  time of
analysis. These standards should be  prepared with nitric acid  and at the same
concentrations as the analytical solution.

    5.7   Iodine  solution  (IN).  Dissolve  20  g potassium  iodide (KI),  in 50 ml
of  water.  Add  12.7  g iodine  (12)   and  dilute  to 100 ml. Store  in  a brown
bottle.

    5.8   Cyanogen  iodide  solution. Add  4.0 mL  ammonium hydroxide,  6.5 g
potassium cyanide  (KCN), and 5.0 mL  of iodine solution to  50 ml of water. Mix
and dilute to 100 ml with water. Do not  keep longer than  2  weeks.

    CAUTION: This  reagent  cannot  be mixed  with  any acid solutions  because
             toxic hydrogen cyanide will  be  produced.

    5.9  Air.

    5.10  Acetylene.

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

    6.1   All  samples must  have been collected  using  a  sampling  plan that
addresses the considerations discussed in Chapter  Nine of this  manual.

    6.2   All  sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers  are both  suitable.

    6.3  Aqueous samples must be acidified  to a pH <  2 with nitric  acid.


                                 7760 - 2                       Revision  1
                                                                December  1987
-------
    6.4  When possible,  standards  and  samples  should  be  stored  in the dark and
in brown bottles.

    6.5  Nonaqueous samples shall  be refrigerated, when  possible, and analyzed
as soon as possible.

7.0  PROCEDURE

    7.1  Sample preparation - Aqueous samples should be prepared according to
Steps 7.2  and  7.3.  The applicability of a  sample  preparation  technique to a
new  matrix type  must  be  demonstrated  by analyzing  spiked  samples   and/or
relevant standard  reference materials.

    7.2  Preparation of aqueous samples

         7.2.1  Transfer a  representative aliquot of the well-mixed sample to
    a beaker and add 3  ml  of concentrated HNOs. Cover the  beaker with  a watch
    glass. Place  the  beaker on a hot plate  and  cautiously evaporate  to near
    dryness,  making certain that  the  sample  does  not boil. DO NOT BAKE. Cool
    the beaker  and  add another 3-mL  portion  of  concentrated HN03. Cover the
    beaker with  a  watch  glass  and  return   to  the  hot  plate.  Increase the
    temperature of the hot plate so  that a  gentle  reflux action occurs.

    NOTE:  If  the sample   contains  thiosulfates,  this  step  may  result  in
           splatter  of sample  out of  the  beaker as  the sample  approaches
           dryness. This has been reported to occur  with  certain photographic
           types of samples.

         7.2.2  Continue heating, adding additional  acid,  as necessary, until
    the digestion is complete (generally indicated when  the digestate is light
    in  color or  does  not change  in appearance  with  continued  refluxing).
    Again, evaporate to near dryness and cool  the  beaker.  Add a small quantity
    of HN03 so  that  the final  dilution  contains  0.5% (v/v) HN03 and warm the
    beaker to dissolve any precipitate or residue  resulting from evaporation.

         7.2.3  Wash  down  the  beaker walls  and watch  glass with  water and,
    when necessary, filter  the sample to remove silicates  and  other  insoluble
    material  that  could  clog  the nebulizer.  Adjust the volume to some
    predetermined  value based on the expected  metal concentrations. The sample
    is now ready for analysis.

    7.3    If  plating  out  of  AgCl  is  suspected,  the  precipitate  can  be
redissolved by  adding  cyanogen iodide  to  the sample.  This  can  be done only
after digestion and after  neutralization of the sample to  a  pH  > 7 to  prevent
formation of toxic cyanide under  acid conditions.  In this case do not  adjust
the  sample volume  to  the predetermined  value until  the  sample has  been
neutralized to  pH > 7  and  cyanogen  iodide  has been added.  If  cyanogen  iodide
addition to the sample is necessary, then the  standards  must be treated in the
same  manner.  Cyanogen  iodide  must not  be   added  to  the acidified  silver
standards. New standards  must  be made,  as  directed  in  Steps 5.5  and 5.6,
except that the acid  addition  step  must be omitted.  For example,  to obtain a
100 mg/L working standard,  transfer  10 ml of  stock  solution to  a small  beaker.
Add  water  to make  about  70 ml.  Make the solution  basic  (pH  above  7) with

                                 7760  -  3                       Revision 1
                                                                December 1987
-------
ammonium  hydroxide.  Rinse  the  pH  meter  electrodes  into the  solution  with
water.  Add  1  ml  cyanogen  iodide  and allow  to  stand  1  hour.  Transfer
quantitatively to a 100-mL volumetric  flask and bring to volume with water.

    CAUTION:  CNI  reagent  can be  added  only  after  digestion  to  prevent
              formation of toxic cyanide under acidic conditions.  CNI reagent
              must not be added to the acidified silver standards.

    NOTE:  Once the  sample  or sample  aliquot has  been  treated with  the  CNI
           reagent  and  diluted per instruction, the  solution has  a cyanide
           concentration of approximately 260 mg/L. A solution of that cyanide
           concentration must  be  considered  a potential  hazardous  waste  and
           must be  disposed of using  an approved  safety  plan  in  accordance
           with local authority requirements.  Until  such time that a detailed
           disposal plan can be fully documented and approved, the use of the
           CNI reagent should be avoided.

    7.4  The  328.1 nm  wavelength  line and background  correction  shall  be
employed.

    7.5  An oxidizing air-acetylene  flame shall  be used.

    7.6  Follow  the  manufacturer's  operating  instructions  for  all  other
spectrophotometer parameters.

    7.7  Either   (1)  run  a  series  of silver  standards and  construct  a
calibration curve  by  plotting  the concentrations of the standards against the
absorbances,  or  (2)  for  the method  of  standard  additions,  plot  added
concentration versus  absorbance.  For instruments  that  read directly  in
concentration, set the curve corrector to read out the proper  concentration.

    7.8  Analyze  all  Extraction Procedure  (EP) extracts, all  samples  analyzed
as  part of a delisting  petition,  and  all  samples  that  suffer  from matrix
interferences by the method of standard additions.

    7.9  Calculate metal  concentrations:  (1)  by  the  method of standard
additions,  (2) from a calibration curve, or (3)  directly from  the instrument's
concentration  read-out.  All dilution or concentration  factors  must be taken
into account.

8.0 QUALITY CONTROL

    8.1  All quality  control data should be maintained and available  for easy
reference or inspection.

    8.2  Calibration  curves  must be  composed of  a minimum  of  a  calibration
blank  and  three  standards.  A calibration curve  should  be  made for every hour
of continuous sample analysis.

    8.3  Dilute  samples if  they  are more  concentrated  than the highest
standard or if they fall on the plateau of  a  calibration curve.
                                 7760 - 4                       Revision 1
                                                                December 1987
-------
    8.4  Employ a minimum of  one  reagent  blank per sample batch to determine
if contamination or any memory effects  are  occurring.

    8.5  Verify  calibration  with  an   independently prepared  qualtiy control
reference sample every 15 samples.

    8.6  Run  one  spiked  replicate   sample  for  every  10  samples or  per
analytical  batch, whichever is more frequent.   A replicate sample is a sample
brought through the entire sample  preparation  and analytical process.

    8.7  The method of standard additions  (see Method 7000, Step 8.7) shall be
used for the analysis of all  EP extracts, on all analyses  submitted as part of
a delisting petition, and whenever a new sample matrix  is  being analyzed.

    8.8  Duplicates, spiked samples, and check standards  should be routinely
analyzed.

9.0 METHOD PERFORMANCE

    9.1  Precision and accuracy data are available  in Method 272.1 of "Methods
for Chemical Analysis of Water and Wastes."

    9.2  The data  shown in Table  1 were  obtained  from records  of  state and
contractor laboratories.  The  data are  intended to show the  precision  of the
combined sample preparation and analysis method.

10.0  REFERENCES

1.  Methods  for Chemical  Analysis of Water   and  Wastes;  U.S.   Environmental
    Protection  Agency.  Office of  Research  and  Development.  Environmental
    Monitoring and  Support  Laboratory.  ORD Publication Offices  of Center for
    Environmental   Research  Information:   Cincinnati,  OH,  1983;  EPA-
    600/4-79-020.

2.  Gaskill, A., Compliation  and  Evaluation of RCRA Method Performance Data,
    Work Assignment No. 2, EPA Contract No.  68-01-7075,  December  1987.

3.  Rohrbough,  W.G.;  et al.  Reagent  Chemicals,  American Chemical Society
    Specifications. 7th ed.; American  Chemical Society:  Washington, DC,  1986.

4.  1985 Annual  Book of  ASTM Standards.  Vol. 11.01;   "Standard  Specification
    for Reagent Water"; ATSM: Philadelphia,  PA, 1985; D1193-77.
                                 7760 - 5                       Revision 1
                                                                December 1987
-------
                                  TABLE  1.
                           METHOD  PERFORMANCE  DATA
       Sample                      Preparation                Laboratory
       Matrix                        Method                   Replicates


Wastewater treatment sludge           3050                   2.3, 1.6 ug/g

Emission control dust                 3050                   1.8, 4.2 ug/g
                                 7760 - 6                        Revision 1
                                                                 December 1987
-------
                                               METHOD 7760
                     SILVER  (ATOMIC  ABSORPTION,  DIRECT  ASPIRATION)
         Stipltl coataiaiaf
          oil,  friat*. or
           vax
                  Sludf«-typ«
                    •aaploi
7.1 Pr«p«r« iaipl«
according to Motkod
       3040
7.3.1  Traaafar aaipl*
 aliqaot to boakar:
add come altrle acid:
  tYaporata to saar
 drynaaa: cool: add
  cone altric acid:
boat ao faatla raflu
    actioa oceira
7.1 Prapar* aaapla
according to Matkod
      3660
                          7.2.2 Coaplata
                            dlfaatioa:
                         traporata to laar
                        dryaaaa: cool: add
                         coac aitric acid:
                         van to diaaolTO
                        any praeipitat* or
                              raaidia
                        7.2.S Flltar aaapla
                           If aacaaaary:
                        adJoat volaaa vitk
                               vatar
                          7.3 laitraliza
                       laapla: add cyaaofaa
                       lodida to dlaaolra
                       pracipltata: raiaka
                        ataadarda oaittiif
                       acid:  traaafar ali-
                       qsot of atock aola-
                        tlon  to baakar: add
                             vatar:
                                                                        T.J /UJl.t  pK vitk
                                                                        tuoiiti kydroxida:
                                                                        rim alactrodaa
                                                                         Imto toll vltk
                                                                        vatar: tdd  cytiofti
                                                                         iodlda: valt 1
                                                                        loir: traaafar to
                                                                         flask: briaf to
                                                                        Tol»« vltk vatar
                                                                            7.4-« Sat
                                                                           laatraiaat
                                                                           paraaatara
  7.7 Co»triet
calibration cirvo
                                                   7.1 Aaalyza  by
                                                 aatkod of ittadtrd
                                                    tdditioa if
                                                     ••coaiary
                                                 T.t Calcilati i.tal
                                                   coacoatratioa
                                                                              Stop
                                                7760 - 7
                                                                         Revision  1
                                                                         December  1987
-------
                                METHOD  7780

              STRONTIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)


1.0  SCOPE AND APPLICATION

    1.1  See Section 1.0 of Method 7000.

2.0  SUMMARY OF METHOD

    2.1  See Section 2.0 of Method 7000.

3.0  INTERFERENCES

    3.1  See Section 3.0 of Method 7000.

    3.2  Chemical  interference caused by  silicon,  aluminum,  and  phosphate  are
controlled  by  adding  lanthanum  chloride.  Potassium chloride  is  added to
suppress the ionization of strontium.  All  samples and standards should contain
1 ml of lanthanum chloride/potassium chloride solution (Step 5.3) per 10 mL of
solution.

4.0  APPARATUS AND MATERIALS

    4.1  For basic apparatus, see Section  4.0 of Method 7000.

    4.2  Instrument parameters (general):

         4.2.1  Strontium hollow cathode lamp.

         4.2.2  Wavelength:  460.7 nm.

         4.2.3  Fuel:  Acetylene.

         4.2.4  Oxidant:  Air.

         4.2.5  Type of flame:  Oxidizing  (fuel  lean).

         4.2.6  Background correction: not required.

5.0  REAGENTS

    5.1  See Section 5.0 of Method 7000.

    5.2  Preparation of standards

         5.2.1   Stock  solution:    (1.0  ml =  1.0 mg  Sr).  Dissolve 2.415 g of
    strontium nitrate,  Sr(NOs)2,  in 10 mL of concentrated  HC1 and  700  mL of
    water. Dilute  to 1 liter with  water. Alternatively,  procure  a  certified
    standard from a supplier and verify by comparison with a second standard.
                                 7780 -  1                        Revision  0
                                                                 December  1987
-------
         5.2.2   Prepare  dilutions of  the  stock  solution  to  be  used as
    calibration standards at the  time  of analysis. The calibration standards
    should be prepared  using the  same  type of acid  as  the samples and cover
    the range of expected concentrations  in the samples. Calibration standards
    should also contain 1  ml of lanthanum chloride/potassium  chloride  solution
    per 10 ml.

    5.3   Lanthanum  Chloride/Potassium  Chloride  Solution.  Dissolve 11.73 g of
lanthanum oxide, La203, in  a minimum amount of concentrated  hydrochloric  acid
(approximately 50 ml).  Add  1.91  g of potassium chloride,  KC1. Allow  solution
to cool to room temperature and dilute  to 100  ml with water.

    CAUTION: REACTION IS  VIOLENT!   Add acid  slowly  and  in small  portions to
             control the reaction rate  upon mixing.

6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

    6.1  See Chapter Three, Step 3.1.3,  Sample Handling  and Preservation.

7.0  PROCEDURE

    7.1  Sample preparation - The procedures for preparation  of the  sample are
given in Chapter Three,  Step 3.2.

    7.2  See Method 7000,  Step  7.2,  Direct Aspiration.

8.0  QUALITY CONTROL

    8.1  See Section 8.0 of Method 7000.

9.0 METHOD PERFORMANCE

    9.1   The  performance characteristics  for  an   aqueous sample  free of
interferences are:

         Optimum concentration  range:   0.3-5 mg/L at a wavelength  of
         460.7 nm.
         Sensitivity: 0.15 mg/L.
         Detection limit: 0.03  mg/L.

         9.1.1   Recoveries of  known  amounts  of strontium in  a  series of
    prepared standards were as  given in Table 1.

10.0  REFERENCES

1.   Annual Book of ASTM Standards;  ASTM:  Philadelphia,  PA,  1983; D3920.
                                 7780 - 2                        Revision 0
                                                                 December 1987
-------
                                  TABLE 1.
                                  RECOVERY

Amount
added,
mg/L

Amount
found,
mg/L
Significant
(95 %
% confidence
Bias Bias level)
      1.00
      0.50
      0.10
         Reagent Water Type II

     0.998         -0.002      -0.2
     0.503         +0.003      +0.6
     0.102         +0.002      +2

            Water of Choice
                                        no
                                        no
                                        no
1.00
0.50
0.10
1.03
0.504
0.086
+0.03
+0.004
-0.014
+ 3
+ 0.8
-14
no
no
no
Reference:
Annual
D3920.
Book of  ASTM Standards; ASTM:  Philadelphia,  PA,  1983;
                                 7780 - 3
                                                  Revision 0
                                                  December 1987
-------
                     METHOD 7780
STRONTIUM  (ATOMIC  ABSORPTION,  DIRECT  ASPIRATION)
                        6.3  Pripar*
                         •tlldaril
                       7.1  for
                        Kturntioi, it*
                        pUr S, St*p 3.3
                      7.3  AatlTZ* ••!«(
                       N«tko« 7000. St«p
                      7780  - 4
Revision 0
December 1987
-------
                                 METHOD 3510B

                  SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0   SCOPE AND APPLICATION

      1.1   This method describes  a  procedure  for isolating organic compounds
from  aqueous  samples.   The  method  also  describes concentration  techniques
suitable for  preparing  the extract for the  appropriate  determinative methods
described in Section 4.3 of Chapter Four.

      1.2   This method  is applicable to  the  isolation and  concentration of
water-insoluble and slightly water-soluble organics in preparation for a variety
of chromatographic procedures.


2.0   SUMMARY OF METHOD

      2.1   A measured volume  of sample, usually 1 liter,  at  a  specified pH  (see
Table 1),  is  serially  extracted with methylene  chloride  using a  separatory
funnel.   The extract is dried, concentrated (if necessary),  and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative method to
be used (see Table 1 for appropriate exchange solvents).


3.0   INTERFERENCES

      3.1   Refer to Method 3500.

      3.2   Under basic extraction  conditions required to separate analytes for
the packed columns of Method 8250,  the decomposition of some analytes has been
demonstrated.   Organochlorine  pesticides may dechlorinate, phthalate esters may
exchange, and  phenols may react to form tannates.   These reactions increase with
increasing pH,  and  are decreased  by  the  shorter reaction  times available in
Method 3510.   Methods 3520/8270, 3510/8270, and  3510/8250,  respectively,  are
preferred over Method 3520/8250 for the analysis of these classes of compounds.


4.0   APPARATUS AND MATERIALS

      4.1   Separatory funnel  - 2 liter,  with Teflon stopcock.

      4.2   Drying column  - 20 mm  ID Pyrex chromatographic column  with  Pyrex
glass wool  at  bottom and a Teflon stopcock.

      NOTE: Fritted  glass  discs are  difficult  to decontaminate after  highly
            contaminated extracts  have  been  passed through.   Columns without
            frits may  be  purchased.   Use  a  small  pad  of Pyrex glass wool to
            retain the  adsorbent.   Prewash the glass wool  pad with  50  mL of
            acetone followed by  50 mL of elution  solvent prior to  packing the
            column with adsorbent.
                                  3510B  -  1                         Revision 2
                                                                 November 1992
-------
      4.3   Kuderna-Danish (K-D) apparatus.

            4.3.1 Concentrator tube -  10 ml, graduated (Kontes K-570050-1025 or
      equivalent).  A ground-glass  stopper  is used to prevent  evaporation of
      extracts.

            4.3.2 Evaporation    flask  -    500  mL  (Kontes  K-570001-500  or
      equivalent).   Attach  to  concentrator  tube  with   springs,  clamps,  or
      equivalent.

            4.3.3 Snyder  column  -  Three ball  macro (Kontes  K-503000-0121 or
      equivalent).

            4.3.4 Snyder  column -  Two ball  micro  (Kontes  K-569001-0219  or
      equivalent).

            4.3.5 Springs -  1/2 inch (Kontes  K-662750 or equivalent).

      4.4   Boiling chips - Solvent extracted,  approximately 10/40 mesh (silicon
carbide or equivalent).

      4.5   Water  bath   - Heated,  with  concentric  ring  cover,  capable  of
temperature control (±5°C).   The bath  should be used in a hood.

      4.6   Vials - 2 ml, glass with Teflon  lined screw-caps or crimp tops.

      4.7   pH indicator paper - pH range including the desired extraction pH.

      4.8   Erlenmeyer flask - 250 ml.

      4.9   Syringe - 5 ml.

      4.10  Graduated cylinder - 1 liter.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all  reagents  shall conform  to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society, where
such specifications are available. Other grades may  be used, provided it is first
ascertained that  the reagent  is of sufficiently high  purity to permit its use
without lessening the accuracy of the determination. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.

      5.2   Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sodium  hydroxide solution  (ION),  NaOH.   Dissolve 40 g  NaOH in
organic-free reagent water and dilute to 100 mL.

      5.4   Sodium sulfate (granular, anhydrous), Na2S04.   Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium sulfate is precleaned with methylene chloride,

                                   3510B - 2                        Revision  2
                                                                 November  1992
-------
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.

      5.5   Sulfuric acid solution  (1:1 v/v), H2SO,.   Slowly add 50 ml of H2S04
(sp. gr. 1.84) to 50 mL of organic-free reagent water.

      5.6   Extraction/exchange solvents

            5.6.1 Methylene chloride, CH2C12  - Pesticide quality or equivalent.

            5.6.2 Hexane, C6HU  -  Pesticide quality or equivalent.

            5.6.3 2-Propanol, CH3CH(OH)CH3 -  Pesticide quality or  equivalent.

            5.6.4 Cyclohexane, C6H12 - Pesticide quality or  equivalent.

            5.6.5 Acetonitrile, CH3CN -  Pesticide quality or equivalent.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the  introductory  material to this chapter, Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Using a  1  liter graduated cylinder, measure  1  liter  (nominal)  of
sample  and transfer it  quantitatively  to   the  separatory  funnel.   If high
concentrations are anticipated, a smaller volume  may be  used and then diluted
with  organic-free reagent  water  to  1  liter.   Add  1.0  mL of the surrogate
standards  to  all  samples,   spikes,  and  blanks  (see   Method 3500   and  the
determinative method to be used, for details  on the surrogate standard  solution
and the matrix spike  solution).  For the sample in each analytical batch  selected
for spiking, add  1.0 mL of the matrix spiking standard.   For base/neutral-acid
analysis, the amount  added of the surrogates and matrix spiking  compounds  should
result in a final concentration of  100  ng/p.1 of each base/neutral analyte and
200 ng//xL of  each acid  analyte  in the extract to  be  analyzed (assuming a 1  /*L
injection).  If Method 3640, Gel-Permeation Cleanup, is to be used,  add twice the
volume of surrogates  and matrix  spiking compounds since half the extract is lost
due to loading of the GPC column.

      7.2   Check  the  pH  of  the  sample  with  wide-range  pH  paper  and,  if
necessary,  adjust the  pH  to  that indicated  in Table  1  for  the   specific
determinative method that will be used to analyze the extract.

      7.3   Add 60 mL of methylene  chloride to the separatory funnel.

      7.4   Seal  and  shake the separatory funnel  vigorously for 1-2 minutes with
periodic venting to release excess  pressure.

      NOTE: Methylene  chloride   creates   excessive   pressure  very   rapidly;
            therefore,  initial  venting  should be  done  immediately  after the
            separatory funnel has been sealed and shaken once.  Venting  of the

                                   3510B  -  3                         Revision 2
                                                                 November 1992
-------
            separatory funnel should be into a hood to avoid needless exposure
            of the analyst to solvent vapors.

      7.5   Allow the  organic layer  to  separate from  the  water phase  for  a
minimum of 10 minutes.   If  the  emulsion  interface  between  layers is more than
one-third the  size  of the  solvent  layer,  the analyst  must  employ  mechanical
techniques to complete the phase separation.  The  optimum technique depends upon
the sample and may  include  stirring,  filtration  of the  emulsion through glass
wool, centrifugation, or other physical methods.  Collect the  solvent extract in
an Erlenmeyer flask.   If the emulsion cannot be broken (recovery of < 80% of the
methylene chloride,  corrected for the water solubility of methylene chloride),
transfer the  sample,  solvent, and  emulsion  into the extraction chamber  of  a
continuous extractor and proceed as described in Method 3520,  Continuous Liquid-
Liquid Extraction.

      7.6   Repeat the extraction  two more times using fresh portions of solvent
(Sections 7.3 through 7.5).   Combine the three solvent extracts.

      7.7   If further pH adjustment and extraction is required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1.  Serially extract
three  times  with 60  mL of  methylene chloride,  as  outlined  in Sections 7.3
through 7.5.  Collect  and combine the extracts and label  the combined extract
appropriately.

      7.8   If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration.  However, in  some situations,
separate concentration and analysis  of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral or base compounds at low concentrations must be determined, separate
extract analyses may be warranted).

      7.9   Perform  the  concentration  (if  necessary)  using the Kuderna-Danish
(K-D) Technique (Sections 7.10.1  through 7.10.4).

      7.10  K-D Technique

            7.10.1      Assemble  a  Kuderna-Danish  (K-D)   concentrator  by
      attaching a 10  mL  concentrator  tube  to a 500 mL evaporation  flask.  Dry
      the extract by passing  it through a drying column containing about  10 cm
      of  anhydrous  sodium   sulfate.    Collect  the   dried  extract  in   a K-D
      concentrator.   Rinse  the Erlenmeyer  flask,  which contained  the solvent
      extract, with 20-30 mL  of methylene chloride and  add it  to the column to
      complete the quantitative transfer.

            7.10.2      Add  one  or  two clean  boiling chips to  the flask and
      attach  a  three ball  Snyder column.   Prewet  the Snyder column by adding
      about 1 mL of methylene chloride to the top of  the column.  Place the K-D
      apparatus  on  a hot water bath  (15-20°C  above  the  boiling point  of the
      solvent) so that  the  concentrator  tube is  partially immersed in the hot
      water and the entire lower rounded surface of the flask is bathed with hot
      vapor.   Adjust  the  vertical   position of the  apparatus  and  the  water
      temperature as  required to  complete  the concentration in 10-20 minutes.
      At the  proper  rate of  distillation the balls of the column will actively
      chatter,  but  the chambers will  not  flood.   When  the apparent volume of

                                   3510B -  4                        Revision  2
                                                                 November 1992
-------
      liquid reaches  1  mL,  remove the K-D  apparatus  from the water  bath and
      allow it to drain and cool for at least 10 minutes.

            7.10.3      If a solvent exchange is required (as  indicated in Table
      1), momentarily  remove the  Snyder column,  add  50  ml of  the  exchange
      solvent,  a new boiling chip,  and  reattach the Snyder column.  Concentrate
      the extract, as described  in  Section 7.11, raising the temperature of the
      water bath, if necessary,  to maintain proper distillation.

            7.10.4      Remove the Snyder  column  and  rinse  the  flask  and its
      lower joints into the concentrator  tube with  1-2 ml of methylene chloride
      or  exchange solvent.   If  sulfur  crystals  are  a  problem, proceed  to
      Method 3660 for cleanup.  The extract may be  further concentrated by using
      the technique outlined  in  Section  7.11  or adjusted to  10.0 ml  with the
      solvent last used.

      7.11  If further concentration  is indicated  in Table 1, either the micro-
Snyder column technique  (7.11.1) or nitrogen blowdown technique  (7.11.2) is used
to adjust the extract to the final  volume required.

            7.11.1      Micro-Snyder Column Technique

                  7.11.1.1    If further  concentration  is indicated in Table 1,
            add another clean boiling chip to the concentrator tube and attach
            a two ball  micro-Snyder column.  Prewet the column by adding 0.5 ml
            of methylene chloride or  exchange  solvent to the top of the column.
            Place the K-D  apparatus in a hot water  bath  so that the concentrator
            tube is partially immersed in the hot  water.   Adjust the  vertical
            position of the  apparatus and the water temperature, as required, to
            complete the concentration in 5-10 minutes.  At the proper rate of
            distillation the balls  of the column will actively chatter, but the
            chambers will  not  flood.  When the apparent  volume of liquid reaches
            0.5 mL,  remove the K-D apparatus from the water  bath and allow it to
            drain and cool  for at least  10  minutes.  Remove  the  Snyder column
            and rinse the  flask  and its lower joints into the concentrator tube
            with 0.2 ml  of extraction solvent.  Adjust the final volume to 1.0-
            2.0 mL,  as indicated in Table 1, with  solvent.

            7.11.2      Nitrogen Blowdown Technique

                  7.11.2.1    Place the concentrator tube in  a warm bath (35°C)
            and evaporate  the  solvent volume to 0.5 mL using a gentle stream of
            clean, dry nitrogen (filtered through a column of activated carbon).

                  CAUTION:    New plastic tubing must not be  used between the
                              carbon   trap  and  the  sample,  since   it   may
                              introduce interferences.

                  7.11.2.2    The internal wall of  the tube must be rinsed down
            several  times  with methylene chloride or appropriate solvent during
            the operation.  During  evaporation,  the tube  solvent  level  must be
            positioned to avoid water condensation.  Under normal  procedures,
            the extract  must not be allowed  to become dry.


                                  3510B - 5                         Revision  2
                                                                 November  1992
-------
                  CAUTION:    When the volume of solvent  is reduced below 1 ml,
                              semivolatile analytes may be lost.

      7.12  The extract may now be  analyzed  for the target  analytes using the
appropriate determinative technique(s)  (see  Section  4.3  of  this Chapter).   If
analysis  of  the  extract  will  not  be  performed  immediately,  stopper  the
concentrator tube and store  refrigerated.   If the extract will be stored longer
than 2 days it should be transferred to  a  vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.


8.0   QUALITY CONTROL

      8.1   Any reagent blanks or matrix  spike  samples  should be subjected to
exactly the same analytical  procedures as those used on actual samples.

      8.2   Refer to  Chapter  One  for specific  quality  control  procedures and
Method 3500 for extraction and sample preparation procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


10.0  REFERENCES

1.    U.S. EPA 40  CFR Part 136, "Guidelines Establishing  Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act;  Final Rule and Interim
      Final Rule and Proposed Rule," October 26, 1984.
                                   3510B - 6                        Revision 2
                                                                 November  1992
-------



















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-------
                              METHOD 3510B
              SEPARATORY  FUNNEL LIQUID-LIQUID  EXTRACTION
       C   Start    J
           7 1 Add
          surrogate
       stands  to all
       samples,  spikes
         and blanks
Yes
                         7  7 Collect
                         and combine
                        extracts and
                           label
                                      7 8
                                    CC/MS
                                  analysis
                                 (Method 8250
                                  8270) being
                                  performed?
                                                 7 8 Combine
                                                base/neutral
                                                  extracts
                                                  prior to
                                                concentration
 7 2  Check
and adjust pH
           7 3-7  6
          Extract 3
            times
                          7  9-7  11
                         Concentrate
                          extract
                                     7  12
                                   Ready for
                                   analysis
7 7 Further
ex t ractions
 required'
                               3510B -  8
                                                          Revision 2
                                                       November 1992
-------
                                 METHOD 3520B

                      CONTINUOUS  LIQUID-LIQUID  EXTRACTION
1.0   SCOPE AND APPLICATION

      1.1   This method describes a  procedure  for  isolating  organic compounds
from  aqueous  samples.   The  method  also  describes concentration  techniques
suitable  for  preparing the  extract  for  the  appropriate determinative  steps
described in Section 4.3 of Chapter Four.

      1.2   This method  is applicable to  the  isolation and  concentration  of
water-insoluble and slightly  soluble organics  in preparation  for  a  variety  of
chromatographic procedures.

      1.3   Method 3520 is  designed for extraction solvents with greater density
than the  sample.   Continuous extraction devices are available  for  extraction
solvents that are less dense  than  the sample.  The analyst must demonstrate the
effectiveness of any  such  automatic  extraction device before employing  it  in
sample extraction.


2.0   SUMMARY OF METHOD

      2.1   A measured  volume of sample,  usually  1 liter,  is  placed  into  a
continuous liquid-liquid extractor, adjusted, if necessary, to a specific pH (see
Table 1), and extracted with  organic solvent for 18-24  hours.   The  extract  is
dried, concentrated (if necessary), and,  as  necessary, exchanged into a solvent
compatible with the cleanup or determinative method being employed (see Table 1
for appropriate exchange solvents).


3.0   INTERFERENCES

      3.1   Refer to Method 3500.

      3.2   Under basic extraction conditions required to separate analytes for
the packed columns of Method  8250, the decomposition of some analytes has been
demonstrated.  Organochlorine pesticides  may dechlorinate, phthalate esters may
exchange, and phenols  may react to form tannates.  These reactions increase with
increasing pH,  and  are decreased by the shorter  reaction times  available  in
Method 3510.   Methods 3520/8270,  3510/8270, and 3510/8250,  respectively,  are
preferred over Method  3520/8250 for the analysis of these classes of compounds.


4.0   APPARATUS AND MATERIALS

      4.1   Continuous liquid-liquid  extractor -  Equipped with Teflon or glass
connecting joints and  stopcocks requiring  no  lubrication (Kontes  584200-0000,
584500-0000, 583250-0000,  or  equivalent).

      4.2   Drying column  -  20 mm ID Pyrex chromatographic column  with  Pyrex
glass wool at bottom and a Teflon stopcock.

                                  3520B  -  1                         Revision 2
                                                                 November 1992
-------
      NOTE: Fritted glass  discs  are difficult  to decontaminate  after  highly
            contaminated extracts have  been  passed through.   Columns  without
            frits may be  purchased.   Use a  small  pad  of Pyrex glass wool  to
            retain the  adsorbent.   Prewash the glass  wool  pad with 50  ml  of
            acetone followed by 50 mL of elution  solvent  prior to packing the
            column with adsorbent.

      4.3   Kuderna-Danish (K-D)  apparatus

            4.3.1 Concentrator tube  -  10 ml graduated (Kontes K-570050-1025 or
      equivalent).  A ground  glass  stopper is used to prevent evaporation  of
      extracts.

            4.3.2 Evaporation  flask  -    500  ml   (Kontes  K-570001-500  or
      equivalent).   Attach  to concentrator tube  with   springs,  clamps,  or
      equivalent.

            4,3.3 Snyder column -   Three ball macro (Kontes  K-503000-0121  or
      equivalent).

            4.3.4 Snyder  column  -   Two ball micro (Kontes  K-569001-0219  or
      equivalent).

            4.3.5 Springs -  1/2  inch  (Kontes K-662750  or equivalent).

      4.4   Boiling chips - Solvent extracted, approximately  10/40 mesh (silicon
carbide or equivalent).

      4.5   Water  bath   -  Heated,  with concentric ring  cover,  capable  of
temperature control (± 5°C).   The  bath  should be used in  a hood.

      4.6   Vials - 2 ml, glass with Teflon lined  screw-caps or crimp tops.

      4.7   pH indicator paper -  pH range including the desired extraction pH.

      4.8   Heating mantle - Rheostat  controlled.

      4.9   Syringe - 5 ml.


5.0   REAGENTS

      5.1   Reagent grade chemicals  shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical  Reagents  of the American Chemical Society, where
such specifications are  available. Other grades may be used, provided it is first
ascertained that the reagent  is of  sufficiently high purity to permit  its use
without lessening the accuracy of the determination. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.

      5.2   Organic-free reagent  water - All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
                                   3520B -  2                         Revision 2
                                                                 November 1992
-------
      5.3   Sodium  hydroxide  solution  (ION),  NaOH.   Dissolve  40 g  NaOH  in
organic-free reagent water and dilute to  100 ml.

      5.4   Sodium sulfate (granular, anhydrous), Na2S04.   Purify by heating  at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.   If the sodium sulfate  is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.

      5.5   Sulfuric acid solution  (1:1 v/v), H2SO,.   Slowly  add 50 ml of H2S04
(sp. gr. 1.84) to 50 ml of organic-free reagent water.

      5.6   Extraction/exchange solvents

            5.6.1 Methylene chloride, CH2C12  - Pesticide quality or equivalent.

            5.6.2 Hexane, C6HU -  Pesticide quality or  equivalent.

            5.6.3 2-Propanol,  (CH3)2CHOH  - Pesticide  quality  or equivalent.

            5.6.4 Cyclohexane, C6H12 - Pesticide quality or equivalent.

            5.6.5 Acetonitrile, CH3CN -  Pesticide quality or  equivalent.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the  introductory  material to this chapter,  Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Using a 1 liter graduated cylinder, measure out 1  liter  (nominal)  of
sample and  transfer  it quantitatively to the  continuous  extractor.   If high
concentrations are anticipated, a smaller volume  may be  used and then diluted
with organic-free reagent water to 1 liter. Check the  pH of the sample with wide-
range pH paper and adjust the  pH, if necessary,  to the pH  indicated in Table 1
using 1:1  (V/V)  sulfuric  acid or 10 N sodium hydroxide.   Pipet  1.0  mL of the
surrogate standard spiking solution into  each sample  into  the extractor and mix
well.  (See Method 3500 and  the determinative method  to be used, for details  on
the surrogate standard solution and the matrix spike  solution.)  For the sample
in each analytical batch selected for spiking, add 1.0  mL  of the matrix spiking
standard.   For  base/neutral-acid analysis,  the  amount of the surrogates  and
matrix  spiking   compounds  added  to  the  sample  should  result   in  a  final
concentration of  100 ng//iL of each  base/neutral  analyte  and  200 ng//iL of each
acid analyte  in  the  extract  to be  analyzed  (assuming  a   1 piL  injection).    If
Method 3640,  Gel-Permeation  Cleanup, is  to  be  used, add  twice  the  volume  of
surrogates and matrix spiking  compounds since half the extract is  lost due  to
loading of the GPC column.

      7.2   Add 300-500 mL of methylene chloride to the distilling flask.  Add
several  boiling chips to the flask.


                                   3520B  - 3                         Revision 2
                                                                 November 1992
-------
      7.3   Add sufficient water to the extractor to ensure proper operation and
extract for 18-24 hours.

      7.4   Allow to cool; then detach the boiling flask.   If extraction at a
secondary pH is not required (see Table 1), the extract is dried and concentrated
using one of the techniques referred to in Section 7.7.

      7.5   Carefully, while stirring, adjust the pH of the aqueous phase to the
second pH  indicated  in Table 1.   Attach a clean  distilling  flask  containing
500 ml of methylene  chloride  to  the continuous extractor.   Extract  for 18-24
hours, allow to cool, and detach the distilling flask.

      7.6   If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration.  However,  in  some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g.  if for regulatory purposes the presence or absence of specific
acid/neutral  and  base  compounds  at  low concentrations must be  determined,
separate extract analyses may be warranted).

      7.7   Perform concentration  (if necessary) using  the Kuderna-Danish (K-D)
Technique (Sections 7.8.1 through 7.8.4).

      7.8   K-D Technique

            7.8.1 Assemble a Kuderna-Danish (K-D) concentrator  by  attaching a 10
      ml concentrator tube to a 500  ml evaporation flask.   Dry the  extract by
      passing it through  a drying column containing about  10  cm of anhydrous
      sodium sulfate.  Collect the dried extract in a K-D concentrator.   Rinse
      the flask which contained the solvent extract with 20-30 ml of methylene
      chloride and add it to the column to complete the quantitative transfer.

            7.8.2 Add one or two clean boiling chips to the flask and attach a
      three ball  Snyder column.   Prewet the Snyder column by adding about 1 ml
      of methylene chloride to the top of the column.  Place the K-D apparatus
      on a hot water  bath (15-20°C  above  the  boiling point  of the solvent) so
      that the concentrator tube  is partially  immersed  in the hot water and the
      entire  lower rounded  surface  of  the  flask is  bathed  with  hot  vapor.
      Adjust the vertical position of the apparatus and the water temperature,
      as  required,  to complete the  concentration in  10-20 minutes.   At  the
      proper rate of distillation  the balls of the column will actively chatter,
      but  the  chambers will  not  flood.   When the apparent  volume  of  liquid
      reaches 1 ml_, remove the K-D apparatus from the water  bath and allow it to
      drain  and  cool  for at  least  10  minutes.  Remove the Snyder  column and
      rinse the flask and its lower joints into the concentrator tube with 1-2
      mL of extraction solvent.

            7.8.3  If a solvent exchange  is required  (as indicated in Table 1),
      momentarily  remove  the  Snyder column, add 50 ml  of the exchange solvent,
      a  new boiling chip,  and  reattach  the  Snyder column.   Concentrate the
      extract, as described in Section 7.9, raising the temperature of the water
      bath, if necessary, to maintain proper distillation.

            7.8.4  Remove  the  Snyder column and rinse  the  flask  and its lower
      joints  into  the concentrator tube with  1-2  ml of  methylene chloride or

                                   3520B  - 4                         Revision  2
                                                                 November 1992
-------
      exchange solvent.   If sulfur crystals are a  problem,  proceed to Method
      3660 for cleanup.   The  extract  may  be further concentrated by using the
      techniques outlined in Section 7.9 or adjusted to 10.0 ml with the solvent
      last used.

      7.9   If further concentration is indicated in Table  1, either the micro-
Snyder column technique (7.9.1) or nitrogen blowdown technique (7.9.2) is used
to adjust the extract to the final volume required.

            7.9.1 Micro-Snyder Column Technique

                  7.9.1.1     Add another one or two clean  boiling chips to the
            concentrator tube and  attach a two ball  micro-Snyder column.  Prewet
            the  column  by  adding 0.5 ml  of  methylene  chloride or  exchange
            solvent to the top of  the  column.   Place the K-D apparatus in a hot
            water bath so  that the  concentrator tube  is  partially immersed in
            the hot water.  Adjust  the vertical position  of  the  apparatus and
            the water temperature, as required, to complete  the concentration in
            5-10 minutes.  At the proper rate of distillation the balls of the
            column will  actively chatter, but the chambers will not flood.  When
            the  apparent  volume  of  liquid reaches  0.5 ml, remove  the  K-D
            apparatus from the water bath  and allow it to drain and cool for at
            least 10 minutes.  Remove the Snyder column, rinse the flask and its
            lower joints  into  the concentrator tube with  0.2 ml of methylene
            chloride or exchange  solvent,  and adjust the final volume to 1.0 to
            2.0 ml, as indicated  in Table 1, with  solvent.

            7.9.2 Nitrogen Blowdown Technique

                  7.9.2.1     Place the concentrator tube  in  a warm bath (35°C)
            and evaporate the solvent  volume to 0.5 ml using a gentle stream of
            clean, dry nitrogen (filtered through a  column of activated carbon).

                  CAUTION:    New plastic tubing must not  be used between the
                              carbon  trap   and  the  sample,  since   it   may
                              introduce interferences.

                  7.9.2.2     The internal  wall of  the tube must  be rinsed down
            several times with methylene chloride or appropriate  solvent during
            the operation.  During evaporation, the tube  solvent  level must be
            positioned to  avoid water  condensation.   Under normal  procedures,
            the extract must not  be allowed to become dry.

                  CAUTION:    When the volume of solvent is reduced below 1 ml,
                              semivolatile analytes may be lost.

      7.10  The extract may now be analyzed  for the  target analytes using the
appropriate determinative  technique(s) (see  Section 4.3 of this  Chapter).   If
analysis  of  the  extract  will  not  be  performed  immediately,   stopper  the
concentrator tube and store refrigerated.   If the extract will be  stored longer
than 2 days it should be  transferred to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.
                                   3520B  -  5                         Revision 2
                                                                 November 1992
-------
8.0   QUALITY CONTROL

      8.1   Any reagent  blanks,  matrix spike, or replicate  samples  should be
subjected to  exactly the same analytical  procedures  as those  used  on actual
samples.

      8.2   Refer to  Chapter  One for  specific quality  control  procedures and
Method 3500 for extraction and sample-preparation procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


10.0  REFERENCES

1.    U.S. EPA 40  CFR Part 136, "Guidelines Establishing  Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act;  Final Rule and Interim
      Final Rule and Proposed Rule," October 26,  1984.
                                   3520B -  6                        Revision 2
                                                                 November 1992
-------
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                                   METHOD  3520B
                    CONTINUOUS  LIQUID-LIQUID  EXTRACTION
  C
      Start
7 1 Add appropriate
  surrogate  and
  matron »piking
    solution*
 7  2 Add m«thyl«n«
   chlorid* lo
 distilling flask
  7  3 Add r«ag«nt
*at«r to cutractor.
 ••tract for 18-24
      hours
 7  5 Adjust pH of
 aqueous phase,
 extract for 18-24
 hour* with clean
      flask
 7 6 Combine acid
 and base/neutral
 extracts prior  to
   concentration
                                              77-78 Concentrate
                                                   ••tract
                                                                     783 Add exchange
                                                                         solvent
                                                                     concentrate ex tract
                                                  7 9 Further
                                              concentrate extract
                                                 if necessary,
                                              ad just final volume
                                              7 10 Analyze using
                                              organic techniques
                                       3520B  - 8
                                                                                     Revision  2
                                                                                November  1992
-------
                                 METHOD 3540B

                              SOXHLET EXTRACTION
1.0   SCOPE AND APPLICATION
      1.1   Method 3540  is a procedure  for  extracting nonvolatile  and  semi-
volatile organic compounds from  solids  such as soils, sludges, and wastes.  The
Soxhlet extraction process ensures intimate contact of the sample matrix with the
extraction solvent.

      1.2   This method is applicable to the isolation and concentration of water
insoluble and slightly water  soluble organics in preparation  for a variety of
chromatographic procedures.


2.0   SUMMARY OF METHOD

      2.1   The solid sample is mixed with anhydrous sodium sulfate, placed in
an extraction thimble or between two plugs of  glass wool, and extracted using an
appropriate  solvent   in  a  Soxhlet  extractor.   The  extract is then  dried,
concentrated  (if  necessary),  and,   as  necessary,  exchanged into   a  solvent
compatible with the cleanup or determinative  step being employed.


3.0   INTERFERENCES

      3.1   Refer to Method 3500.
4.0   APPARATUS AND MATERIALS

      4.1   Soxhlet extractor - 40 mm ID, with 500 mL round bottom flask.

      4.2   Drying column  -  20 mm ID Pyrex chromatographic  column  with  Pyrex
glass wool at bottom.

      NOTE: Fritted  glass  discs are  difficult  to decontaminate  after  highly
            contaminated extracts  have  been  passed through.   Columns  without
            frits may  be  purchased.   Use a small  pad of Pyrex glass wool  to
            retain the  adsorbent.   Prewash the glass  wool  pad with 50 mL  of
            acetone followed by 50 mL of elution  solvent  prior to packing the
            column with adsorbent.

      4.3   Kuderna-Danish (K-D) apparatus

            4.3.1 Concentrator tube -  10 mL, graduated  (Kontes K-570050-1025 or
      equivalent).   A  ground glass stopper is used to  prevent evaporation  of
      extracts.

            4.3.2 Evaporation  flask  -    500  mL   (Kontes   K-570001-500  or
      equivalent).  Attach  to  concentrator   tube  with  springs,   clamps,  or
      equivalent.

                                   3540B -  1                         Revision 2
                                                                 November  1992
-------
            4.3.3 Snyder column  - Three  ball  macro (Kontes  K-503000-0121  or
      equivalent).

            4.3.4 Snyder column   -  Two  ball  micro  (Kontes   K-569001-0219  or
      equivalent).

            4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.4   Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.5   Water  bath  -  Heated,  with  concentric ring  cover,  capable  of
temperature control (+ 5°C).   The bath  should be used in a  hood.

      4.6   Vials - Glass,  2  ml capacity,  with Teflon lined screw or crimp top.

      4.7   Glass or paper thimble or glass wool - Contaminant free.

      4.8   Heating mantle -  Rheostat controlled.

      4.9   Disposable glass  pasteur pipet and bulb.

      4.10  Apparatus for determining percent dry weight.

            4.10.1       Oven  - Drying.

            4.10.2       Desiccator.

            4.10.3       Crucibles - Porcelain or disposable aluminum.

      4.11  Apparatus for grinding

      4.12  Analytical balance -  0.0001 g.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all  tests.  Unless otherwise
indicated, it is intended that all  reagents  shall conform to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society, where
such specifications are  available.   Other grades may be used,  provided it is
first ascertained that the  reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.

      5.2   Organic-free reagent  water.  All  references  to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sodium sulfate (granular, anhydrous), Na2S04.  Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning  the sodium sulfate with
methylene chloride. If the sodium sulfate  is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is  no  interference from
the sodium sulfate.
                                   3540B -  2                         Revision 2
                                                                 November 1992
-------
      5.4   Extraction solvents

            5.4.1 Soil/sediment  and  aqueous  sludge samples shall be extracted
      using either of the following  solvent systems:

                  5.4.1.1     Acetone/Hexane   (1:1)   (v/v),    CH3COCH3/CH6HU.
            Pesticide quality or equivalent.

                  NOTE: This solvent system  has  lower disposal  cost and lower
                        toxicity.

                  5.4.1.2     Methylene    chloride/Acetone    (1:1    v/v),
            CH2C12/CH3COCH3.  Pesticide quality or equivalent.

            5.4.2 Other samples shall be extracted using the following:

                  5.4.2.1     Methylene chloride, CH2C12.   Pesticide quality or
            equivalent.

                  5.4.2.2     Toluene/Methanol   (10:1)   (v/v),   C6H5CH3/CH3OH.
            Pesticide quality or equivalent.

      5.5   Exchange solvents

            5.5.1 Hexane, C6H14.  Pesticide quality or equivalent.

            5.5.2 2-Propanol, (CH3)2CHOH.   Pesticide  quality or  equivalent.

            5.5.3 Cyclohexane,  C6H12.  Pesticide quality or  equivalent.

            5.5.4 Acetonitrile, CH3CN.  Pesticide quality  or equivalent.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic Analysis,
Section 4.1.


7.0   PROCEDURE

      7.1   Sample Handling

            7.1.1 Sediment/soil samples -  Decant  and  discard any water layer on
      a sediment sample.  Mix sample  thoroughly, especially composited samples.
      Discard any foreign objects such as sticks, leaves,  and rocks.

            7.1.2 Waste samples  -  Samples consisting  of  multiphases  must  be
      prepared by the phase  separation method  in Chapter Two before extraction.
      This procedure is for solids only.

            7.1.3 Dry waste samples  amenable  to  grinding  - Grind or otherwise
      subdivide the waste so that it either passes through a 1 mm sieve or can


                                  3540B -  3                         Revision 2
                                                                 November 1992
-------
      be extruded through  a  1  mm hole.  Introduce sufficient  sample  into the
      grinding apparatus to yield at least 10 g after grinding.

            7.1.4 Gummy, fibrous  or oily materials  not amenable  to  grinding
      should be  cut,  shredded,  or  otherwise broken  up to allow  mixing,  and
      maximum exposure of the sample surfaces for extraction.  The professional
      judgment of the  analyst is required for handling  these difficult matrixes.

      7.2   Determination  of sample % dry  weight  -   In certain  cases,  sample
results are desired based on dry weight basis.   When such data  are desired, a
portion of sample for  this  determination  should be weighed out at the same time
as the portion used for analytical determination.

      WARNING:    The drying oven  should be contained in  a hood  or  vented.
                  Significant laboratory contamination may result from a heavily
                  contaminated  hazardous waste sample.

      However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be overdried because
of concerns for personal safety.  Laboratory discretion is advised.  It may be
prudent to delay  overdrying  of the  weighed-out  portion until  other analytical
results are available.

            7.2.1 Immediately after weighing the sample for extraction, weigh 5-
      10 g of the sample into a tared crucible.  Determine the % dry weight of
      the sample  by drying overnight  at  105°C.  Allow to  cool  in a desiccator
      before weighing:

            % dry weight = q of dry sample x 100
                             g of sample

      7.3   Blend 10 g of the solid  sample with 10  g of anhydrous  sodium sulfate
and place in  an extraction thimble.  The extraction thimble must drain freely for
the duration of the extraction  period.   A glass wool  plug above and below the
sample in the Soxhlet extractor is  an acceptable  alternative for the thimble.
Add 1.0 ml of the surrogate standard spiking  solution onto the sample (see Method
3500 for details on the surrogate standard and matrix spiking solutions).  For
the sample  in  each analytical   batch  selected  for spiking, add  1.0 ml  of the
matrix spiking standard.  For base/neutral-acid  analysis, the amount added  of the
surrogates and matrix spiking compounds  should result in a final concentration
of 100 ng//iL of each base/neutral analyte and 200  ng/juL of each  acid analyte in
the extract  to  be analyzed (assuming a  1 ML injection).   If Method 3640, Gel
Permeation  Chromatography  Cleanup,  is to  be  used,   add  twice  the volume  of
surrogates and matrix spiking  compounds  since  half  the extract is  lost due to
loading of the GPC column.

      7.4    Place approximately 300 ml of the extraction solvent (Section 5.4)
into  a  500  ml round  bottom  flask containing one or  two  clean boiling chips.
Attach the flask to the extractor and extract the  sample for  16-24  hours  at 4-6
cycles/hr.

      7.5   Allow the extract  to  cool  after the extraction is complete.
                                   3540B - 4                        Revision 2
                                                                 November 1992
-------
      7.6   Assemble  a Kuderna-Danish  (K-D)  concentrator  (if necessary)  by
attaching a 10 ml concentrator tube to a 500 ml evaporation flask.

      7.7   Dry the  extract  by passing it through a  drying  column containing
about 10 cm of  anhydrous  sodium sulfate.   Collect the dried  extract  in a K-D
concentrator.  Wash the extractor flask and sodium sulfate column with 100 to 125
ml of extraction solvent to complete the quantitative transfer.

      7.8   Add one or two clean boiling chips to the flask and attach a three
ball Snyder column.   Prewet the Snyder column  by adding about  1 ml of methylene
chloride to the top of the column.   Place  the  K-D apparatus on a hot water bath
(15-20°C above the boiling point of the solvent)  so that the concentrator tube
is partially immersed  in the hot water and the entire lower rounded surface of
the  flask  is  bathed  with hot  vapor.  Adjust  the  vertical  position  of the
apparatus and  the water temperature,  as required, to complete the concentration
in 10-20 minutes.  At  the  proper  rate of  distillation the balls of the column
will actively  chatter,  but the chambers will not flood.  When the apparent volume
of liquid reaches 1-2 ml, remove the K-D apparatus  from the water bath and allow
it to drain and cool  for at least 10 minutes.

      7.9   If  a solvent  exchange  is required  (as  indicated  in Table  1),
momentarily remove the Snyder  column,  add  approximately  50  ml of  the  exchange
solvent and a  new boiling chip, and reattach the Snyder column.  Concentrate the
extract as described in Section 7.8,  raising the temperature of the water bath,
if necessary,  to maintain proper distillation.  When the apparent volume again
reaches 1-2 ml, remove the K-D  apparatus  from the  water  batch and allow it to
drain and cool for at  least 10 minutes.

      7.10   Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or  exchange solvent.
If sulfur  crystals  are a  problem,  proceed to Method 3660  for cleanup.   The
extract may be further  concentrated by using the techniques described in Section
7.11 or adjusted to 10.0 ml with the solvent last used.

      7.11  If further concentration is indicated in Table 1,  either micro Snyder
column technique (Section 7.11.1) or nitrogen blowdown technique (Section 7.11.2)
is used to adjust the  extract to the final volume required.

            7.11.1      Micro Snyder Column Technique

                  7.11.1.1    Add another one  or two clean boiling chips to the
            concentrator tube and  attach a two ball  micro  Snyder column.  Prewet
            the column by adding about 0.5  ml  of methylene chloride or exchange
            solvent to the top of  the column.  Place the K-D apparatus in a hot
            water bath so  that  the  concentrator tube  is  partially immersed in
            the hot water.  Adjust  the vertical position  of the apparatus and
            the water temperature,  as required, to  complete the concentration in
            5-10 minutes.  At the proper rate of distillation the balls of the
            column will actively chatter, but the chambers will not flood.  When
            the  apparent  volume  of  liquid  reaches  0.5  ml,  remove  the  K-D
            apparatus from the water bath  and  allow  it to  drain and cool for at
            least 10 minutes.   Remove the  Snyder column and rinse the flask and
            its  lower  joints  with  about  0.2 ml of  solvent  and add  to  the


                                   3540B -  5                         Revision 2
                                                                 November 1992
-------
            concentrator  tube.    Adjust  the  final  volume  to  1.0-2.0  ml,  as
            indicated in Table 1, with solvent.

            7.11.2      Nitrogen Slowdown Technique

                  7.11.2.1    Place the concentrator tube in a warm water bath
            (approximately  35°C)  and  evaporate  the  solvent  volume   to  the
            required  level   using a  gentle  stream  of  clean,  dry  nitrogen
            (filtered through a column of activated carbon).

                  CAUTION:    Do not use plasticized tubing between the carbon
                              trap and the sample.

                  7.11.2.2    The internal wall of the tube must be rinsed down
            several times with  the appropriate solvent  during  the operation.
            During evaporation,  the solvent level in the tube must be positioned
            to prevent water from condensing  into  the  sample (i.e., the  solvent
            level should be  below the  level  of the water bath).   Under normal
            operating conditions, the  extract  should  not be allowed to become
            dry.

                  CAUTION:    When the volume of solvent is reduced below 1 ml,
                              semivolatile analytes may be lost.

      7.12  The extracts obtained may  now be analyzed for the target analytes
using the appropriate organic technique(s)  (see Section 4.3 of this Chapter).
If  analysis  of  the  extract will  not be  performed  immediately,  stopper  the
concentrator tube and store  in  a  refrigerator.  If the extract will  be stored
longer than 2 days,  it should be transferred to a vial  with a Teflon lined screw
cap or crimp top, and labeled appropriately.


8.0   QUALITY CONTROL

      8.1   Any reagent blanks  or matrix  spike samples should be subjected to
exactly the same analytical  procedures as those used on actual samples.

      8.2   Refer to Chapter One for specific  quality control  procedures  and
Method 3500 for extraction and sample preparation  procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


10.0  REFERENCES

1.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures  for the
      Analysis of Pollutants Under the Clean Water Act; Final  Rule and  Interim
      Final Rule and Proposed Rule," October 26, 1984.
                                   3540B -  6                        Revision 2
                                                                 November 1992
-------
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                                           METHOD 3540B
                                       SOXHLET  EXTRACTION
        7.1
  Use appropriate
  sample handling
     technique
        7.2
Determine sample %
     dry weight
       7.3
  Add appropriate
surrogate and matrix
 spiking standards
       7.4
   Add extraction
  solvent to flask:
  extract for 16-24
      hours
       7.5
   Cool extract
      7.6
  Assemble K-D
  concentrator
       7.7
  Dry and collect
   extract in K-D
   concentrator
       7.8
 Concentrate using
   Snyder column
 and K-D apparatus
       7.9
     Is solvent
exchange required?
                           7.12
                       Analyze using
                     organic techniques
 Proceed
to Method
 3660 for
 cleanup
       7.9
  Add exchange
     solvent,
reconcentrate extract
                                              3540B -  8
                                                               Revision 2
                                                           November 1992
-------
                                  METHOD 3541

                         AUTOMATED SOXHLET EXTRACTION
1.0   SCOPE AND APPLICATION

      1.1   Method 3541 describes the extraction of organic analytes from soil,
sediment, sludges, and waste solids.   The method uses a commercially available,
unique, three stage extraction system to  achieve analyte recovery comparable to
Method 3540, but in a much shorter time.  There are two differences between this
extraction method  and  Method  3540.   In the initial extraction stage of Method
3541, the sample-loaded extraction thimble is immersed into the boiling solvent.
This ensures very  rapid  intimate contact between the specimen and solvent and
rapid extraction of  the  organic  analytes.   In the second  stage  the thimble is
elevated above the  solvent, and  is  rinse-extracted as  in  Method 3540.   In the
third stage, the  solvent is evaporated,  as would  occur  in  the  Kuderna-Danish
(K-D) concentration step in  Method 3540.  The concentrated  extract  is then ready
for cleanup (Method 3600) followed by measurement of the organic analytes.

      1.2   The method is applicable to the extraction and concentration of water
insoluble  or  slightly  water  soluble  polychlorinated   biphenyls  (PCBs)  in
preparation for gas  chromatographic  determination  using either  Method  8080 or
8081.  This method is applicable to  soils, clays,  solid  wastes and sediments
containing from 1 to 50  |ig of PCBs (measured as Arochlors) per gram of sample.
It has been statistically evaluated at  5 and 50 jig/g of Arochlors 1254 and 1260,
and  found   to  be  equivalent  to  Method 3540  (Soxhlet  Extraction).    Higher
concentrations of PCBs are measured following volumetric dilution with hexane.

      1.3   The method  is also  applicable  the extraction  and concentration of
organochlorine pesticides and semivolatile organics in preparation  for GC/MS
analysis by Method 8270  or by analysis using specific GC or HPLC methods.


2.0   SUMMARY OF METHOD

      2.1   Organochlorine pesticides and semivolatile organics:  A 10-g solid
sample  (the sample  is  pre-mixed with anhydrous  sodium  sulfate  for  certain
matrices) is placed in an extraction thimble and usually  extracted with 50 ml of
1:1 (v/v) acetone/hexane for 60 minutes in  the boiling extraction solvent.  The
thimble with sample is then  raised into the  rinse position and extracted for an
additional  60 minutes.   Following the extraction steps,  the extraction solvent
is concentrated to 1 to  2 ml.

      2.2   PCBs:  Moist solid samples  (e.g., soil/sediment samples) may be air-
dried and ground prior to extraction or chemically dried with anhydrous sodium
sulfate. The prepared sample  is extracted using 1:1 (v/v)  acetone:hexane in the
automated  Soxhlet  following the  same  procedure as outlined  for  semivolatile
organics in Section  2.1.  The extract  is then concentrated  and  exchanged  into
pure hexane prior to final  gas chromatographic PCB measurement.
                                   3541 - 1                         Revision 0
                                                                 November 1992
-------
3.0   INTERFERENCES

      3.1   Refer to Method 3500.

      3.2   The extraction thimble and the o-rings used to seal the extraction
cup are both a source  of  interference.   Both  should  be checked by including a
method blank and  following the extraction procedure as written.  Solvent rinsing
or  extraction,  prior  to  use,   may be necessary   to  eliminate  or  reduce
interferences.   Viton  seals  contributed least  to the  interference  problem,
however,  even  they contributed  some interference peaks when  the  extraction
solvent was  analyzed  by the electron capture detector.  Use  of butyl  or EPDM
rings  are not recommended  since  they  were  found to  contribute significant
background when  the  extraction  solvent  was 1:1 v/v  hexane/acetone  or  1:1 v/v
methylene chloride/acetone.


4.0   APPARATUS AND MATERIALS

      4.1   Automated Soxhlet Extraction System - with  temperature-controlled oil
bath (Soxtec, or  equivalent).  Tecator bath oil (catalog number  1000-1886) should
be used with the  Soxtec.  Silicone oil must  not be  used because  it destroys the
rubber parts.  See Figure 1.  The apparatus is used in a hood.

      4.2   Accessories and consumables  for the automated Soxhlet  system.  (The
catalog  numbers  are Fisher  Scientific  based on the  use of  the  Soxtec HT-6,
however, other sources  that are equivalent are acceptable.)

            4.2.1   Cellulose   extraction  thimbles   -   26  mm   ID   x   60  mm
      contamination free, catalog number 1522-0034, or equivalent.

            4.2.2   Glass  extraction  cups (80 ml)  -  (set of  six required for the
      HT-6), catalog number 1000-1820.

            4.2.3   Thimble  adapters  -   (set  of  six  required for  the  HT-6),
      catalog number 1000-1466.

            4.2.4   Viton  seals  -  catalog number  1000-2516.

      4.3   Syringes -  100  and 1000  |iL and 5 ml.

      4.4   Apparatus  for Determining Percent Dry  Weight

            4.4.1   Drying Oven.

            4.4.2   Desiccator.

            4.4.3   Crucibles,  porcelain.

            4.4.4   Balance, analytical.

      4.5   Apparatus  for grinding - Fisher Cyclotec,  Fisher Scientific catalog
number  1093, or  equivalent.
       4.6    Spatula
                                    3541  -  2                          Revision  0
                                                                  November  1992
-------
      4.7   Graduated cylinder - 100 ml.

      4.8   Aluminum weighing dish - VWR Scientific catalog number 25433-008 or
equivalent.

      4.9   Graduated, conical-bottom glass tubes - 15 mL, Kimble catalog number
45166 or equivalent, or 10 ml KD concentrator tube.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all  reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used,  provided it is first
ascertained that the reagent  is  of sufficiently  high  purity  to permit  its use
without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.  All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sodium sulfate (granular, anhydrous), Na2S04.  Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  A method blank must be analyzed, demonstrating that there
is no interference from the sodium sulfate.

      5.4   Extraction solvents:

            5.4.1  Organochlorine  pesticides/PCB extraction:

                   5.4.1.1    Acetone/hexane    (1:1    v/v),    C
            Pesticide quality or equivalent.

            5.4.2  Semivolatile  organics extraction:

                   5.4.2.1    Acetone/hexane    (1:1    v/v),    CH3COCH3/C6HU.
            Pesticide quality or equivalent.

                   5.4.2.2    Acetone/methylene    chloride    (1:1     v/v),
            CH3COCH3/CH2C12.   Pesticide quality  or equivalent.

      5.5   Hexane, C6HU.  Pesticide quality or equivalent.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to this chapter,  Organic Analytes,
Section 4.1.
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7.0   PROCEDURE

      7.1   Sample handling

            7.1.1  Sediment/soil  samples  -  Decant  and  discard any water layer
      on  a  sediment  sample.    Mix sample  thoroughly, especially  composited
      samples.  Discard any foreign objects such as sticks,  leaves, and rocks.

                   7.1.1.1    PCBs or high-boiling organochlorine pesticides -
            Air-dry the sample at room temperature  for  48 hours in a glass tray
            or on hexane-cleaned aluminum  foil, or dry the sample by mixing with
            anhydrous sodium  sulfate  until  a free-flowing  powder is obtained
            (see Section 7.2).

                   NOTE:      Dry, finely ground soil/sediment allows the best
                              extraction efficiency for non-volatile, non-polar
                              organics, e.g., PCBs, 4,4'-DDT, etc.  Air-drying
                              is  not  appropriate for the analysis of the more
                              volatile  organochlorine   pesticides  (e.g.  the
                              BHCs) or  the  more volatile of the semivolatile
                              organics  because  of  losses   during the  drying
                              process.

            7.1.2  Dried  sediment/soil  and  dry   waste  samples  amenable  to
      grinding - Grind or otherwise subdivide the waste  so that it either passes
      through a  1 mm  sieve  or can be  extruded through  a  1  mm hole.  Introduce
      sufficient sample into the grinding  apparatus to yield at least  20 g after
      grinding.      Disassemble  grinder   between  samples,  according   to
      manufacturer's  instructions, and  clean  with  soap and  water, followed by
      acetone and hexane rinses.

            NOTE:  The  same warning on loss of volatile analytes applies to the
                   grinding  process.   Grinding  should only be performed when
                   analyzing  for non-volatile organics.

            7.1.3  Gummy,  fibrous, or oily materials not  amenable to grinding
      should  be  cut, shredded,  or otherwise broken up  to  allow mixing,  and
      maximum exposure  of the sample  surfaces for  extraction.  If grinding of
      these materials is preferred, the addition and mixing  of anhydrous sodium
      sulfate  with  the  sample  (1:1)  may  improve  grinding  efficiency.   The
      professional  judgment  of  the  analyst is  required  for  handling  such
      difficult matrices.

            7.1.4  Multiple phase waste samples  - Samples consisting of multiple
      phases  must  be prepared  by the phase separation method  in Chapter Two
      before extraction.  This  procedure  is for solids only.

      7.2   For  sediment/soil  (especially gummy clay) that  is moist and cannot
be air-dried because  of loss  of volatile  analytes - Mix 5 g  of sample with 5 g
of anhydrous sodium sulfate  in a small  beaker using a spatula.  Use this approach
for any solid sample that requires dispersion of the sample  particles to ensure
greater solvent  contact throughout the  sample mass.
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      7.3   Determination of sample percent dry weight - In certain cases, sample
results are desired based on dry  weight  basis.   When  such data are desired, a
portion of sample for this determination  should be weighed out at the same time
as the portion used for analytical determination.

      WARNING:     The  drying  oven should be contained  in a  hood  or vented.
                   Significant  laboratory contamination  may  result  from  the
                   drying of a heavily contaminated hazardous waste sample.

            7.3.1  Immediately after weighing the sample for extraction, weigh
      5-10 g of the sample into a tared crucible.   Determine  the % dry weight of
      the sample by drying  overnight  at  105°C.   Allow  to cool  in  a desiccator
      before weighing:

            % dry weight = g of dry sample x 100
                              g of sample

      7.4   Check the heating oil level in the automated Soxhlet unit and  add oil
if needed.  See service manual  for details.  Set  the temperature on the service
unit at 140°C when using hexane-acetone (1:1,  v/v)  as  the extraction solvent.

      7.5   Press the "MAINS" button;  observe  that the  switch lamp is now "ON".

      7.6   Open the cold water tap for the reflux condensers.  Adjust the flow
to 2 L/min to prevent solvent loss through the condensers.

      7.7   Weigh  10 g  of sample  into  extraction thimbles.   For samples mixed
with  anhydrous  sodium  sulfate,  transfer the  entire  contents  of  the  beaker
(Section 7.2) to the thimble.  Add  surrogate spikes to each sample and the matrix
spike/matrix spike duplicate to the selected sample.

      NOTE: When  surrogate   spikes  and/or  matrix  spikes  contain  relatively
            volatile compounds  (e.g., trichlorobenzenes, BHCs,  etc.), steps 7.8,
            7.9, and 7.10 must  be  performed quickly to avoid evaporation losses
            of these  compounds.   As the  spike is added  to  the  sample in each
            thimble,   the thimble  should immediately  be  transferred  to  the
            condenser and lowered into the extraction solvent.

      7.8   Immediately transfer the thimbles containing the weighed samples into
the condensers.  Raise the knob to the  "BOILING"  position.  The magnet will  now
fasten to the thimble.  Lower the knob to the "RINSING" position.   The thimble
will now hang just below the condenser valve.

      7.9   Insert the extraction cups containing boiling chips, and load each
with 50 mL of extraction solvent (normally 1:1  (v/v) hexane:acetone, see Section
5.4).  Using the cup  holder,  lower the  locking handle, ensuring that the safety
catch engages.  The cups are now clamped into position.   (The seals must be pre-
rinsed or pre-extracted with extraction solvent prior to initial use.)

      7.10  Move the extraction knobs to the "BOILING" position.  The thimbles
are now immersed in solvent.   Set the timer for 60 minutes. The condenser valves
must be in the "OPEN" position.  Extract for the preset time.
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      7.11  Move the extraction knobs to the "RINSING" position.  The thimbles
will now hang above the solvent surface.  Set timer for 60 minutes.  Condenser
valves are still open.  Extract for the preset time.

      7.12  After rinse time has elapsed, close the condenser valves by turning
each a quarter-turn, clockwise.

      7.13  When all  but  2 to  5 ml  of solvent  have  been  collected,  open the
system and remove the cups.

      7.14  Transfer the contents of the cups to  15 ml  graduated, conical-bottom
glass tubes.  Rinse the cups using hexane (methylene chloride if 1:1 methylene
chloride-acetone was used for extraction and analysis is by GC/MS) and add the
rinsates to the glass  tubes.  Concentrate the extracts to 1 to  10 ml.  The final
volume  is  dependent on  the determinative  method  and the  quantisation  limit
required.  Transfer a portion to a GC vial  and store  at 4°C until  analyses are
performed.

      NOTE:         The  recovery  solvent volume  can  be  adjusted by  adding
                    solvent  at  the top  of  the condensers.   For  more details
                    concerning  use  of the extractor,  see  the  operating manual
                    for  the  automated extraction system.

      7.15          Shutdown

            7.15.1      Turn "OFF" main switch.

            7.15.2      Turn "OFF" cold water tap.

            7.15.3      Ensure  that all condensers are free of  solvent.  Empty
      the solvent that is recovered in  the evaporation step  into an appropriate
      storage container.

      7.16  The extract is now  ready for cleanup or analysis, depending on the
extent of interfering co-extractives.  See  Method 3600 for guidance on cleanup
methods and Method 8000 for guidance  on  determinative  methods.   Certain cleanup
and/or determinative  methods may require a  solvent  exchange  prior to cleanup
and/or determination.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for general quality  control procedures and to
Method 3500 for specific extraction and sample preparation QC procedures.

      8.2   Before processing any samples, the analyst should demonstrate through
the analysis of an  organic-free solid matrix (e.g., reagent sand) method blank
that  all  glassware and  reagents are interference-free.   Each time  a set of
samples  is  extracted,  or when  there  is a  change in  reagents,  a  method blank
should be processed as a safeguard against chronic laboratory contamination.  The
blank samples should be carried through  all  stages of the sample preparation and
measurement.    This is  especially important  because  of the  possibility of
interferences being extracted  from the  extraction cup seal.


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      8.3   Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision  of the sampling
technique.  Each  analysis  batch  of 20 or less  samples must  contain:  a method
blank,  either  a  matrix  spike/matrix spike  duplicate  or  a  matrix  spike  and
duplicate  sample  analysis,  and  a   laboratory control  sample,  unless  the
determinative  method provides  other  guidance.   Also,   routinely  check  the
integrity of the instrument seals.

      8.4   Surrogate standards must be added to all samples when specified in
the appropriate determinative method.


9.0   METHOD PERFORMANCE

      9.1   Multi-laboratory accuracy and precision  data were obtained for PCBs
in soil.  Eight laboratories spiked Arochlors  1254 and 1260 into three portions
of 10 g of  Fuller's  Earth  on  three non-consecutive  days  followed by immediate
extraction using Method 3541.  Six of the laboratories  spiked each Arochlor at
5 and 50 mg/kg  and two laboratories  spiked  each Arochlor  at  50 and  500 mg/kg.
All extracts were analyzed by Oak Ridge National Laboratory, Oak  Ridge, TN, using
Method 8080.  These data are listed in a table found in Methods 8080 and 8081,
and were taken from Reference 1.

      9.2   Single-laboratory  accuracy  data   were  obtained  for  chlorinated
hydrocarbons,  nitroaromatics, haloethers, and organochlorine pesticides in a clay
soil.  The spiking concentrations ranged from 500 to 5000 ng/kg,  depending on the
sensitivity of the  analyte to  the  electron  capture  detector.   The  spiking
solution was mixed into the soil during addition and then immediately transferred
to the  extraction device  and  immersed  in  the  extraction solvent.   The  data
represents  a   single  determination.    Analysis  was by  capillary column  gas
chromatography/electron  capture  detector  following  Methods   8081  for  the
organochlorine   pesticides,   8091   for  the  nitroaromatics,  8111   for   the
hydrocarbons,  and 8121 for the chlorinated hydrocarbons.  These data are listed
in a table located in their respective methods  and were taken from Reference 2.

      9.3   Single-laboratory  accuracy  and  precision  data  were obtained  for
semi volatile organics in  soil  by spiking  at  a concentration of 6 mg/kg for each
compound.  The spiking solution was mixed into the soil during addition and then
allowed to  equilibrate for approximately  1  hr prior to extraction.    Three
determinations   were   performed   and  each   extract   was  analyzed   by   gas
chromatography/mass spectrometry following Method 8270.   The low recovery of the
more  volatile  compounds   is  probably  due   to  volatilization  losses  during
equilibration.  These data  are listed  in a Table located  in Method 8270 and were
taken from Reference 2.
10.0  REFERENCES

1.    Stewart,  J.    "Intra-Laboratory Recovery  Data for  the PCB  Extraction
      Procedure"; Oak  Ridge National  Laboratory,  Oak Ridge,  TN,  37831-6138;
      October 1989.
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                                                                 November 1992
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2.    Lopez-Avila, V. (Beckert, W., Project Officer), "Development of a Soxtec
      Extraction  Procedure  for  Extracting  Organic  Compounds  from  Soils  and
      Sediments", EPA  600/X-91/140,  US EPA,  Environmental  Monitoring Systems
      Laboratory-Las Vegas, October 1991.
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             Figure 1
Automated Soxhlet Extraction System
           Condenser
            Thimble


         Glass Wool Plug


            Sample


    Aluminum beaker (cup)


            Hot plate
             3541 - 9
   Revision 0
November 1992
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                              METHOD 3541
                     AUTOMATED SOXHLET EXTRACTION
       Start
       7.1
 Use appropriate
 sample handling
    technique.
       7.2
 Add anhydrous
    Na2SO4if
    necessary
       7.3
Determine percent
   dry weight.
       7.4
    Check oil
     level in
   Soxhlet unit.
       7.5
   Press "Mains"
      button.
        I
        7.6
  Open Cold water
  tap.  Adjust flow.
        7.7
 Weigh sample into
 extraction thimbles.
   Add surrogate
      spike.
        7.8
 Transfer samples
 into condensers.
 Adjust position of
magnet and thimble.
                                   7.9
                             Insert extraction
                              cups and load
                               with solvent.
                                  7.10
                             Move extraction
                                knobs to
                               "Boiling" for
                                60 mins.
                                  3541 - 10
       7.11
  Move extraction
     knobs to
   "Rinsing" for
     60 mins.
                                                                I
                                    7.12
                                   Close
                              condenser valves.
       7.13
  Remove cups.
                                     I
      7.14
Transfer contents
   to collection
  vials, dilute or
  concentrate to
     volume.
                                     I
                                    7.15
                                 Shutdown
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                                       November  1992
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                                 METHOD 3550A

                             ULTRASONIC  EXTRACTION


>ee DISCLAIMER-1.  See manufacturer's specifications for operational settings.


 .0   SCOPE AND APPLICATION

      1.1   Method 3550  is a procedure  for extracting nonvolatile  and  semi-
/olatile organic compounds from  solids such  as  soils, sludges, and wastes.  The
jltrasonic  process  ensures  intimate contact  of  the  sample  matrix with  the
extraction solvent.

      1.2   The  method  is divided  into two sections,  based  on  the expected
:oncentration  of  organics  in  the  sample.    The  low  concentration  method
'^individual organic components of <  20  mg/kg)  uses  a  larger sample size  and a
 ore rigorous extraction procedure (lower concentrations are more difficult to
extract).  The medium/high concentration method (individual organic components
Df > 20 mg/kg) is much simpler and therefore faster.

      1.3   It is highly recommended  that the  extracts  be  cleaned up prior to
analysis.  See Chapter Four (Cleanup), Section 4.2.2,  for applicable methods.


2.0   SUMMARY OF METHOD

      2.1   Low  concentration method  -  A 30 g  sample  is mixed  with anhydrous
sodium sulfate to form a free flowing powder.  This is solvent extracted  three
times using ultrasonic  extraction.   A  portion of  the extract  is  removed  for
cleanup and/or analysis.

      2.2   Medium/high  concentration method  - A   2  g sample  is  mixed  with
anhydrous sodium sulfate.  This  mixture is solvent  extracted three times  using
ultrasonic extraction.   The  extract  is separated  from  the sample  by  vacuum
filtration or centrifugation.  The extract is ready  for cleanup and/or analysis
following concentration.


3.0   INTERFERENCES

      3.1   Refer to Method 3500.


4.0   APPARATUS AND MATERIALS

      4.1   Apparatus for grinding dry waste samples.

      4.2   Ultrasonic preparation - A horn type device  equipped with a titanium
tip, or a device that will give  equivalent performance, shall  be used.
                                   3550A  -  1                         Revision 1
                                                                 November 1992
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            4.2.1 Ultrasonic Disrupter - The disrupter must have a minimum power
      wattage of  300  watts, with  pulsing  capability.   A device  designed  tc
      reduce the  cavitation sound is  recommended.   Follow  the  manufacturers
      instructions for preparing the  disrupter  for  extraction  of samples witf
      low and medium/high concentration.

            Use a 3/4"  horn for the low concentration method and a 1/8" taperec
      microtip attached to  a 1/2" horn for the medium/high concentration method.

      4.3   Sonabox - Recommended with above disrupters for decreasing cavitatior
sound (Heat Systems -  Ultrasonics,  Inc.,  Model  432B or equivalent).

      4.4   Apparatus  for determining percent dry weight.

            4.4.1 Oven -  Drying.

            4.4.2 Desiccator.

            4.4.3 Crucibles - Porcelain or disposable aluminum.

      4.5   Pasteur glass pipets -  1  ml,  disposable.

      4.6   Beakers -  400 ml.

      4.7   Vacuum or  pressure filtration  apparatus.

            4.7.1 Buchner funnel.

            4.7.2 Filter paper - Whatman  No. 41 or equivalent.

      4.8   Kuderna-Danish (K-D) apparatus.

            4.8.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
      equivalent).  A  ground  glass stopper is  used  to  prevent  evaporation  of
      extracts.

            4.8.2 Evaporation   flask  -   500   ml   (Kontes  K-570001-500   or
      equivalent).  Attach  to  concentrator tube  with  springs,  clamps,  or
      equivalent.

            4.8.3 Snyder column  -  Three ball  macro  (Kontes K-503000-0121  or
      equivalent).

            4.8.4 Snyder  column -  Two ball  micro  (Kontes K-569001-0219  or
      equivalent).

            4.8.5 Springs  - 1/2 inch  (Kontes K-662750 or equivalent).

      4.9   Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.10  Water  bath  -   Heated,  with  concentric  ring  cover,  capable  of
temperature control (+ 5°C).  The batch should  be used in a hood.

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      4.11  Balance - Top loading, capable of accurately weighing to the nearest
0.01 g.

      4.12  Vials - 2 mL,  for  GC  autosampler,  with Teflon lined screw caps or
crimp tops.

      4.13  Glass scintillation vials - 20 ml, with Teflon lined screw caps.

      4.14  Spatula - Stainless steel or Teflon.

      4.15  Drying column  -  20 mm ID Pyrex chromatographic  column  with Pyrex
glass wool at bottom.

      NOTE:       Fritted  glass discs  are difficult  to  decontaminate  after
                  highly  contaminated  extracts  have  been  passed  through.
                  Columns without frits may be purchased.   Use  a small  pad of
                  Pyrex glass wool to retain the adsorbent.  Prewash the glass
                  wool pad with 50 ml of  acetone  followed by 50 ml of elution
                  solvent prior to packing the column with adsorbent.

      4.16  Syringe - 5 ml.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be used  in all tests.  Unless
otherwise specified,  it  is  intended that all inorganic reagents shall conform to
the  specifications  of the  Committee on Analytical  Reagents of  the American
Chemical Society, where  such specifications are available.  Other grades may be
used, provided it is  first ascertained that the reagent  is  of sufficiently high
purity to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.  All references  to  water  in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sodium sulfate (granular, anhydrous),  Na2S04.   Purify by heating at
400 °C for  4 hours in  a shallow  tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium  sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.

      5.4   Extraction solvents.

            5.4.1 Low concentration  soil/sediment and  aqueous  sludge samples
      shall be extracted  using a solvent system that gives optimum, reproducible
      recovery  for  the  matrix/analyte combination  to  be  measured.   Suitable
      solvent choices are given in Table 1.

            5.4.2 Methylene  chloride:Acetone,  CH2C12:CH3COCH3   (1:1,   v:v).
      Pesticide quality or equivalent.

            5.4.3 Methylene chloride, CH2C12.   Pesticide quality or equivalent.


                                  3550A -  3                         Revision 1
                                                                 November 1992
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            5.4.4 Hexane, C6HU.  Pesticide quality or equivalent.

      5.5   Exchange solvents.

            5.5.1 Hexane, C6HU.  Pesticide quality or equivalent.

            5.5.2 2-Propanol, (CH3)2CHOH.  Pesticide quality or equivalent.

            5.5.3 Cyclohexane, C6H12.  Pesticide quality or equivalent.

            5.5.4 Acetonitrile, CH3CN.   Pesticide  quality  or  equivalent.

            5.5.5 Methanol, CH3OH.   Pesticide quality  or equivalent.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the  introductory  material  to this Chapter,  Organic  Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Sample handling

            7.1.1 Sediment/soil samples -  Decant and discard any water layer on
      a sediment sample.  Mix sample thoroughly, especially composited samples.
      Discard any foreign objects such as sticks,  leaves,  and rocks.

                  7.1.1.2     Determine the dry weight  of the sample (Section
            7.2)  remaining  after decanting.   Measurement of soil  pH may  be
            required.

            7.1.2 Waste  samples  -  Samples  consisting  of  multiphases  must  be
      prepared by the phase separation  method  in Chapter Two before extraction.
      This procedure is for solids only.

            7.1.3 Dry waste  samples amenable  to grinding  -  Grind or otherwise
      subdivide the waste so that it either passes through a  1 mm sieve or can
      be extruded through  a 1 mm hole.   Introduce sufficient sample into the
      grinder to yield at least 100 g after grinding.

            7.1.4 Gummy,  fibrous  or oily materials  not  amenable  to grinding
      should  be cut, shredded,  or  otherwise broken  up to allow  mixing,  and
      maximum exposure of the sample surfaces  for  extraction.  The professional
      judgment  of the  analyst is  required for  handling of  these  difficult
      matrices.

      7.2   Determination  of percent   dry  weight  -  In certain  cases,  sample
results are desired based on a dry weight basis.  When such data  are desired,
or required, a portion of sample for this determination should  be  weighed out at
the same time as the portion used for analytical determination.


                                   3550A -  4                        Revision  1
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      WARNING:    The  drying  oven should  be  contained  in  a hood  or vented.
                  Significant laboratory contamination may result from drying a
                  heavily contaminated hazardous waste sample.

      However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be overdried because
of concerns for personal safety.  Laboratory discretion is advised.  It may be
prudent to delay overdrying of the weighed-out  portion until other analytical
results are available.

            7.2.1 Immediately after weighing the sample for extraction, weigh 5-
      10 g of the sample into a tared crucible.   Determine the % dry weight of
      the sample by drying  overnight  at  105°C.  Allow to cool  in  a desiccator
      before weighing:

            % dry weight = g of dry sample x 100
                              g of sample

      7.3   Extraction method for  samples expected to contain  low concentrations
of organics and pesticides (< 20 mg/kg):

            7.3.1 The following step should be performed rapidly to avoid loss
      of the  more  volatile  extractables.  Weigh approximately 30  g of sample
      into a 400 mL beaker.   Record the weigh to the nearest 0.1 g.  Nonporous
      or wet samples (gummy  or clay type) that do not  have a free-flowing sandy
      texture must  be mixed with 60  g  of  anhydrous sodium  sulfate,  using  a
      spatula.  If required, more sodium sulfate may be added.  After addition
      of  sodium sulfate, the  sample should  be free  flowing.   Add  1  ml  of
      surrogate standards to  all  samples,  spikes,  standards,  and  blanks (see
      Method 3500 for details on the surrogate standard solution and the matrix
      spike solution).   For the sample  in each analytical  batch  selected for
      spiking, add 1.0 ml of the matrix spiking standard.  For base/neutral-acid
      analysis, the amount added of the  surrogates and matrix spiking compounds
      should result in a final concentration of 100 ng/jitL of each base/neutral
      analyte and 200 ng//xL of each acid analyte in the extract to be analyzed
      (assuming a 1 p.1 injection).  If Method 3640, Gel-Permeation Cleanup,  is
      to  be  used,  add  twice  the  volume  of  surrogates and matrix  spiking
      compounds since  half  of the extract is lost  due to loading  of the GPC
      column.  Immediately add 100 ml of 1:1 methylene chloride:acetone.

            7.3.2 Place  the  bottom surface  of  the  tip  of  the  #207 3/4  in.
      disrupter horn about 1/2 in. below the surface of the  solvent, but above
      the sediment layer.

            7.3.3 Extract ultrasonically for 3 minutes, with  output control knob
      set at  10 (full power)  and with  mode  switch on  Pulse  (pulsing  energy
      rather  than  continuous  energy)  and  percent-duty  cycle knob  set  at 50%
      (energy on 50% of time and off 50% of time).  Do not use microtip probe.

            7.3.4 Decant and filter extracts through Whatman  No. 41 filter paper
      (or  equivalent)  using  vacuum  filtration  or  centrifuge,  and  decant
      extraction solvent.
                                   3550A -  5                         Revision 1
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      7.3.5 Repeat the extraction two or more  times  with two additional
100 ml portions of solvent.   Decant off the solvent after each ultrasonic
extraction.  On the final ultrasonic extraction,  pour the entire sample
into the Buchner funnel and rinse with  extraction solvent.

      7.3.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching  a 10  ml concentrator tube  to a  500  ml evaporator  flask.
Transfer filtered extract to a 500 ml evaporator flask and proceed to the
next section.

      7.3.7 Add one to two clean boiling chips to the evaporation flask,
and attach a three ball Snyder column.  Prewet  the  Snyder  column by adding
about 1 mL methylene  chloride  to the top.  Place  the K-D apparatus on a
hot water  bath (80-90 °C)  so that the  concentrator tube  is  partially
immersed in  the  hot water  and  the  entire lower  rounded  surface  of the
flask  is  bathed  with  hot  vapor.  Adjust  the vertical  position  of the
apparatus  and  the water  temperature,  as required,  to complete  the
concentration in 10-15 min.   At the proper rate of distillation the balls
of the column will actively  chatter,  but the chambers will not flood with
condensed  solvent.   When the apparent volume  of liquid reaches  1 ml,
remove the K-D apparatus and  allow it  to  drain and cool  for at least 10
min.

      7.3.8  If a solvent exchange is required (as indicated in Table 1),
momentarily  remove the Snyder  column,  add  50  ml of the exchange solvent
and a new boiling chip, and  re-attach the Snyder column.  Concentrate the
extract as  described  in Section 7.3.8,  raising  the  temperature  of the
water  bath,  if necessary,  to maintain proper distillation.   When the
apparent volume again reaches 1-2 ml, remove the K-D apparatus and allow
it to drain  and cool for at least 10 minutes.

      7.3.9  Remove the Snyder column and rinse the  flask and  its lower
joints  into  the  concentrator tube  with 1-2 ml  of methylene chloride or
exchange solvent.   If sulfur crystals  are a  problem,  proceed  to Method
3660 for cleanup.  The extract may  be  further concentrated by using the
technique  outlined in Section  7.3.11  or adjusted  to 10.0 ml  with the
solvent last used.

      7.3.10       If further concentration is indicated in Table 1, either
micro  Snyder column  technique (Section 7.3.11.1)  or nitrogen  blow down
technique  (Section 7.3.11.2)  is  used to  adjust the extract to the  final
volume required.

             7.3.10.1    Micro Snyder Column Technique

                   7.3.10.1.1        Add a clean boiling chip and attach a
             two ball micro Snyder column to the concentrator tube.  Prewet
             the  column  by  adding  approximately 0.5  ml  of  methylene
             chloride  or  exchange  solvent  through  the  top.   Place the
             apparatus  in the hot water bath.  Adjust the vertical position
             and  the  water  temperature,  as   required,  to  complete the
             concentration   in  5-10  minutes.    At  the  proper  rate  of
             distillation the balls  of  the column will actively chatter,

                             3550A  -  6                          Revision 1
                                                           November 1992
-------
                  but the chambers will not flood.  When the liquid reaches an
                  apparent volume of approximately 0.5 ml, remove the apparatus
                  from the water bath and allow to drain and cool for at least
                  10 minutes.   Remove the  micro  Snyder column  and  rinse its
                  lower joint with approximately 0.2 mL of appropriate solvent
                  and add to the concentrator  tube.  Adjust the final volume to
                  the  volume required  for  cleanup or  for  the  determinative
                  method (see Table 1).

                  7.3.10.2    Nitrogen Blowdown Technique

                        7.3.10.2.1        Place the concentrator  tube  in a warm
                  water bath (approximately 35 °C) and  evaporate  the solvent
                  volume to  the required level using a gentle stream of clean,
                  dry nitrogen (filtered through a column of activated carbon).

                        CAUTION:    Do not  use plasticized  tubing  between the
                                    carbon trap and the sample.

                        7.3.10.2.2        The internal  wall  of  the tube must be
                  rinsed down several  times  with the appropriate solvent during
                  the operation.  During evaporation,  the solvent level  in the
                  tube must be positioned to prevent water from condensing into
                  the sample (i.e.,  the solvent level should be below the level
                  of the water  bath).   Under  normal  operating  conditions, the
                  extract should not be allowed to become dry.

                        CAUTION:    When the volume of solvent  is reduced below
                                    1 ml, semivolatile analytes may be lost.

      7.4   If analysis of the extract will not be performed immediately, stopper
the concentrator tube  and  store refrigerated.  If the  extract will  be  stored
longer than 2 days, it should be transferred to a vial  with a Teflon lined cap
and labeled appropriately.

      7.5   Extraction method for samples expected to contain high concentrations
of organics (> 20 mg/kg):

            7.5.1 Transfer approximately 2 g (record weight to  the nearest 0.1
      g) of sample to a 20 mL vial.  Wipe the mouth of the vial with a tissue to
      remove any sample material.  Record the exact weight of  sample taken.  Cap
      the  vial  before proceeding with  the next  sample to  avoid any  cross
      contamination.

            7.5.2 Add 2 g of anhydrous sodium sulfate to sample in the  20 ml
      vial and mix well.

            7.5.3 Surrogate  standards  are added  to  all samples,  spikes,  and
      blanks (see Method 3500 for details on the surrogate standard solution and
      on the matrix spike solution).  Add 2.0 ml of surrogate spiking solution
      to sample mixture.   For the sample in each analytical  batch selected for
      spiking, add 2.0  ml of  the matrix spiking standard.  For base/neutral-acid
      analysis, the amount  added of  the surrogates and matrix spiking compounds

                                  3550A - 7                         Revision 1
                                                                 November 1992
-------
      should result in a final  concentration of 200 ng//iL of each base/neutral
      analyte and 400 ng/jiiL of each acid analyte in the extract to be analyzed
      (assuming a 1 juL injection).  If Method 3640, Gel-Permeation Cleanup, is
      to  be used,  add  twice  the  volume   of  surrogates  and  matrix  spiking
      compounds since half the extract is lost due to loading of the GPC column.

            7.5.4 Immediately add whatever  volume of solvent  is  necessary to
      bring  the  final  volume to 10.0  ml   considering  the  added volume  of
      surrogates and matrix spikes.  Disrupt the sample with the 1/8 in. tapered
      microtip ultrasonic probe for 2 minutes  at  output  control  setting 5 and
      with  mode  switch on  pulse  and  percent duty  cycle at 50%.   Extraction
      solvents are:

            1.    Nonpolar compounds (i.e., organochlorine pesticides and PCBs),
                  hexane or appropriate solvent.

            2.    Extractable priority pollutants, methylene chloride.

            7.5.5 Loosely pack disposable Pasteur  pipets  with  2  to 3 cm Pyrex
      glass wool  plugs.  Filter the extract through the glass wool and collect
      5.0  ml in  a concentrator  tube  if further concentration  is  required.
      Follow Section 7.3.11 for details  on concentration.   Normally, the 5.0 ml
      extract is concentrated to approximately 1.0 ml or less.

            7.5.6 The extract is ready for cleanup or analysis, depending on the
      extent of interfering co-extractives.


8.0   QUALITY CONTROL

      8.1   Any reagent  blanks  or matrix spike samples should  be  subject to
exactly the same analytical procedures as those used on actual samples.

      8.2   Refer  to  Chapter One  for specific  quality  control  procedures and
Method 3500 for extraction  and sample preparation procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative method for performance data.


10.0  REFERENCES

1.    U.S.  EPA 40 CFR Part  136, "Guidelines Establishing Test  Procedures for the
      Analysis of  Pollutants Under the Clean Water Act;  Final Rule and  Interim
      Final Rule and Proposed Rule," October 26,  1984.

2.    U.S.  EPA,  Interlaboratory  Comparison  Study:   Methods  for Volatile and
      Semi-Volatile  Compounds, Environmental  Monitoring  Systems Laboratory,
      Office of Research and Development, Las Vegas, NV, EPA 600/4-84-027,  1984.
                                   3550A - 8                        Revision  1
                                                                 November  1992
-------
3.    Christopher S. Hein,  Paul  J.  Marsden, Arthur S. Shurtleff, "Evaluation of
      Methods 3540 (Soxhlet)  and 3550 (Sonication) for Evaluation of Appendix IX
      Analytes form Solid Samples", S-CUBED,  Report for EPA Contract 68-03-33-
      75, Work Assignment No. 03,  Document No.  SSS-R-88-9436, October 1988.
                                  3550A - 9                         Revision 1
                                                                 November 1992
-------
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-------
                        METHOD 3550A
                  ULTRASONIC  EXTRACTION
                             START
                       7 1  Prepare samples
                        using appropriate
                         method for th«
                          wast* matrix
                        7 2  Determine the
                       percent dry weight
                          of the sample
7 5 2 Add annydrous
 sodium sulfate to
     sampla
                                              7 3 1 Add  surrogat*
                                              s tandards to all
                                              samples ,  spilta* ,
                                                 and blanks
7  5  3 Add surrogate
 s tandards to all
 samples  spixes
    and blank*
                                                 732-735
                                              Sonicate sample at
                                                 lea* t 3  times
   7  5 4 Adjust
  volume  dis rupt
sample with tapered
micro tip ultrasonic
      probe
                                                7 3 7  Dry and
                                              callect extract in
                                              K-D concent ra tor
7 5
through
5 Filter
glass wool
                                               738 Concentrate
                                              extract and collect
                                              in X~D Concentrator
                         3550A  -  12
                                                                          Revision  1
                                                                      November  1992
-------
             METHOD 3550A
               continued
                              7  3.9  Is
                              a  solvent
                              exchange
                              required?
7 3.9 Add exchange
     solvent;
concentrate extract
7 3.10 Use Method
3660 for cleanup
                               7.3.10  Do
                            sulfur  crystals
                                 form?
                           7  3.11  Further
                         concentrate and/or
                           adjust volume
                        Cleanup  or analyze
               3550A - 13
                                                   Revision 1
                                                November 1992
-------
                                 METHOD 5040A

  ANALYSIS OF SQRBENT CARTRIDGES FROM VOLATILE  ORGANIC  SAMPLING  TRAIN  (VOST1:
                GAS CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 5040 was formerly Method 3720 in the Second Edition of this
manual.

      1.2   This method covers the determination of volatile principal organic
hazardous constituents  (POHCs),  collected  on  Tenax and Tenax/charcoal sorbent
cartridges  using  a volatile  organic  sampling train,  VOST  (1).   Much  of the
description for purge-and-trap GC/MS analysis is described in Method 8240 of this
chapter.  Because the majority of gas  streams  sampled using VOST will contain a
high concentration of water,  the analytical  method  is based on the quantitative
thermal desorption of volatile POHCs from the Tenax  and  Tenax/charcoal traps and
analysis by purge-and-trap GC/MS.  For  the purposes of definition, volatile POHCs
are those POHCs with boiling  points less than 100°C.

      1.3   This  method is  applicable  to  the analysis of  Tenax  and  Tenax/
charcoal cartridges used to collect volatile POHCs  from wet stack gas effluents
from hazardous waste incinerators.

      1.4   The sensitivity of the analytical method for a particular volatile
POHC depends on the level of interferences and the presence of detectable levels
of  volatile POHCs  in  blanks.    The  desired  target  detection  limit of  the
analytical method is  0.1 ng/L  (20 ng on a single pair  of traps) for a particular
volatile  POHC  desorbed  from  either a single  pair  of Tenax  and  Tenax/charcoal
cartridges or  by  thermal desorption of  up  to  six pairs of  traps  onto a single
pair of Tenax and Tenax/charcoal traps.   The resulting single pair of traps is
then thermally desorbed and analyzed by purge-and-trap GC/MS.

      1.5   This  method  is   recommended  for  use  only  by  experienced  mass
spectroscopists or under the  close supervision of such qualified persons.


2.0   SUMMARY OF METHOD

      2.1   A schematic diagram of the analytical  system is shown in Figure 1.
The contents of the sorbent cartridges are  spiked with  an internal standard and
thermally desorbed for 10 min at 180°C with  organic-free nitrogen or helium gas
(at a  flow  rate of 40  mL/min),  bubbled through 5 ml  of organic-free reagent
water,  and  trapped  on  an analytical  adsorbent  trap.    After  the 10  min.
desorption,  the analytical adsorbent trap is rapidly heated to 180°C, with the
carrier gas flow reversed so  that the  effluent  flow from the analytical trap is
directed  into  the GC/MS.   The  volatile POHCs  are  separated by  temperature
programmed gas chromatography and detected  by low-resolution mass spectrometry.
The concentrations of volatile POHCs are calculated using the internal standard
technique.
                                   5040A  -  1                         Revision 1
                                                                 November 1992
-------
3.0   INTERFERENCES

      3.1   Refer to Methods 3500 and 8240.


4.0   APPARATUS AND MATERIALS

      4.1   Thermal desorption unit:

            4.1.1 The   thermal   desorption   unit   (for   Inside/Inside   VOST
      cartridges,  use  Supelco  "clamshell"  heater;   for   Inside/Outside  VOST
      cartridges,  user-fabricated  unit  is  required)  should  be  capable  of
      thermally desorbing the sorbent resin tubes.  It should  also be capable of
      heating the  tubes to  180 +  10°C with  flow of  organic-free  nitrogen  or
      helium through the tubes.

      4.2   Purge-and-trap unit:

            4.2.1 The purge-and-trap unit consists of three separate pieces of
      equipment:   the sample purger,  trap,  and the  desorber.   It  should  be
      capable  of meeting  all  requirements  of  Method  5030  for  analysis  of
      purgeable organic compounds from water.

      4.3   GC/MS system:  As described in Method 8240.


5.0   REAGENTS

      5.1   Organic-free reagent water.  All  references  to  water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.2   Methanol, CH3OH - Pesticide grade, or equivalent.

      5.3   Analytical trap  reagents:

            5.3.1 2,6-Diphenylene oxide polymer:  Tenax  (60/80 mesh), chromato-
      graphic grade or equivalent.

            5.3.2 Methyl silicone packing:  3% OV-1 on Chromosorb W  (60/80 mesh)
      or equivalent.

            5.3.3 Silica  gel:   Davison  Chemical (35/00  mesh),  Grade  15,  or
      equivalent.

            5.3.4 Charcoal:  Petroleum-based  (SKC Lot 104  or equivalent).

      5.4   Stock standard solution:

            5.4.1 Stock standard solutions will be prepared from pure standard
      materials or purchased as  certified solutions.  The stock standards should
      be prepared  in  methanol  using assayed  liquids  or  gases, as appropriate.
      Because of the toxicity of some of the organohalides,  primary  dilutions of
      these materials should be prepared  in a hood.  A NIOSH/MESA approved toxic


                                   5040A  -  2                         Revision  1
                                                                 November 1992
-------
      gas respirator should be used when the analyst handles high concentrations
      of such materials.

            5.4.2 Fresh stock standards should be prepared weekly for volatile
      POHCs with boiling points of <35°C.   All other standards must be replaced
      monthly, or sooner if comparison with check standards indicates a problem.

      5.5   Secondary dilution standards:

            5.5.1 Using  stock   standard   solutions,   prepare,   in  methanol,
      secondary  dilution   standards  that  contain  the  compounds  of  interest,
      either singly or mixed together.   The secondary dilution standards should
      be prepared at concentrations such that the desorbed  calibration standards
      will bracket the working range of the analytical  system.

      5.6   4-Bromofluorobenzene (BFB) standard:

            5.6.1 Prepare  a 25 ng//iL solution of BFB in methanol.

      5.7   Deuterated benzene:

            5.7.1 Prepare  a 25 ng//nL solution of benzene-d6 in methanol.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Refer to Method 0030, Chapter Ten.

      6.2   Sample trains  obtained from the VOST should be analyzed within 2-6
weeks of sample collection.


7.0   PROCEDURE

      7.1   Assembly of PTD device:

            7.1.1 Assemble a purge-and-trap desorption device (PTD) that meets
      all the requirements of Method 5030 (refer to Figure 1).

            7.1.2 Connect  the  thermal  desorption  device to  the  PTD  device.
      Calibrate the PTD-GC/MS system using the internal standard technique.

      7.2   Internal standard calibration procedure:

            7.2.1 This approach  requires the  use of deuterated  benzene as the
      internal standard for these  analyses.  Other internal  standards may be
      proposed  for  use  in certain  situations.    The  important  criteria for
      choosing a  particular compound as an  internal  standard are that it be
      similar in analytical behavior to the compounds  of  interest and  that it
      can  be  demonstrated  that  the  measurement of  the  internal  standard be
      unaffected by method or matrix  interferences.  Other  internal  standards
      that have been used  are d10-ethylbenzene and d4-l,2-dichloroethane.   One
      adds 50 ng of BFB to all  sorbent cartridges (in addition to one or more


                                   5040A -  3                        Revision 1
                                                                 November 1992
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internal  standards)  to  provide   continuous  monitoring  of  the  GC/MS
performance relative to BFB.

      7.2.2 Prepare  calibration   standards   at  a  minimum   of  three
concentration levels for each analyte of interest.

      7.2.3 The  calibration  standards are prepared  by spiking  a blank
Tenax or Tenax/charcoal  trap with a methanolic  solution  of the calibration
standards (including 50 ng of  the  internal  standard,  such as deuterated
benzene), using  the  flash  evaporation technique.   The flash evaporation
technique requires  filling the needle  of a  5.0  p.1 syringe  with clean
methanol and drawing air  into  the  syringe to the 1.0  fj.L  mark.   This is
followed by  drawing  a  methanolic  solution of the calibration standards
(containing 25 M9/ML of the  internal  standard)  to the  2.0 /il_ mark.  The
glass  traps  should  be  attached  to  the   injection  port  of  a  gas
chromatograph while maintaining the  injector  temperature  at 160°C.  The
carrier  gas  flow through  the traps  should   be  maintained at  about 50
mL/min.

      7.2.4 After directing the gas flow through the trap,  the contents of
the  syringe  should  be slowly  expelled  through  the  gas  chromatograph
injection port over about  15  sec.  After 25 sec have  elapsed, the gas  flow
through  the  trap should be shut off, the syringe removed,  and the  trap
analyzed by  the  PTD-GC/MS  procedure  outlined  in Method 8240.   The total
flow of gas through the traps during  addition  of calibration standards to
blank cartridges, or internal standards to sample cartridges,  should be 25
ml or less.

      7.2.5 Analyze each  calibration  standard for both Tenax and Tenax/
charcoal cartridges according to Section 7.3.  Tabulate the area response
of the  characteristic  ions  of  each analyte  against the concentration of
the  internal  standard  and calculate  the response factor  (RF)  for  each
compound, using  Equation 1.

      RF = AsCis/AisCs                                                 (1)

where:

      As   =      Area  of  the  characteristic  ion for  the  analyte to be
                  measured.

      Ais  =       Area  of   the  characteristic   ion   for  the  internal
                  standard.

      Cis  =       Amount  (ng) of the  internal standard.

      Cs   =      Amount   (ng)  of the   volatile POHC   in  calibration
                  standard.

       If the RF value over the working range is a constant  (<10% RSD), the
RF can  be  assumed to  be  invariant,  and the  average RF can be used for
calculations.    Alternatively,  the  results  can  be   used  to  plot   a
calibration  curve of response ratios, As/Ais versus  RF.


                             5040A - 4                         Revision  1
                                                           November  1992
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            7.2.6 The working calibration curve or RF must be verified on each
      working  day  by  the  measurement  of  one  or  more  of  the  calibration
      standards.  If the response varies by more  than ±25%  for  any analyte,  a
      new calibration standard must be prepared and analyzed for that analyte.

      7.3   The schematic of  the  PTD-GC/MS  system is shown in  Figure  1.   The
sample cartridge  is placed in  the  thermal  desorption apparatus  (for Inside/
Inside VOST cartridges,  use  Supelco  "clamshell" heater; for Inside/Outside VOST
cartridges, user fabricated  unit is required) and desorbed  in the purge-and-trap
system by heating to 180°C for 10 min at a flow rate of 40 mL/min.  The desorbed
components pass into the bottom  of the  water column, are purged from the water,
and collected on  the  analytical  adsorbent  trap.   After the  10  min desorption
period, the compounds are desorbed from the analytical  adsorbent trap into the
GC/MS system according to the procedures described in Method 8240.

      7.4   Qualitative analysis

            7.4.1 The qualitative  identification of compounds determined by this
      method is based on retention  time, and  on comparison  of the sample mass
      spectrum,  after  background correction,  with characteristic  ions  in  a
      reference mass spectrum.  The reference mass  spectrum must  be generated by
      the laboratory using  the  conditions of  this  method.   The  characteristic
      ions from the reference mass spectrum  are defined to be the three ions of
      greatest relative intensity,  or  any ions over  30% relative intensity if
      less than  three  such  ions  occur in  the reference  spectrum.   Compounds
      should be identified as present when the criteria below are met.

                  7.4.1.1     The intensities of the characteristic  ions  of a
            compound maximize in the same scan or within one  scan of each other.
            Selection of a peak by a data system target compound search routine,
            where   the   search   is  based  on  the   presence  of   a  target
            chromatographic  peak  containing   ions  specific  for  the  target
            compound at a compound-specific  retention time, will  be accepted as
            meeting this criterion.

                  7.4.1.2     The RRT of the sample component is within ± 0.06
            RRT units of the RRT of the standard component.

                  7.4.1.3     The relative  intensities  of  the  characteristic
            ions agree within 30% of the relative  intensities of these ions in
            the reference spectrum.   (Example:  For an ion with an abundance of
            50%  in  the  reference spectrum,  the  corresponding  abundance  in  a
            sample spectrum can range between 20% and 80%.)

                  7.4.1.4     Structural isomers that produce very similar mass
            spectra should  be identified as  individual  isomers  if  they  have
            sufficiently different GC retention times.  Sufficient GC resolution
            is achieved if the height of the valley between two isomer peaks is
            less  than  25% of  the sum  of  the two peak  heights.   Otherwise,
            structural  isomers are identified as isomeric  pairs.

                  7.4.1.5     Identification is hampered when sample components
            are  not resolved  chromatographically and  produce  mass  spectra
            containing  ions  contributed by  more than  one analyte.   When gas

                                  5040A - 5                         Revision 1
                                                                 November 1992
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      chromatographic  peaks  obviously  represent  more  than one  sample
      component  (i.e.,  a broadened  peak with  shoulder(s)  or a  valley
      between  two  or  more  maxima),  appropriate  selection of  analyte
      spectra  and  background  spectra  is  important.    Examination  of
      extracted ion current profiles of  appropriate  ions  can  aid  in the
      selection  of  spectra,  and   in   qualitative   identification  of
      compounds.  When  analytes  coelute  (i.e.,  only  one chromatographic
      peak is apparent), the  identification criteria can be met, but each
      analyte  spectrum  will  contain  extraneous ions contributed  by the
      coeluting compound.

      7.4.2 For  samples containing components  not  associated with the
calibration standards,  a  library search  may be made for  the  purpose of
tentative  identification.   The  necessity  to  perform  this  type  of
identification will be determined by the type of  analyses being conducted.
Guidelines for making tentative  identification are:

      (1)   Relative  intensities of major ions in the reference spectrum
(ions >  10%  of the most  abundant  ion)  should be present  in  the  sample
spectrum.

      (2)   The relative intensities of the major ions should agree within
± 20%.   (Example:  For an ion  with an abundance of  50% in the standard
spectrum, the  corresponding sample ion abundance must  be  between  30 and
70%).

      (3)   Molecular ions present  in  the reference spectrum  should be
present in the sample spectrum.

      (4)   Ions present in the  sample spectrum but not in the reference
spectrum  should  be  reviewed  for  possible  background  contamination  or
presence of coeluting compounds.

      (5)   Ions present in the  reference spectrum but not in the sample
spectrum  should  be  reviewed  for possible  subtraction from  the  sample
spectrum  because of  background contamination or coeluting  peaks.   Data
system   library  reduction   programs   can   sometimes  create   these
discrepancies.

      Computer  generated  library  search  routines   should   not  use
normalization  routines  that  would misrepresent the  library  or  unknown
spectra when compared to each other.  Only after visual comparison of the
sample  with   the  nearest  library  searches  will   the  mass  spectral
interpretation specialist assign a tentative identification.

7.5   Quantitative analysis

      7.5.1 When   an   analyte   has   been   qualitatively   identified,
quantitation should be based  on the integrated  abundance from the EICP of
the primary  characteristic  ion chosen  for that analyte.   If the sample
produces  an interference for the primary characteristic ion, a secondary
characteristic ion should be used.
                             5040A -  6                        Revision 1
                                                           November 1992
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                  7.5.1.1     Using the internal standard calibration procedure,
            the amount of  analyte  in  the  sample  cartridge is calculated using
            the response factor  (RF) determined in Section  7.2.5 and Equation 2.

                  Amount of POHC  =  AsCis/A1sRF                             (2)

            where:

                  As   =      Area of the  characteristic ion  for the analyte to
                              be measured.

                  Ais   =       Area for the  characteristic  ion  of the internal
                              standard.

                  C.   =       Amount  (ng)  of internal standard.
                   IS
                  7.5.1.2     The  choice  of  methods   for  evaluating  data
            collected using  VOST  for incinerator trial  burns  is  a regulatory
            decision.  The procedures used  extensively by one user are outlined
            below.

                  7.5.1.3     The  total  amount  of  the  POHCs  of  interest
            collected on a pair of traps should be summed.

                  7.5.1.4     The observation of high concentrations of POHCs of
            interest   in  blank   cartridges   indicates    possible   residual
            contamination of the sorbent cartridges prior to shipment to and use
            at the  site.  Data that fall  in  this category  (especially data
            indicating high concentrations  of POHCs in blank sorbent cartridges)
            should be qualified with regard to validity, and blank data should
            be reported  separately.  The applicability of data of this type to
            the  determination   of  ORE is  a regulatory  decision.    Continued
            observation  of  high   concentrations  of  POHCs  in  blank  sorbent
            cartridges  indicates   that  procedures  for  cleanup,  monitoring,
            shipment, and storage  of sorbent  cartridges  by  a particular user be
            investigated to eliminate this problem.

                  7.5.1.5     If any internal standard recoveries fall outside
            the control  limits established  in Section 8.4, data for all analytes
            determined  for  that   cartridge(s)  must  be   qualified  with  the
            observation.
8.0   QUALITY CONTROL

      8.1   Refer to  Chapter  One for specific quality  control  procedures and
Method 0030 for sample preparation procedures.

      8.2   Each laboratory that  uses this method  is required to operate a formal
quality control  program.  The minimum requirements of this program consist of an
initial demonstration of laboratory capability and the analysis of blank Tenax
and  Tenax/charcoal  cartridges  spiked with  the  analytes  of  interest.    The
laboratory is required to maintain performance records to define the quality of
data  that  are generated.   Ongoing performance  checks  must be compared  with

                                   5040A  -  7                         Revision 1
                                                                 November 1992
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established performance criteria  to determine if results are within the expected
precision and accuracy limits of the method.

            8.2.1 Before performing any analyses, the analyst must demonstrate
      the  ability to  generate  acceptable  precision  and  accuracy with  this
      method.  This ability is established as described in Section 7.2.

            8.2.2 The  laboratory  must  spike   all  Tenax  and  Tenax/charcoal
      cartridges with the internal  standard(s) to monitor continuing laboratory
      performance.  This procedure is described in Section 7.2.

      8.3   To  establish  the  ability  to  generate  acceptable  accuracy  and
precision, the analyst must spike blank Tenax and Tenax/charcoal cartridges with
the analytes of interest at two concentrations in the working range.

            8.3.1 The average response  factor (R) and the standard deviation (S)
      for each must be calculated.

            8.3.2 The average recovery and standard deviation must fall within
      the expected range for  determination of volatile  POHCs using this method.
      The expected range for  recovery of volatile POHCs using  this method is 50-
      150%.

      8.4   The  analyst  must  calculate  method  performance  criteria  for  the
internal standard(s).

            8.4.1 Calculate  upper   and   lower  control  limits   for  method
      performances using the  average area response (A)  and standard deviation(s)
      for internal standard:

            Upper Control Limit  (UCL) = A + 3S
            Lower Control Limit  (LCL) = A - 3S

            The UCL  and  LCL  can  be used to construct  control  charts  that are
      useful  in  observing  trends in performance.   The  control  limits must be
      replaced by method performance criteria as they become available from the
      U.S. EPA.

      8.5   The laboratory is required  to spike all  sample cartridges (Tenax and
Tenax/charcoal) with  internal standard.

      8.6   Each  day,  the  analyst must demonstrate through  analysis  of blank
Tenax  and  Tenax/charcoal  cartridges  and  organic-free  reagent  water  that
interferences from the analytical system are under control.

      8.7   The  daily GC/MS  performance  tests  required  for this  method  are
described in Method 8240.
9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.
                                   5040A -  8                        Revision 1
                                                                 November 1992
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10.0  REFERENCES

1.    Protocol  for  Collection  and Analysis  of Volatile  POHC's  Using  VOST.
      EPA/600/8-84-007, March 1984.

2.    Validation  of  the  Volatile  Organic  Sampling Train   (VOST)  Protocol.
      Volumes I and II.  EPA/600/4-86-014a, January 1986.
                                  5040A - 9                         Revision 1
                                                                 November 1992
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                                          METHOD  5040A
ANALYSIS OF SORBENT  CARTRIDGES  FROM VOLATILE ORGANIC  SAMPLING  TRAIN
                    GAS  CHROMATOGRAPHY/MASS  SPECTROMETRY  TECHNIQUE
                                                             (VOST)
     7.1.1  X**«»bl«
       deioxptlon
         device
      7.1.2  Connect
         thermal
       desozption
         d«vio*f
      c»lIb.   tyttmm
        internal
        •tandazd
      7.2.3  Pxepar•
       calibration
     •tandard*   «*ioa
     f la«h  evaporat.
        technique
      7.2.4  Diz«Ct
        ga*  flow
      through  trap*
  7.9.4  Ixpel
  content*   of
•yiinge  through
 GC  injection
     port
 7.2.4  Analyze
 txap  by  P- T-D
     GC/H9
   proocdur*
 (Kethod  1240}
  •ach  calIb.
 •tandard   for
both  caztzidge*
   <>ee 7.3)
                              7.2.5  Tabulat*
                               7 . 2 . «  V«r 1 f y
  factor  »ach
      day
                            7.1  rlao»
                             sample
                          car trld?«   In
                         d««ozp.   appaz. ,
                          desozb  lo  P - T
                           7 . 3  D»«orb
                           into  CC/M3
                             ay»tern
                          (Hatbod  «24»)
                              7.4-1
                          Ouantatlvaly
                            identify
                         volatile  POHCi
                          (Method  S240}
                            7.51  U»e
                             pz inazy
                         ohai*o(«rl»tlc
                             ion  for
                         quan ti f icat ion
                                                            7.5.1.1
                                                           Calculate
                                                          analyte  in
                                                            •ample
                                                                                  each  pair
                                                                                      trap*
7.5.1.4  Analyse
  blank*  Cox
   •igni  of
   reaidval
                                                                                 7  5 . 1.5  Compaze
                                                                                    Int   >td.
                                                                                   tection  t.4
                                                                                 control  linlt*.
                                                       • top
                                            5040A  -  10
                                                           Revision  1
                                                       November 1992
-------
METHOD 5040A
  continued
 5040A - 11
   Revision 1
November 1992
-------
                                  METHOD  5041

       PROTOCOL  FOR ANALYSIS  OF  SORBENT CARTRIDGES  FROM  VOLATILE ORGANIC
             SAMPLING TRAIN:  WIDE-BORE CAPILLARY COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   This method  describes  the analysis of volatile  principal  organic
hazardous  constituents  (POHCs)  collected  from the  stack  gas  effluents  of
hazardous waste incinerators using the VOST methodology (1). For a comprehensive
description of  the  VOST  sampling methodology see Method  0030.   The following
compounds may be determined by this method:
      Compound Name
CAS No.'
Acetone
Acrylonitrile
Benzene
Bromodi chl oromethane
Bromoformb
Bromomethanec
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chloroethanec
Chloroform
Chl oromethane0
Dibromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Di chl oroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene6
lodomethane
Methylene chloride
Styreneb
1,1,2 , 2-Tetrachl oroethaneb
Tetrachl oroethene
Toluene
1,1,1-Trichloroethane
1 , 1 , 2-Tr i chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
Vinyl chloride0
67-64-1
107-13-1
71-43-2
75-27-4
75-25-2
74-83-9
75-15-0
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
74-95-3
75-35-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-01-5
10061-02-6
100-41-4
74-88-4
75-09-2
100-42-5
79-34-5
127-18-4
108-88-3
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
      Xylenes
                                   5041 -  1
                Revision 0
             November  1992
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      3  Chemical  Abstract Services Registry Number.

      b  Boiling  point  of this compound  is  above 132°C.   Method  0030  is not
appropriate for quantitative sampling of this analyte.

      c  Boiling point of this compound is below  30°C. Special precautions must
be taken when sampling for this analyte by Method 0030. Refer  to Section 1.3 for
discussion.

      1.2   This method  is most successfully applied to the analysis  of non-polar
organic compounds  with  boiling points between 30°C and 100'C.  Data are applied
to the calculation of destruction and removal  efficiency  (ORE), with limitations
discussed below.

      1.3   This method may be applied to  analysis of  many compounds which boil
above 100°C,  but Method 0030 is always inappropriate for  collection  of compounds
with boiling points above 132°C. All target analytes with boiling points greater
than 132°C  are so noted in the  target  analyte list presented in Section  1.1.  Use
of Method  0030 for collection of  compounds boiling  between  100°C and 132°C is
often  possible,   and  must  be  decided  based on  case  by  case  inspection  of
information  such  as sampling method  collection  efficiency,  tube desorption
efficiency, and analytical  method  precision and  bias.  An organic compound with
a boiling  point below 30°C  may break through the  sorbent  under the conditions
used  for sample collection.  Quantitative values obtained  for compounds with
boiling points below 30°C must be qualified, since  the  value obtained represents
a minimum value for the compound if breakthrough  has occurred.   In certain cases,
additional  QC measures may have been taken during sampling  very low  boilers with
Method  0030.     This   information   should  be   considered   during  the  data
interpretation stage.

      When Method  5041  is used for survey analyses, values  for compounds boiling
above 132°C may be  reported and qualified since the quantity obtained represents
a minimum value for the compound.   These minimum values  should not be used for
trial burn ORE calculations or to prove insignificant risk.

      1.4   The VOST analytical methodology can be used  to quantitate volatile
organic  compounds that  are  insoluble  or slightly  soluble  in  water.    When
volatile,  water soluble compounds are  included in  the VOST organic  compound
analyte list, quantitation limits  can be expected  to be  approximately ten times
higher than quantitation limits for water  insoluble compounds  (if the compounds
can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC®) is poor.

      1.5   Overall sensitivity of the method  is dependent  upon  the  level  of
interferences  encountered  in  the  sample  and  the  presence  of  detectable
concentrations of volatile POHCs in blanks.  The target  detection limit of this
method is 0.1 ng/m  (ng/L)  of  flue gas,  to permit  calculation  of a  ORE equal to
or greater than 99.99% for volatile  POHCs which  may be  present  in  the waste
stream at  100 ppm.  The upper end of the range  of applicability of this method
is limited by the dynamic range of the analytical instrumentation, the overall
loading  of organic compounds  on  the exposed  tubes,  and breakthrough  of the
volatile POHCs on  the sorbent traps used to collect the sample.  Table 1 presents
                                   5041 - 2                         Revision 0
                                                                 November 1992
-------
retention  times  and characteristic  ions  for volatile compounds which  can be
determined by this method.  Table 2 presents method detection  limits for a range
of volatile compounds analyzed by the wide-bore VOST methodology.

      1.6   The wide-bore VOST analytical methodology is restricted to use by,
or under the supervision of, analysts experienced in the use of sorbent media,
purge-and-trap systems,  and gas chromatograph/mass spectrometers,  and skilled in
the interpretation of mass spectra and their use as a quantitative tool.


2.0  SUMMARY OF METHOD

      2.1   The sorbent tubes are thermally desorbed by heating  and purging with
organic-free helium.   The  gaseous effluent  from the  tubes  is  bubbled through
pre-purged organic-free reagent water and trapped on an analytical sorbent trap
in a purge-and-trap unit (Figure 2).  After desorption, the analytical sorbent
trap is heated rapidly and  the gas  flow from  the analytical trap is directed to
the head of a wide-bore column under subambient conditions. The  volatile organic
compounds  desorbed from  the  analytical trap  are  separated  by  temperature
programmed high  resolution  gas  chromatography and  detected  by  continuously
scanning low  resolution mass spectrometry  (Figure 3).  Concentrations of volatile
organic compounds are  calculated from a multi-point calibration  curve, using the
method of response factors.


3.0   INTERFERENCES

      3.1   Sorbent tubes which are to be  analyzed for volatile organic compounds
can be  contaminated  by diffusion of  volatile  organic compounds  (particularly
Freon® refrigerants and common organic solvents) through the external container
(even through a Teflon® lined screw cap on a  glass container) and the Swagelok®
sorbent tube caps during shipment  and  storage.  The  sorbent  tubes  can also be
contaminated if organic solvents  are  present  in the analytical  laboratory.  The
use of  blanks  is  essential  to assess the extent of  any  contamination.   Field
blanks must be prepared and taken to the field.  The end caps of the tubes are
removed for the period of time required  to  exchange  two  pairs  of traps on the
VOST sampling apparatus.  The tubes are recapped and shipped and handled exactly
as the actual  field samples are shipped and handled.   At least one pair of field
blanks is included with each six pairs of sample cartridges collected.

      3.2   At  least  one   pair  of  blank  cartridges  (one  Tenax-GC®,  one
Tenax-GC®/charcoal) shall  be included with shipment of cartridges to a hazardous
waste incinerator site as trip blanks.  These trip blanks will  be treated like
field blanks  except that the  end  c-aps will not be removed during storage at the
site.  This pair  of traps will  be  analyzed  to  monitor potential  contamination
which may occur during storage and shipment.

      3.3   Analytical  system   blanks   are  required   to   demonstrate  that
contamination  of  the  purge-and-trap unit  and  the  gas  chromatograph/mass
spectrometer has not occurred or that, in the event  of  analysis  of sorbent tubes
with very  high  concentrations of organic compounds,  no  compound  carryover is
occurring. Tenax® from the same preparation batch  as  the Tenax® used for field
                                   5041 - 3                         Revision 0
                                                                 November 1992
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sampling should be used  in  the  preparation  of  the  method  (laboratory)  blanks.
A sufficient number of  cleaned  Tenax®  tubes from the same  batch  as  the field
samples should be reserved in the laboratory for use as  blanks.

      3.4   Cross contamination  can occur whenever low-concentration samples are
analyzed after high-concentration samples,  or  when  several  high-concentration
samples are analyzed  sequentially.   When an unusually  concentrated  sample is
analyzed,  this analysis should be followed by a method blank to  establish that
the  analytical  system  is  free  of  contamination.    If analysis  of a  blank
demonstrates that the  system is contaminated, an additional bake cycle should be
used.  If the analytical system is still  contaminated after  additional  baking,
routine system maintenance  should be performed:  the  analytical  trap  should be
changed and  conditioned,  routine column  maintenance should be  performed  (or
replacement of the column  and conditioning of the new  column, if necessary), and
bakeout of the ion source  (or cleaning of the ion source  and rods, if required).
After system maintenance has been performed,  analysis of a blank is required to
demonstrate that the cleanliness of the system is acceptable.

      3.5   Impurities in the purge gas and from organic compounds out-gassing
in tubing account  for the majority  of  contamination  problems.   The analytical
system must be demonstrated to be free from contamination under  the conditions
of the analysis by  analyzing two sets of clean, blank sorbent  tubes with organic-
free reagent purge water as  system blanks.   The  analytical system is acceptably
clean when these two sets of blank tubes  show values  for the analytes which are
within one  standard deviation  of the normal  system blank.   Use of  plastic
coatings,  non-Teflon®  thread  sealants,  or  flow  controllers  with  rubber
components should  be avoided.

      3.6   VOST tubes are handled in the laboratory to spike standards and to
position the  tubes within the  desorption  apparatus.  When sorbent  media  are
handled in  the  laboratory atmosphere,  contamination  is possible  if  there are
organic solvents in use anywhere  in the laboratory.   It is therefore necessary
to make daily  use of system blanks to monitor the cleanliness  of the sorbents and
the absence of contamination from  the analytical system.   A single  set of system
blank  tubes shall  be exposed  to normal  laboratory handling  procedures  and
analyzed as a sample.   This sample  should be within  one standard deviation of
normal VOST  tube blanks  to  demonstrate  lack of contamination  of  the  sorbent
media.

      3.7   If the emission  source has a high concentration of non-target organic
compounds (for example, hydrocarbons at concentrations of  hundreds of ppm), the
presence of these non-target compounds will interfere  with the performance of the
VOST  analytical  methodology.   If one or more  of  the  compounds  of interest
saturates  the  chromatographic  and mass  spectrometric  instrumentation,  no
quantitative calculations can be made and  the tubes which have been sampled under
the same conditions will  yield no  valid data for any of the saturated compounds.
In the presence of a very high organic loading, even if the compounds of interest
are not saturated, the instrumentation is  so saturated that the linear range has
been surpassed.  When  instrument saturation occurs, it is possible that compounds
of  interest  cannot  even  be identified  correctly  because  a  saturated mass
spectrometer  may  mis-assign  masses.   Even if  compounds  of interest  can be
identified,  accurate  quantitative   calculations  are  impossible  at  detector
saturation.   No  determination can be made at detector saturation, even  if the
target compound itself is  not saturated.  At  detector  saturation,  a negative  bias

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will be encountered in analytical measurements and no accurate calculation can
be made for the Destruction and Removal Efficiency if analytical values may be
biased negatively.

      3.8   The recoveries of the surrogate compounds, which are spiked on the
VOST tubes  immediately before analysis,  should  be monitored  carefully  as an
overall indicator of  the  performance  of the  methodology.   Since the matrix of
stack emissions is so  variable, only a general guideline for recovery of 50-150%
can be used for surrogates.  The  analyst cannot use the surrogate recoveries as
a guide for correction of  compound recoveries.  The surrogates are valuable only
as a general indicator of correct operation of the methodology.  If surrogates
are not observed or if recovery of one or more of  the  surrogates is outside the
50-150% range,  the VOST methodology is not operating correctly.  The  cause of the
failure  in  the methodology  is not  obvious.   The  matrix  of  stack emissions
contains large  amounts of water,  may be  highly acidic, and may contain  large
amounts  of target  and non-target  organic  compounds.   Chemical   and  surface
interactions may be  occurring on the tubes. If recoveries of surrogate compounds
are  extremely  low  or surrogate  compounds  cannot even be identified in  the
analytical process,  then failure  to observe an analyte may  or may not imply that
the compound of interest has  been removed from the emissions with a high degree
of efficiency (that is, the Destruction  and Removal Efficiency  for that analyte
is high).


4.0   APPARATUS AND MATERIALS

      4.1   Tube desorption apparatus: Acceptable performance of the methodology
requires:   1)  temperature regulation  to ensure  that  tube  temperature  during
desorption is regulated to 180°C + 10°;   2)  good  contact between tubes and the
heating apparatus to  ensure  that the sorbent bed  is  thoroughly and uniformly
heated  to  facilitate desorption  of  organic  compounds;     and 3)  gas-tight
connections to  the ends of the tubes to ensure flow of desorption gas through the
tubes without leakage  during the heating/desorption process. A  simple clamshell
heater which will  hold tubes  which are  3/4"  in  outer diameter will  perform
acceptably as a desorption apparatus.

      4.2   Purge-and-trap device:  The  purge-and-trap device consists of three
separate pieces of equipment:   a  sample  purge vessel,  an analytical  trap,  and a
desorber.  Complete devices are commercially available from a variety of sources,
or the separate components may be assembled.   The cartridge thermal desorption
apparatus  is  connected  to the  sample  purge  vessel  by  1/8"  Teflon®  tubing
(unheated transfer line).  The tubing which connects the desorption chamber to
the sample purge vessel should be as short as is  practical.

            4.2.1 The sample  purge vessel is required to hold 5 ml  of organic-
      free reagent water,  through which the gaseous effluent from the VOST tubes
      is routed.  The  water column  should be at least 3 cm deep.   The gaseous
      headspace between the water column and the analytical trap  must have a
      total volume  of less than  15 ml.   The purge gas must pass  through  the
      water column as finely  divided bubbles with  a diameter of less than 3 mm
      at  the  origin.    The   sample  purger  shown  in  Figure   4  meets  these
      requirements.   Alternate sample  purging vessels  may be used if equivalent
      performance is demonstrated.


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      4.2.2 The  analytical  trap  must  be  at  least  25 cm  and have  an
internal diameter of at least  0.105  in.  The analytical trap must contain
the following components:

      2,6-diphenylene oxide polymer:      60/80 mesh, chromatograph grade
                                          (Tenax-GC®, or equivalent)

      methyl silicone packing:            OV-1 (3%) on Chromosorb-W 60/80
                                          mesh, or equivalent

      silica gel:                         35/60 mesh,  Davison grade 15 or
                                          equivalent

      coconut charcoal:                   prepare  from Barneby  Cheney,
                                          CA-580-26,   or  equivalent,  by
                                          crushing   through   26   mesh
                                          screen.

      The  proportions  are:   1/3  Tenax-GC®,  1/3  silica  gel,  and  1/3
charcoal,  with  approximately  1.0 cm  of  methyl  silicone  packing.  The
analytical trap should be conditioned for four  hours at 180°C  with gas flow
(10 mL/min)  prior  to use in sample analysis.   During  conditioning,  the
effluent of the trap should not be vented  to the analytical  column.   The
thermal desorption apparatus is connected  to the injection system of the
mass spectrometer by a transfer line which is heated  to 100°C.

      4.2.3 The desorber must  be capable of rapidly heating the analytical
trap to 180°C for desorption.   The polymer section of the trap should not
exceed 180°C, and the remaining sections should not exceed  220°C,  during
bake-out mode.

4.3   Gas chromatograph/mass spectrometer/data system:

      4.3.1 Gas  chromatograph:    An  analytical  system complete with  a
temperature  programmable oven  with  sub-ambient temperature  capabilities
and all required accessories,  including  syringes,  analytical columns, and
gases.

      4.3.2 Chromatographic column:  30 m x  0.53 mm  ID wide-bore  fused
silica capillary column, 3 2m film thickness, DB-624 or equivalent.

      4.3.3 Mass spectrometer:  capable of scanning from 35-260 amu every
second  or  less, using 70  eV  (nominal)  electron  energy in  the electron
ionization  mode and  producing a mass  spectrum  that  meets all of the
criteria in Table 3 when 50 ng of 4-bromofluorobenzene (BFB) is injected
into the water  in the purge vessel.

      4.3.4 Gas  chromatograph/mass  spectrometer  interface:   Any   gas
chromatograph  to  mass  spectrometer  interface  that  gives  acceptable
calibration points at 50 ng or  less per injection of each of  the analytes,
and achieves  the performance  criteria  for 4-bromofluorobenzene shown in
Table 3, may be used.   If a glass jet separator is used  with  the wide-bore
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      column, a helium make-up  flow of approximately 15 ml,  introduced after the
      end  of the  column  and  prior  to the  entrance of  the  effluent  to  the
      separator, will be required for optimum performance.

            4.3.5 Data  system:   A computer system that  allows  the continuous
      acquisition  and  storage  on machine  readable  media of  all  mass  spectra
      obtained throughout the  duration  of  the  chromatographic program  must be
      interfaced to the mass  spectrometer.  The computer must have software that
      allows searching any gas  chromatographic/mass spectrometric data file for
      ions of a specified mass and plotting such ion abundances versus  time or
      scan number.   This  type  of plot  is defined as  an  Extracted  Ion  Current
      Profile  (EICP).    Software must  also  be  available   that  allows  the
      integration of the  ion abundances in  any EICP  between  specified  time or
      scan number limits.  The  most recent version of  the  EPA/NIST Mass Spectral
      Library should also be available.

      4.4   Wrenches:  9/16",  1/2", 7/16",  and 5/16".

      4.5   Teflon®  tubing:  1/8" diameter.

      4.6   Syringes: 25 juL  syringes (2), 10 /xL  syringes  (2).

      4.7   Fittings:  1/4" nuts,  1/8" nuts,  1/16" nuts, 1/4" to 1/8" union, 1/4"
to 1/4" union, 1/4" to 1/16" union.

      4.8   Adjustable  stand to  raise  the  level of  the desorption unit,  if
required.

      4.9   Volumetric flasks:   5 ml, class A with ground glass stopper.

      4.10  Injector port or equivalent, heated  to 180°C  for loading standards
onto VOST tubes prior to analysis.

      4.11  Vials:  2 mL,  with Teflon®  lined screw caps or crimp tops.

      4.12  Syringe:  5 ml, gas-tight with  shutoff valve.


5.0   REAGENTS

      5.1   Reagent grade  chemicals shall be used in all tests. Unless otherwise
indicated, it is intended  that  all  reagents  shall conform to the specifications
of the Committee on Analytical  Reagents  of the American Chemical Society, where
such specifications are available. Other grades  may be used, provided it is first
ascertained that the reagent is  of sufficiently  high  purity  to  permit  its  use
without lessening the accuracy of the determination.

      5.2   Organic-free reagent water - All  references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

            5.2.1 It is advisable to  maintain the stock of organic-free  reagent
      water generated for  use in the purge-and-trap apparatus with a continuous
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      stream of inert gas bubbled through the water.   Continuous bubbling of the
      inert gas maintains  a positive pressure  of  inert gas above the water as a
      safeguard against contamination.

      5.3   Methanol,  CH3OH.    Pesticide  quality  or  equivalent.   To  avoid
contamination with  other  laboratory  solvents, it  is advisable to  maintain a
separate stock of methanol  for the preparation of standards for VOST analysis and
to regulate the use of this methanol very carefully.

      5.4   Stock  standard solutions  -  Can  be  prepared  from pure  standard
materials or  can  be purchased as certified solutions.   Commercially prepared
stock standards can be used if they  are verified  against EPA standards.  If EPA
standards are not  available for  verification,  then  standards certified by the
manufacturer  and   verified  against  a standard  made  from  pure  material  is
acceptable.  Stock standard solutions must  be  prepared in high purity methanol.
All  preparation of  standards should  take place  in  a  hood,  both to  avoid
contamination and to ensure safety of the analyst preparing the standards.

            5.4.1 Place about 4 ml  of high  purity methanol in  a 5 ml volumetric
      flask.  Allow the flask  to  stand, unstoppered,  for about 10 min, or until
      all alcohol  wetted surfaces have dried.

                  5.4.1.1      Add appropriate volumes of neat liquid chemicals
            or certified solutions, using a syringe of the appropriate volume.
            Liquid which  is  added  to the volumetric flask  must  fall  directly
            into the alcohol  without contacting the neck of the flask.  Gaseous
            standards  can be  purchased  as  methanol  solutions   from  several
            commercial vendors.

                  5.4.1.2     Dilute  to  volume  with  high   purity  methanol,
            stopper, and then  mix by inverting the flask several times.  Calcu-
            late concentration by the dilution of  certified solutions or neat
            chemicals.

            5.4.2 Transfer the stock standard solution into  a Teflon® sealed
      screw  cap bottle.   An  amber  bottle may  be  used.  Store,  with  minimal
      headspace, at  -10°C  to -20°C,  and protect from  light.

            5.4.3 Prepare fresh standards every two months for gases. Reactive
      compounds such  as styrene may need to  be prepared  more frequently.   All
      other standards must be  replaced after six months, or sooner  if comparison
      with check standards indicates a problem.

      5.5   Secondary  dilution standards:    Using  stock standard  solutions,
prepare, in  high  purity methanol,  secondary  dilution standards containing the
compounds  of interest, either singly  or mixed  together.   Secondary dilution
standards must be  stored with minimal headspace and  should  be checked frequently
for  signs  of degradation  or  evaporation,  especially just  prior  to preparing
calibration standards  from them.

      5.6   Surrogate  standards:    The recommended  surrogates are  toluene-d8,
4-bromofluorobenzene,  and l,2-dichloroethane-d4.  Other compounds may be used as
surrogate compounds, depending upon  the requirements of the analysis.  Surrogate
compounds are selected to  span the  elution range of the compounds of interest.

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Isotopically labeled compounds are selected to preclude the observation of the
same compounds in the stack emissions.   More than one surrogate is used so that
surrogate measurements can still be made even if analytical interferences with
one or more of the surrogate compounds are encountered.  However, at least three
surrogate compounds  should  be used to monitor the performance of the methodology.
A stock surrogate compound solution in high purity methanol should be prepared
as described in Section 5.4, and a surrogate standard spiking solution should be
prepared  from  the  stock  at  a concentration  of 250 /xg/10 mL in  high purity
methanol.  Each pair of VOST tubes (or each individual  VOST tube,  if the tubes
are analyzed  separately)  must be spiked with  10  /xL of  the surrogate  spiking
solution prior to GC/MS analysis.

      5.7   Internal  standards:    The  recommended  internal   standards  are
bromochloromethane,  1,4-difluorobenzene, and chlorobenzene-d5.  Other compounds
may be used as internal  standards as long as they have retention times similar
to the  compounds  being  analyzed by GC/MS.   The internal  standards  should be
distributed through  the chromatographic elution range.  Prepare internal standard
stock  and secondary  dilution  standards  in  high  purity  methanol  using  the
procedures described in Sections 5.2 and 5.3.  The secondary dilution standard
should be prepared at a concentration of 25 mg/L of each  of the internal standard
compounds.  Addition of 10 /iL of this  internal  standard  solution  to each pair
of VOST tubes (or to each  VOST tube, if  the tubes are analyzed individually) is
the equivalent of 250 ng total.

      5.8   4-Bromofluorobenzene (BFB)  standard:  A standard solution containing
25 ng/juL of BFB in  high purity methanol should be prepared for use as a tuning
standard.

      5.9   Calibration standards:  Calibration standards at a minimum of five
concentrations will  be required from the secondary dilution of stock standards
(see Sections 5.2 and 5.3).   A range  of concentrations for calibration can be
obtained  by  use of different  volumes  of a 50  mg/L  methanol  solution  of  the
calibration  standards.     One of  the  concentrations   used should  be  at  a
concentration  near, but  above,  the method  detection limit.   The  remaining
concentrations should correspond to the expected range of concentrations found
in field samples but should not exceed  the linear range of the GC/MS analytical
system (a typical  range for a  calibration would be 10, 50, 100, 350, and 500 ng,
for example).    Each calibration  standard  should contain  each  analyte  for
detection by this method.  Store calibration  standards for one  week only in a
vial  with no headspace.

      5.10  Great care must be taken to maintain the integrity of all  standard
solutions.  All standards  of  volatile  compounds  in methanol must  be stored at
-10° to -20°C  in amber bottles with Teflon® lined screw caps or crimp tops.   In
addition, careful attention must be paid to the use of syringes  designated  for
a specific purpose  or for use with only a single standard solution since cross
contamination of volatile organic standards can occurs  very readily.


6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1   See Method 0030 for the VOST Sampling Methodology.
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                                                                 November 1992
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      6.2   VOST samples are collected on paired cartridges.   The first of the
pair of  sorbent cartridges  is  packed with approximately  1.6 g of  Tenax-GC®
resin.   The second cartridge of  the pair is packed with Tenax-GC® and petroleum
based charcoal  (3:1  by  volume;  approximately  1 g of each).   In  sampling,  the
emissions gas stream passes through the Tenax-GC® layer first and then through
the charcoal layer.   The Tenax-GC® is cleaned and reused; charcoal is not reused
when tubes are prepared.  Sorbent is cleaned and the tubes are  packed.  The tubes
are desorbed  and subjected  to a  blank check prior  to  being sent  to the field.
When the tubes are used for sampling (see Figure 5 for a schematic diagram of the
Volatile  Organic  Sampling  Train (VOST)), cooling  water is  circulated  to  the
condensers and the temperature of the  cooling water is maintained  near 0°C.  The
end caps  of the sorbent cartridges are placed in a clean, screw capped glass
container during sample collection.

      6.3   After  the  apparatus  is leak   checked,   sample  collection   is
accomplished  by opening the valve to the first condenser,  turning on the pump,
and sampling at a rate of 1  liter/min  for 20 minutes.  The volume of sample for
any pair of traps  should not exceed 20 liters.   An alternative set of conditions
for sample collection requires sampling at a reduced flow rate, where the overall
volume of sample collected  is 5 liters at a rate of 0.25 L/min for 20 minutes.
The 20 minute period  is required for collecting an integrated sample.

      6.4   Following collection of  20  liters of sample, the train  is  leak
checked a second time at the highest pressure drop encountered during  the run to
minimize the  chance  of vacuum desorption of organics from the Tenax®.

      6.5   The train is returned  to  atmospheric pressure  and the two sorbent
cartridges are removed.  The end caps are replaced and  the cartridges  are placed
in a suitable environment for storage  and transport until analysis.  The sample
is considered invalid if the leak test does not meet specifications.

      6.6   A new  pair  of  cartridges  is  placed  in the  VOST,  the VOST is leak
checked, and the sample collection  process  is  repeated  until  six pairs of traps
have been exposed.

      6.7   All  sample  cartridges  are kept  in  coolers on  cold  packs  after
exposure and during shipment.  Upon  receipt at the laboratory,  the cartridges are
stored in a refrigerator at 4°C  until  analysis.


7.0   PROCEDURE

      7.1   Recommended   operating   conditions   for   cartridge   desorber,
purge-and-trap unit,  and gas chromatograph/mass spectrometer using the wide-bore
column are:

      Cartridge Desorption  Oven
      Desorb  Temperature                    180°C
      Desorb  Time                           11  minutes
      Desorption Gas  Flow                   40 ml/min
      Desorption/Carrier Gas                Helium, Grade 5.0
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      Purqe-and-Trap Concentrator
      Analytical Trap Desorption Flow
      Purge Temperature
      Purge Time
      Analytical Trap Desorb Temperature
      Analytical Trap Desorb Time

      Gas Chromatograph
      Column
      Carrier Gas Flow
      Makeup Gas Flow
      Injector Temperature
      Transfer Oven Temperature
      Initial Temperature
      Initial Hold Time
      Program Rate
      Final Temperature
      Final Hold Time

      Mass Spectrometer
      Manifold Temperature
      Scan Rate
      Mass Range
      Electron Energy
      Source Temperature
2.5 mL/min helium
Ambient
11 minutes
180°C
5 minutes
DB-624,  0.53  mm  ID x  30 m  thick
film (3 /urn) fused silica capillary,
or equivalent
15 mL/min
15 mL/min
200°C
240°C
5°C
2 minutes
6°C/min
240°C
1 minute, or until  elution  ceases
105°C
1 sec/cycle
35-260 amu
70 eV (nominal)
According    to
specifications
manufacturer's
      7.2   Each GC/MS  system  must  be hardware tuned to meet  the criteria in
Table 3 for a 50 ng injection of 4-bromofluorobenzene (2 jitL  injection of the BFB
standard  solution  into the water of the purge vessel).   No  analyses  may be
initiated until the criteria presented in Table 3 are met.

      7.3   Assemble a  purge-and-trap device  that  meets  the specifications in
Method 5030.  Condition  the analytical trap overnight at 180°C in the purge mode,
with an inert gas flow of at least 20 mL/min.   Prior to use each day, condition
the trap for 10 minutes by backflushing at 180°C, with the  column  at  220°C.

      7.4   Connect the purge-and-trap device to a  gas chromatograph.

      7.5   Assemble  a  VOST   tube   desorption  apparatus  which  meets  the
requirements of Section 4.1.
unit.
      7.6   Connect the  VOST  tube desorption apparatus to  the purge-and-trap
      7.7   Calibrate the instrument using the internal  standard procedure, with
standards  and  calibration  compounds  spiked  onto  cleaned  VOST  tubes  for
calibration.

            7.7.1 Compounds in methanolic solution are  spiked  onto  VOST tubes
      using the flash evaporation technique.  To perform flash evaporation, the
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      injector of a  gas  chromatograph  or an equivalent piece of  equipment  is
      required.

                  7.7.1.1     Prepare a syringe with the appropriate volume  of
            methanolic standard solution (either surrogates, internal standards,
            or calibration compounds).

                  7.7.1.2     With the injector port heated to 180°C,  and with
            an inert gas flow of  10  mL/min  through  the  injector  port,  connect
            the paired VOST tubes (connected as in  Figure  1,  with gas  flow  in
            the same direction as the sampling  gas flow) to the  injector port;
            tighten  with  a wrench so  that  there  is  no leakage  of gas.   If
            separate  tubes  are  being  analyzed,   an   individual   Tenax®  or
            Tenax®/charcoal tube  is connected to the injector.

                  7.7.1.3     After  directing  the gas  flow  through the  VOST
            tubes, slowly inject the first standard solution over a period of 25
            seconds.  Wait  for  5  sec before withdrawing the  syringe  from the
            injector port.

                  7.7.1.4     Inject  a  second  standard  (if  required)  over  a
            period of  25 seconds and  wait  for 5  sec  before withdrawing  the
            syringe from the injector port.

                  7.7.1.5     Repeat  the sequence above as required until all  of
            the necessary compounds are spiked  onto the VOST  tubes.

                  7.7.1.6     Wait for 30 seconds, with gas  flow, after the last
            spike before disconnecting the tubes.  The total time the tubes are
            connected to the injector port  with gas flow should  not exceed 2.5
            minutes.   Total  gas  flow  through  the tubes  during  the  spiking
            process should not exceed 25 ml to prevent break through of adsorbed
            compounds  during  the spiking  process.   To allow  more time  for
            connecting and disconnecting tubes,  an on/off valve may be installed
            in the  gas  line to  the  injector port  so  that  gas is  not  flowing
            through the tubes during  the connection/disconnection process.

      7.8   Prepare the purge-and-trap  unit with  5  mL  of organic-free reagent
water in the purge vessel.

      7.9   Connect the paired VOST tubes to  the gas lines in the tube desorption
unit.  The tubes must be connected so that  the  gas flow during desorption will
be opposite to the flow  of  gas  during  sampling:  i.e.,  the  tube  desorption gas
passes through the charcoal portion of the  tube first.   An  on/off valve may be
installed in the gas  line leading to the tube desorption unit in order to prevent
flow of gas through the tubes during  the connection process.

      7.10  Initiate tube desorption/purge  and  heating of the  VOST tubes in the
desorption apparatus.

      7.11  Set the oven of the  gas chromatograph to subambient temperatures by
cooling with liquid nitrogen.

      7.12  Prepare the GC/MS system for data acquisition.

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      7.13  At the conclusion of the tube/water purge time, attach the analytical
trap to the gas  chromatograph,  adjust  the purge-and-trap device to the desorb
mode,  and  initiate  the  gas   chromatographic   program   and  the  GC/MS  data
acquisition.  Concurrently,  introduce   the  trapped   materials  to  the  gas
chromatographic  column  by  rapidly heating the  analytical  trap  to 180°C while
backflushing the  trap  with inert gas  at  2.5 mL/min for  5 min.   Initiate the
program for the gas chromatograph and simultaneously initiate data acquisition
on the GC/MS system.

      7.14  While  the   analytical   trap   is  being  desorbed  into  the  gas
chromatograph, empty the purging vessel.  Wash the purging vessel with a minimum
of two  5  ml flushes  of organic-free  reagent water (or  methanol  followed by
organic-free reagent  water) to  avoid  carryover  of analytes  into subsequent
analyses.

      7.15  After the sample has been desorbed,  recondition the analytical trap
by employing a bake cycle on the purge-and-trap unit.   The analytical trap may
be  baked   at  temperatures  up  to  220°C.    However,   extensive  use  of  high
temperatures  to   recondition  the trap  will  shorten  the  useful  life  of the
analytical trap.   After  approximately  11  minutes,  terminate  the trap bake and
cool  the trap to ambient temperatures in  preparation for  the next sample.  This
procedure is a convention for reasonable samples and should be adequate if the
concentration of contamination does not saturate the analytical  system.  If the
organic compound concentration is so high  that the analytical system is saturated
beyond the point where even extended system bakeout is not sufficient to clean
the system, a more extensive system maintenance must be performed.  To perform
extensive system maintenance, the analytical  trap is replaced and the new trap
is conditioned.   Maintenance is  performed on the GC  column  by removing at least
one foot  from  the front end  of the column.   If the  chromatography  does not
recover after column maintenance, the chromatographic  column  must be replaced.
The ion source  should  be baked  out  and,  if  the bakeout  is  not sufficient to
restore mass spectrometric  peak  shape  and  sensitivity,  the ion  source and the
quadrupole rods must be cleaned.

      7.16  Initial calibration for the analysis of  VOST  tubes:  It is essential
that calibration be performed in the mode in which analysis will be performed.
If tubes are being analyzed as pairs, calibration standards should be prepared
on paired  tubes.   If tubes are being analyzed individually,  a calibration should
be performed on individual  Tenax® only tubes and Tenax®/charcoal  tubes.

            7.16.1      Prepare the calibration  standards by spiking VOST tubes
      using the procedure described in  Section  7.7.1.   Spike  each pair of VOST
      tubes  (or  each of  the individual  tubes) immediately  before  analysis.
      Perform the calibration analyses  in order from low concentration to high
      to minimize the compound carryover.  Add  5.0  ml  of organic-free reagent
      water to the purging  vessel.   Initiate tube desorb/purge according to the
      procedure described above.

            7.16.2      Tabulate the area response of the  characteristic primary
      ions  (Table 1)  against  concentration for each  target  compound,  each
      surrogate compound, and each internal standard.   The first criterion for
      quantitative  analysis  is  correct  identification  of   compounds.    The
      compounds must elute  within  + 0.06 retention time  units  of the elution
      time of the standard  analyzed  on  the  same  analytical  system on the day of

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the analysis.  The analytes  should  be quantitated relative to the closest
eluting  internal  standard,  according  to  the scheme  shown in  Table  4.
Calculate response factors (RF) for each compound relative to the internal
standard  shown in  Table 4.   The  internal  standard  selected for  the
calculation  of RF is  the  internal standard that  has a retention time
closest to the compound being measured.  The RF  is calculated as follows:

      RF " (Ax/C,-s)/(Ais/Cx)

where:

      Ax  = area  of  the characteristic   ion   for  the  compound  being
            measured.

      Ais « area  of the characteristic  ion for the  specific  internal
            standard.

      Cjs = concentration of the specific internal  standard.

      Cx  = concentration of the compound being measured.

      7.16.3      The average RF must be calculated for each compound. A
system performance check should  be  made  before  the calibration curve is
used.  Five compounds  (the System Performance Check Compounds, or SPCCs)
are checked  for a  minimum average  response  factor.   These  compounds are
chloromethane, 1,1-dichloroethane,  bromoform, 1,1,2,2-tetrachloroethane,
and chlorobenzene.  The minimum acceptable average RF for these compounds
should be 0.300 (0.250  for bromoform).  These compounds  typically have RFs
of 0.4  -  0.6,  and are used  to check compound  instability  and check for
degradation  caused by  contaminated  lines or  active  sites  in the system.
Examples of these occurrences are:

            7.16.3.1    Chloromethane:  This compound  is the most likely
      compound to be lost if the purge flow is too fast.

            7.16.3.2    Bromoform:   This  compound is one of the compounds
      most likely to be purged very poorly  if the purge flow is too slow.
      Cold  spots  and/or active  sites in  transfer lines  may adversely
      affect response.  Response  of the primary quantitation ion  (m/z 173)
      is directly affected by the tuning for 4-bromofluorobenzene at the
      ions of masses 174 and 176. Increasing the ratio of ions  174 and 176
      to   mass   95    (the   base   peak   of   the   mass    spectrum   of
      bromofluorobenzene) may improve bromoform response.

             7.16.3.3    1,1,2,2-Tetrachloroethane and 1,1-dichloroethane:
      These  compounds  are  degraded by  contaminated   transfer  lines  in
      purge-and-trap systems and/or active sites in trapping materials.

      7.16.4      Using the  response factors from the  initial calibration,
calculate  the  percent  relative  standard  deviation  (%RSD)  for  the
Calibration  Check Compounds (CCCs).

      %RSD   =  (SD/X)  x 100
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                                                           November 1992
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where:

      %RSD     =       percent relative standard deviation

      RF,      =       individual RF measurement

      RF       =       mean of 5 initial  RFs for a compound  (the 5 points
                       over the calibration range)

      SD       =       standard deviation of average RFs for a compound,
                       where SD is calculated:
      SD =
                N (RF,  -  RF)2
I
                     N-l
      The %RSD  for  each  individual  CCC should be  less  than 30 percent.
This criterion must be met in order for the individual calibration to be
valid.  The CCCs are: 1,1-dichloroethene, chloroform, 1,2-dichloropropane,
toluene, ethylbenzene, and vinyl chloride.

7.17  Daily GC/MS Calibration

      7.17.1    Prior  to  the  analysis of  samples,  purge  50 ng  of  the
4-bromofluorobenzene standard.  The  resultant  mass  spectrum for the BFB
must meet all  of the criteria  given  in  Table 3  before  sample analysis
begins.   These  criteria must  be  demonstrated  every  twelve  hours  of
operation.

      7.17.2   The  initial  calibration  curve (Section  7.16)  for  each
compound of interest must be  checked  and verified once every twelve hours
of  analysis  time.   This verification  is  accomplished  by  analyzing  a
calibration  standard  that   is  at  a  concentration  near  the  midpoint
concentration for the  working range of the GC/MS  and checking the SPCC
(Section 7.16.3) and CCC (Section 7.16.4).

      7.17.3   System  Performance Check  Compounds (SPCCs):    A  system
performance check must be made each  twelve hours of  analysis.  If the SPCC
criteria  are  met,  a comparison  of  response  factors is  made for  all
compounds.  This  is the same  check  that  is applied  during  the initial
calibration.  If the minimum response factors are not achieved, the system
must be evaluated, and corrective  action must be taken before analysis is
allowed to begin.  The minimum response factor for  volatile SPCCs is 0.300
(0.250  for  bromoform).    If  these  minimum  response  factors are  not
achieved, some  possible  problems may be degradation  of  the  standard
mixture, contamination of the  injector port,  contamination  at the front
end  of  the   analytical  column,  and  active  sites  in  the  column  or
chromatographic system.  If the problem is active  sites at the front end
of the analytical column, column maintenance (removal  of approximately 1
foot from the front end of the column) may remedy  the problem.
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      7.17.4   Calibration Check Compounds:  After the system performance
check has been met, CCCs listed  in Section  7.16.4 are  used  to  check the
validity of  the  initial calibration.  Calculate the percent  difference
using the following equation:

                        (RF,- - RFC)  x  100
      % Difference = 	
                              RF,

where:

      RFi  =    average response factor from initial calibration

      RFC  =    response factor from current calibration check standard.

      If the percent difference for any compound is greater than 20, the
laboratory should  consider  this  a warning limit.  Benzene,  toluene, and
styrene will  have problems with response factors if Tenax® decomposition
occurs  (either  as  a  result  of  sampling   exposure  or  temperature
degradation), since these  compounds are decomposition products of Tenax®.
If the  percent difference  for  each  CCC is less than 25%,  the initial
calibration  is  assumed  to  be valid.    If  the  criterion  of  percent
difference less  than 25%  is not met for any  one CCC,  corrective action
MUST be taken.   Problems similar to those listed  under SPCCs could affect
this criterion.   If a  source of the problem  cannot  be determined after
corrective action  is taken,  a new five-point calibration  curve MUST be
generated.   The  criteria  for the  CCCs  MUST be  met  before quantitative
analysis can begin.

      7.17.5       Internal standard responses  and retention times in the
check calibration  standard must be evaluated immediately after or during
data acquisition.  If the retention time for any  internal standard changes
by more  than 30  seconds  from the last  check calibration  (12  hr), the
chromatographic system must be inspected for malfunctions and corrections
must be made,  as required.   A factor which may influence the retention
times of the internal  standards on sample  tubes is the level of overall
organic compound loading on  the VOST tubes.   If the VOST tubes are very
highly  loaded  with either  a single compound  or with  multiple organic
compounds, retention times for standards and compounds of interest will be
affected.    If  the area  for the  primary  ion  of  any  of  the  internal
standards changes  by a factor of two (-50% to  +100%) from the last daily
calibration check, the gas chromatograph and mass spectrometer should be
inspected for malfunctions and corrections must be made, as appropriate.
If the level  of organic loading of samples  is  high, areas for the primary
ions  of both  compounds  of  interest  and  standards  will   be  adversely
affected.  Calibration  check standards should not be subject to variation,
since the concentrations of organic compounds  on these  samples are set to
be  within the  linear  range  of   the  instrumentation.    If instrument
malfunction has  occurred,  analyses of samples  performed under conditions
of malfunction may be  invalidated.
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7.18  GC/MS Analysis of Samples

      7.18.1      Set  up  the cartridge desorption  unit,  purge-and-trap
unit, and GC/MS as described above.

      7.18.2      BFB  tuning criteria  and  daily  GC/MS  calibration check
criteria must be met before analyzing samples.

      7.18.3      Adjust  the helium purge gas  flow  rate  (through  the
cartridges and  purge  vessel) to approximately 40 mL/min.   Optimize  the
flow rate to provide the best response for chloromethane and bromoform, if
these compounds are analytes. A  flow rate  which  is  too  high reduces  the
recovery of chloromethane, and an insufficient gas flow rate reduces  the
recovery of bromoform.

      7.18.4      The first analysis performed after the tuning check and
the calibration or daily calibration check  is  a method blank.  The method
blank consists of clean VOST tubes (both Tenax® and Tenax®/charcoal) which
are spiked with surrogate  compounds and  internal  standards  according to
the procedure described in Section  7.7.1.   The tubes which  are used  for
the method blanks  should be from the same batch of sorbent as the sorbent
used for the field samples.   After the  tubes are cleaned and prepared  for
shipment to the field, sufficient pairs of tubes should be retained from
the same  batch in the laboratory  to  provide method  blanks  during  the
analysis.

      7.18.5      The organic-free reagent  water  for the purge vessel  for
the analysis  of each  of  the VOST  samples  should  be  supplied  from  the
laboratory inventory which is maintained with constant  bubbling of inert
gas to avoid contamination.

      7.18.6      If  the  analysis  of a   pair  of  VOST  tubes  has  a
concentration of analytes that exceeds the initial  calibration range, no
reanalysis of desorbed VOST tubes is possible.  An additional calibration
point can be added to  bracket the higher concentration encountered in  the
samples so that the calibration database encompasses six or more points.
Alternatively,  the data may be  flagged  in the  report  as  "extrapolated
beyond the upper range of  the calibration." The use of the secondary ions
shown in Table 1 is permissible  only in the case of interference with  the
primary quantitation  ion.   Use  of  secondary  ions to calculate compound
concentration  in  the   case of  saturation  of  the primary  ion  is  not an
acceptable procedure,  since a negative  bias of an unpredictable magnitude
is  introduced  into the quantitative data when  saturation  of  the mass
spectrum of a compound is encountered.   If high organic loadings, either
of  a  single  compound   or of  multiple compounds,  are encountered,  it is
vital that a  method blank be analyzed prior  to  the analysis  of another
sample  to demonstrate that no  compound  carryover  is  occurring.    If
concentrations of organic compounds are sufficiently high that carryover
problems are profound, extensive bakeout of the purge-and-trap unit will
be  required.   Complete replacement  of  the  contaminated  analytical trap,
with the associated requirement for conditioning the  new trap, may also be
required for VOST samples which show excessive concentrations of organic
compounds.  Other  measures  which  might  be required for decontamination of
the  analytical  system   include  bakeout   of  the  mass   spectrometer,

                             5041 -  17                         Revision 0
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replacement of the filament  of  the mass spectrometer, cleaning of the ion
source of the mass spectrometer, and/or  (depending  on  the  nature  of the
contamination) maintenance of the chromatographic column or replacement of
the  chromatographic   column,   with  the  associated  requirement   for
conditioning the new chromatographic column.

7.19  Data Interpretation

      7.19.1      Qualitative analysis:

            7.19.1.1    The  qualitative   identification   of  compounds
      determined  by  this  method is  based on  retention  time,  and  on
      comparison of the sample mass spectrum, after background correction,
      with  characteristic  ions  in  a  reference mass spectrum.    The
      reference mass spectrum must  be generated  by  the laboratory using
      the conditions of  this  method.   The characteristic  ions  from the
      reference mass  spectrum are defined to be the three ions of greatest
      relative intensity, or any ions over  30% relative intensity if less
      than three  such  ions  occur in the reference  spectrum.   Compounds
      should be identified as present when the criteria below are met.

                  7.19.1.1.1  The intensities of the characteristic ions
            of a compound maximize  in  the same scan  or within one scan of
            each  other.   Selection of  a peak  by  a data  system  target
            compound search  routine where  the search  is  based  on  the
            presence of  a target  chromatographic  peak containing  ions
            specific for the  target compound  at  a  compound  specific
            retention time will be accepted as meeting this criterion.

                  7.19.1.1.2  The RRT of the sample  component is within +
            0.06 RRT units of the RRT of the standard component.

                  7.19.1.1.3  The    relative     intensities    of    the
            characteristic  ions  agree  within  30%  of   the  relative
            intensities  of  these   ions  in   the   reference  spectrum.
            (Example:    For  an  ion with  an   abundance  of  50%  in  the
            reference  spectrum, the corresponding abundance  in  a sample
            spectrum can range between 20% and 80%.)

                  7.19.1.1.4  Structural isomers that produce very similar
            mass  spectra  should be identified as individual  isomers if
            they   have  sufficiently  different  GC   retention  times.
            Sufficient GC  resolution is  achieved  if the  height  of the
            valley between two isomer peaks is less than 25% of the sum of
            the  two  peak  heights.    Otherwise,  structural  isomers  are
            identified as isomeric pairs.

                  7.19.1.1.5  Identification  is  hampered  when  sample
            components are  not  resolved  chromatographically and produce
            mass  spectra containing ions  contributed  by  more  than one
            analyte.  When gas chromatographic peaks obviously represent
            more  than  one  sample component (i.e.,  a broadened peak with
            shoulder(s)  or  a  valley   between  two  or  more  maxima),
            appropriate  selection  of  analyte   spectra  and  background

                             5041  -  18                        Revision 0
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      spectra is  important.   Examination  of extracted ion current
      profiles  of appropriate  ions  can aid  in  the  selection  of
      spectra, and in qualitative identification of compounds.  When
      analytes  coelute  (i.e.,  only  one  chromatographic peak  is
      apparent), the identification  criteria  can  be met, but each
      analyte spectrum will contain extraneous ions contributed by
      the coeluting compound.

      7.19.1.2    For samples containing components not associated
with the calibration standards,  a library search may be made for the
purpose of tentative identification.  The necessity to perform this
type of  identification will  be  determined  by  the  type of analyses
being conducted.   Guidelines for  making  tentative identification
are:

      (1)   Relative intensities  of major  ions  in  the  reference
spectrum (ions > 10% of  the most abundant ion) should be present in
the sample spectrum.

      (2)   The relative intensities  of the  major ions should agree
within + 20%.   (Example:  For an ion with an  abundance  of  50% in the
standard spectrum,  the corresponding sample ion abundance must be
between 30 and 70%).

      (3)   Molecular ions present  in the reference spectrum should
be present in the sample spectrum.

      (4)   Ions  present  in  the  sample spectrum  but not  in  the
reference  spectrum should  be  reviewed  for  possible  background
contamination or presence of coeluting  compounds.

      (5)   Ions present in  the reference  spectrum  but  not  in  the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum  because  of background  contamination  or  coeluting
peaks.  Data system library reduction programs can sometimes create
these discrepancies.

      Computer generated  library   search  routines  should not  use
normalization  routines  that  would  misrepresent   the library  or
unknown  spectra  when  compared to  each  other.  Only  after  visual
comparison of sample with the nearest library searches will the mass
spectral    interpretation    specialist    assign    a    tentative
identification.

7.19.2      Quantitative analysis:

      7.19.2.1    When   a  compound   has   been   identified,   the
quantitative  analysis  of  that  compound  will  be  based  on  the
integrated abundance from the extracted ion current profile of the
primary  characteristic  ion  for that compound (Table  1).   In  the
event that  there  is  interference with the  primary  ion so  that
quantitative measurements cannot be  made,  a  secondary ion  may be
used.
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                                                     November 1992
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      NOTE: Use  of  a  secondary   ion   to   perform  quantitative
            calculations  in  the event  of the  saturation of  the
            primary ion is not  an  acceptable  procedure because of
            the unpredictable extent of the negative bias which is
            introduced.   Quantitative calculations  are  performed
            using the  internal  standard technique.   The internal
            standard used  to perform quantitative calculations shall
            be the internal standard nearest the retention time of
            a given analyte (see Table 4).

      7.19.2.2    Calculate the amount  of each  identified analyte
from the VOST tubes as follows:

      Amount (ng)  =  (AsCjs)/(AisRF)

where:

      As  = area of  the  characteristic  ion for the  analyte  to be
            measured.

      A.  = area of the characteristic ion of the internal standard.
        i s

      Cis  = amount (ng) of the internal  standard.

      7.19.2.3    The  choice   of   methods   for   evaluating   data
collected using the VOST methodology for incinerator  trial burns is
a  regulatory decision.    Various  procedures are  used  to  decide
whether  blank  correction  should  be  performed  and  how  blank
correction should be performed.  Regulatory agencies to which VOST
data are submitted  also vary in their preferences for data which are
or which are not blank corrected.

      7.19.2.4    The  total   amount  of  the  POHCs  of  interest
collected on a pair of traps should be summed.

      7.19.2.5    The occurrence of high concentrations of analytes
on method blank cartridges indicates possible residual contamination
of  sorbent cartridges prior to shipment and use  at the sampling
site.  Data with  high associated blank values must be  qualified with
respect  to  validity,  and  all  blank   data  should be  reported
separately.   No blank  corrections should  be  made  in  this  case.
Whether or not data of this type can be applied to the determination
of  Destruction  and Removal  Efficiency  is a  regulatory decision.
Continued  observation  of  high  concentrations  of. analytes on blank
sorbent cartridges indicates that procedures for cleanup and quality
control for  the  sampling  tubes are inadequate.   Corrective action
MUST  be applied  to tube  preparation  and  monitoring procedures to
maintain  method  blank  concentrations  below detection  limits  for
analytes.

      7.19.2.6    Where applicable, an estimate of concentration for
noncalibrated components  in the sample  may be made.  The formulae
for  quantitative calculations  presented above  should be used with
the following modifications:  The areas Ax and Ajs should be from the

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            total   ion   chromatograms,   and  the  Response   Factor   for  the
            noncalibrated  compound  should be  assumed  to be  1.    The  nearest
            eluting internal standard free from interferences in the total ion
            chromatogram should  be  used to determine the concentration.   The
            concentration which is obtained should be reported indicating:  (1)
            that the value is an estimate; and (2)  which internal standard was
            used.

                  7.19.2.7    If any internal standard recoveries fall  outside
            the control  limits established  in Section 8.4, data for all analytes
            determined  for  that  cartridge(s)  must  be  qualified  with  the
            observation.    Report  results  without   correction   for  surrogate
            compound recovery data.  When  duplicates  are  analyzed,  report the
            data obtained with the sample results.


8.0   QUALITY CONTROL

      8.1   Each laboratory  that  uses  these methods is required to  operate a
formal quality control program.  The minimum Quality  Control requirements of are
specified in Chapter One.  In addition, this program should consist of an initial
demonstration of laboratory capability  and  an ongoing analysis of check samples
to evaluate and document data quality.   The laboratory must maintain records to
document the  quality of the data generated.  Ongoing data quality checks are
compared with established  performance criteria to determine  if  the results of
analyses meet the  performance  characteristics of  the method.    When  sample
analyses indicate atypical  method performance,  a quality control   check standard
(spiked method  blank) must be analyzed to confirm  that  the  measurements were
performed in an in-control  mode of instrument operation.

      8.2   Before  processing  any  samples,  the  analyst should demonstrate,
through the analysis of  a method  blank (laboratory blank sorbent  tubes,  reagent
water purge) that interferences from the analytical  system,  glassware,  sorbent
tube  preparation,  and reagents  are under  control.   Each time a new  batch of
sorbent tubes  is analyzed,  a method blank should be processed  as  a safeguard
against chronic laboratory contamination.  Blank tubes which  have been carried
through all  the stages of sorbent preparation and  handling should  be used in the
analysis.

      8.3   The  experience of the  analyst performing  the  GC/MS  analyses  is
invaluable to the success of  the analytical methods.   Each day that the analysis
is  performed,  the  daily calibration check  standard should  be evaluated  to
determine  if the  chromatographic  and   tube  desorption  systems  are  operating
properly.  Questions that should be asked are:  Do the peaks look normal?  Is the
system response obtained comparable to the  response from previous calibrations?
Careful examination of the  chromatogram of the calibration standard can indicate
whether column maintenance  is required  or  whether the column  is  still  usable,
whether there  are  leaks in  the  system, whether  the injector septum  requires
replacing,  etc.  If changes are made to the system  (such  as change of a column),
a calibration check must be carried out and a new multipoint calibration must be
generated.
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      8.4   Required  instrument  quality control  is  found  in  the following
sections:

            8.4.1 The mass spectrometer must be tuned to meet the  specifications
      for 4-bromofluorobenzene in Section 7.2  (Table 3).

            8.4.2An    initial    calibration    of    the    tube
      desorption/purge-and-trap/GC/MS must  be performed as specified in Section
      7.7.

            8.4.3 The GC/MS  system  must meet  the SPCC  criteria specified  in
      Section 7.16.3 and the CCC criteria in Section 7.16.4 each twelve hours  of
      instrument operation.

      8.5   To  establish  the  ability  to   generate  acceptable  accuracy and
precision, the analyst must  perform the  following  operations.

            8.5.1 A quality control  (QC) check sample concentrate  is required
      containing each  analyte  at a  concentration of  10  mg/L  in high purity
      methanol.    The QC check  sample  concentrate may  be prepared from  pure
      standard materials or  purchased as certified solutions.   If the QC  check
      sample  concentrate is  prepared by the  laboratory,  the  QC check sample
      concentrate must be prepared using stock  standards  prepared independently
      from the stock standards used for  calibration.

            8.5.2 Spike four pairs of cleaned, prepared  VOST tubes with  10  ;uL
      of the  QC  check sample concentrate and  analyze  these spiked VOST  tubes
      according to the method beginning  in  Section 7.0.

            8.5.3 Calculate  the  average  recovery  (X)  in  ng  and the standard
      deviation of the recovery  (s)  in ng for each  analyte using  the results  of
      the four analyses.

            8.5.4 The average recovery  and  standard deviation  must  fall within
      the expected range for determination  of  volatile organic compounds  using
      the VOST  analytical  methodology.   The  expected  range  for recovery  of
      volatile  organic  compounds  using this  method  is  50-150%.   Standard
      deviation will be compound dependent, but should,  in general,  range from
      15 to 30 ng.   More detailed method performance  criteria must be generated
      from historical records in  the  laboratory or  from interlaboratory studies
      coordinated by the Environmental Protection Agency.  Since  the additional
      steps of  sorbent tube  spiking and desorption  are superimposed upon the
      methodology of Method  8240, direct transposition of  Method 8240 criteria
      is questionable.  If the recovery and standard  deviation  for all analytes
      meet the acceptance criteria, the system  performance  is acceptable and the
      analysis of field samples may begin.   If any individual  standard deviation
      exceeds the precision  limit or any individual  recovery falls  outside the
      range for accuracy,  then the system performance  is unacceptable for that
      analyte.

            NOTE: The large  number  of  analytes listed  in Table 1 presents  a
                  substantial probability that one or more will  fail at  least
                  one of the acceptance criteria  when  all  analytes for  this
                  method are determined.

                                   5041  - 22                         Revision 0
                                                                 November 1992
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            8.5.5 When one or more of the analytes tested fails at least one of
      the acceptance criteria,  the analyst must proceed according to one of the
      alternatives below.

                  8.5.5.1     Locate and correct the source of any problem with
            the methodology and repeat the  test for all  the analytes beginning
            with Section 8.5.2.

                  8.5.5.2     Beginning with Section 8.5.2,  repeat the test only
            for those analytes  that have  failed to meet acceptance criteria.
            Repeated failure,  however,  will  confirm a general  problem either
            with  the measurement  system  or  with  the  applicability  of  the
            methodology to the particular analyte (especially if the analyte in
            question is  not listed  in Table 1).   If the problem is identified as
            originating in the measurement system,  locate and correct the source
            of the problem and  repeat the  test for all  compounds  of interest
            beginning with Section 8.5.2.

      8.6   To determine acceptable accuracy and precision limits for surrogate
standards,  the following procedure should  be  performed.

            8.6.1 For each sample  analyzed, calculate the  percent  recovery of
      each  surrogate compound in the sample.

            8.6.2 Once a minimum of thirty samples has been  analyzed, calculate
      the average percent recovery  (p) and the standard deviation of the percent
      recovery (s) for each of the surrogate  compounds.

            8.6.3 Calculate  the upper  and  lower  control  limits  for  method
      performance for each surrogate standard.   This calculation is performed as
      follows:

            Upper Control Limit (UCL) = p + 3s
            Lower Control Limit (LCL) = p  - 3s

            For reference, the  comparable control  limits  for recovery  of  the
      surrogate compounds from water and soil  in Method 8240  are:

            4-Bromofluorobenzene   Water:  86-115%    Soil:   74-121%

            l,2-Dichloroethane-d4  Water:  76-114%     Soil:  70-121%

            Toluene-d8              Water:  88-110%     Soil:  81-117%

            The control  limits  for  the VOST methodology would be expected to be
      similar, but exact data are not presently available.  Individual laboratory
      control  limits can be  established by the  analysis of  replicate samples.

            8.6.4 If surrogate  recovery  is not within the limits established by
      the laboratory, the following  procedures are  required: (1)  Verify  that
      there are  no  errors in  calculations, preparation  of surrogate  spiking
      solutions,  and  preparation of internal  standard spiking solutions. Also,
      verify that  instrument performance criteria have been met. (2)  Recalculate
      the data and/or analyze a replicate sample,  if replicates  are available.

                                   5041  - 23                         Revision 0
                                                                 November  1992
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      (3)  If all  instrument performance  criteria  are  met  and recovery  of
      surrogates from spiked blank VOST tubes  (analysis  of  a  method blank)  is
      acceptable, the problem is due to the  matrix.   Emissions samples may  be
      highly acidic and may be highly loaded  with target and non target organic
      compounds.  Both of  these conditions will affect the  ability  to recover
      surrogate compounds which  are  spiked on the field samples.  The surrogate
      compound  recovery  is thus a valuable  indicator of the  interactions  of
      sampled compounds  with the matrix.    If surrogates  spiked  immediately
      before  analysis  cannot  be  observed  with  acceptable  recovery,  the
      implications for target organic analytes which  have been sampled in the
      field must be assessed very carefully.  If chemical  or other interactions
      are occurring on the exposed tubes, the failure to observe an analyte may
      not necessarily imply that the Destruction and Removal  Efficiency for that
      analyte is high.

      8.7   It  is  recommended  that  the laboratory  adopt  additional  quality
assurance practices for use with this method.  The specific  practices that are
most productive depend upon  the needs of the laboratory  and the nature of the
samples analyzed.  Field duplicates  may be analyzed to assess the precision  of
the environmental measurements.  When doubt exists  over the  identification of i
peak on  the chromatogram, confirmatory techniques such as gas  chromatography with
a dissimilar column or a different ionization mode  using a mass spectrometer may
be used, if replicate  samples showing the same compound are available.  Whenever
possible,  the  laboratory  should  analyze  standard  reference  materials  and
participate in relevant performance  evaluation  studies.


9.0  METHOD PERFORMANCE

      9.1   The method detection limit (MDL)  is defined in Chapter One.  The MDL
concentrations listed in Table  2 were obtained  using cleaned blanked VOST tubes
and reagent water.   Similar results  have been achieved with  field samples.  The
MDL actually  achieved  in  a given  analysis will  vary depending upon instrument
sensitivity and the effects of the matrix.  Preliminary spiking studies indicate
that under these conditions, the method detection limit for  spiked compounds in
extremely complex matrices may be larger by a factor of 500-1000.


10.0  REFERENCES

1.    Protocol  for  Collection  and  Analysis  of  Volatile  POHCs Using  VOST.
      EPA/600/8-84-007, March, 1984.

2.    Validation  of  the  Volatile  Organic  Sampling Train  (VOST)  Protocol.
      Volumes I and II.   EPA/600/4-86-014A,  January, 1986.

3.    U. S.  EPA  40  CFR  Part 136,  "Guidelines Establishing Test Procedures for
      Analysis of Pollutants Under the Clean Water Act, Method  624," October 26,
      1984.

4.    Bellar, T. A., and J. J. Lichtenberg, J. Amer. Water Works  Assoc., 66(12),
      739-744,  1974.
                                   5041  -  24                        Revision 0
                                                                 November 1992
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5.    Bellar, T. A., and J. J. Lichtenberg, "Semi-Automated Headspace Analysis
      of Drinking Waters and  Industrial Waters  for  Purgeable Volatile Organic
      Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
      and Wastewater, ASTM STP 686, pp 108-129, 1979.
                                   5041  - 25                         Revision 0
                                                                 November 1992
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                                      TABLE 1.
          RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
                        WHICH CAN BE ANALYZED BY METHOD  5041
Retention
Compound Time (min)
Acetone
Acrylonitrile
Benzene
Bromochl oromethane
Bromodi chl oromethane
4-Bromofl uorobenzene
Bromoform
Bromomethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chl orodi bromomethane
Chloroethane
Chloroform
Chl oromethane
Di bromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1,2-Di chl oroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,4-Difl uorobenzene
Ethyl benzene
lodomethane
Methyl ene chloride
Styrene
1 , 1 , 2, 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1 , 1 , 1-Tri chl oroethane
1,1,2-Tri chl oroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl chloride
Xylenes*
7.1
8.6
13.3
12.0
16.0
23.4
22.5
4.1
7.1
12.6
20.5
19.3
4.2
12.2
3.0
15.4
10.0
13.3
6.4
8.6
15.2
17.0
18.2
14.2
21.1
7.0
8.1
22.3
24.0
18.6
17.4
12.4
18.4
14.5
5.1
24.0
3.2
22.2
Primary Ion
Mass
43
53
78
128
83
95
173
94
76
117
112
129
64
83
50
93
63
62
96
96
63
75
75
114
106
142
84
104
83
164
92
97
97
130
101
75
62
106
Secondary Ion(s)
Mass(es)
58
52, 51
52, 77
49, 130, 51
85, 129
174, 176
171, 175, 252
96, 79
78
119, 121
114, 77
208, 206
66, 49
85, 47
52, 49
174, 95
65, 83
64, 98
61, 98
61, 98
62, 41
77, 39
77, 39
63, 88
91
127, 141
49, 51, 86
78, 103
85, 131, 133
129, 131, 166
91, 65
99, 117
83, 85, 99
95, 97, 132
103, 66
110, 77, 61
64, 61
91
*  The retention  time  given is for m-  and  p-xylene,  which coelute  on  the Megabor
   column.  o-Xylene elutes approximately 50 seconds later.
                                      5041  -  26
   Revision 0
November 1992
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                                      TABLE 2.
               PRELIMINARY METHOD DETECTION LIMITS AND BOILING POINTS
                   FOR VOLATILE ORGANICS ANALYZED BY METHOD 5041*
Compound
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methyl ene chloride
Acetone
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
trans- 1,2-Dichloroethene
Chloroform
1,2-Dichloroethane
1 , 1 , 1-Tri chloroethane
Carbon tetrachloride
Bromodi chloromethane
1,1,2 , 2-Tetrachl oroethane**
1 , 2 -Di chl oropropane
trans-1 ,3-Dichloropropene
Trichloroethene
Di bromochl oromethane
1 , 1 , 2-Tri chl oroethane
Benzene
ci s - 1 , 3-Duihl oropropene
Bromoform
Tetrachloroethene
Toluene
Chlorobenzene^
Ethyl benzene
Styrene *
Tri chl orof 1 uoromethane
lodomethane
Acrylonitrile
Dibromomethane
1 , 2 , 3 -Tri chl oropropane**
total Xylenes *
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-35-3
156-60-5
67-66-3
107-06-2
71-55-6
56-23-5
75-27-4
79-34-5
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
75-25-2
127-18-4
108-88-3
108-90-7
100-41-4
100-42-5
75-69-4
74-88-4
107-13-1
74-95-3
96-18-4

Detection
Limit, ng
58
26
14
21
9
35
11
14
12
11
11
13
8
8
11
23
12
17
11
21
26
26
27
26
11
15
15
21
46
17
9
13
14
37
22
Boiling
Point, °C
-24
4
-13
13
40
56
46
32
57
48
62
83
74
77
88
146
95
112
87
122
114
80
112
150
121
111
132
136
145
24
43
78
97
157
138-144
*  The method  detection  limit  (MDL)  is  defined as  the  minimum concentration  of a
   substance that can be measured  and  reported  with  99%  confidence that the analyte
   concentration is greater than zero and is determined from analysis of a sample in
   a given  matrix  containing the  analyte.   The detection  limits cited  above  were
   determined according to Title 40 CFR,  Part 136, Appendix B, using standards spiked
   onto clean VOST tubes.  Since clean VOST tubes were used,  the values cited above
   represent the best that the methodology can achieve.  The presence of an emissions
   matrix will  affect the ability of the  methodology to perform at its optimum level.
** Not appropriate for quantitative sampling by Method 0030.
                                      5041  -  27
   Revision 0
November 1992
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                                   TABLE 3.
              KEY  ION  ABUNDANCE  CRITERIA  FOR 4-BROMOFLUOROBENZENE
Mass                           Ion Abundance  Criteria
 50                            15 to  40% of mass  95
 75                            30 to  60% of mass  95
 95                            base peak,  100% relative  abundance
 96                            5 to 9% of mass 95
173                            less than 2% of mass  174
174                            greater than 50% of mass  95
175                            5 to 9% of mass 174
176                            greater than 95%,  but less than  101% of mass  174
177                            5 to 9% of mass 176
                                   5041 - 28                        Revision 0
                                                                 November  1992
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                                   TABLE 4.
           VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
3romoch1oromethane

Acetone
Acrylonitrile
Bromomethane
Carbon disulfide
Chloroethane
Chloroform
Chioromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
Trichloroethene
trans-1,2-Dichloroethene
lodomethane
Methylene chloride
Tri chl orofl uoromethane
Vinyl chloride
1,4-Difluorobenzene

Benzene
Bromodi chloromethane
Bromoform
Carbon tetrachloride
Chlorodi bromomethane
Dibromomethane
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,1,1-Trichloroethane
1,1,2-Tri chloroethane
                               Ch1orobenzene-d5
                               4-Bromofluorobenzene (surrogate)
                               Chlorobenzene
                               Ethyl benzene
                               Styrene
                               1,1,2,2-Tetrachloroethane
                               Tetrachloroethene
                               Toluene
                               Toluene-d8  (surrogate)
                               1,2,3-Trichloropropane
                               Xylenes
                                   5041  - 29
                    Revision 0
                 November 1992
-------
                                   i  i
                                  0  ©
Figure 1.   Cartridge Desorption Flow
             5041  - 30
   Revision 0
November 1992
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                                                    'oO
Figure 2.  Cartridge Desorption Unit with Purge and Trap Unit
                          5041 - 31
   Revision 0
November 1992
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Figure 3.  Schematic Diagram of Overall  Analytical  System
                        5041  -  32
   Revision 0
November 1992
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       Water Fill  Line
Sintered Glass Frit
     Gas Flow
                          Figure 4.  Sample  Purge Vessel
                                     5041 - 33
   Revision  0
November  1992
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Figure 5.  Schematic of Volatile Organic Sampling Train (VOST)
                           5041  -  34
   Revision 0
November 1992
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                                    METHOD  5041
PROTOCOL  FOR  ANALYSIS  OF  SORBENT  CARTRIDGES FROM  VOLATILE ORGANIC
         SAMPLING  TRAIN:  WIDE-BORE  CAPILLARY  COLUMN TECHNIQUE
             C
           7  1  Conditions for
                Ca r t ridge
            Desorption Oven,
             Purge & Trap
            Concentrator, CC,
                 and MS
             7  2  Dai 1y, tune
             the  GC/MS with
             BFB and check
             calib curve
             See  sect 7 17
                73-76
              Assemble the
                sys tern
           7  7  1 Calibrate the
          instrument ays tern us *
          ing the internal s td
           procedure  Stds and
          calibration cmpds are
           spiked into cleaned
          VOST  tubes using the
            flash evaporation
               technique
              7 8 Prep the
              purge A trap
              unit with 5ml
              o rganic-free
             reagent water
               7 9 Connect
               paired VOST
              tubes to the
              gas  1ines fo r
               des o rption
    7 10 Initiate
        tube
     desorption/
      purge and
      heating
   7 11 Set  the CC
   oven to subam-
   bient tempera -
      ture with
   1 iquid nit rogan
    7 12  Prep the
    CC/MS system
      for data
     aquisition
   7 13  After the
  tube/water purge
  time,  attach the
 analytical trap to
    the  CC/MS for
     desorption
   7 14  Hash purg-
   ing vessel with
   two 5ml  flushes
   of organic-free
   reagent  water
7 15 Recondition the
 analytical trap by
  baking  11 out a t
temps up  to 220 C for
11 mm Trap replace-
ment may  be necessary
  if the  analytical
  trap is  saturated
   beyond  cleanup
     7  16  1 Prep
    cal ib  s tds as
    in  7 7 1  Add
   water to vessel
     and desorb
    7 16 2
 Tabulate the
 area response
 of all  cmpds
 of interest
    7 16 3
 CaIculate the
average RF for
 each compound
 of inter es t
 7 16 4 Calcu-
 late the XRSD
 for the CCCs
 The %RSD must
   be <30*
  7 18 CC/MS
  analysis  of
   samples
7 19 1 Qualita-
 tive analysis
  of data  and
 ident  guide-
1 ines of cmpds
7 19 2 Quanti-
tative ana lysis
of data for  the
 compounds of
   interes t
C
Stop
                                    5041  - 35
                                              Revision 0
                                          November  1992
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                                  METHOD  5100

     DETERMINATION OF THE VOLATILE ORGANIC CONCENTRATION OF WASTE SAMPLES


1.0   SCOPE AND APPLICATION

      1.1   This  method  is  applicable  to the  determination  of  the  volatile
organic concentration of hazardous wastes.

      1.2   Performance  of this  method   should  not be  attempted by  persons
unfamiliar with the  operation  of a flame ionization detector  (FID) or  a Hall
electrolytic conductivity detector (HECD), because knowledge beyond the scope of
this presentation is required.


2.0   SUMMARY OF METHOD

      2.1   A sample of waste is collected from a source as close to the point
of generation as practical.  The sample is then heated and purged with nitrogen
to separate the volatile  organic compounds.  Part of the sample is analyzed for
carbon concentration, as methane, with an  FID, and part of the sample is analyzed
for chlorine concentration,  as  chloride,  with  an HECD.  The  volatile  organic
concentration is the sum of the measured carbon and chlorine concentrations of
the sample.


3.0   INTERFERENCES

      3.1   Refer to Methods 5030 and 8000.

      3.2   Samples  can  be  contaminated by  diffusion  of volatile  organics
(particularly chlorofluorocarbons  and  methylene chloride)   through the  sample
container  septum  during  shipment  and  storage.   A  field blank  prepared  from
organic-free reagent water and  carried through  sampling and subsequent  storage
and handling can serve as a check on such contamination.


4.0   APPARATUS AND MATERIALS

      4.1   Sampling. The following equipment  is required:

            4.1.1 Static  Mixer.  Installed  in-line or as a by-pass  loop, sized so
      that the drop  size  of  the dispersed phase is no greater than 1,000  urn.
      If the installation  of the mixer is in  a by-pass  loop,  then  the  entire
      waste stream must be diverted through  the mixer.

            4.1.2 Tap. Installed no further  than two pipe diameters  downstream
      of the static mixer outlet.

            4.1.3 Sampling Tube. Flexible Teflon,  0.25 in.  ID.

            4.1.4 Sample  Container. Borosilicate glass or Teflon, 15  to  50 mL,
      and a Teflon lined  screw  cap capable of  forming an air tight seal.

                                   5100 - 1                          Revision 0
                                                                 November 1992
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      4.1.5 Cooling Coil.  Fabricated from 0.25  in. ID 304 stainless steel
tubing with a thermocouple at the coil outlet.

4.2   Analysis. The following equipment is required:

      4.2.1 Purging Apparatus. For separating the volatile organics from
the waste sample.  A schematic of the  system is  shown  in  Figure 1.  The
purging apparatus consists of the following major components:

            4.2.1.1     Purging Chamber.  A glass container  to  hold the
      sample while  it  is  heated  and purged with  dry nitrogen.   Exact
      dimensions are shown in Figure 3.

            The  cap of  the  purging  chamber   is   equipped  with  three
      fittings:  one for  a mechanical stirrer (fitted with  the #11 Ace
      thread),  one  for  a thermometer  (top fitting),  and  one for the Teflon
      exit tubing (side fitting)  as shown in Figure 3.

            The base of the  purging chamber is  a 50 mm  inside diameter
      (ID) cylindrical  glass tube.  One end of the tube is fitted with a
      50 mm Ace-thread fitting, while the other end is sealed.  Near the
      sealed end in the side  wall  is a  fitting  for a glass purging lance.

            4.2.1.2     Purging Lance. Glass tube,  6 mm ID  by 15.25 cm
      long, bent into  an "L"  shape.   The "L" end of the  tube is sealed,
      and then pierced with fifteen holes, each 1 mm in diameter.

            4.2.1.3     Mechanical  Stirrer.   Stainless steel  or Teflon
      stirring rod driven by an electric motor.

            4.2.1.4     Coalescing   Filter.      Porous   fritted   disc
      incorporated  into  a  container with  the  same  dimensions  as the
      purging chamber.   The details of the design are shown  in Figure 3.

            4.2.1.5     Constant Temperature Bath.  Capable of maintaining
      a temperature around  the purging chamber and coalescing  filter of 75
      ± 5°C.

            4.2.1.6     Three-way   Valves.     Two,   manually  operated,
      stainless steel.

            4.2.1.7     Flow Controller.   Capable of maintaining a purge
      gas flow rate of 6 ± 0.006 L/min.

            4.2.1.8     Rotameters.   Two  for  monitoring  the  air flow
      through the purging system (0-20 L/min).

            4.2.1.9     Sample Splitters.  Two heated  flow  restrictors.
      At a purge rate of up to 6 L/min, one will supply  a constant flow of
      70  to  100 mL/min  to the  analyzers.   The second  will  split the
      analytical flow between the FID and the HECD.  The approximate flow
      to the FID will be 40 mL/min and to the HECD will be 15 mL/min, but
      the exact flow must be adjusted to be compatible with the individual
      detector and to meet its linearity requirement.

                             5100 -  2                         Revision 0
                                                           November 1992
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                  4.2.1.10    Adsorbent  Tube.    To  hold  10 g  of  activated
            charcoal.  Excess purge gas is vented through the adsorbent tube to
            prevent  any  potentially  hazardous  materials   from  entering  the
            laboratory.

            4.2.2 Volatile Organic Measurement  System.  Consisting of an FID to
      measure the carbon concentration  of the sample, and  an  HECD to measure the
      chlorine concentration (as chloride).

                  4.2.2.1     FID.  An  FID meeting the following specifications
            is required:

                        4.2.2.1.1   Linearity.   A linear  response (+ 5 percent)
                  over  the  operating  range  as  demonstrated  by  the  procedures
                  established in Section 8.1.1.

                        4.2.2.1.2   Range.    A  full  scale range  of  50  pg
                  carbon/sec to 50 nq carbon/sec.  Signal attenuators shall be
                  available to produce a minimum signal  response of 10 percent
                  of full scale.

                        4.2.2.1.3   Data Recording  System.   Analog strip chart
                  recorder or digital integration system compatible with the FID
                  for permanently recording the output of the detector.

                  4.2.2.2     HECD.      An   HECD    meeting   the   following
            specifications is required:

                        4.2.2.2.1   Linearity.  A linear response  (+ 10 percent)
                  over the response range as demonstrated by the procedures in
                  Section 8.1.2.

                        4.2.2.2.2   Range.   A full scale  range of 5.0 pg/sec to
                  500 ng/sec chloride.  Signal attenuators shall be available to
                  produce a minimum signal response of 10  percent of full  scale.

                        4.2.2.2.3   Data Recording  System.   Analog strip chart
                  recorder or digital  integration  system compatible  with  the
                  output voltage range of HECD.


5.0  REAGENTS

      5.1   Reagent grade chemicals  shall be used in all tests.  Unless otherwise
indicated, it is intended that all  reagents  shall conform to the specifications
of the Committee on Analytical Reagents  of the American Chemical  Society, where
such specifications  are  available.   Other  grades may be used, provided  it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without adversely impacting the accuracy of the  determination.

      5.2   Organic-free reagent water. All  references to water in this  method
refer to organic-free reagent water as defined  in Chapter One.
                                   5100 - 3                         Revision 0
                                                                 November 1992
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5.3   Sampling.

      5.3.1 Polyethylene glycol  (PEG),  98 percent pure  with  an average
molecular  weight  of  400.    Remove any  organic  compounds  that may be
detected as volatile organics already present in the polyethylene glycol
before it is used, by heating it to 250°C  and purging it with nitrogen at
a flow rate of  1  to  2  L/min  for 2  hours.   Waste PEG must be disposed of
properly (consult local, State and Federal guidelines and regulations).

5.4   Analysis.

      5.4.1 Sample Separation.  The following are  required for the sample
purging step:

            5.4.1.1     Polyethylene glycol.  Same as Section 5.3.1.

            5.4.1.2     Silicone, Mineral, or Peanut Oil.  For use as the
      heat dispersing medium  in the constant temperature bath.

            5.4.1.3     Purging Gas. Zero grade nitrogen (N2), containing
      less than 1 ppm carbon.

      5.4.2 Volatile Organics Measurement. The following are required for
measuring the volatile organic concentrations:

            5.4.2.1     Hydrogen (H2).  Zero grade  H2, 99.999  percent pure.

            5.4.2.2     Combustion  Gas.   Zero  grade air or  oxygen, as
      required  by the FID.

            5.4.2.3     FID Calibration Gases.

                  5.4.2.3.1   Low-level  Calibration Gas.   Gas mixture
            standard with a nominal concentration  of 35  ppm  (v/v) propane
            in  N2.

                  5.4.2.3.2   Mid-level  Calibration Gas.   Gas mixture
            standard with a nominal  concentration of 175 ppm  (v/v) propane
            in  N2.

                  5.4.2.3.3   High-level  Calibration Gas.   Gas mixture
            standard with a nominal  concentration of 350 ppm  (v/v) propane
            in  N2.

            5.4.2.4     HECD  Calibration  Gases.

                  5.4.2.4.1   Low-level  CaTibration Gas.    Gas mixture
            standard  with  a nominal concentration  of  20 ppm (v/v)  1,1-
            dichloroethene  in N2.

                  5.4.2.4.2   Mid-level  Calibration Gas.    Gas mixture
            standard  with  a nominal concentration of 100 ppm (v/v)  1,1-
            dichloroethene  in N2.


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                        5.4.2.4.3   High-level Calibration  Gas.    Gas  mixture
                  standard with a  nominal  concentration  of  200 ppm (v/v) 1,1-
                  dichloroethene in N2.

                  5.4.2.5     n-Propanol, CH3CH2CH2OH.  ACS grade or better.

                  5.4.2.6     Electrolyte Solution.  For use  in  the conductivity
            detector.  Mix together 500 ml of water and 500 ml of n-propanol and
            store in a glass container.
                  5.4.2.7
Charcoal.  Activated coconut,  12 to 30 mesh.
6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  Volume  One,  Section  B,  Chapter  Four,  "Organic  Analytes,"
Section 4.1.

      6.2   Sampling Plan Design and Development.  Use the procedures given in
Volume Two, Part III, Chapter Nine, "Sampling Plan."

      6.3   Waste in Enclosed Pipes.  Sample  as  close  as practical to the point
of waste generation  in  order to minimize the loss  of organics.   Assemble the
sampling apparatus as shown in Figure 4.   Install the static mixer  in the process
line or  in a by-pass line.   Locate the tap  within two pipe  diameters  of the
static mixer outlet.

      6.4   Prepare the sampling containers as follows:  Pour into the container
an amount of PEG equal  to the total  volume of the  sample container, less 10 mL.
PEG will  reduce,  but not eliminate,  the loss of volatile organic compounds during
sample collection.  Weigh the sample container with the screw cap, the PEG and
any labels to the nearest 0.01 g, and record the weight (m^).  Before sampling,
store the containers in  an ice bath  until  the temperature of the PEG is less than
4°C.

      6.5   Begin sampling by purging the sample lines and cooling coil with at
least four volumes of waste.  Collect the purged material in a separate container
and dispose of it properly.

      6.6   After purging, stop the sample flow  and  direct the sampling tube to
a preweighed sample container, prepared as described  in Section 6.4.  Keep the
tip of the tube below the surface of the PEG during sampling to minimize contact
with the atmosphere.   Sample at a  flow rate such that  the  temperature  of the
waste  is  less than  10°C.   Fill  the  sample  container and immediately  cap it
(within 5 seconds) so that a minimum headspace exists in the container.   Store
immediately in a cooler  and cover with ice.
                            •
      6.7   Alternative sampling techniques may be used upon the approval of the
Administrator.
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7.0   PROCEDURE

      7.1   Sample Recovery.  Remove the sample container from the cooler, and
wipe the exterior of  the container to remove any extraneous  ice, water, or other
debris.   Reweigh the sample container  and  sample  to the  nearest  0.01  g, and
record the weight  (msf).   Pour  the  contents of the  sample container into the
purging flask.  Rinse the sample  container three times with PEG, transferring the
rinsings to the purging flask after  each rinse.  The  total  volume of PEG in the
purging flask shall be approximately 50 ml.  Add approximately 50 ml of water.

      7.2   Apparatus Assembly.   Assemble  the  purging  apparatus  as  shown  in
Figure 2,  leaving  the purging  chamber  out of the  constant  temperature bath.
Adjust the stirring  rod  so that it nearly  reaches  the  bottom  of the chamber.
Position  the sparger so that it  is within 1  cm of the bottom,  but  does not
interfere with  the stirring rod.  Lower  the thermometer  so  that it extends into
the liquid.

      7.3   Sample Analysis. Turn on the constant temperature bath and allow the
temperature to  equilibrate at 75 ± 5°C.  Turn the bypass  valve so that the purge
gas bypasses the  purging chamber.  Turn on  the purge gas.   Allow both the  FID and
the HECD to warm up until  a stable baseline is  achieved  on  each detector.  Pack
the adsorbent tube with 10 g of charcoal.   Replace  the charcoal after each run
and dispose of  the spent charcoal  properly.  Place the assembled chamber in the
constant  temperature bath.   When  the  temperature of the PEG reaches 75 ± 5°C,
turn the  bypass valve so that the purge gas flows  through the purging chamber.
Begin recording  the  response of the  FID  and  the  HECD.   Compare  the readings
between the two rotameters in the system.    If the readings differ by more than
five percent, stop  the purging and  determine the source of the discrepancy before
resuming.

      As  purging continues, monitor the output of the FID to make certain that
the separation  is proceeding correctly,  and that the  results are being properly
recorded.  Every 10 minutes, read  and  record the purge flow rate and the liquid
temperature.  Continue purging  for 30 minutes.

      7.4   Initial  Performance Check of  Purging  System.   Before placing the
system in operation,  after a shutdown  of greater than six months, and after any
major modification, conduct the  linearity checks described in Sections 7.4.1 and
7.4.2.   Install  all  calibration gases at  the  three-way  calibration gas valve.
See Figure 1.

            7.4.1  FID Linearity Check and  Calibration.   With the purging system
      operating as in Section 7.3, allow the FID to  establish  a stable baseline.
      Set the  secondary  pressure  regulator of the  calibration gas cylinder to
      the same pressure  as the  purge  gas  cylinder,  and  inject the calibration
      gas by turning  the calibration gas valve to switch  flow from the purge gas
      to  the  calibration  gas.    Continue  the  calibration  gas  flow  for
      approximately  two minutes  before  switching   to  the purge  gas.    Make
      triplicate injections of each  calibration gas  (Section  5.4.2.3), and then
      calculate the average response factor for each concentration (Rt),  as well
      as  the overall  mean of the response  factor  values,  R .   The instrument
      linearity  is acceptable if  each Rt  is within  5 percent of R  and if the
      relative standard deviation  (Section  7.7.10)  for  each set of triplicate


                                    5100 - 6                         Revision 0
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      injections is less than 5 percent.  Record the overall mean value of the
      propane response factor values as the FID calibration response  factor, R0.

            7.4.2 HECD Linearity Check and Calibration.  With the purging system
      operating  as in  Section  7.3,  allow  the HECD  to  establish  a  stable
      baseline.  Set  the  secondary pressure regulator  of the  calibration gas
      cylinder to the same pressure as  the  purge gas  cylinder,  and  inject the
      calibration gas by turning the calibration gas valve to switch flow from
      the purge gas to the calibration gas.   Continue the calibration gas flow
      for about two minutes before switching to  the purge  gas.  Make triplicate
      injections of each calibration gas (Section 5.4.2.4), and then calculate
      the average  response factor for each  concentration, Rth,  as well  as the
      overall mean of the  response factors, Roh.  The  instrument linearity is
      acceptable if each Rth  (Section  7.7.5)  is  within  10  percent of Roh and if
      the  relative  standard  deviation  (Section  7.7.10)   for  each  set  of
      triplicate injections  is  less than  10 percent.   Record the overall mean
      value of the chlorine response factors as the HECD response factor, Roh.

      7.5   Daily Calibrations.

            7.5.1 FID Daily Calibration.  Inject duplicate samples from the mid-
      level  FID  calibration  gas  (Section  5.4.2.3.2)  as  described  in Section
      7.4.1, and  calculate the  average  daily  response factor  (DRt).   System
      operation is adequate if the DRt is within 5 percent of the R0 calculated
      during the  initial  performance  test  (Section  7.4.1).  Use the DRt for
      calculation of carbon content in the samples.

            7.5.2 HECD Daily  Calibration.   Inject  duplicate samples  from the
      mid-level HECD calibration gas (Section 5.4.2.4.2) as described in Section
      7.4.2, and calculate the  average daily response  factor DRth.   The system
      operation  is adequate  if  the  DRth  is  within  10  percent   of  the Roh
      calculated during the initial performance test (Section 7.4.2).  Use the
      DRth  for  calculation  of chlorine  in the samples.

      7.6   Water Blank.  Transfer about 60 ml of organic-free reagent water into
the purging chamber.   Add  50  ml of PEG to the purging chamber.  Treat the blank
as described in Sections 7.2 and 7.3.

      7.7   Calculations

            7.7.1 Nomenclature.

            Ab    =     Area under the water blank response curve,  counts.

            As    =     Area under the sample response curve, counts.

            C     =     Concentration   of  volatile  organic  in  the  sample,
                        ppm(w/w).

            Cc    =     Concentration  of FID calibration gas, ppm(v/v).

            Ch    =     Concentration  of HECD calibration gas,  ppm(v/v).

            DRt   =     Average daily  response factor of the FID,  jug C/counts.

                                   5100 - 7                         Revision  0
                                                                 November 1992
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      DRth   =     Average daily response factor of the HECD  detector,  M9
                  Cl"/counts.
      m...    =     Mass  of carbon,  as methane,  in  the  FID  calibration
       CO
                  standard, ng.
      mch    =     Mass of chloride in the HECD calibration  standard,  fj.g.
      ms    =     Mass of the waste sample, g.
      msc    =     ^ass °f carDon» as methane,  in  the  sample,  ;ug.
      msf    =     Mass of sample container and waste  sample,  g.
      msh    =     Mass of chloride in the sample,  jug.
      mst    =     Mass of sample container prior  to sampling, g.
      mvo    =     Mass of volatile organic in  the sample,  p.g.
      Pa    =     Ambient barometric pressure  in  the  laboratory, Torr.
      Qc    =     Flowrate of calibration gas, L/min.
      tc    =     Length  of  time  standard  gas  is   delivered  to  the
                  analyzer, min.
      T.    =     Ambient temperature in the laboratory,  °K.
       a
      7.7.2 Mass of Carbon,  as Methane  in  the  FID  Calibration Gas.
      "co -  k2 Cc te Qc (Pa/Ta)              Eq.  1
where k2 = 0.5773 ng  C-°K/Ml-Torr
      7.7.3 Mass of Chloride in  the  HECD Detector  Calibration Gas.
      •"eh -  k3 Ch te Qc (Pa/TJ              Eq.  2
where k3 = 1.1371 M9  Cl-°K/Ml-Torr
      7.7.4 FID Response Factor.
      Rt = mco/A                            Eq.  3
      7.7.5 HECD Response  Factor.
      Rth -  mch/A                           Eq.  4
      7.7.6 Mass of Carbon in the  Sample.
      msc =  DRt  (As -  Ab)                    Ecl-  5
                              5100  -  8                          Revision 0
                                                            November 1992
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            7.7.7 Mass of Chloride in the Sample.

            msh  -  DRth (As -  Ab)                  Eq. 6

            7.7.8 Mass of Volatile Organic in the Sample.

            m = msc  + msh                        Eq. 7

            7.7.9 Standard Deviation.


            SD =  lOOx [ S(xrx)2/(n-l)]1/*       Eq. 8
                       i=l

            7.7.10      Relative Standard Deviation.

            RSD = SD/x                          Eq. 9

            7.7.11      Mass of Sample.

            ms = msf  - mst                       Eq. 10

            7.7.12      Concentration of Volatile Organic in Waste.

            C = mvo/ms                           Eq. 11


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific Quality Control procedures.

      8.2   Maintain  a  record  of  performance  of  all  system  checks  and
calibrations.

      8.3   Calibrate analytical balance against standard weights.


9.0   METHOD PERFORMANCE

      9.1   Performance data are not currently available.


10.0  REFERENCES

1.    "Determination of  the Volatile Organic  Content  of Waste Samples" Method
      25D; Proposed Amendment to 40 CFR Part 60, Appendix A, January 1989.
                                   5100 - 9                         Revision 0
                                                                 November 1992
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                           FIGURE 1
                       Purging Apparatus
  CALIBRATION GAS
  VALVE
             FLOW
            METER

VALVE;      |\
     t
                    FLOW
         COALESCING METER
PURGING    .FILTER
CHAMBER   4
   *A      A
                                                   Vent
                                                                  FID
                                                           *N;N- SPLITTER
                      \   CONSTANT TEMPERATURE

               VALVE     DATH
                i

NITROGEN       1   /
          FLOW
          REGULATOR
                         "' IIYI'ASS VALVE
                         CALIBRATION
                         GAS
                          5100  - 10
                                                              Revision 0
                                                           November 1992
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                               FIGURE 2
     ROTAMETER
DATMIIOATOR/
CONTOOLLER
                            ST1RRINO
                             MOTOR
                                                              DGTECTORS
                                                              OIL 0 ATI I
                     PURGING CHAMBER
COALESCING FILTER
                               5100 - 11
               Revision 0
            November 1992
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                       FIGURE 3
                    Purging Chamber
                            	 "S^TACETHRED
   TRUBORE
   STIRRER
GLASS
                #7ACETHRED
                       5100 - 12
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November 1992
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                                   FIGURE 4
                 WASTE UNB
FROM SOURCE
                STATIC MIXER
                                         VALVES
                 OPTIONAL PUMP
REDUCER (1/4 " TUBE FITTING)
                                                TEFLON OR STAINLESS STEEL COIL


                                                ICE DAT) I
             SAMPLE CONTAINER
                                   5100 - 13
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                                         METHOD 5100
       DETERMINATION OF  THE  VOLATILE ORGANIC  CONCENTRATION  OF WASTE  SAMPLES
        Start
        7.1
 Pour sample contents
    in purge flask
        7.1
Rinse sample container
  3 times with OOP
        7.1
  Assemble purging
 apparatus as shown
     in Figure 1
       7.2
    Equilibrate
    the system
        7.2
   Direct purge gas
through purge chamber
                                                       7.2
                                                 Record response of
                                                   FID and HECO
       7.2
    Oorotameter
   readings differ
     by>5%?
     7.2
Stop operations
 and readjust
                                           5100 -  14
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                                  METHOD 5110

        DETERMINATION OF ORGANIC PHASE VAPOR PRESSURE IN WASTE SAMPLES


1.0   SCOPE AND APPLICATION

      1.1   This method  is  applicable  for  determining  the organic phase vapor
pressure  of waste  samples  from treatment,  storage,  and  disposal  facilities
(TSDF).

      1.2   Performance  of  this  method should  not be  attempted  by  persons
unfamiliar with the operation of a Flame lonization  Detector  (FID) nor by those
who are unfamiliar with  source sampling, because knowledge beyond the scope of
this presentation is required.


2.0   SUMMARY OF METHOD

      2.1   A waste sample  is collected from a source as close to the point of
generation  as  practical.  The headspace vapor  of the sample  is  analyzed for
carbon content by a headspace analyzer, which uses an FID.


3.0   INTERFERENCES

      3.1   Samples  can  be  contaminated  by  diffusion  of  volatile  organics
(particularly  chlorofluorocarbons  and  methylene chloride) through  the  sample
container septum during shipment and storage.  A field sample blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.

      3.2   Contamination by  carryover  can occur  whenever a  low-concentration
sample is analyzed after  a high-concentration  sample.  To reduce carryover, the
sample syringe  must be  rinsed  out  between samples with  organic-free  reagent
water.  Whenever an unusually concentrated sample is encountered,  it should be
followed by an analysis  of organic-free reagent water.   It may be necessary to
wash out the syringe with detergent, rinse with distilled  water,  and dry in a
150°C  oven between analyses.

      3.3   Before processing daily samples, the analyst should demonstrate that
the entire  analytical  system  is  free from interference by the  analysis  of an
organic-free reagent water or solvent blank.


4.0   APPARATUS AND MATERIALS

      4.1   Sampling.  The following equipment is required:

            4.1.1 Sample  Containers.   Vials,  glass, with  butyl  rubber  septa,
      Perkin-Elmer Corporation Part Numbers 0105-0129 (glass  vials), B001-0728
      (gray butyl rubber  septa,  plug  style), 0105-0131  (butyl  rubber septa), or
      equivalent.   The seal  must be made from butyl rubber.   Silicone  rubber
      seals are not acceptable.

                                   5110 - 1                         Revision 0
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            4.1.2 Vial Sealer.  Perkin-Elmer Number 105-0106,  or equivalent.

            4.1.3 Gas-Tight   Syringe.     Perkin-Elmer  Number   00230117,   or
      equivalent.

      4.2   The following  equipment  is  required if sampling  from  an enclosed
pipe:

            4.2.1 Static Mixer.  Installed in-line or as a by-pass loop, sized
      so that the drop size of the dispersed phase is not greater that 1,000 ^m.
      If the  installation  of  the  mixer  is in a  by-pass loop,  then the entire
      waste stream must be diverted through the mixer.

            4.2.2 Tap.

            4.2.3 Tubing, Teflon,  0.25 in. ID.

            4.2.4 Cooling  Coil.  Stainless  steel  (304), 0.25  in.  ID, equipped
      with a thermocouple at the coil outlet.

      4.3   Analysis.  The following equipment is required:

            4.3.1 Balanced Pressure Headspace Sampler.  Perkin-Elmer HS-6, HS-
      100,  or equivalent,  equipped  with  a glass  bead  column  instead  of a
      chromatographic column.

            4.3.2 Flame  lonization  Detector.   An  FID  meeting  the  following
      specifications  is required:

                  4.3.2.1     Linearity.  A  linear  response  (+5 percent) over
            the operating range, as demonstrated by the procedures established
            in Sections 7.2.2 and 8.1.1.

                  4.3.2.2     Range.  A  full  scale range of 1  to 10,000  ppm CH4.
            Signal attenuators should be available to produce a minimum signal
            response  of 10 percent of full scale.

            4.3.3 Data Recording System.  Analog strip chart recorder  or digital
      integration system compatible with the FID for permanently recording the
      output of the detector.

            4.3.4 Thermometer.  Capable  of reading temperatures  in  the range of
      30° to 60°C with an accuracy  of ±0.1°C.


5.0   REAGENTS

      5.1   Analysis.  The following reagents are required for analysis:

            5.1.1 Hydrogen (H2).  Zero grade.

            5.1.2 Carrier  Gas.  Zero grade nitrogen,  containing  less  than  1  ppm
      carbon and  less than 1  ppm carbon dioxide.


                                   5110 - 2                          Revision 0
                                                                 November  1992
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      FID.
            5.1.3 Combustion Gas.  Zero grade air or oxygen, as required by the
      5.2   Calibration and Linearity Check.

            5.2.1 Stock  Cylinder Gas  Standard.    100 percent  propane.   The
      manufacturer shall  (a) certify  the  gas  composition  to be accurate to +3
      percent or better  (see Section  5.2.1.1);   (b)  recommend a maximum shelf
      life over which the gas concentration does not change by greater than ±5
      percent from the certified value; and (c) affix the date of gas cylinder
      preparation, certified  propane  concentration,  and  recommended  maximum
      shelf life to the cylinder before shipment to the buyer.

                  5.2.1.1     Cylinder    Standards    Certification.       The
            manufacturer shall  certify the concentration of  the calibration gas
            in  the  cylinder by  (a)  directly  analyzing  the cylinder  and  (b)
            calibrating  his  analytical   procedure   on  the day  of  cylinder
            analysis.  To calibrate his analytical  procedure, the manufacturer
            shall use, as a minimum, a three-point calibration curve.

                  5.2.1.2     Verification   of   Manufacturer's   Calibration
            Standards.    Before  using,   the   manufacturer  shall  verify  the
            concentration of each calibration  standard by (a)  comparing it to
            gas mixtures prepared in accordance with  the procedure described in
            Section 7.1 of Method 106 of 40 CFR Part 61,  Appendix B, or by (b)
            calibrating it against Standard Reference Materials  (SRMs), prepared
            by the National Institute  of  Science and Technology,  if such SRMs
            are  available.   The agreement between  the   initially  determined
            concentration value and the verification concentration value must be
            within ±5 percent.   The manufacturer must reverify all calibration
            standards on a time interval that  is consistent  with the shelf life
            of the cylinder standards sold.

      5.3   Blanks

            5.3.1 Organic-free reagent water.   All  references to water in this
      method refer to organic-free reagent water as defined in Chapter One.
6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this Chapter,  Organic Analytes,
Section 4.1.

      6.2   Sampling Plan Design and Development.   Use the procedures given in
Chapter Nine, "Sampling Plan."

      6.3   Collect samples according to the  procedures  in Chapter 9, or, if it
is necessary to  sample from an enclosed pipe,  sample according to the procedures
described below.

            6.3.1 The apparatus  designed to sample  from  an enclosed  pipe is
      shown in Figure 1.  The apparatus consists of an in-line static mixer,  a
      tap,  a  cooling coil  immersed in  an  ice bath,  a flexible Teflon  tube
                                 .  5110 - 3
   Revision 0
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      connected to the outlet of the cooling coil, and sample container.  Locate
      the tap within two pipe diameters of the static mixer outlet.  Install the
      static mixer in  the process line or in a by-pass  line.

            6.3.2 Begin  sample  collection  by purging  the  sample  lines  and
      cooling coil with  at  least four volumes of  waste.   Collect  the  purged
      material in a separate container.

            6.3.3 After purging, stop the  sample flow  and  transfer  the  Teflon
      sampling tube to  a  sample  container.   Sample at a flow rate such that the
      temperature of the  waste  is <10°C.  Fill the sample container halfway (±5
      percent) and cap  immediately (within 5 seconds).

            6.3.4 Store the  collected  samples  on ice or in a refrigerator until
      analysis.

            6.3.5 Alternative sampling techniques may be used upon the approval
      of the Administrator.
7.0  PROCEDURE

      7.1   Calibration

            7.1.1 Maintain a record of each item.

            7.1.2 Use the procedures in Section 7.1.3 to calibrate the headspace
      analyzer and FID,  and to check  for  linearity  before  the  system is first
      placed in operation, after  any shutdown that is longer than 6 months, and
      after any modification of the system.

            7.1.3 Calibration and  Linearity.    Use  the  procedures  in  Section
      6.2.1 of Method 18  of 40 CFR Part 60, Appendix  A, to prepare the standards
      and calibrate the flowmeters, using propane as  the  standard gas.  Fill the
      calibration standard vials  halfway  (±5 percent) with organic-free reagent
      water.  Prepare  a  minimum  of three  concentrations  that will  bracket the
      applicable cutoff.   For a  cutoff of 5.2  kPa  (0.75  psi),  prepare nominal
      concentrations of 30,000, 50,000, and 70,000 ppm as propane.  For a cutoff
      of 27.6 kPa (4.0  psi), prepare nominal concentrations  of 200,000, 300,000,
      and 400,000 ppm as  propane.

                  7.1.3.1     Use the  procedures in Section 7.2.3 to measure the
            FID response  of each  standard.  Use  a linear regression analysis to
            calculate the values  for the slope (k)  and the y-intercept (b).  Use
            the procedures in Section 7.2  and  7.3 to test  the  calibration and
            the linearity.

            7.1.4 Daily  FID  Calibration  Check.   Check the  calibration  at the
      beginning  and at  the end  of  the  daily runs by  using the  following
      procedures.   Prepare  two  calibration  standards  at  the nominal  cutoff
      concentrations using the procedures in  Section 7.1.3  Place  one  at the
      beginning and end of the daily run.  Measure  the FID response of the daily
      calibration standard.  Use the values for k and b obtained from the most
      recent calibration  and use  Equation  4 to calculate the concentration of

                                   5110 - 4                          Revision 0
                                                                 November 1992
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the daily standard.  Use  an  equation  similar  to Equation 2 to calculate
the percent difference between the daily standard and  Cs.   If the percent
difference is within five,  then the previous  values  for  k and  b can be
used.  Otherwise, use the procedures in Section 7.1.3 to recalibrate the
FID.

7.2   Analysis.

      7.2.1 Allow one hour for the headspace vials to equilibrate at the
temperature specified in  the  regulation.  Allow the  FID to warm until  a
stable baseline is achieved on the detector.

      7.2.2 Check the calibration of the FID daily, using the procedures
in Section 7.1.4.

      7.2.3 Follow  the  manufacturer's  recommended  procedures   for  the
normal operation of the headspace sampler and  FID.

      7.2.4 Use the procedures  in  Sections  7.3.4 and  7.3.5 to calculate
the organic vapor pressure in the samples.

      7.2.5 Monitor the output  of  the  detector  to make certain  that the
results are being properly recorded.

7.3   Calculations

      7.3.1 Nomenclature

      A     =     Measurement  of  the  area under the response  curve,
                  counts.

      b     =     y-intercept of the linear regression line.

      Ca    =     Measured vapor phase  organic  concentration  of sample,
                  ppm as propane.

      C^    =     Average measured  vapor  phase  organic concentration of
                  standard, ppm as propane.

      Cm    =     Measured vapor phase  organic concentration of standard,
                  ppm as propane.

      Cs    =     Calculated standard concentration,  ppm as propane.

      k     =     Slope of the linear regression line.

      ''bar   =     Atmosphere pressure at analysis conditions,  mm Hg (in.
                  Hg).

      p*    =     Organic vapor pressure in the sample, kPa (psi).

      B     =     1.333  x  10~6  kPa/[(mm Hg)(ppm)],  4.91  x  10"7  psi/
                  [(in.Hg)(ppm)])
                             5110 - 5                         Revision 0
                                                           November 1992
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            7.3.2 Linearity.  Use Equation  1 to calculate the measured standard
      concentration for each standard vial.

            cm =  k A + b                                          Eq. 1

                  7.3.2.1     Calculate   the   average    measured    standard
            concentration (C  )  for each set of triplicate  standards,  and use
            Equation 2 to calculate the percent difference between C^  and Cs

                                          cs '  C.
                  Percent Difference =    	   x 100           Eq. 2
                                             Cs

                  The  instrument  linearity  is  acceptable  if  the  percent
            difference is less than or equal to five for each standard.

            7.3.3 Relative  standard  Deviation  (RSD).    Use  Equation  3  to
      calculate the RSD for each triplicate set of standards.
                        100
           %RSD =       —
      - CJ
                                           2
     Em    IIKI '
    	                        Eq.  3
'=1  (n - 1)
            The calibration is acceptable  if the RSD is within five percent for
      each standard concentration.

            7.3.4 Concentration of Organics in the Headspace.  Use Equation 4 to
      calculate the concentration of vapor phase organics in each sample.

             Ca = k A + b                                         Eq. 4

            7.3.5 Vapor Pressure of Organics in the Headspace.  Use Equation 5
      to calculate the vapor pressure of organics in the sample.

             P* - B Ptar Ca                                        Eq. 5


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific Quality Control procedures.

      8.2   Maintain  a  record  of  performance  of  all  system  checks  and
calibrations.
9.0   METHOD PERFORMANCE

      9.1   No performance data are currently available.
                                   5110 - 6                         Revision 0
                                                                 November 1992
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10.0  REFERENCES

1.    "Determination of Vapor Phase Organic  Concentrations  in  Waste Samples,"
      Method 25E;  Proposed  Amendment  to 40  CFR  Part 60, Appendix  A,  January
      1989.

2.    "Headspace," Method 3810; U.S.  Environmental  Protection  Agency,  SW-846,
      3rd Ed.,  1986.
                                   5110 - 7                         Revision 0
                                                                 November 1992
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                                     FIGURE 1
                 WASTE UNE
FROM SOURCE
                                           (X)
                STATIC MIXER
t
                                         VALVES
                 OPTIONAL PUMP
  REDUCER (1/4 " TUOE FITTING)
                                                TEFLON OR STAINLESS STEEL COIL  f /^


                                                JCE OATH
               SAMPLE CONTAINER
                                     5110 - 8
                           Revision  0
                        November  1992
-------
                               METHOD 5110
   DETERMINATION OF ORGANIC PHASE  VAPOR PRESSURE  IN WASTE  SAMPLES
           t. a. x t
      system    t
    A o: va ± 1 i fc» T: a t
    £01:   3.   li o va. :
•7.2.3    X3 o   cl » i 1 y
FID   «=«fcli.toa:«.tion
    o fe • o X.    v&«»Xn0
^VOO««I\AV««    £ v o
« «» o t i o rx    7.X.4L.
             o c> o -r a t o
  '7.2.-0.    Monito:
                                                "7.3.2    C «L 1 c
                                                     « <3 u. «. t i o n. »
                                                *7  . 3 . 5
                                                          O&3.<^u.lo.te
                                                                o f
                                                                i rx
                                 5110  - 9
   Revision  0
November 1992
-------
                                 METHOD 3600B

                                    CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   Method 3600 provides general guidance on selection of cleanup methods
that are appropriate for the target analytes of interest.  Cleanup methods are
applied to the extracts prepared  by one of the extraction methods, to eliminate
sample interferences.  The following table lists the cleanup methods and provides
a brief description of the type of cleanup.

                            SW-846 CLEANUP METHODS
 Method #    Method Name                              Cleanup Type


 3610        Alumina   Cleanup                         Adsorption

 3611        Alumina Cleanup & Separation             Adsorption
             for  Petroleum Waste

 3620        Florisil  Cleanup                        Adsorption

 3630        Silica Gel  Cleanup                      Adsorption

 3640        Gel-Permeation Cleanup                   Size-Separation

 3650        Acid-Base Partition Cleanup              Acid-Base Partitioning

 3660        Sulfur Cleanup                           Oxidation/Reduction

 3665        Sulfuric  Acid/Permanganate               Oxidation/Reduction
             Cleanup


      1.2   The purpose of applying a cleanup method to an extract is to remove
interferences  and high boiling material  that  may result  in:    (1)  errors  in
quantitation (data may be  biased low  because of analyte  adsorption  in  the
injection port  or front of the  GC  column or biased high because of overlap with
an interference peak);  (2) false positives because of interference peaks falling
within the analyte retention time window; (3)  false negatives caused by shifting
the  analyte  outside the  retention  time  window; (4)  rapid deterioration  of
expensive capillary columns; and, (5) instrument downtime  caused by cleaning and
rebuilding of detectors and ion sources.  Most extracts of  soil and waste require
some degree of  cleanup, whereas, cleanup for water extracts may be unnecessary.
Highly  contaminated  extracts  (e.g.   sample  extracts of oily  waste or  soil
containing oily residue) often require a  combination  of  cleanup methods.   For
example,  when  analyzing  for  organochlorine pesticides  and PCBs,  it  may  be
necessary to use  gel   permeation chromatography  (GPC),  to eliminate  the high
boiling  material   and  a  micro  alumina  or  Florisil   column  to  eliminate
interferences with the analyte peaks on the GC/ECD.

                                   3600B -  1                         Revision 2
                                                                 November 1992
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      1.3   The following techniques  have been applied to extract purification:
adsorption  chromatography;  partitioning  between  immiscible  solvents;  gel
permeation chromatography; oxidation of interfering substances with acid, alkali,
or oxidizing agents.  These  techniques may  be  used  individually or in various
combinations, depending on the extent and nature of the co-extractives.

            1.3.1       Adsorption column chromatography - Alumina (Methods 3610
      and 3611), Florisil  (Method 3620), and silica gel  (Method 3630) are useful
      for separating analytes of  a relatively  narrow  polarity range away from
      extraneous,  interfering  peaks of  a  different  polarity.   These  are
      primarily  used  for cleanup  of  a  specific chemical group  of relatively
      non-polar analytes, i.e.,  organochlorine pesticides, polynuclear aromatic
      hydrocarbons  (PAHs),  nitrosamines,  etc..     Solid   phase  extraction
      cartridges have been added as an option.

            1.3.2       Acid-base  partitioning   (Method  3650)   -  Useful  for
      separating acidic or basic  organics from  neutral  organics.  It  has been
      applied to analytes such as  the chlorophenoxy herbicides and phenols.  It
      is very useful  for separating  the neutral PAHs  from  the  acidic phenols
      when analyzing a site contaminated with creosote and pentachlorophenol.

            1.3.3       Gel  permeation chromatography  (GPC)  (Method 3640) - The
      most  universal  cleanup  technique  for  a  broad  range of semi volatile
      organics   and  pesticides.     It   is    capable   of   separating   high
      molecular-weight,  high boiling  material from the  sample analytes.  It has
      been used  successfully for  all  the  semivolatile  base, neutral,  and acid
      compounds  associated with  the  EPA Priority Pollutant  and  the Superfund
      Target  Compound  list  prior to GC/MS  analysis  for   semivolatiles  and
      pesticides.  GPC may not be applicable to  elimination of extraneous peaks
      on a chromatogram which interfere with the analytes of interest.  It is,
      however,  useful for  the removal of  high boiling  materials  which  would
      contaminate  injection  ports and column  heads,  prolonging column  life,
      stabilizing the instrument, and reducing column reactivity.

            1.3.4       Sulfur cleanup  (Method  3660)  -  Useful  in  eliminating
      sulfur from sample extracts,  which may cause chromatographic interference
      with analytes of interest.

      1.4   Several of the methods are also  useful for fractionation of complex
mixtures of analytes.   Use the solid  phase extraction cartridges  in Method 3630
(Silica Gel) for separating the PCBs away from most organochlorine pesticides.
Method 3611 (Alumina)  is for the  fractionation of aliphatic, aromatic and polar
analytes.  Method 3620 (Florisil) provides fractionation of the  organochlorine
pesticides.

      1.5   Cleanup capacity is  another  factor  that must  be  considered  in
choosing a  cleanup technique.   The  adsorption  methods  (3610,  3620,  and 3630)
provide the option of using standard column chromatography techniques or solid
phase extraction cartridges.  The decision process in  selecting  between the
different options available generally depends on the amount of interferences/high
boiling material in the  sample extract and the degree of cleanup required by the
determinative method.  The solid phase extraction cartridges require  less elution
solvent and  less time,  however,  their cleanup  capacity is drastically reduced
when comparing  a 0.5  or 1.0 g Florisil cartridge to  a  20  g standard Florisil

                                   3600B  -  2                        Revision 2
                                                                 November 1992
-------
column.  The same  factor enters into the choice of the 70 g gel permeation column
specified in Method 3640 versus a high efficiency column.

      1.6   Table  1  indicates  the  recommended  cleanup   techniques  for  the
indicated groups of compounds.  This information  can also be used as guidance for
compounds that are not listed.  Compounds that are chemically similar to these
groups  of compounds  should  behave similarly when  taken  through  the  cleanup
procedure,however, this must be demonstrated by determining recovery of standards
taken through the method.


2.0   SUMMARY OF METHOD

      2.1   Refer to the  specific cleanup method for a summary of the procedure.


3.0   INTERFERENCES

      3.1   Analytical interferences may be caused by contaminants in solvents,
reagents,  glassware,   and  other sample  processing  hardware.    All  of  these
materials must be routinely demonstrated to be free of interferences, under the
conditions of the analysis, by running laboratory reagent blanks.

      3.2   More extensive procedures than  those outlined in the methods may be
necessary for reagent purification.


4.0   APPARATUS AND MATERIALS

      4.1   Refer to  the  specific  cleanup  method for  apparatus and  materials
needed.
5.0   REAGENTS

      5.1   Refer to the specific cleanup method for the reagents needed.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic  Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Prior to  using  the cleanup  procedures, samples  normally  undergo
solvent  extraction.   Chapter  Two,  Section 2.0,  may be used  as a  guide  for
choosing the appropriate extraction  procedure based  on the physical composition
of the waste and  on the  analytes of interest in the matrix (see also Method 3500
for  a  general  description  of the  extraction  technique).    For  some  organic
liquids, extraction prior to cleanup may not be  necessary.
                                  3600B  - 3                         Revision 2
                                                                 November 1992
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      7.2   Most soil/sediment and waste sample extracts will  require some degree
of cleanup.  The extract is then analyzed by one of the determinative methods.
If interferences still preclude analysis for the analytes of interest, additional
cleanup may be required.

      7.3   Many of the determinative methods specify cleanup  methods that should
be  used   when   determining  particular  analytes  (e.g.   Method   8060,   gas
chromatography of phthalate esters, recommends using either Method 3610 (Alumina
column cleanup)  or Method 3620 (Florisil column cleanup)  if interferences prevent
analysis.   However,  the  experience of  the  analyst may prove  invaluable  in
determining which cleanup  methods are  needed.   As  indicated in Section  1.0 of
this method, many matrices  may  require a combination of cleanup procedures in
order to ensure proper analytical determinations.

      7.4   Guidance  for cleanup is specified  in  each of the methods that follow.
The amount of extract cleanup required  prior to  the final determination depends
on the concentration  of  interferences in the sample, the selectivity of both the
extraction procedure and  the determinative method and  the  required detection
limit.

      7.5   Following cleanup,  the sample is concentrated to whatever volume is
required  in  the determinative method.    Analysis follows as specified  in  the
determinative procedure.


8.0   QUALITY CONTROL

      8.1   Refer to  Chapter One for specific quality  control  procedures.

      8.2   The analyst must  demonstrate that  the  compounds  of interest  are
being quantitatively recovered by the cleanup technique  before the cleanup is
applied  to actual samples.    For sample extracts that are  cleaned up,  the
associated  quality  control  samples   (e.g.  spikes,  blanks,   replicates,  and
duplicates) must also be processed through the same cleanup  procedure.

      8.3   The  analysis  using  each  determinative method  (GC, GC/MS,  HPLC)
specifies  instrument calibration  procedures  using  stock   standards.    It  is
recommended  that  cleanup  also  be  performed  on  a  series of the same  type of
standards  to  validate  chromatographic  elution  patterns for the compounds of
interest and to verify the absence of  interferences from reagents.


9.0   METHOD PERFORMANCE

      9.1   Refer to the specific cleanup method for performance data.


10.0  REFERENCES

      10.1  Refer to the specific cleanup method.
                                   3600B -  4                         Revision 2
                                                                 November 1992
-------
                                   TABLE 1.
       RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Analyte Group
Determinative8
   Method
   Cleanup
Method Options
Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Chlorinated hydrocarbons
Organophosphorus pesticides
Chlorinated herbicides
Semivolatile organics
Petroleum waste
PCDDs and PCDFs by LR/MS
PCDDs and PCDFs by HR/MS
N-methyl carbamate pesticides
8040 3630b, 3640,
8060/8061
8070
8080/8081
8080/8081
8090
8100/8310
8120/8121
8140/8141
8150/8151
8250/8270
8250/8270
8280
8290
8318
3610,
3610,
3620,


3611,



3640,




3650, 8040C
3620,
3620,
3640,

3620,
3630,
3620,
j
8150d<
3650,
3611,



3640
3640
3660
3665
3640
3640
3640
3620
3620
3660
3650
8280
8290
8318
a   The GC/MS Methods, 8250 and 8270, are also appropriate determinative methods
    for all  analyte groups,  unless  lower detection  limits  are  required.

b   Cleanup  applicable to derivatized phenols.

c   Method 8040  includes a derivatization technique  followed by GC/ECD analysis,
    if interferences are  encountered using  GC/FID.

d   Method 8150  incorporates an acid-base cleanup step as an integral part of the
    method.
                                  3600B  - 5
                                Revision  2
                             November  1992
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                    METHOD  3600B
                       CLEANUP
       7.1
    Do solvent
     extraction
        I
        7.2
  Analyze analyte
 by a determinative
method from Sec. 4.3
      7.2 Are
     analytes
   undeterminable
      due to
    interference?
        7.3
 Use cleanup method
  specified for the
determinative method
                                         7.5
                                  Concentrate sample
                                   to required volume
                         3600B -  6
                                 Revision 2
                             November  1992
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                                 METHOD 3630B

                              SILICA GEL CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   Silica  gel  is a  regenerative  adsorbent of amorphous  silica with
weakly acidic properties.  It is produced from sodium silicate and sulfuric acid.
Silica gel can be used in  column chromatography for  the separation of  analytes
from interfering  compounds of a different chemical  polarity.  It  may be used
activated after heating to 150  - 160°C or  deactivated  with  up to  10% water.

      1.2   This method includes guidance  for  standard column cleanup of sample
extracts  containing polynuclear  aromatic  hydrocarbons,  derivatized  phenolic
compounds, organochlorine pesticides and,  PCBs as Aroclors.

      1.3   This  method  also  provides cleanup  procedures  using  solid-phase
extraction cartridges  for pentafluorobenzyl  bromide  derivatized  phenols  and
organochlorine pesticides/PCBs  as Aroclors.   This technique also provides the
best separation of  PCBs from most single component organochlorine pesticides.
When only PCBs are  to be measured, this method can be used in conjunction with
sulfuric acid/permanganate cleanup (Method 3665).

      1.4   Other analytes may  be cleaned  up  using  this method if the analyte
recovery meets the  criteria specified in Section 8.0.


2.0   SUMMARY OF METHOD

      2.1   This  method provides the  option  of  using either  standard column
chromatography techniques or  solid-phase extraction  cartridges.  Generally, the
standard column chromatography techniques  use larger amounts of adsorbent and,
therefore, have a greater cleanup capacity.

      2.2   In the  standard column cleanup protocol, the column is packed with
the required amount  of adsorbent, topped with a water adsorbent, and then loaded
with the  sample  to  be  analyzed.  Elution  of  the analytes  is  effected with a
suitable solvent(s)  leaving the  interfering compounds on the column.  The eluate
is then concentrated (if necessary).

      2.3   The cartridge cleanup protocol  uses  silica solid-phase extraction
cartridges packed with 1 g or 2 g of adsorbent.  Each  cartridge is solvent washed
immediately prior to use.   Aliquots of sample  extracts  are  loaded  onto  the
cartridges which are then  eluted with suitable solvent(s).   A vacuum manifold is
required to obtain reproducible  results.  The collected fractions may be further
concentrated prior  to gas chromatographic analysis.

      2.4   The appropriate gas chromatographic method is  listed  at the end of
each technique.   Analysis may also  be  performed   by  gas  chromatography/mass
spectrometry (Method 8270).
                                   3630B  -  1                         Revision 2
                                                                 November 1992
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3.0   INTERFERENCES

      3.1   Solvents, reagents,  glassware,  and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.  All  these materials  must be demonstrated to be free from
interferences under the conditions of the analysis, by analyzing reagent blanks.
See Section 8 for guidance on a reagent blank check.

      3.2   Phthalate  ester  contamination  may  be  a  problem  with  certain
cartridges  The more inert  the column and/or  cartridge material (i.e., glass or
Teflon),  the  less  problem  with phthalates.   Phthalates create  interference
problems for all method analytes,  not just the phthalate esters themselves.

      3.3   More extensive procedures than  those outlined in this method may be
necessary for reagent purification.


4.0   APPARATUS AND MATERIALS

      4.1   Chromatographic column - 250 mm  long x 10 mm ID;  with Pyrex glass
wool at bottom and a Teflon stopcock.

      NOTE: Fritted  glass  discs are difficult  to  decontaminate  after highly
            contaminated extracts  have  been passed  through.   Columns  without
            frits may  be  purchased.   Use  a  small pad  of Pyrex glass  wool  to
            retain  the adsorbent.   Prewash  the glass wool  pad with 50  ml of
            acetone followed  by 50 ml of elution solvent  prior to packing the
            column with adsorbent.

      4.2   Beakers - 500 ml.

      4.3   Vials -  2, 10,  25 ml,  glass  with Teflon  lined  screw-caps or crimp
tops.

      4.4   Muffle furnace.

      4.5   Reagent bottle -  500 ml.

      4.6   Erlenmeyer flasks - 50 and 250 ml.

      4.7   Vacuum    manifold:    VacElute   Manifold    SPS-24   (Analytichem
International),  Visiprep  (Supelco,  Inc.)  or equivalent,  consisting of glass
vacuum basin, collection rack and funnel, collection vials, replaceable stainless
steel delivery  tips, built-in  vacuum  bleed valve  and  gauge.   The  system is
connected to a vacuum pump or water aspirator through a vacuum  trap made from a
500 ml sidearm flask fitted with a one-hole  stopper  and  glass tubing.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be  used in all tests.  Unless otherwise
indicated, it is intended that all  reagents shall conform to the specifications
of the Committee on Analytical Reagents  of  the American Chemical Society, where
such specifications are available. Other grades may be used,  provided it  is first

                                   3630B -  2                        Revision 2
                                                                 November 1992
-------
ascertained that the  reagent  is of sufficiently high purity to permit  its  use
without lessening the accuracy  of  the determination.

      5.2   Organic-free reagent water.  All  references to water in  this method
refer to organic-free reagent water, as defined  in Chapter One.

      5.3   Silica gel for chromatography columns.

            5.3.1 Silica Gel for Phenols and  Polynuclear Aromatic Hydrocarbons:
      100/200 mesh desiccant (Davison Chemical grade 923 or equivalent).  Before
      use, activate for at least 16 hr.  at 130°C in a shallow glass tray,  loosely
      covered with foil.

            5.3.2 Silica Gel for Organochlorine  pesticides/PCBs:  100/200 mesh
      desiccant  (Davison Chemical grade  923  or  equivalent).   Before  use,
      activate for at least 16 hr. at  130°C  in  a  shallow glass tray,  loosely
      covered with foil.  Deactivate it to 3.3%  with reagent water  in a 500 ml
      glass jar.   Mix the  contents thoroughly and allow  to equilibrate for 6
      hours.  Store the  deactivated  silica gel  in  a  sealed glass jar inside a
      desiccator.

      5.4   Silica cartridges: 40 jim  particles, 60 A pores.  The cartridges from
which this method were developed consist of 6  ml serological-grade polypropylene
tubes, with the 1 g of silica held between two polyethylene or  stainless steel
frits with 20 \im  pores.   2 g silica cartridges are also used in  this  method,  and
0.5 g cartridges  are  available.   The  compound elution patterns  must  be verified
when cartridges other than the  specified size are used.

      5.5   Sodium sulfate  (granular, anhydrous), Na2SO,.  Purify by heating at
400°C for 4 hours in  a shallow tray,  or by precleaning the sodium sulfate with
methylene chloride.  A method blank must be analyzed in order to  demonstrate that
there is no interference from the  sodium sulfate.

      5.6   Eluting solvents

            5.6.1 Cyclohexane,  C6H12 -  Pesticide quality  or equivalent.

            5.6.2 Hexane, C6H14  - Pesticide quality or equivalent.

            5.6.3 2-Propanol, (CH3)2CHOH -  Pesticide  quality or equivalent.

            5.6.4 Toluene,  C6H5CH3  - Pesticide quality or  equivalent.

            5.6.5 Methylene chloride, CH2C12  - Pesticide quality or equivalent.

            5.6.6 Pentane,  C5H12  -  Pesticide  quality or equivalent.

            5.6.7 Acetone,  CH3COCH3 - Pesticide quality  or equivalent.

            5.6.8 Diethyl Ether,  C2H5OC2Hj.   Pesticide  quality or  equivalent.
      Must  be  free of  peroxides  as indicated  by test  strips  (EM  Quant,  or
      equivalent).   Procedures  for removal of peroxides are provided with the
      test strips.   After cleanup, 20 ml of ethanol  preservative must be added
      to each liter of ether.

                                   3630B - 3                         Revision 2
                                                                 November 1992
-------
6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this chapter,  Organic  Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   General Guidance

            7.1.1 The procedure contains two cleanup options  for the derivatized
      phenols and organochlorine pesticides/Aroclors, but only one technique for
      the   polynuclear   aromatic    hydrocarbons    (PAHs)    (standard   column
      chromatography).  Cleanup techniques by standard column chromatography for
      all analytes are found in Section 7.2.  Cleanup techniques by solid-phase
      cartridges for derivatized phenols and PAHs are found in Section 7.3.  The
      standard column chromatography  techniques are packed with a greater amount
      of silica gel adsorbent and,  therefore, have a greater cleanup capacity.
      A  rule  of thumb  relating to  cleanup  capacity  is  that  1  g  of  sorbent
      material  will  remove  10  to  30 mg  of total  interferences.   (However,
      capacity   is   also   dependent  on   the   sorbent   retentiveness   of  the
      interferences.)   Therefore,  samples  that  exhibit  a  greater degree  of
      sample interference should be cleaned up by this technique.  However, both
      techniques have limits on the amount of interference that can be removed.
      If the interference is caused by high boiling material, then Method 3640
      should be  used  prior to  this  method.   If the  interference  is caused by
      relatively polar compounds of the same boiling range as  the analytes, then
      multiple  column  or  cartridge  cleanups may be required.   If crystals of
      sulfur are noted in  the extract, then Method 3660 should be utilized prior
      to this method.  The cartridge cleanup techniques are often faster and use
      less solvent, however they have less cleanup capacity.

            7.1.2 Allow the extract  to reach room  temperature if it was in cold
      storage.   Inspect  the  extracts  visually  to ensure  that  there are  no
      particulates or phase separations  and  that  the volume  is as stated in the
      accompanying documents.   Verify that  the  solvent  is compatible  with the
      cleanup procedures.  If crystals of  sulfur  are visible  or if the presence
      of sulfur  is suspected, proceed with Method 3660.

            7.1.3 The  extract   solvent  for most  cleanup techniques  must  be
      exchanged  to hexane  if  it  is in  methylene chloride.   (For the  PAHs,
      exchange  to cyclohexane  as  per  Section  7.2.1).    Follow  the  standard
      Kuderna-Danish concentration technique provided in  each  extraction method.
      The volume  of  methylene  chloride  should  have been  reduced  to  1  -  2 mL.
      Add 40 mL of hexane, a fresh boiling chip and repeat the concentration as
      written.  The final  volume required for the  cleanup techniques  is normally
      2 mL.

      7.2   Standard Column Cleanup Techniques

            7.2.1  Polynuclear aromatic hydrocarbons

                   7.2.1.1     Before the  silica  gel cleanup technique  can be
            utilized, the extract  solvent  must  be  exchanged to cyclohexane. The

                                   3630B  -  4                        Revision 2
                                                                 November 1992
-------
exchange  is  performed  by  adding  4  ml of  cyclohexane following
reduction  of the sample extract to  1-2  ml  using the macro Snyder
column.   Attach the  two  ball  micro Snyder  column  and reduce the
volume to  2  ml.

      CAUTION:    When the volume of solvent is reduced below  1 ml,
                  semi volatile  analytes  may  be  lost.     If the
                  extract goes  to  dryness,  the extraction must be
                  repeated.

      7.2.1.2     Prepare a slurry of 10 g of  activated silica gel
(Section 5.3.1) in methylene chloride and place this into a 10  mm ID
chromatographic column.  Tap the column to settle the silica gel and
elute the  methylene chloride.   Add  1 to  2  cm of anhydrous sodium
sulfate to the top  of the silica gel.

      7.2.1.3     Preelute the  column with  40 ml of pentane.   The
rate for all elutions should be about 2  mL/min.   Discard the eluate
and just prior to exposure of the sodium sulfate layer to  the air,
transfer the 2 ml cyclohexane sample extract onto the column  using
an additional 2 ml cyclohexane to complete the transfer.  Just  prior
to exposure  of the  sodium sulfate layer to  the  air,  add  25 ml of
pentane  and continue  the elution  of the  column.    Discard  this
pentane eluate,

      7.2.1.4     Next, elute  the  column with 25  mL  of methylene
chloride/pentane (2:3)(v/v) into a 500 mL K-D flask  equipped with a
10 ml  concentrator tube.   Concentrate  the  collected  fraction to
whatever volume  is  required  (1-10  ml).   Proceed with HPLC  (Method
8310) or GC analysis (Method 8100).  Validated components that  elute
in this fraction are:

      Acenaphthene
      Acenaphthylene
      Anthracene
      Benzo(a)anthracene
      Benzo(a)pyrene
      Benzo(b)fluoranthene
      Benzo(g,h,i)perylene
      Benzo(k)fluoranthene
      Chrysene
      Dibenzo(a,h)anthracene
      Fluoranthene
      Fluorene
      Indeno(l,2,3-cd)pyrene
      Naphthalene
      Phenanthrene
      Pyrene

7.2.2  Derivatized Phenols

      7.2.2.1     This silica gel cleanup procedure  is performed on
sample  extracts  that  have  undergone  pentafluorobenzyl   bromide
derivatization as described  in Method 8040. The sample extract must

                      3630B -  5                        Revision 2
                                                     November 1992
-------
be in 2 ml of hexane at this point.

      7.2.2.2     Place  4.0  g  of activated  silica gel  (Section
5.3.1) into a 10 mm  ID  chromatographic column.   Tap the column to
settle the silica gel  and add  about 2 g of anhydrous sodium sulfate
to the top of the silica gel.

      7.2.2.3     Preelute the column with 6 ml of hexane.  The rate
for all elutions should be about 2 mL/min.   Discard the eluate and
just prior to exposure of the sodium sulfate layer to the air, pipet
onto  the  column 2  ml  of  the hexane solution  that contains  the
derivatized sample or standard.   Elute the  column with 10.0 ml of
hexane and discard the eluate.

      7.2.2.4     Elute the column, in order, with  10.0 ml  of 15%
toluene in hexane  (Fraction  1);  10.0  ml of 40%  toluene in  hexane
(Fraction 2); 10.0 ml  of 75% toluene  in hexane  (Fraction 3);  and
10.0  ml of 15% 2-propanol in  toluene  (Fraction  4).   All  elution
mixtures are prepared on  a volume:volume basis.   Elution patterns
for the phenolic derivatives are shown  in Table 1.  Fractions may be
combined,   as  desired,  depending  upon   the  specific   phenols  of
interest  or  level  of  interferences.    Proceed  with  GC  analysis
(Method 8040).

7.2.3 Organochlorine Pesticides and Aroclors

      7.2.3.1     Transfer a 3 g portion of deactivated silica gel
(Section 5.3.2)  into a 10 mm ID glass chromatographic column and top
it with 2 to 3  cm of anhydrous sodium  sulfate.

      7.2.3.2     Add 10 ml of hexane to the  top of the column to
wet and rinse  the sodium sulfate  and silica  gel.  Just  prior to
exposure of the  sodium sulfate layer to air, stop the hexane eluate
flow by closing  the stopcock on the chromatographic column.  Discard
the eluate.

      7.2.3.3     Transfer the sample extract  (2 ml in hexane) onto
the column. Rinse the extract vial twice with 1  to  2 ml of hexane
and add each rinse to the column.  Elute the  column with 80 ml of
hexane  (Fraction  I)  at a rate  of about  5  mL/min.    Remove  the
collection flask and  set  it aside for later concentration.   Elute
the column  with 50  ml of  hexane (Fraction  II)  and  collect  the
eluate.  Perform a third  elution  with 15 ml of methylene chloride
(Fraction  III).  The  elution  patterns  for  the  organochlorine
pesticides, Aroclor-1016, and Aroclor-1260  are shown in Table 2.

      7.2.3.4     Prior  to   gas   chromatographic  analysis,   the
extraction solvent must be  exchanged  to hexane.  Fractions  may be
combined,     as     desired,     depending     upon    the    specific
pesticides/Aroclors  of  interest  or  level   of interferences.   If
mixtures  of  Aroclors  and pesticides are expected,  it  is best to
analyze  Fraction  I   separately  since  it   contains  the  Aroclors
separated  from  most  pesticides.  Proceed with GC analysis  as  per
Method 8080 or 8081.

                       3630B  - 6                         Revision 2
                                                     November 1992
-------
7.3   Cartridge Cleanup Techniques

      7.3.1  Cartridge Set-up and Conditioning

            7.3.1.1     Arrange the  1  g  Florisil  cartridges  (2 g  for
      phenol  cleanup)  on the manifold in the closed-valve position.  Other
      size cartridges  may  be  used,  however  the data  presented in  the
      Tables  is all  based on  1 g cartridges for pesticides/Aroclors  and 2
      g cartridges  for phenols.  Therefore, supporting recovery data must
      be developed  for other  sizes.   Larger  cartridges  will  probably
      require larger volumes of elution solvents.

            7.3.1.2     Turn vacuum pump  on  and set  pump  vacuum to  10
      inches   or  254  mm   of  Hg.  Do  not   exceed  the  manufacturer's
      recommendation for manifold  vacuum. Flow rates can be  controlled by
      opening and closing cartridge valves.

            7.3.1.3     Condition  the cartridges by adding 4 ml of hexane
      to each cartridge.  Slowly open the cartridge valves to allow hexane
      to pass through the  sorbent beds to the lower frits.  Allow  a few
      drops  per cartridge to pass  through  the manifold  to remove all  air
      bubbles.  Close  the valves and allow the solvent to  soak  the entire
      sorbent bed for 5 minutes.   Do not turn off the  vacuum.

            7.3.1.4     Slowly  open cartridge valves  to allow  the hexane
      to pass through  the  cartridges.  Close the cartridge valves  when
      there  is still  at least 1 mm of solvent above the sorbent  bed.   Do
      not allow cartridges  to become dry.   If cartridges go dry, repeat
      the conditioning step.

      7.3.2  Derivatized Phenols

            7.3.2.1      Reduce  the sample extract volume to 2 ml  prior to
      cleanup.  The extract solvent must  be hexane and the  phenols  must
      have undergone derivatization by pentafluorobenzyl  bromide as  per
      Methods 8040  or 8041.

            7.3.2.2      Transfer  the   extract   to  the 2   g  cartridge
      conditioned as described in Section 7.3.1.  Open the cartridge  valve
      to  allow  the   extract  to  pass  through  the   cartridge   bed  at
      approximately  2  mL/minute.

            7.3.2.3      When  the entire extract has  passed through  the
      cartridges, but  before  the cartridge becomes  dry, rinse  the sample
      vials with an  additional 0.5 ml of hexane,  and add the rinse to the
      cartridges to  complete  the quantitative  transfer.

            7.3.2.4      Close the  cartridge valve and turn off  the vacuum
      after  the solvent has passed through,  ensuring that the cartridge
      never gets dry.

           7.3.2.5      Place a 5 ml vial or volumetric  flask  into  the
      sample  rack corresponding  to the cartridge  position.   Attach  a
      solvent-rinsed stainless  steel solvent  guide  to the manifold cover

                            3630B - 7                         Revision  2
                                                          November  1992
-------
and align with the collection vial.

      7.3.2.6     Add 5 ml of hexane to the cartridge.  Turn on the
vacuum pump and adjust the pump pressure to 10 inches or 254 mm of
Hg.  Allow the solvent to soak the sorbent bed  for  1 minute or less.
Slowly open the  cartridge  valve,  and  collect the  eluate  (this is
Fraction 1, and should be discarded).

      NOTE: If cartridges smaller than 2 g are used,  then Fraction
            1 cannot be  discarded,  since it  contains  some  of the
            phenols.

      7.3.2.7     Close the cartridge  valve, replace the collection
vial, and add 5 ml of toluene/hexane (25/75, v/v) to the cartridge.
Slowly open  the cartridge valve  and  collect  the  eluate  into the
collection vial.   This  is Fraction 2, and should  be retained for
analysis.

      7.3.2.8     Adjust the final volume of the eluant to a known
volume which will result in analyte concentrations appropriate for
the  project  requirements  (normally  1-10   ml).   Table 3  shows
compound  recoveries  for 2  g silica  cartridges.   The  cleaned up
extracts are ready for analysis by Methods 8040 or 8041.

7.3.3 Organochlorine Pesticides/Aroclors

NOTE: The   silica   cartridge   procedure   is  appropriate   when
      polychlorinated biphenyls are known to  be present.

      7.3.3.1     Reduce the sample extract volume to 2 ml prior to
cleanup.  The extract solvent must be hexane.

      7.3.3.2     Use the 1 g cartridges conditioned as described in
Section 7.3.1.

      7.3.3.3     Transfer the extract to the cartridge.  Open the
cartridge valve to allow the extract to pass  through the cartridge
bed  at approximately 2 mL/minute.

      7.3.3.4     When  the  entire extract has  passed  through the
cartridges, but before the cartridge becomes  dry,  rinse the sample
vials with an additional  0.5  mL of solvent, and add the  rinse to the
cartridges to complete the quantitative transfer.

      7.3.3.5     Close the cartridge  valve and  turn  off the vacuum
after the  solvent has  passed through, ensuring that the cartridge
never goes dry.

      7.3.3.6     Place  a  5 ml vial  or  volumetric flask into the
sample  rack corresponding  to the cartridge  position.   Attach  a
solvent-rinsed  stainless steel solvent guide  to the  manifold cover
and  align with  the collection vial.
                       3630B - 8                        Revision 2
                                                     November  1992
-------
                  7.3.3.7     Add 5 mL of hexane to the cartridge.  Turn on the
            vacuum pump and adjust the pump pressure to 10 inches or 254 mm of
            Hg.  Allow the solvent  to  soak the sorbent bed for 1 minute or less.
            Slowly open  the cartridge valve  and collect the eluate  into the
            collection vial (Fraction 1).

                  7.3.3.8     Close the cartridge valve, replace the collection
            vial,  and add  5  ml of diethyl  ether/hexane  (50/50, v/v)  to the
            cartridge.  Slowly open the cartridge valve and collect the eluate
            into the  collection vial  (Fraction 2).

                  7.3.3.9     Adjust the final volume of the  two fractions to a
            known volume which will result in analyte concentrations appropriate
            for the project requirements  (normally  1-10 mL).   The fractions
            may be  combined prior to  final  adjustment of volume,  if analyte
            fractionation  is  not required.   Table 4 shows compound recoveries
            for 1 g silica cartridges.   The  cleaned up extracts are ready for
            analysis  by Methods 8080 or 8081.


3.0   QUALITY CONTROL

      8.1   Refer to  Chapter  One for specific quality control  procedures and
Method 3600 for cleanup procedures.

      8.2   A reagent blank (consisting of the elution  solvents) must be passed
through the column or  cartridge  and checked for the compounds  of interest, prior
to the use of this method.  This  same performance check is required with each new
lot of adsorbent or cartridges.  The  level  of interferences  must be below the
method detection limit before this method is performed on actual samples.

      8.3   The analyst must demonstrate that the compounds of interest are being
quantitatively recovered before  applying this method to actual samples.  See the
attached Tables for acceptable recovery data.   For compounds  that have not been
tested, recovery must be > 85%.

            8.3.1 Before  any  samples  are  processed  using  the  solid-phase
      extraction cartridges, the efficiency of the cartridge must be verified.
      A recovery check must be performed  using standards of the target analytes
      at known concentration.   Only lots  of  cartridges that  meet the recovery
      criteria for the spiked compounds can be used to process the samples.

            8.3.2 A check  should also be performed on each  individual  lot of
      cartridges and for every 300 cartridges of a particular lot.

      8.4   For sample  extracts that  are  cleaned  up  using  this method,  the
associated quality control  samples should also be  processed through this cleanup
method.
9.0   METHOD PERFORMANCE

      9.1   Table 1  provides  performance information on the  fractionation of
phenolic derivatives using standard column chromatography.

                                   3630B  - 9                         Revision 2
                                                                 November 1992
-------
      9.2   Table 2  provides  performance information on the  fractionation of
organochlorine pesticides/Aroclors using standard column chromatography.

      9.3   Table 3 shows recoveries of derivatized phenols obtained using 2 g
silica cartridges.

      9.4   Table  4  shows recoveries   and  fractionation  of  organochlorine
pesticides obtained using 1 g silica cartridges.


10.0  REFERENCES

      1.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures
            for the Analysis of Pollutants Under the Clean Water Act; Final Rule
            and Interim Final  Rule and Proposed Rule,11 October 26, 1984.

      2.    U.S EPA "Evaluation of  Sample  Extract Cleanup  Using Solid-Phase
            Extraction Cartridges," Project Report, December 1989.
                                  3630B  -  10                         Revision  2
                                                                 November  1992
-------
                                    TABLE 1
                   SILICA GEL  FRACTIONATION OF PFBB DERIVATIVES
                                        Percent Recovery by Fraction8

Parameter                          123
2-Chlorophenol
2-Nitrophenol
Phenol
2,4-Dimethylphenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chl oro-3-methyl phenol
Pentachlorophenol
4-Nitrophenol
90

90
95
95
50 50
84
75 20

1
9
10
7
1

14

1

90






90
a  Eluant composition:

    Fraction 1 - 15% toluene in hexane.
    Fraction 2 - 40% toluene in hexane.
    Fraction 3 - 75% toluene in hexane.
    Fraction 4 - 15% 2-propanol in toluene.

Data from Reference 1 (Method 604)
                                  3630B - 11                        Revision 2
                                                                 November 1992
-------
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                                      TABLE  3
                  PERCENT RECOVERIES AND ELUTION PATTERNS FOR 18
                        PHENOLS FROM 2 g SILICA CARTRIDGES8
                                                    Fraction 2
                                                Average     Percent
      Compound                                  Recovery      RSD
Phenol
2-Methyl phenol
3-Methyl phenol
4-Methyl phenol
2, 4-Dimethyl phenol
2-Chlorophenol
2,6-Dichlorophenol
4-Chl oro-3-methyl phenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
2,3,6-Trichlorophenol
2,4,5-Trichlorophenol
2,3,5-Trichlorophenol
2,3,5 , 6-Tetrachl orophenol
2,3,4,6-Tetrachlorophenol
2, 3, 4-Trichl orophenol
2,3,4,5-Tetrachlorophenol
Pentachl orophenol
74.1
84.8
86.4
82.7
91.8
88.5
90.4
94.4
94.5
97.8
95.6
92.3
92.3
97.5
97.0
72.3
95.1
96.2
5.2
5.2
4.4
5.0
5.6
5.0
4.4
7.1
7.0
6.6
7.1
8.2
8.2
5.3
6.1
8.7
6.8
8.8
a     Silica cartridges  (Supelco,  Inc.)  were  used;  each cartridge was conditioned
      with 4 mL of hexane prior to use.   Each  experiment was performed  in duplicate
      at three spiking concentrations (0.05 jig,  0.2  ng,  and 0.4  \ig per  compound per
      cartridge).   Fraction  1 was  eluted with  5  mL  hexane  and  was discarded.
      Fraction 2 was eluted with 5 mL toluene/hexane (25/75,  v/v).

Data from Reference 2
                                    3630B - 14                           Revision  2
                                                                      November  1992
-------
                                      TABLE 4
                   PERCENT RECOVERIES AND  ELUTION PATTERNS FOR  17
               ORGANOCHLORINE PESTICIDES FROM 1 g SILICA CARTRIDGES8
Compound
     Fraction 1
Average     Percent
Recovery      RSD
     Fraction 2
Average     Percent
Recovery      RSD
alpha-BHC
gamma -BHC
beta-BHC
Heptachlor
delta-BHC
Aldrin
Heptachlor epoxide
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
4,4'-DDD
Endosulfan II
4,4'-DDT
Endrin aldehyde
Endosulfan sulfate
4,4'-Methoxychlor
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1264
0
0
0
97.3 1.3
0
95.9 1.0
0
0
99.9 1.7
0
0
10.7 41
0
94.1 2.0
0
0
0
124
93.5
118
116
114
108
112
98.7
94.8
94.3
0
90.8
0
97.9
102
0
92.3
117
92.4
96.0
0
59.7
97.8
98.0







2.3
1.9
3.0

2.5

2.1
2.3

2.0
2.6
3.3
2.2

2.6
2.1
2.4







      Silica cartridges  (Supelco,  Inc.  lot SP0161) were  used;  each cartridge was
      conditioned with 4 mL  hexane prior to use.  The organochlorine  pesticides were
      tested separately  from  PCBs.   Each  organochlorine pesticides experiment was
      performed in duplicate, at three spiking concentrations (0.2  jig, 1.0 ng, and
      2.0 ng per compound per cartridge).  Fraction 1 was eluted with 5 mL  of hexane,
      Fraction 2 with 5 mL of diethyl ether/hexane  (50/50, v/v).  PCBs were spiked
      at 10 \ig per cartridge and were eluted with 3 mL of hexane.   The value given
      for PCBs is the percent recovery for a single determination.

Data from Reference 2
                                    3630B - 15
                                          Revision 2
                                       November 1992
-------
                METHOD  3630B
            SILICA  GEL CLEANUP
  OC Pesticide
PCBsi Phenols -
  >10 -30 mg
£
  7.2 Standard
Column Cleanup
Derivatized \
Phenols
7.2.2.1 Do PFBB
denvatization on
sample extract
(8040)
1
7.2.Z2 Place
activated silica gel
in chromatographic
column; add
anhydrous Na^SO.
i
7.2.Z3 Preelute
column with hexane;
pipet hexane
solution onto column;
elute
i
7.2.2.4 Elute column
with specified
solvents
*
Analyze
byGC
(Method
\8040) }
^









"OCgptodas
7.2.3.1 Deactivate
silica gel, prepare
column
*
7.2.3.2 Bute the
GC column
with hexane
*
7.2.3.3 Transfer
extract onto column
and elute with
specified solvents
t
7.3.4 Exchange the
elution solvent
to hexane (Section
7.1.3)
*
Analyze by
GC Method
8080 or
\ 8081 /
                                                                           PAHs
                                                                               O
                                       -<10- 30 mg
                                                 7.3 Cartridge
                                                   Cleanup
                                                7.3.1 Cartridge
                                                  Set-up &
                                                 Conditioning
                                      Derivatized
                                       Phenols
                                                                               OC Pesticides
                                                                                  iPCBs
                                   7.3.Z1 Do PFBB
                                   denvatization on
                                    sample extract
                                        (8040)
                                        I
                                                               i.
                                                                               7.3.3.1 Exchange
                                                                                  solvent to
                                                                                   hexane
                                   7.3.2.3 & 7.3.2.4
                                   Transfer extract
                                     to cartridge
                                                                                    I
                                                                                7.3.3.3 & 7.3.3.4
                                                                                Transfer extract
                                                                                  to cartridge
                                   7.3.2.6 & 7.3.2.7
                                    Rinse cartridge
                                    with hexane &
                                       discard
                                                                               7.3.3.6 & 7.3.3.7
                                                                                Elute cartridge
                                                                                with hexane as
                                                                                  Fraction I
                                     7.3.2.8 Bute
                                     cartridge with
                                    toluene/hexane
                                        I
                                                                                7.3.3.8 Bute
                                                                                cartridge with
                                                                               ether/hexane as
                                                                                 Fraction II
                                      Analyze
                                   by GC Method
                                   8040orGC/MS
                                    Method 8270
                                                                                   Analyze
                                                                                 each fraction
                                                                                by GC Method
                                                                                .8080 or 8081
                   3630B  -  16
                                                                                         Revision  2
                                                                                     November  1992
-------
  METHOD  3630B
   (continued)
    ©
      (PAHs)
   7.2 Standard
 Column Cleanup

 7.2.1.1 Exchange
 extract solvent to
cydohexane during
   K-D procedure

  7.2.1.2 Prepare
  slurry activated
 silica gel, prepare
      column

  7.2.1.3PreekJte
    column with
  pentane, transfer
extract onto column
   and elute with
      pentane

 7.2.1.4 Bute column
   withCH2CI2/
pentane; concentrate
  collected fraction;
   adjust volume

      Analyze
   by GC Method
  8100orGC/MS
    Method 8270
   3630B  -  17
    Revision  2
November 1992
-------
                                 METHOD 3640A

                            GEL-PERMEATION CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   Gel-permeation  chromatography  (GPC) is  a size  exclusion  cleanup
procedure  using  organic solvents  and hydrophobic gels  in the  separation  of
synthetic macromolecules (1).  The packing gel is porous and is characterized by
the range or uniformity (exclusion range) of that pore size.   In the choice of
gels, the exclusion  range must be larger than the molecular size of the molecules
to be separated (2).  A cross  linked divinylbenzene-styrene copolymer (SX-3 Bio
Beads or equivalent) is specified for this method.

      1.2   General  cleanup application - GPC is recommended for the elimination
from the sample of  lipids,  polymers,  copolymers,  proteins,  natural  resins and
polymers, cellular components, viruses, steroids, and dispersed high-molecular-
weight compounds (2).   GPC  is appropriate for both polar and non-polar analytes,
therefore, it  can be  effectively used to cleanup extracts containing  a broad
range of analytes.

      1.3   Specific application -  This method  includes guidance for cleanup of
sample extracts containing  the following analytes from the RCRA Appendix VIII and
Appendix IX lists:
      Compound Name                                            CAS No.a


      Acenaphthene                                             83-32-9
      Acenaphthylene                                          208-96-8
      Acetophenone                                             98-86-2
      2-Acetylaminofluorene                                    53-96-3
      Aldrin                                                  309-00-2
      4-Aminobiphenyl                                          92-67-1
      Aniline                                                  62-53-3
      Anthracene                                              120-12-7
      Benomyl                                                17804-35-2
      Benzenethiol                                            108-98-5
      Benzidine                                                92-87-5
      Benz(a)anthracene                                        56-55-3
      Benzo(b)fluoranthene                                    205-99-2
      Benzo(a)pyrene                                           50-32-8
      Benzo(ghi)perylene                                      191-24-2
      Benzo(k)fluoranthene                                    207-08-9
      Benzoic acid                                             65-85-0
      Benzotrichloride                                         98-07-7
      Benzyl alcohol                                          100-51-6
      Benzyl chloride                                         100-44-7
      alpha-BHC                                               319-84-6
      beta-BHC                                                319-85-7
      gamma-BHC                                                58-89-9

                                  3640A  -  1                         Revision 1
                                                                 November 1992
-------
Compound Name
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-butyl -4,6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Chloro-3-methyl phenol
4-Chloroaniline
Chi orobenzi late
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
3-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial late
Dibenzo(a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzothiophene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
trans- l,4-Dichloro-2-butene
cis-l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3, 3 '-Dichl orobenzi dine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
2,4-Dichlorotoluene
l,3-Dichloro-2-propanol
CAS No.a
319-86-8
101-55-3
85-68-7
88-85-7
86-74-8
10605-21-7
5103-71-9
5566-34-7
59-50-7
106-47-8
510-15-6
111-91-1
111-44-4
108-60-1
91-58-7
95-57-8
106-48-9
108-43-0
7005-72-3
542-76-7
218-01-9
95-48-7
108-39-4
106-44-5
50-18-0
72-54-8
72-55-9
50-29-3
84-74-2
2303-16-4
192-65-4
189-55-9
224-42-0
53-70-3
132-64-9
132-65-0
96-12-8
106-93-4
110-57-6
1476-11-5
95-50-1
106-46-7
541-73-1
91-94-1
87-65-0
94-75-7
120-83-2
95-73-8
96-23-1
3640A - 2
   Revision 1
November 1992
-------
Compound Name
Dieldrin
Diethyl phthalate
Dimethoate
Dimethyl phthalate
p-Dimethyl ami noazobenzene
7, 12-Dimethyl -benz(a)anthracene
2,4-Dimethylphenol
3,3-Dimethylbenzidine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1,2-Diphenylhydrazine
Disulfoton
Endosulfan sulfate
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans-Isosafrole
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methyl chol anthrene
2-Methyl naphthalene
Methyl parathion
4,4'-Methylene-bis(2-chloroaniline)
CAS No.a
60-57-1
84-66-2
60-51-5
131-11-3
60-11-7
57-97-6
105-67-9
119-93-7
534-52-1
99-65-0
51-28-5
121-14-2
606-20-2
122-39-4
101-84-8
122-66-7
298-04-4
1031-07-8
959-98-8
33213-65-9
72-20-8
7421-93-4
53494-70-5
62-50-0
97-63-2
117-81-7
52-85-7
86-73-7
206-44-0
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
1888-71-7
193-39-5
465-73-6
78-59-1
17627-76-8
4043-71-4
143-50-0
109-77-3
150-50-5
72-43-5
56-49-5
91-57-6
298-00-0
101-14-4
3640A - 3
   Revision 1
November 1992
-------
Compound Name
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitrosodi -n-butylamine
N-Nitrosodiethanolamine
N-Ni trosodi ethyl ami ne
N-Nitrosodi methyl ami ne
N-Ni trosodi phenyl ami ne
N-Nitrosodi -n-propylamine
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorpholine
N-Nitrosopiperidine
N-Nitrosopyrolidine
Di-n-octyl phthalate
Parathion
Pentachl orobenzene
Pentachloroethane
Pentachl oronitrobenzene (PCNB)
Pentachl orophenol
Phenacetin
Phenanthrene
Phenol
1,2-Phenylenediamine
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1,2, 4, 5-Tetrachl orobenzene
2,3,5 , 6-Tetrachl oroni trobenzene
2,3,5,6-Tetrachlorophenol
2,3,4 , 6-Tetrachl orophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
Thiourea, l-(o-chlorophenyl)
Toluene-2,4-diamine
1,2, 3 -Trichl orobenzene
1, 2, 4-Trichl orobenzene
CAS No.a
91-20-3
130-15-4
91-59-8
134-32-7
99-55-8
88-74-4
99-09-2
100-01-6
98-95-3
79-46-9
100-02-7
924-16-3
1116-54-7
55-18-5
62-75-9
86-30-6
621-64-7
10595-95-6
59-89-2
100-75-4
930-55-2
117-84-0
56-38-2
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
95-54-5
298-02-2
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
117-18-0
935-95-5
58-90-2
3689-24-5
79-19-6
106-49-0
95-53-4
5344-82-1
95-80-7
87-61-6
120-82-1
3640A - 4
   Revision 1
November 1992
-------
      Compound Name                                             CAS No.'
      2,4,6-Trichlorophenol                                    88-06-2
      2,4,5-Trichlorophenol                                    95-95-4
      2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)              93-76-5
      2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP)          93-72-1
      Warfarin                                                 81-81-2
      a  Chemical  Abstract Services Registry Number.

      Table 1 presents average percent recovery and percent RSD data for these
analytes, as  well  as the  retention  volumes of each  analyte  on a  single  GPC
system.   Retention volumes vary  from  column  to  column.   Figure  1  provides
additional information on  retention  volumes  for certain  classes of compounds.
The data for the semivolatiles was determined by GC/MS, whereas, the pesticide
data was  determined  by  GC/ECD or  GC/FPD.   Compounds not amenable  to  GC were
determined by HPLC.   Other analytes may also be appropriate  for this  cleanup
technique, however, recovery through the GPC should be >70%.

      1.4   Normally, this method is most efficient for removing high boiling
materials that condense in the injection port area of a gas chromatograph (GC)
or  the  front  of   the  GC   column.    This  residue  will  ultimately  reduce  the
chromatographic separation efficiency or column capacity because of adsorption
of the target analytes on  the  active sites.   Pentachlorophenol  is  especially
susceptible to this problem.  GPC, operating on the principal of size exclusion,
will not usually remove interference  peaks that appear in the chromatogram since
the molecular size  of these compounds is relative similar to the target analytes.
Separation cleanup techniques, based on other molecular characteristics (i.e.,
polarity), must be used to eliminate this type of interference.


2.0   SUMMARY OF METHOD

      2.1   The  column  is packed   with  the  required amount  of  preswelled
absorbent, and  is  flushed  with solvent  for  an  extended period.   The column is
calibrated and then loaded with the sample extract  to be cleaned  up.  Elution is
effected with a suitable solvent(s)  and the product is then concentrated.


3.0   INTERFERENCES

      3.1   A reagent blank should be analyzed for the compound  of interest prior
to  the  use of  this  method.   The  level  of interferences  must be  below  the
estimated quantitation limits  (EQLs) of the analytes  of interest  before this
method is performed on actual  samples.

      3.2   More extensive procedures than  those outlined in this method may be
necessary for reagent purification.
                                   3640A  -  5                         Revision 1
                                                                 November 1992
-------
4.0   APPARATUS

      4.1   Gel-permeation chromatography  system  -  GPC Autoprep Model  1002 A
or B, or equivalent,  Analytical  Biochemical  Laboratories, Inc.   Systems that
perform  very  satisfactorily  have  also  been  assembled  from  the  following
components - an HPLC pump, an auto sampler or a valving system with sample loops,
and a fraction collector.  All systems, whether automated or manual, must meet
the calibration requirements of Section 7.2.2.

            4.1.1 Chromatographic column -  700 mm x 25 mm ID glass column.  Flow
      is upward.   (Optional)   To  simplify switching from the UV detector during
      calibration to the GPC  collection device during extract cleanup, attach a
      double  3-way  valve  (Rheodyne  Type  50  Teflon  Rotary  Valve  #10-262  or
      equivalent) so that the column exit flow can be shunted either to the UV
      flow-through cell or to the GPC collection device.

            4.1.2 Guard column -  (Optional) 5 cm, with appropriate fittings to
      connect  to  the  inlet side  of  the analytical  column  (Supelco  5-8319 or
      equivalent).

            4.1.3 Bio Beads (S-X3) -  200-400 mesh, 70 gm (Bio-Rad Laboratories,
      Richmond, CA,  Catalog 152-2750 or equivalent).  An additional 5 gm of Bio
      Beads is required if the optional guard column is employed.   The quality
      of Bio Beads may vary from lot to lot because of excessive fines in some
      lots.   The UV chromatogram of  the  Calibration solution  should  be very
      similar to that  in  Figure  2,  and the backpressure should be within 6-10
      psi.  Also, the gel swell  ratio  in  methylene  chloride  should be in the
      range of 4.4  -  4.8 mL/gm.   In  addition  to fines  having a detrimental
      effect on  chromatography,  they  can also  pass  through  the column screens
      and damage the valve.

            4.1.4 Ultraviolet detector - Fixed wavelength  (254 nm) with a semi-
      prep flow-through cell.

            4.1.5 Strip chart recorder, recording  integrator or laboratory data
      system.

            4.1.6 Syringe - 10 mL with  Luerlok fitting.

            4.1.7 Syringe  filter assembly, disposable  -  Bio-Rad  "Prep  Disc"
      sample  filter  assembly  #343-0005, 25 mm,  and  5 micron  filter  discs or
      equivalent.   Check each  batch  for  contaminants.    Rinse  each  filter
      assembly (prior to  use) with methylene chloride if necessary.

      4.2   Analytical balance - 0.0001 g.

      4.3   Volumetric flasks, Class A  - 10 mL to 1000 mL

      4.4   Graduated cylinders
                                   3640A -  6                        Revision 1
                                                                 November 1992
-------
5.0  REAGENTS

      5.1   Methylene chloride, CH2C12.   Pesticide quality or  equivalent.

            5.1.1 Some brands  of  methylene chloride may  contain  unacceptably
      high levels  of  acid (HC1).   Check the  pH by shaking equal  portions of
      methylene chloride and water, then check the pH of the water layer.

                  5.1.1.1     If the pH  of the  water layer  is < 5, filter the
            entire  supply  of solvent through  a 2  in.  x  15  in.  glass  column
            containing  activated  basic  alumina.    This  column  should  be
            sufficient for  processing  approximately 20-30  liters  of solvent.
            Alternatively, a different  supply  of  methylene  chloride should be
            found.

      5.2   Cyclohexane,  C6H12.  Pesticide quality or equivalent.

      5.3   n-Butyl chloride, CH3CH2CH2CH2C1.   Pesticide quality or equivalent.

      5.4   GPC  Calibration  Solution.    Prepare  a calibration   solution  in
methylene chloride containing the following analytes (in elution order):

      Compound                            mq/L
      corn oil                            25,000
      bis(2-ethylhexyl) phthalate           1000
      methoxychlor                           200
      perylene                                20
      sulfur                                  80

      NOTE: Sulfur  is  not  very soluble   in methylene chloride,  however,  it is
            soluble in warm corn oil.  Therefore,  one approach is to weigh out
            the corn oil,  warm  it and transfer the  weighed  amount of sulfur into
            the warm corn  oil.  Mix it and then  transfer into a volumetric flask
            with methylene chloride, along with the other calibration compounds.

      Store the calibration solution in an amber glass bottle with a Teflon lined
screw-cap at 4°C,  and protect from light.  (Refrigeration may cause the corn oil
to precipitate.   Before  use,  allow the  calibration solution  to  stand  at room
temperature until  the  corn  oil  dissolves.)  Replace the  calibration standard
solution every 6 months,  or more frequently if necessary.

      5.5   Corn Oil Spike for Gravimetric Screen.  Prepare a solution of corn
oil in methylene chloride (5 mg/100 /uL).


6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic Analytes,
Section 4.1.
                                   3640A  -  7                         Revision 1
                                                                 November 1992
-------
7.0  PROCEDURE

      7.1   It  is  very important  to  have consistent  laboratory  temperatures
during an entire GPC run,  which  could  be  24 hours or more.  If temperatures are
not consistent,  retention times will  shift,  and  the  dump and collect  times
determined by the calibration standard will no longer be appropriate.  The ideal
laboratory temperature to prevent outgassing  of  the methylene chloride is 72°F.

      7.2   GPC Setup and Calibration

            7.2.1 Column Preparation

                  7.2.1.1     Weigh out  70 gm of Bio  Beads  (SX-3).   Transfer
            them to a  quart  bottle  with a  Teflon  lined cap  or  a  500  ml
            separatory funnel  with  a large bore  stopcock, and add approximately
            300 ml  of  methylene chloride.  Swirl  the  container to ensure the
            wetting of all beads.  Allow the  beads to swell for a  minimum of 2
            hours.   Maintain enough solvent to sufficiently cover  the beads at
            all times.  If a guard column is  to be used, repeat the above with
            5 gm of Bio  Beads  in a 125 mL bottle  or a  beaker,  using  25  ml of
            methylene chloride.

                  7.2.1.2     Turn  the  column  upside  down  from  its  normal
            position,  and remove  the inlet  bed  support  plunger  (the  inlet
            plunger  is longer than  the outlet plunger).   Position  and tighten
            the outlet bed support plunger as near the end as possible,  but no
            closer  than 5 cm (measured from the gel packing to  the collar).

                  7.2.1.3     Raise the  end   of  the outlet  tube  to keep  the
            solvent  in the GPC  column, or close the  column outlet  stopcock if
            one is  attached.  Place a small  amount of solvent in the column to
            minimize the formation of air bubbles at the base of poured column
            packing.

                  7.2.1.4     Swirl the bead/solvent slurry to get a homogeneous
            mixture  and,  if the wetting  was  done  in  a  quart  bottle,  quickly
            transfer  it   to  a  500 ml  separatory  funnel  with a  large  bore
            stopcock.  Drain  the excess  methylene chloride  directly  into the
            waste beaker, and  then  start  draining the slurry into the column by
            placing  the  separatory funnel tip against the column  wall.   This
            will help to minimize bubble  formation.  Swirl occasionally to keep
            the slurry homogeneous. Drain enough to fill the  column.  Place the
            tubing  from the column  outlet into a waste  beaker below the column,
            open the stopcock  (if  attached)  and allow the excess  solvent to
            drain.   Raise the  tube  to stop the flow and close the stopcock when
            the  top of the gel  begins to look  dry.   Add additional  methylene
            chloride to just rewet the gel.

                  7.2.1.5     Wipe  any remaining  beads  and  solvent  from the
            inner  walls  of the  top of  the  column with a laboratory  tissue.
            Loosen  the  seal  slightly  on the  other  plunger   assembly  (long
            plunger) and  insert  it  into  the  column.   Make  the  seal just tight
            enough  so that  any beads  on the  glass  surface  will  be  pushed
            forward, but loose enough  so  that the plunger can be pushed forward.

                                   3640A  - 8                         Revision  1
                                                                 November 1992
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      CAUTION:    Do not tighten the seal if beads are between the
                  seal  and  the  glass  surface  because  this  can
                  damage the seal and cause leakage.

      7.2.1.6     Compress the column  as  much  as possible without
applying excessive force.  Loosen  the  seal  and gradually pull out
the plunger.  Rinse and wipe  off  the  plunger.   Slurry any remaining
beads and transfer them into the column.  Repeat Section 7.2.1.5 and
reinsert the plunger.   If the plunger cannot be  inserted and pushed
in  without allowing  beads to  escape   around  the  seal,  continue
compression of the beads without tightening the  seal, and loosen and
remove the  plunger as  described.   Repeat  this  procedure  until the
plunger is  successfully inserted.

      7.2.1.7     Push  the plunger  until  it  meets the  gel,  then
compress the column bed about four centimeters.

      7.2.1.8     Pack the optional  5 cm column with approximately
5 gm  of preswelled  beads  (different  guard  columns  may  require
different  amounts).  Connect the guard  column  to the  inlet of the
analytical   column.

      7.2.1.9     Connect the column  inlet to the solvent reservoir
(reservoir  should be placed higher than the top of the column) and
place  the  column  outlet  tube  in  a  waste  container.    Placing  a
restrictor  in the outlet tube will  force air out of the column more
quickly.    A  restrictor can  be  made  from a  piece of  capillary
stainless  steel  tubing  of 1/16"  OD x  10/1000"  ID x  2".   Pump
methylene chloride through the  column at a rate  of 5 mL/min for one
hour.

      7.2.1.10    After washing the  column  for at  least  one hour,
connect the column outlet tube, without  the restrictor, to the inlet
side of the UV detector.   Connect  the  system outlet to  the outlet
side of  the UV detector.  A  restrictor (same   size as  in  Section
7.2.1.9) in the outlet  tube from the UV  detector will prevent bubble
formation which causes  a noisy UV baseline.  The restrictor will not
effect flow rate.   After  pumping  methylene chloride through the
column for  an  additional  1-2 hours,  adjust the  inlet  bed  support
plunger until  approximately 6-10 psi backpressure is  achieved.  Push
the plunger in  to  increase pressure or slowly pull outward to reduce
pressure.

      7.2.1.11    When the GPC  column is not to  be used for several
days, connect the column outlet line  to  the column inlet to prevent
column drying and/or channeling.  If channeling  occurs, the gel must
be removed  from  the  column,  reswelled, and repoured  as  described
above.   If  drying occurs,  methylene   chloride  should  be  pumped
through the column until the observed  column pressure  is constant
and the column  appears  wet.  Always recalibrate after column drying
has occurred to verify retention  volumes have  not changed.
                      3640A  -  9                         Revision 1
                                                     November 1992
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7.2.2 Calibration of the GPC Column

      7.2.2.1     Using a 10 ml syringe, load  sample  loop #1 with
calibration solution (Section 5.6).  With the ABC automated system,
the 5 ml sample loop requires a minimum of 8 ml of the calibration
solution.  Use a firm, continuous pressure to push the sample onto
the loop.  Switch the valve so that GPC flow is through the UV flow-
through cell.

      7.2.2.2     Inject the calibration solution  and  obtain a UV
trace  showing  a discrete  peak for  each  component.   Adjust  the
detector and/or recorder sensitivity to produce a UV trace similar
to Figure  2 that meets  the following requirements.   Differences
between manufacturers' cell  volumes and detector sensitivities may
require a dilution  of  the calibration solution  to achieve similar
results.  An analytical  flow-through  detector  cell  will  require a
much  less  concentrated  solution  than  the semi-prep  cell,  and
therefore the analytical  cell is not acceptable for use.

      7.2.2.3     Following  are criteria  for  evaluating the  UV
chromatogram for column condition.

            7.2.2.3.1   Peaks  must  be  observed,   and  should  be
      symmetrical,  for all  compounds in the calibration solution.

            7.2.2.3.2   Corn oil and  phthalate  peaks  must exhibit
      >85% resolution.

            7.2.2.3.3   Phthalate  and   methoxychlor   peaks   must
      exhibit >85% resolution.

            7.2.2.3.4   Methoxychlor and  perylene peaks must exhibit
      >85% resolution.

            7.2.2.3.5   Perylene  and  sulfur  peaks must  not  be
      saturated and must exhibit >90% baseline resolution.

      7.2.2.4     Calibration   for   Semivolatiles  -  Using  the
information  from the  UV trace, establish  appropriate  collect and
dump  time periods   to  ensure collection  of all  target  analytes.
Initiate  column  eluate collection  just  before elution  of bis(2-
ethylhexyl) phthalate and after the elution of the corn oil.   Stop
eluate collection shortly after the elution of perylene.  Collection
should  be  stopped  before sulfur elutes.    Use  a  "wash" time  of 10
minutes after the elution of sulfur.  Each laboratory is required to
establish  its  specific time sequences.  See Figure 2  for general
guidance on retention time.   Figure  1  illustrates retention volumes
for different classes of compounds.

      7.2.2.5     Calibration for Organochlorine Pesticides/PCBs  -
Determine  the  elution  times  for  the  phthalate,  methoxychlor,
perylene, and sulfur.  Choose a dump time which  removes >85% of the
phthalate,  but collects  >95% of the methoxychlor. Stop collection
after the elution of perylene, but before  sulfur elutes.

                       3640A  - 10                        Revision  1
                                                     November 1992
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            7.2.2.6     Verify the flow rate by collecting column eluate
      for 10 minutes in  a graduated cylinder and measure the volume, which
      should be 45-55 ml (4.5-5.5 mL/min).  If the flow rate is outside of
      this  range,  corrective  action  must be taken,  as  described above.
      Once the flow rate is within the range of  4.5-5.5 mL/min, record the
      column pressure (should be 6-10 psi)  and  room temperature.  Changes
      in  pressure,  solvent  flow  rate,  and  temperature  conditions  can
      affect analyte retention times, and must  be  monitored.  If the flow
      rate and/or column pressure do not fall within the above ranges, a
      new column should be prepared.   A  UV trace  that does  not meet the
      criteria in Section 7.2.2.3 would  also indicate that  a new column
      should be prepared.  It may  be  necessary  to  obtain a new lot of Bio
      Beads if the column fails all  the criteria.

            7.2.2.7     Reinject   the    calibration    solution   after
      appropriate collect and dump cycles have been set, and the solvent
      flow and column pressure have been established.

                  7.2.2.7.1   Measure and record the volume of collected
            GPC eluate in a  graduated cylinder.  The volume of GPC eluate
            collected for each  sample extract  processed may be  used to
            indicate problems with the system during sample processing.

                  7.2.2.7.2   The retention  times for bis(2-ethylhexyl)
            phthalate and perylene must  not vary more  than  +5% between
            calibrations.   If  the   retention  time shift  is >5%,  take
            corrective action. Excessive retention time  shifts are caused
            by:

                        7.2.2.7.2.1  Poor 1 aboratory temperature control or
                  system leaks.

                        7.2.2.7.2.2  An unstabilized column that requires
                  pumping methylene  chloride through it  for several  more
                  hours or overnight.

                        7.2.2.7.2.3  Excessive  laboratory  temperatures,
                  causing outgassing  of the methylene chloride.

            7.2.2.8     Analyze a GPC blank by loading 5 ml of methylene
      chloride into  the GPC.   Concentrate the methylene chloride  that
      passes through the system during the  collect cycle using a Kuderna-
      Danish  (KD)   evaporator.    Analyze  the   concentrate  by  whatever
      detectors will  be  used for the analysis of future samples.  Exchange
      the  solvent  if necessary.   If the  blank  exceeds the  estimated
      quantitation  limit of  the  analytes,  pump additional  methylene
      chloride through  the  system for 1-2  hours.  Analyze  another GPC
      blank  to ensure  the  system is  sufficiently  clean.   Repeat  the
      methylene chloride pumping if necessary.

7.3   Extract Preparation

      7.3.1 Adjust the  extract  volume to 10.0  ml.   The  solvent extract
must  be  primarily  methylene  chloride.   All  other  solvents,   e.g.  1:1

                            3640A -  11                        Revision 1
                                                           November 1992
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methylene chloride/acetone, must  be  concentrated  to 1 mL  (or  as  low as
possible if a  precipitate  forms)  and diluted to  10.0  ml  with  methylene
chloride.  Thoroughly mix the sample before proceeding.

      7.3.2 Filter the extract through a 5 micron filter disc by attaching
a syringe filter assembly containing the filter disc to a 10 ml syringe.
Draw the sample  extract  through  the filter assembly and  into  the 10 ml
syringe.  Disconnect  the filter assembly  before transferring  the sample
extract  into a  small  glass container,  e.g. a 15 ml  culture tube with a
Teflon lined screw cap.  Alternatively, draw the extract into the syringe
without  the filter  assembly.   Attach the  filter  assembly  and  force the
extract  through the filter  and into  the glass  container.   The  latter is
the preferred  technique  for viscous extracts or extracts  with  a lot of
solids.  Particulate  larger than  5  microns may  scratch the valve, which
may result in  a system leak and cross-contamination of  sample extracts in
the sample loops.  Repair of the damaged valve is  quite expensive.

      NOTE: Viscosity of a  sample  extract  should not exceed the viscosity
            of  1:1  water/glycerol.   Dilute  samples  that exceed  this
            viscosity.

7.4   Screening the Extract

      7.4.1 Screen the extract to determine the concentration of dissolved
residue  by  evaporating  a  100  /xL  aliquot to  dryness  and  weighing the
residue.  The  concentration of dissolved residue loaded on the GPC column
cannot exceed  0.500 g.  Concentrations exceeding 0.500  g will very likely
result  in  incomplete extract  cleanup  and   contamination of  the  GPC
switching valve (which results in cross-contamination of sample extracts).

            7.4.1.1     Transfer  100 p.1  of  the  filtered  extract  from
      Section 7.3.2 to a tared aluminum weighing dish.

            7.4.1.2     A suggested  evaporation technique is to  use a heat
      lamp.   Set up a 250  watt  heat lamp in a hood so that it  is 8 +
      0.5 cm from a surface covered with a clean sheet of aluminum foil.
      Surface temperature should be 80-100°C (check temperature by placing
      a  thermometer on the foil  and under the lamp).   Place the weighing
      dish under the  lamp  using tongs.  Allow  it  to stay under the lamp
      for 1 min.  Transfer the weighing dish to an analytical  balance or
      a  micro  balance and  weigh  to  the nearest 0.1  mg.   If the residue
      weight is  less  than  10 mg/100 p.1,  then  further  weighings are not
      necessary.  If the  residue weight is greater  than  10 mg/100 /uL, then
      determine  if constant weight has  been  achieved  by placing the
      weighing dish  and  residue  back under the heat lamp  for  2 or more
      additional  0.5  min.   intervals.    Reweigh  after  each  interval.
      Constant weight  is achieved when three weights agree within ±10%.

            7.4.1.3     Repeat the above residue analysis on a blank and
      a  spike.   Add 100 /xL of the  same methylene chloride used for the
      sample  extraction,  to a  weighing  dish  and determine  residue as
      above.   Add  100 juL  of a  corn oil  spike  (5 mg/100  juL)  to another
      weighing dish and repeat the residue determination.


                            3640A -  12                        Revision  1
                                                           November  1992
-------
      7.4.2 A residue weight of 10 mg/100 fj,l of extract represents 500 mg
in 5  ml  of extract.  Any  sample  extracts  that exceed the  10  mg/100 p.1
residue weight must be diluted so that the 5 ml loaded on the GPC column
does  not exceed 0.500 g.   When  making  the  dilution,  keep in mind that a
minimum  volume of  8 ml  is  required  when  loading  the  ABC  GPC  unit.
Following is a calculation that may be  used to determine what dilution is
necessary if the residue exceeds  10 mg.

      Y ml taken  =     10 ml final   x    10 mg maximum
      for dilution        volume          X mg of residue

Example:

      Y ml taken  =     10 ml final   x    10 mg maximum
      for dilution        volume          15 mg of residue

      Y ml taken for dilution  =  6.7 ml

      Therefore, taking 6.7 ml of sample extract from Section 7.3.2, and
diluting to 10 ml with methylene chloride, will result in 5 ml of diluted
extract loaded on the GPC column that contains 0.500 g of residue.

      NOTE: This dilution  factor must be included in the final calculation
            of analyte concentrations.  In the above example, the dilution
            factor is 1.5.

7.5   GPC Cleanup

      7.5.1 Calibrate the  GPC  at  least  once  per  week following  the
procedure outlined  in Sections 7.2.2  through  7.2.2.6.   Ensure  that UV
trace requirements,  flow rate and column pressure criteria are acceptable.
Also, the  retention  time  shift must be  <5% when compared  to  retention
times in the last calibration UV trace.

            7.5.1.1     If these  criteria are not met,  try  cleaning the
      column by loading one or  more  5  ml portions  of butyl  chloride and
      running  it  through  the column.    Butyl  chloride  removes  the
      discoloration and  particulate that may have precipitated out of the
      methylene chloride  extracts.  If  a  guard  column  is  being  used,
      replace it with a new one.  This may correct the problem.  If column
      maintenance does not restore acceptable performance, the column must
      be repacked with new Bio Beads and calibrated.

      7.5.2 Draw a minimum of 8 ml of extract (diluted, if necessary, and
filtered) into a 10 ml syringe.

      7.5.3 Attach the syringe  to the  turn lock on  the  injection  port.
Use firm,  continuous  pressure to  push  the  sample onto  the  5-mL sample
loop.  If the sample is difficult  to  load, some part of the system may be
blocked.  Take  appropriate  corrective  action.   If the back pressure is
normal (6-10 psi),  the blockage  is probably in the valve.  Blockage may be
flushed  out  of the valve  by  reversing the  inlet  and outlet  tubes  and
pumping solvent through the  tubes.   (This  should be done  before sample
loading.)

                            3640A - 13                         Revision 1
                                                           November 1992
-------
            NOTE:  Approximately 2 ml of the extract remains in the lines between
                  the injection port and  the  sample loop;  excess sample  also
                  passes through the sample loop  to  waste.

            7.5.4  After loading a loop, and before removing the syringe from the
      injection port,  index the GPC to the next loop.  This will prevent loss of
      sample caused by unequal  pressure in the loops.

            7.5.5  After loading each sample loop, wash the loading  port  with
      methylene chloride in a PTFE wash bottle to minimize cross-contamination.
      Inject approximately  10  ml of  methylene chloride to  rinse the  common
      tubes.

            7.5.6  After loading all  the sample loops,  index the  GPC  to  the 00
      position, switch  to  the  "RUN"  mode and  start  the automated  sequence.
      Process each sample using the  collect and dump cycle times established in
      Section 7.2.2.

            7.5.7  Collect each  sample in a 250  ml  Erlenmeyer flask, covered with
      aluminum foil to reduce solvent evaporation, or directly into  a Kuderna-
      Danish evaporator.  Monitor sample volumes  collected.   Changes  in sample
      volumes collected may indicate one or more of  the following problems:

                  7.5.7.1     Change in solvent flow rate, caused by  channeling
            in the column or changes in column pressure.

                  7.5.7.2     Increase in column operating  pressure  due to the
            absorption of particles  or gel fines onto either the guard column or
            the analytical  column gel,  if a guard column is  not used.

                  7.5.7.3     Leaks  in the system or  significant variances in
            room temperature.

      7.6   Concentrate the extract by the standard K-D technique (see  any of the
extraction methods, Section 4.2 of this chapter).  See the determinative methods
(Chapter Four, Section 4.3)  for the  final volume.

      7.7   It  should  be remembered that only half of the sample extract is
processed by the GPC (5 ml  of the  10 ml extract is loaded onto the GPC column),
and thus,  a dilution factor of 2 (or  2  multiplied  by any dilution  factor in
Section 7.4.2) must be used  for quantitation of the sample in the determinative
method.


8.0   QUALITY CONTROL

      8.1   Refer  to Chapter One  and Method 3600 for specific quality control
procedures.

      8.2   The analyst should  demonstrate that the  compound(s) of interest are
being quantitatively recovered before applying this  method  to actual  samples.
                                  3640A - 14                        Revision 1
                                                                 November 1992
-------
      8.3   For  sample  extracts that  are cleaned  up  using this  method,  the
associated quality control samples must also be processed through this cleanup
method.
9.0   METHOD PERFORMANCE

      9.1   Refer to Table 1 for single laboratory performance data.


10.0  REFERENCES

1.    Wise, R.H.; Bishop, D.F.; Williams, R.T.; Austern, B.M.  "Gel Permeation
      Chromatography in  the  GC/MS  Analysis of Organics  in  Sludges";  U.S. EPA
      Municipal Environmental Research Laboratory:  Cincinnati, Ohio 45268.

2.    Czuczwa, J.; Alford-Stevens, A.  "Optimized  Gel Permeation Chromatographic
      Cleanup for Soil,  Sediment, Waste and Waste Oil Sample  Extracts for GC/MS
      Determination of Semivolatile Organic Pollutants, JAOAC, submitted April
      1989.

3.    Marsden, P.O.; Taylor, V.; Kennedy, M.R.   "Evaluation of Method 3640 Gel
      Permeation  Cleanup";   Contract  No.   68-03-3375,   U.S.   Environmental
      Protection Agency, Cincinnati, Ohio, pp. 100, 1987.
                                  3640A - 15                        Revision 1
                                                                 November 1992
-------
                  TABLE 1
GPC RECOVERY AND RETENTION VOLUMES FOR RCRA
          APPENDIX VIII  ANALYTES
Compound
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylaminofluorene
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Benomyl
Benzenethiol
Benzidine
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzo(k)fluoranthene
Benzoic acid
Benzotri chloride
Benzyl alcohol
Benzyl chloride
alpha-BHC
beta-BHC
gamma- BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2 -sec-butyl -4, 6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4 - Chi oro- 3 -methyl phenol
4-Chloroanil ine
Chlorobenzilate
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2-Chloronaphthalene
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
3-Cresol
% Rec1
97
72
94
97
99
96
93
89
131
92
95
100
93
93
90
91
66
93
95
99
84
94
93
102
93
104
103
99
131
97
93
87
88
92
89
76
83
89
90
86
87
98
80
102
91
70
% RSD2
2
10
7
2
9
7
4
2
8
11
5
3
5
3
6
4
7
7
17
4
13
9
4
7
1
3
18
5
8
2
2
1
3
5
1
2
2
1
1
3
2
2
5
1
1
3
Ret. Vol.3 (ml
196-235
196-235
176-215
156-195
196-215
176-215
196-235
196-235
146-195
196-235
176-215
196-235
196-235
196-235
196-235
196-235
176-195
176-215
176-215
176-215
196-215
196-215
196-215
216-255
176-215
136-175
176-195
196-255
146-195
196-235
196-215
196-255
196-235
176-235
156-195
156-215
156-195
196-235
196-215
196-215
196-215
176-215
176-215
196-235
196-215
196-215
                 3640A - 16
   Revision 1
November 1992
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TABLE 1 (continued)
Compound
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial late
Dibenzo(a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzothiophene
1 , 2-Dibromo-3-chloropropane
1,2-Dibromoethane
trans -l,4-Dichloro-2-butene
cis-l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
2,4-Dichlorotoluene
l,3-Dichloro-2-propanol
Dieldrin
Di ethyl phthalate
Dimethoate
3,3'-Dimethoxybenzidinea
Dimethyl phthalate
p- Dimethyl ami noazobenzene
7, 12-Dimethyl -benz(a)anthracene
2,4-Dimethylphenol
3,3'-Dimethylbenzidine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1 , 2-Di phenyl hydrazine
Disulfoton
Endosulfan sulfate
Endosulfan I
Endosulfan II
Endrin
% Rec1
88
114
94
94
96
104
97
94
99
117
92
94
94
83
121
107
106
81
81
81
98
86
80
87
70
73
100
103
79
15
100
96
77
93
93
100
99
118
93
101
95
67
92
81
94
99
92
95
%RSD2
2
10
4
2
6
3
6
10
8
9
5
1
3
2
8
6
6
1
1
1
3
3
NA
2
9
13
5
3
15
11
1
1
1
2
2
1
2
7
4
2
6
12
1
15
2
8
6
6
Ret. Vol.3 (ml
196-215
146-185
196-235
196-235
176-215
136-175
156-175
216-235
216-235
176-195
196-235
176-235
196-235
176-215
196-215
176-195
176-215
196-235
196-235
196-235
176-215
196-215
76-215
96-215
196-235
176-215
196-215
136-195
146-185
156-195
156-195
176-215
176-215
176-215
156-215
156-195
156-195
176-195
156-195
156-175
176-235
196-215
176-215
146-165
176-195
176-215
196-215
196-215
    3640A - 17
   Revision 1
November 1992
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TABLE 1 (continued)
Compound
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans-Isosafrole
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methyl chol anthrene
2-Methyl naphthal ene
Methyl parathion
4,4'-Methylene-bis(2-chloroaniline)
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di-n-butylamine
N-Nitrosodiethanolamine
N-Nitrosodi ethyl ami ne
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorpholine
N-Nitrosopiperidine
% Rec1
97
94
62
126
101
99
95
94
85
91
108
86
89
85
91
79
98
68
90
88
102
111
93
94
74
67
84
96
95
73
94
96
77
96
96
103
86
95
77
89
104
94
86
99
85
83
86
84
%RSD2
1
4
7
7
1
NA
1
1
2
11
2
2
3
1
2
13
5
7
4
16
NA
9
12
6
12
6
13
1
7
7
8
6
2
8
2
8
2
3
3
4
3
2
13
2
4
7
4
4
Ret. Vol.3 (ml
176-215
176-215
176-235
176-195
120-145
126-165
176-235
196-235
195-215
156-195
196-235
176-215
176-215
196-235
196-235
216-255
196-235
156-195
176-215
156-195
196-235
156-195
126-165
156-195
176-195
196-215
146-185
176-215
196-215
176-215
196-235
196-235
176-195
176-215
176-215
176-215
176-195
176-195
196-215
156-175
146-185
156-175
156-195
156-195
156-175
156-175
156-195
156-195
     3640A - 18
   Revision 1
November 1992
-------
                                 TABLE 1  (continued)
Compound
N-Nitrosopyrolidine
Di-n-octyl phthalate
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
1 , 2 - Phenyl ened i ami ne
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
Streptozotocin3
1,2,4 , 5-Tetrachl orobenzene
2,3,5,6-Tetrachloro-nitrobenzene
2,3,4,6-Tetrachlorophenol
2,3,5,6-Tetrachlorophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
Thiourea, l-(o-chlorophenyl)
Toluene-2,4-diamine
1, 2, 3-Trichl orobenzene
1, 2, 4-Trichl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid
Warfarin
% Rec1
92
83
109
95
74
91
102
100
94
83
91
74
99
105
98
70
93
6
96
85
95
96
89
74
92
87
75
69
87
89
77
95
71
67
94
%RSD2
1
4
14
2
1
8
1
3
2
2
1
NA
14
15
2
6
1
48
2
9
1
7
14
3
3
8
11
7
1
1
1
1
23
NA
2
Ret. Vol.3 (ml
156-175
120-156
146-170
196-235
196-235
156-195
196-215
156-195
196-235
156-195
196-215
116-135
156-215
156-195
215-235
196-215
176-215
225-245
196-235
176-215
196-215
196-215
116-135
146-185
176-235
176-235
166-185
176-215
196-235
196-235
216-235
216-235
156-235
216-215
166-185
NA = Not applicable, recovery presented as the average of two determinations.

a  Not an appropriate analyte for this method.

1  The percent recovery is based on an average of three recovery values.

2  The % relative standard deviation is determined from three recovery values.

3  These Retention Volumes are  for  guidance  only  as  they  will  differ from column to
   column and from system to system.
                                     3640A - 19
   Revision 1
November 1992
-------
                            Figure  1
            GPC RETENTION VOLUME OF CLASSES OF ANALYTES
            PHTHALAT8 —-
   OROANOPHOSPHATE
       PESTICIDES
       CORN OIL —
I	 i      i
                                     w///////////////,
                                  PAH't

                                 3 CHLOR08ENZENES

                       NJTROSAMINES, NITROAROMATICS

                                  AROMATIC AMINES

                           NITROPHENOLS

                               CHLOROPHENOL3

                                  ORQANOCHLORINE
                                  PESTICIOES/PCB't

                               HERBICIDES (6 ISO)
                                               PCP
                                                           C-Collect
    10
20
30        40
TIME (minutes)
50
60
70
                            3640A  - 20
                                            Revision 1
                                         November 1992
-------
                                   Figure 2
                  UV CHROMATOGRAM OF  THE CALIBRATION SOLUTION
      Injection
      5 nLS
      on column
                                             — 0 minutes
      Corn oil
      25 mg/t.iL
      Bis(2-ethylhexyl) .phthaiate
      1.0 mg/mL
      Methoxychlor
      0.2 ng/mL
      Perylene
      0.02 mg/mL  ._._
      Sulfur
      0.08 mg/nL  -
                                                                   15  minuces
                                                                   30 minutes
                                                45 minutes
700 mm X25 am col-
70 £ Bio-Beads SX
Bed length = 490
CH2C12  at 5.0 iiL
254 nn

rrirrJ-
                                   3640A - 21
                                             ."._  60 minutes
                                                    Revision  1
                                                November  1992
-------
                                             METHOD  3640A
                                      GEL-PERMEATION  CLEANUP
                               7.1 Ensure ambient temp, consistent
                                      throughout GPC run.
                                  7.2 GPC Setup and Calibration
                                              J
      7.2.1 Column Preparation
  7.2.1.1 Place Bio Beads and MeCI
      in a container. Swirl and
        allow beads to swell.
    7.2.1 2 Remove column inlet bed
  support plunger.  Position and tighten
outlet bed support plunger to column end.
   7.2.1.3 Ensure GPC column outlet
 contains solvent.  Place small amount
     solvent in column to minimize
          bubble formation.
   7 2.1.4 Transfer bead mixture into
   sep. funnel. Drain excess solvent;
    drain beads into column. Keep
        beads wet throughout.
    7.2.1.5 Loosen seal on opposite
  plunger assembly, insert into column.
 7.2.1.6 Compress column. Slurry
remaining beads and repeat Section
 7.2.1.5 and column compression.
   7.2.1.7 Compress column bed
     approximately four cm.
  7.2.1.8 Pack option 5 cm. guard
     column w/ roughly 5 gm.
 	preswelled beads.
   7.2.1.9 Connect column inlet to
  solvent reservoir. Pump MeCI at
         5 ml/mm, for 1 hr
                                                                                       i
  7.2.1.10 Connect column outlet to
  UV-Vis detector. Place restrictor
  at detector outlet. Run MeCI for
   additional 1 -2 hrs.  Compress
  column bed to provide 6-10 psi
          backpressure.
                                                                         7.2.1.11 Connect outlet line to column
                                                                         inlet when column not in use.  Repack
                                                                         column when channeling is observed.
                                                                         Assure consistent backpressure when
                                                                           beads are rewetted after drying.
                                              3640A  -  22
                       Revision  1
                  November  1992
-------
                                           METHOD 3640A
                                             continued
   7.2.2 Calibration of the GPC column

     7,2.2.1 Load sample loop with
          calibration solution.

  7.2.2.2 Inject calibration soln.; adjust
     recorder or detector sensitivity
  to produce similar UV trace as Fig. 2.

     7.2.2.3 Evaluation criteria for
         UV chromatogram.

  7.2.2.4 Calibration for Semivolatiles
    Use information from UV trace to
     obtain collect and dump times.
Initiate collection before bis(2-ethylhexyl)
 phthalate, stop after perylene. Stop run
          before sulfur elutes.

 7.2.2.5 Calibration for Organochlorine
          Pestkades/PCBs
  Choose dump time which removes
   > 85% phthalate, but collects at
   times > 95% methoxychlor. Stop
   collection between perylene and
           sulfur etution.

   7.2.2.6 Verify column flow rate and
        backpressure. Correct
     inconsistencies when criteria
            are not met
7.2.2.7 Reinject calibration soln. when
  collect and dump cycles are set,
    and column criteria are met

                                                                      7.2.2.7.1 Measure and record
                                                                         volume of GPC eluate.

 7.2.2.7.2 Correct for retention time
       shifts of >W-5% for
    bfe(2-ethylhexyl) phthalate
          and perylene.

7.2.2.8 Inject and analyze GPC blank
   for column cleanliness. Pump
   through MeCI as column wash.
                                            3640A  - 23
                        Revision  1
                    November  1992
-------
                                       METHOD  3640A
                                         continued
         7.3 Extract Preparation
   7.3.1 Adjust extract volume to 10 ml.
    Primary solvent should be MeCI.
                1
 7.3.2 Filter extract through 5 micron filter
    disc/syringe assembly into small
           glass container.
       7.4 Screening the Extract
                ±
    7.4.1 Screen extract by determining
       residue wt of 100 ul aliquot
                I
    7.4.1.1 Transfer 100 ul of filtered
   extract from Section 7.3.2 to tared
       alumi; urn weighing dish.
                i
 7.4.1.2 Evaporate extract solvent under
 heating lamp.  Weigh residue to nearest
              0.1 mg.
                I
7.4.1.3 Repeat residue analysis of Section
    7.4.1.2 w/blank and spike sample.

 7.4.2 Use dilution example to determine
    necessary dilution when residue
            wts. > lOmg.
           7.5 GPC Cleanup
  7.5.1 Calibrate GPC weekly. Assure
  column criteria, UV trace, retention
      time shift criteria are met
  7.5.1.1 Clean column w/butyl chloride
      loadings, or replacement of
 	guard column.	
                                                                              1
                                                                 7.5.2 Draw 8 ml. extract into syringe.

 7.5.3 Load sample into injection loop.
               i
   7.5.4 Index GPC to next loop to
        prevent sample loss.

  7.5.5 Wash sample port w/MeCI
    between sample loadings.
 7.5.6 At end of loadings, index GPC to
   00, switch to "RUN" mode, start
        automated sequence.

7.5.7 Collect sample into aluminum foH
   covered Ertenmeyer flask or into
    Kudema-Danwri evaporator.

                                                                   7.6 Concentrate extract by std.
                                                                     Kudema-Oanish technique.
                                                                              i
                                                                7.7 Note dilution factor of GPC method
                                                                     into final determinations.
                                          3640A -  24
                           Revision 1
                      November 1992
-------
                                  METHOD 3665

                      SULFURIC ACID/PERMANGANATE CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   This method is suitable for the rigorous cleanup of sample extracts
prior to  analysis  for polychlorinated biphenyls.   This method  should  be used
whenever  elevated  baselines  or overly  complex  chromatograms  prevent accurate
quantitation of PCBs.  This method cannot  be used to cleanup extracts for other
target  analytes,   as  it  will  destroy  most  organic  chemicals   including  the
pesticides  Aldrin, Dieldrin,  Endrin,  Endosulfan  (I  and  II),  and  Endosulfan
sulfate.
2.0   SUMMARY OF METHOD

      2.1   An  extract  is  solvent  exchanged  to  hexane,  then  the  hexane  is
sequentially  treated  with (1) concentrated  sulfuric  acid and  (2)  5% aqueous
potassium permanganate.   Appropriate caution  must be taken with these corrosive
reagents.

      2.2   Blanks and replicate analysis samples must be  subjected to the same
cleanup as the samples associated with them.

      2.3   It is important that all the  extracts be exchanged to hexane before
initiating the following treatments.


3.0   INTERFERENCES

      3.1   This technique will  not destroy  chlorinated benzenes,  chlorinated
naphthalenes  (Halowaxes), and a number of chlorinated pesticides.


4.0   APPARATUS

      4.1   Syringe or Class A volumetric pipet, glass;  1.0,  2.0 and 5.0 mL.

      4.2   Vials - 1, 2 and 10 mL,  glass with  Teflon lined screw caps or crimp
tops.

      4.3   Kuderna-Danish (K-D) apparatus.

            4.3.1 Concentrator tube - 10 mL graduated (Kontes K-570050-1025 or
      equivalent).  A ground glass  stopper  is  used to  prevent  evaporation of
      extracts.

            4.3.2 Evaporation    flask  -  500  mL  (Kontes    K-570001-500    or
      equivalent).    Attach  to  concentrator  tube  with  springs,  clamps,  or
      equivalent.
                                   3665 - 1                         Revision 0
                                                                 November 1992
-------
            4.3.3 Snyder column  -  Three ball  macro (Kontes  K-503000-0121  or
      equivalent).

            4.3.4 Snyder column  -  Two ball  micro  (Kontes  K-569001-0219  or
      equivalent).

            4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.4   Vortex mixer.
5.0   REAGENTS

      5.1   Reagent grade chemicals  shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents  of the American Chemical Society, where
such specifications are available. Other grades may be used,  provided it is first
ascertained that the reagent  is  of  sufficiently  high  purity to permit its use
without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.   All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sulfuric acid/Water, H2S04/H20, (1:1, v/v).

      5.4   Hexane, C6HU  - Pesticide grade or equivalent.

      5.5   Potassium permanganate,  KMn04,  5  percent aqueous solution (w/v).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the  introductory material  to this  chapter,  Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Sulfuric acid cleanup

            7.1.1 Using a syringe or a volumetric pipet, transfer  1.0 or 2.0 mL
      of the hexane extract to a 10 mL vial and, in a fume hood, carefully add
      5 mL of the 1:1 sulfuric acid/water solution.

            7.1.2 The volume of hexane extract used  depends  on the requirements
      of  the GC autosampler  used  by  the  laboratory.    If  the autosampler
      functions reliably with 1 mL of sample volume, 1.0 mL  of extract should be
      used.  If the autosampler requires more than 1 mL of sample volume, 2.0 mL
      of extract should be used.

            CAUTION:    Make  sure   that  there  is  no  exothermic  reaction nor
                        evolution of gas prior to proceeding.
                                   3665 - 2                         Revision 0
                                                                 November 1992
-------
      7.1.3 Cap the vial  tightly  and vortex for one minute.  A vortex must
be visible in the vial.

      CAUTION:    Stop the vortexing  immediately  if the vial leaks, AVOID
                  SKIN CONTACT, SULFURIC ACID BURNS.

      7.1.4 Allow the phases to separate for at least 1 minute.  Examine
the top (hexane)  layer;  it  should not be highly colored  nor  should it have
a visible emulsion or cloudiness.

      7.1.5 If  a  clean   phase   separation   is   achieved,  proceed  to
Section 7.1.8.

      7.1.6 If the hexane  layer  is colored  or the emulsion persists for
several minutes,  remove the sulfuric  acid layer from the vial and dispose
of it properly.  Add another 5 ml of the clean 1:1 sulfuric acid/water.

      NOTE: Do not remove any hexane at this stage of the procedure.

      7.1.7 Vortex the  sample for one minute and  allow  the  phases  to
separate.

      7.1.8 Transfer the hexane layer to a clean 10 ml vial.

      7.1.9 Add an additional 1 ml of hexane to the sulfuric acid layer,
cap and  shake.   This second  extraction is done  to  ensure quantitative
transfer of the PCBs and Toxaphene.

      7.1.10      Remove the  second  hexane layer and combine  with the
hexane from Section 7.1.8.

7.2   Permanganate cleanup

      7.2.1 Add  5  ml of  the 5  percent aqueous  potassium permanganate
solution to the combined hexane fractions from 7.1.10.

      CAUTION:    Make  sure  that there is no  exothermic  reaction  nor
                  evolution of gas prior to proceeding.

      7.2.2 Cap the vial tightly and vortex for 1 minute.  A vortex must
be visible in the vial.

      CAUTION:    Stop the  vortexing immediately if the  vial  leaks.  AVOID
                  SKIN CONTACT, POTASSIUM PERMANGANATE BURNS.

      7.2.3 Allow the phases to separate for at least 1 minute.  Examine
the top (hexane)  layer,  it should not be highly colored  nor  should it have
a visible emulsion or cloudiness.

      7.2.4 If  a  clean   phase   separation   is   achieved,  proceed  to
Section 7.2.7.

      7.2.5 If the hexane  layer  is colored  or the emulsion persists for
several minutes,  remove the permanganate solution from  the vial  via  a

                             3665 -  3                         Revision  0
                                                           November 1992
-------
glass pipette and dispose of it properly.  Add another 5 ml of the clean
aqueous permanganate solution.

      NOTE: Do not remove any hexane at this stage of the procedure.

      7.2.6 Vortex the sample and allow the phases to separate.

      7.2.7 Transfer the hexane layer to a clean 10 ml vial.

      7.2.8 Add an additional  1 ml  of  hexane  to the permanganate layer,
cap the vial  securely  and shake.  This second extraction  is done to ensure
quantitative transfer of the PCBs and Toxaphene.

      7.2.9 Remove the  second  hexane layer and combine  with  the hexane
from Section 7.2.7.

7.3   Final preparation

      7.3.1 Reduce  the volume  of  the  combined  hexane  layers  to  the
original  volume   (1   or   2   ml)   using  the   Kuderna-Danish  Technique
(Section 7.3.1.1).

            7.3.1.1     Add one or  two  clean  boiling  chips  to the flask
      and attach a three ball  Snyder column.   Prewet the Snyder column by
      adding about 1 ml of  hexane to the top of the column.   Place the K-D
      apparatus on a  hot water  bath (15-20°C  above the  boiling point of
      the solvent) so  that  the concentrator tube is partially  immersed in
      the hot water and the entire lower rounded surface of the flask is
      bathed  with hot vapor.   Adjust the  vertical  position  of  the
      apparatus and the water  temperature,  as required,  to complete the
      concentration in 10-20 minutes.   At the  proper rate of distillation
      the balls of the column will actively chatter, but  the  chambers will
      not  flood.   When  the  apparent volume  of liquid  reaches  1-2 ml,
      remove the K-D apparatus from the water bath and allow  it to drain
      and cool for at  least 10 minutes.

            7.3.1.2     Remove the Snyder column and rinse the flask and
      its lower joints into the concentrator tube with 1-2 ml of hexane.
      The extract  may  be further concentrated by  using  either the micro
      Snyder  column  technique  (Section  7.3.2)   or  nitrogen  blowdown
      technique (Section 7.3.3).

      7.3.2 Micro  Snyder Column Technique

            7.3.2.1     Add another one or two clean boiling chips to the
      concentrator tube and attach a two ball micro Snyder column.  Prewet
      the  column  by  adding  about  0.5  ml  of  hexane  to  the  top  of the
      column.   Place  the  K-D apparatus in a  hot  water  bath so that the
      concentrator tube  is  partially  immersed in  the  hot water.   Adjust
      the vertical position of the apparatus and the water temperature, as
      required, to complete  the concentration in  5-10  minutes.   At the
      proper rate  of  distillation the  balls of the column will actively
      chatter, but the chambers will not flood.  When  the apparent volume
      of liquid reaches 0.5  ml,  remove the K-D apparatus from the water

                             3665 - 4                         Revision 0
                                                            November 1992
-------
            bath and allow it to drain and cool for at least 10 minutes.  Remove
            the Snyder  column and rinse the  flask and its  lower joints with
            about 0.2 ml of hexane and add to the concentrator tube.  Adjust the
            final  volume to 1.0-2.0 ml, as required, with hexane.

            7.3.3 Nitrogen Slowdown Technique

                  7.3.3.1     Place the concentrator tube in a warm water bath
            (approximately  35°C)  and  evaporate  the  solvent   volume  to  the
            required  level  using a  gentle  stream  of  clean,   dry  nitrogen
            (filtered through a  column of activated carbon).

                  CAUTION:    Do not use plasticized tubing between the carbon
                              trap and the sample.

                  7.3.3.2     The internal  wall  of the  tube must be rinsed down
            several times  with  the appropriate solvent during  the operation.
            During evaporation,  the solvent level in the tube must  be positioned
            to prevent water from condensing  into  the sample  (i.e., the solvent
            level  should be below  the level  of  the water  bath).  Under normal
            operating conditions,  the extract should  not  be allowed to become
            dry.

            7.3.4 Remove  any  remaining  organochlorine   pesticides  from  the
      extracts using Florisil  Column Cleanup (Method 3620)  or Silica Gel Cleanup
      (Method 3630).

            7.3.5 The extracts  obtained may  now  be  analyzed  for  the  target
      analytes using the appropriate organic  technique(s) (see  Section  4.3 of
      this  Chapter).    If  analysis of  the  extract  will  not  be  performed
      immediately,  stopper the  concentrator  tube  and  store in  a refrigerator.
      If the extract will be stored longer than 2 days,  it  should be transferred
      to  a  vial  with  a  Teflon lined  screw cap  or  crimp  top,  and  labeled
      appropriately.
8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.


9.0   METHOD PERFORMANCE

      9.1   No performance data are currently available.


10.0  REFERENCES

      None required.
                                   3665 - 5                         Revision 0
                                                                 November 1992
-------
                               METHOD 3665
                SULFURIC ACID/PERMANGANATE  CLEANUP
    Stir!


1 1 1 Ca r ef j * 1 y
:: 3 •*! c * ". e hexane
w i t, n i. j.
H.SO,/K,0
soi-Lion


7 1 2
Transfer the
appropriate
vo 1 ume t o
vial


Cap vortex
and allow
phas e
s epa ration


    7 1 8
  Trans fer
hexane layer
to clean via 1
  7  1 9 Add
  hex ane to
H,SO, layer
ca p  and s ha l
-------
                                METHOD 8000

                             GAS CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION
     1.1  Gas chromatography is a quantitative  analytical technique useful for
organic compounds  capable of  being  volatilized  without being  decomposed or
chemically rearranged.   Gas chromatography  (GC),  also known as  vapor phase
chromatography  (VPC),  has  two  subcategories distinguished by:   gas-solid
chromatography  (GSC),   and  gas-liquid  chromatography  (GLC)  or  gas-liquid
partition chromatography  (GLPC).  This  last  group  is the most commonly used,
distinguished by type of column adsorbent or  packing.

     1.2  The gas chromatographic methods are recommended for use only by, or
under the close.supervision  of, experienced residue  analysts.

2.0  SUMMARY OF METHOD

     2.1  Each organic  analytical method that  follows provides  a recommended
technique  for extraction, cleanup,  and occasionally, derivatization  of the
samples to be analyzed.   Before the  prepared  sample  is  introduced into the GC,
a procedure for standardization must be  followed to  determine the recovery and
the  limits of  detection for  the  analytes  of  interest.    Following sample
introduction into the GC, analysis proceeds with a comparison of sample values
with standard values.   Quantitative analysis is  achieved through integration
of peak area or measurement  of  peak  height.

3.0  INTERFERENCES

     3.1  Contamination   by  carryover  can occur whenever high-level  and low-
level  samples are  sequentially  analyzed.    To reduce carryover,  the sample
syringe or  purging  device must  be  rinsed out between samples with  water or
solvent.  Whenever an unusually  concentrated sample is encountered, it should
be followed by an analysis  of  a solvent blank  or  of water  to check for cross
contamination.  For volatile samples containing large  amounts of water-soluble
materials,  suspended solids,  high  boiling  compounds or  high  organohalide
levels, it may be necessary  to wash out the  syringe or purging  device with a
detergent solution,  rinse it with distilled water,  and then dry  it in a 105°C
oven between analyses.

4.0  APPARATUS AND MATERIALS

     4.1  Gas  chromatograph  -  Analytical  system  complete with  gas
chromatograph suitable for on-column injections and all required accessories,
including detectors,  column  supplies, recorder, gases, and  syringes.   A data
system for measuring peak height and/or  peak  areas is  recommended.

     4.2  Gas chromatographic columns  -  See the specific determinative method.
Other  packed or  capillary  (open-tubular)  columns may  be  used  if  the
requirements of Step 8.6 are met.


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5.0  REAGENTS

     5.1  See the specific determinative method  for  the  reagents needed.

6.0  SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

     6.1  See  the  introductory material  to this chapter,  Organic Analytes,
Step 4.1.

7.0  PROCEDURE

     7.1  Extraction - Adhere  to  those procedures  specified in the referring
determinative method.

     7.2  Cleanup and separation - Adhere to those procedures  specified  in  the
referring determinative method.

     7.3  The recommended gas chromatographic columns  and operating conditions
for the instrument are specified in the referring determinative method.

     7.4  Calibration

          7.4.1  Establish gas chromatographic operating parameters equivalent
     to  those  indicated  in  Section  7.0  of  the  determinative  method  of
     interest.   Prepare  calibration standards using the  procedures  indicated
     in  Section  5.0 of the  determinative method of interest.  Calibrate  the
     chromatographic system using either the external  standard technique (Step
     7.4.2) or the internal standard technique (Step 7.4.3).

          7.4.2  External standard calibration procedure

               7.4.2.1  For  each  analyte of  interest,  prepare  calibration
          standards at  a minimum of  five concentration  levels  by  adding
          volumes of one or more  stock standards   to  a volumetric flask  and
          diluting to volume with an appropriate solvent.  One of  the  external
          standards  should be  at  a concentration near, but above,  the  method
          detection  limit.   The other  concentrations  should correspond  to  the
          expected  range  of concentrations  found  in  real  samples or  should
          define the working range of the detector.

               7.4.2.2  Inject each  calibration  standard using the technique
          that  will be  used  to  introduce  the  actual  samples  into  the  gas
          chromatograph  (e.g. 2-5-uL  injections,  purge-and-trap,   etc.).
          Tabulate  peak  height or  area  responses against the mass  injected.
          The  results  can be  used to  prepare  a calibration  curve for each
          analyte.   Alternatively,  for  samples  that  are introduced into  the
          gas chromatograph  using  a  syringe, the ratio  of the  response  to  the
          amount  injected,  defined as  the  calibration  factor  (CF),   can  be
          calculated for each  analyte  at each standard  concentration.   If  the
          percent relative standard deviation (%RSD) of the calibration  factor
          is  less  than  20% over the  working   range,  linearity  through  the
          origin  can be assumed,  and  the average  calibration factor  can  be
          used in place of a calibration curve.

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     Ca,1bration factor

*For multiresponse pesticides/PCBs use  the  total  area of all  peaks
used for quantitation.

     7.4.2.3  The working  calibration curve  or calibration  factor
must be verified on  each working day  by  the  injection of one or more
calibration standards.   The  frequency of verification  is dependent
on the detector.  Detectors, such as  the  electron  capture detector,
that  operate   in  the  sub-nanogram  range  are  more  susceptible  to
changes in detector response caused  by GC column and  sample  effects.
Therefore, more  frequent verification of calibration  is  necessary.
The flame  ionization detector is much  less sensitive and  requires
less frequent verification.  If  the response  for any analyte varies
from the  predicted  response  by more  than + 15%,  a  new  calibration
curve must be prepared for that analyte.

                          R,  -  R?
     Percent Difference = -—B—- x  100
                             Rl

where:

     R! = Calibration Factor from first  analysis.

     R2 = Calibration Factor from succeeding analyses.

7.4.3  Internal standard calibration  procedure

     7.4.3.1  To use  this  approach,  the analyst must  select  one  or
more internal  standards  that are similar in  analytical  behavior  to
the compounds  of interest.   The analyst  must further  demonstrate
that the  measurement of the internal standard is  not affected  by
method  or  matrix interferences.    Due  to  these limitations,  no
internal standard applicable to all  samples  can be  suggested.

     7.4.3.2  Prepare  calibration standards  at a minimum  of  five
concentration levels for each analyte of  interest  by adding volumes
of  one  or  more stock  standards  to   a  volumetric  flask.   To  each
calibration standard,  add  a known constant amount  of one   or  more
internal standards and dilute to volume  with an appropriate  solvent.
One of the  standards  should  be at a  concentration near, but  above,
the method detection  limit.   The  other  concentrations  should
correspond to  the expected  range  of concentrations  found   in  real
samples or should define the working  range of the detector.

     7.4.3.3  Inject  each  calibration  standard  using the  same
introduction technique  that  will be  applied  to the  actual   samples
(e.g.  2-  to 5-uL injection,  purge-and-trap,  etc.).    Tabulate the
peak  height or  area  responses  against  the  concentration  of  each
compound and internal standard.   Calculate response factors  (RF) for
each compound as follows:
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                        RF = (AsCis)/(A1sCs)

     where:

          As   =  Response for the analyte to be measured.

          Ais  =  Response for the internal standard.

          Cis  =  Concentration of the internal standard, ug/L.

          Cs   =  Concentration of the analyte to be measured,  ug/L.

     If the  RF value over  the working  range  is  constant  (< 20% RSD),  the
     RF can  be  assumed to  be  invariant,  and the average RF can be  used
     for calculations.   Alternatively,  the results  can be used to  plot  a
     calibration curve  of  response ratios, As/Ais versus  RF.

          7.4.3.4  The  working  calibration  curve or RF must be verified
     on each working day  by  the  measurement of one or more  calibration
     standards.    The  frequency  of  verification  is  dependent  on  the
     detector.    Detectors, such  as  the electron capture detector,  that
     operate  in  the sub-nanogram range  are more susceptible  to  changes in
     detector  response  caused  by  GC  column  and  sample  effects.
     Therefore,  more frequent verification  of  calibration is  necessary.
     The flame  ionization  detector  is much  less sensitive  and requires
     less frequent verification.   If the response for  any analyte  varies
     from the predicted response  by more than ± 15%, a  new calibration
     curve must  be prepared for that compound.

7.5  Retention time windows

     7.5.1  Before  establishing  windows, make  sure  the GC   system  is
within optimum operating conditions.   Make three injections of  all  single
component  standard mixtures  and  multiresponse  products  (i.e.  PCBs)
throughout the  course  of  a 72-hour  period.   Serial injections over less
than  a 72-hour  period result  in retention time  windows  that are  too
tight.

     7.5.2  Calculate  the standard  deviation  of the  three  absolute
retention times  for each  single component  standard.   For  multiresponse
products, choose  one  major  peak from  the  envelope  and calculate  the
standard deviation of the  three retention times for that  peak.  The peak
chosen should   be  fairly immune  to losses  due  to degradation  and
weathering in samples.

          7.5.2.1  Plus or minus  three times the  standard  deviation  of
     the  absolute retention times  for  each standard will  be used  to
     define  the  retention time window;  however,  the  experience  of  the
     analyst should weigh  heavily  in the  interpretation of chromatograms.
     For multiresponse products (i.e.   PCBs), the analyst should  use  the
     retention   time  window but should   primarily  rely  on pattern
     recognition.

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          7.5.2.2  In those  cases where  the standard  deviation for  a
     particular  standard is  zero,  the  laboratory  must substitute  the
     standard deviation  of a  close eluting, similar compound to develop  a
     valid retention time window.

     7.5.3  The laboratory must calculate retention time windows for each
standard on  each  GC column   and whenever  a  new GC column  is  installed.
The data must be retained by  the laboratory.

7.6  Gas chromatographic analysis

     7.6.1  Introduction of  organic  compounds into the gas  chromatograph
varies depending on  the volatility  of the compound.   Volatile organics
are primarily introduced by purge-and-trap (Method 5030).  However,  there
are limited  applications  where direct  injection  is acceptable.  Use of
Method  3810  or 3820  as a  screening  technique for  volatile  organic
analysis may be valuable with some sample matrices to prevent overloading
and  contamination  of   the  GC  systems.    Semivolatile  organics  are
introduced by direct injection.

     7.6.2  The appropriate detector(s) is given in the specific method.

     7.6.3  Samples  are  analyzed  in a  set   referred  to as an  analysis
sequence.   The sequence begins  with instrument  calibration followed by
sample extracts interspersed  with  multilevel  calibration standards.   The
sequence ends  when the set  of samples has  been  injected  or  when
qualitative and/or quantitative QC criteria are exceeded.

     7.6.4  Direct Injection  - Inject  2-5 uL of the sample  extract  using
the solvent flush technique.   Smaller (1.0-uL) volumes can be injected if
automatic  devices  are  employed.    Record the  volume  injected to  the
nearest 0.05 uL and the  resulting  peak size in area units or peak height.

     7.6.5  If  the  responses exceed  the linear range  of the  system,
dilute the  extract  and  reanalyze.  It  is recommended  that extracts  be
diluted so that all  peaks are on scale.  Overlapping peaks are not always
evident  when peaks   are   off   scale.    Computer  reproduction of
chromatograms,  manipulated  to  ensure  all  peaks  are on  scale over  a
100-fold range, are acceptable if  linearity is demonstrated.  Peak height
measurements are recommended  over peak area integration when overlapping
peaks cause errors in area integration.

     7.6.6  If  peak detection  is  prevented  by  the  presence of
interferences, further cleanup is  required.

     7.6.7  Examples of chromatograms  for the compounds  of interest  are
frequently available in  the referring analytical method.

     7.6.8  Calibrate the system immediately prior  to conducting  any
analyses (see  Step  7.4).  A  midlevel  standard must also be  injected at
intervals  specified in  the method  and  at the  end  of  the  analysis
sequence.   The calibration   factor for  each  analyte to  be quantitated,
must not exceed a 15% difference when compared to the initial standard of

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     the analysis sequence.   When this criteria  is  exceeded,  inspect the GC
     system  to  determine  the cause  and  perform  whatever maintenance is
     necessary (see Step 7.7) before recalibrating and proceeding with sample
     analysis.  All samples that were  injected after the sample exceeding the
     criteria must be reinjected.

          7.6.9  Establish daily retention  time windows for each analyte.  Use
     the absolute retention  time for each analyte  from  Step 7.6.8 as the
     midpoint of  the  window for  that  day.   The  daily  retention  time window
     equals the  midpoint  + three times the standard deviation determined in
     Step 7.5.

               7.6.9.1  Tentative identification  of  an analyte  occurs when a
          peak from  a sample extract  falls within  the  daily  retention  time
          window.  Normally, confirmation  is required:  on a  second  GC column,
          by  GC/MS   if  concentration  permits, or by  other  recognized
          confirmation techniques.  Confirmation  may not be  necessary if the
          composition of  the  sample  matrix is  well established  by  prior
          analyses.

               7.6.9.2  Validation of GC system qualitative performance:  Use
          the midlevel standards interspersed throughout  the  analysis  sequence
          (Step 7.6.8) to  evaluate  this criterion.   If  any  of the  standards
          fall outside their daily retention time  window, the system is out of
          control.   Determine  the cause of the  problem and  correct it  (see
          Step 7.7).

     7.7  Suggested chromatography  system   maintenance -  Corrective  measures
may require any one or more of the following remedial  actions.

          7.7.1  Packed columns  -  For  instruments with  injection port traps,
     replace the demister trap, clean,  and  deactivate the glass  injection  port
     insert or  replace with a  cleaned and  deactivated  insert.   Inspect the
     injection end of the column and remove any foreign material  (broken  glass
     from the rim of  the  column or pieces   of septa).  Replace the  glass  wool
     with fresh  deactivated glass wool.   Also,  it may be necessary  to remove
     the first few millimeters of the packing material  if any discoloration is
     noted, also  swab out  the  inside  walls of the  column  if  any  residue is
     noted.   If these procedures fail  to eliminate the degradation  problem, it
     may be necessary to deactivate the metal injector body  (described in Step
     7.7.3) and/or repack/replace the column.

          7.7.2  Capillary  columns - Clean  and deactivate the  glass injection
     port insert or replace with  a cleaned  and deactivated insert.   Break off
     the first few  inches,  up  to one foot,  of the injection port  side of the
     column.    Remove  the column  and  solvent   backflush  according to the
     manufacturer's instructions.   If  these procedures fail  to eliminate the
     degradation problem, it may be necessary to  deactivate  the metal  injector
     body and/or replace the column.

          7.7.3  Metal  injector  body   -  Turn off the  oven and  remove the
     analytical  column when the oven  has cooled.   Remove the  glass injection
     port insert  (instruments  with  off-column injection  or Grob).   Lower the

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 injection port  temperature  to room temperature.   Inspect the  injection
 port and remove any noticeable foreign material.

           7.7.3.1  Place a beaker beneath  the  injector port  inside  the  GC
      oven.  Using a wash bottle, serially rinse the entire  inside  of the
      injector port with acetone and then toluene;  catching the rinsate  in
      the beaker.

           7.7.3.2  Prepare a solution of deactivating  agent  (Sylon-CT  or
      equivalent)  following  manufacturer's  directions.   After  all  metal
      surfaces inside the  injector  body have been thoroughly  coated with
      the  deactivation  solution, serially  rinse  the  injector  body with
      toluene, methanol,acetone, and hexane.  Reassemble  the  injector and
      replace the GC column.

 7.8  Calculations

      7.8.1  External  standard  calibration  -  The  concentration of each
 analyte  in  the  sample may  be  determined  by calculating  the  amount  of
 standard purged  or  injected,  fVom  the  peak  response,  using the
 calibration  curve or  the calibration factor determined  in  Step  7.4.2.
 The concentration of a specific analyte is calculated  as  follows:

 Aqueous samples

      Concentration (ug/L)  =  [(Ax)(A)(Vt)(D)]/[(As)(Vi)(Vs)]

 where:

      Ax = Response for  the  analyte in the sample,  units  may be in area
           counts or peak height.

      A  = Amount of standard injected  or purged,  ng.

      As = Response for the external standard,  units  same  as  for Ax.

      Vi = Volume of extract  injected,  uL.   For purge-and-trap  analysis,
           Vi is not applicable and  therefore  =  1.

      D  = Dilution factor,  if  dilution  was made  on  the  sample prior  to
           analysis.  If no dilution was  made,  D  =  1, dimensionless.

     Vt = Volume of total extract,  uL.   For purge-and-trap  analysis,  MI  is
          not applicable and  therefore  =  1.

     Vs = Volume of sample  extracted or purged, mL.

Nonaqueous samples

     Concentration (ng/g) = [(Ax)(A)(Vt)(D)]/[(As)(Vi)(W)]
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    where:

         W   = Weight of sample extracted or purged,  g.   The wet weight or dry
              weight may be used,  depending upon the specific applications of
              the data.

         AX>  AS,  A,  Vt, D,  and  Vi  have  the  same definition  as  for aqueous
         samples.

         7.8.2  Internal standard  calibration  - For each analyte of  interest,
    the concentration of that analyte  in the sample is calculated as  follows:

    Aqueous samples

         Concentration (ug/L) = [(Ax)(Cis)(D)]/[(Ais)(RF)(Vs)]

    where:

         Ax =  Response of the  analyte  being  measured,  units may  be in area
               counts or peak height.

         Cis = Amount of internal  standard added to extract or volume purged,
               ng.

         D   =  Dilution factor, if a dilution  was made on the sample prior to
               analysis.  If no dilution was made, D = 1, dimensionless.

         Ais = Response of the internal  standard,  units  same as Ax.

         RF  = Response factor for analyte,  as  determined in Step 7.4.3.3.

         Vs =  Volume of water extracted or purged, ml.

    Nonaqueous samples

         Concentration  (ug/kg) = [(As)(Cis)(D)3/[(Ais)(RF)(Ws)]

    where:

         Ws =  Weight  of  sample extracted, g.    Either  a  dry weight  or wet
               weight may be used, depending upon the specific application of
               the data.

         As, C-js> D, AiS, and RF have  the same  definition as for  aqueous
               samples.

8.0 QUALITY CONTROL

    8.1  Each  laboratory that  uses  these methods  is  required  to operate  a
formal  quality  control  program.   The  minimum requirements  of  this program
consist  of  an initial  demonstration  of laboratory  capability and an ongoing
analysis of  spiked samples  to evaluate  and  document quality  data.    The
laboratory must maintain  records  to  document  the  quality  of  the  data

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generated.    Ongoing data quality  checks  are  compared  with established
performance  criteria  to  determine  if the  results  of analyses  meet the
performance characteristics  of the method.   When results  of  sample  spikes
indicate atypical  method  performance, a quality control  check standard  must  be
analyzed to confirm that  the measurements were performed in an in-control  mode
of operation.

    8.2  Before  processing  any  samples,  the  analyst  should demonstrate,
through  the  analysis of a  reagent  blank,  that  interferences  from the
analytical  system,  glassware,  and  reagents are under control.  Each time a set
of samples  is  extracted  or there is  a change  in reagents, a  reagent  water
blank  should  be  processed   as  a  safeguard  against  chronic  laboratory
contamination.   The blank samples  should be  carried through  all  stages  of the
sample preparation  and measurement steps.

    8.3  For each analytical batch (up to 20 samples),  a reagent blank,  matrix
spike,  and  replicate or matrix spike replicate must be analyzed (the frequency
of the spikes may be different for different  monitoring programs).   The blank
and  spiked  samples  must  be  carried through   all  stages  of  the  sample
preparation and measurement steps.

    8.4  The  experience  of   the  analyst performing  gas  chromatography  is
invaluable to  the  success   of the methods.   Each  day  that  analysis  is
performed,  the daily calibration  sample  should  be evaluated to determine  if
the chromatographic system is operating  properly.   Questions that  should  be
asked are:   Do the peaks  look normal?;  Is  the response  obtained comparable  to
the response from previous calibrations?  Careful  examination of the standard
chromatogram can indicate  whether the  column  is  still  good, the  injector  is
leaking, the injector septum needs replacing, etc.   If any changes  are  made  to
the system  (e.g.  column changed),  recalibration of the system must  take place.

    8.5  Required instrument QC

         8.5.1  Step 7.4 requires that  the %RSD vary by  < 20% when comparing
     calibration factors   to  determine  if a  five  point calibration curve  is
     linear.

         8.5.2  Step 7.4  sets a limit  of + 15% difference when  comparing
     daily  response of a given analyte  versus the initial  response.   If the
     limit  is  exceeded, a new  standard curve must be prepared.

         8.5.3  Step 7.5 requires the  establishment  of retention  time
     windows.

         8.5.4  Step 7.6.8 sets  a  limit  of ± 15% difference  when  comparing
     the initial response  of  a  given analyte  versus any  succeeding  standards
     analyzed  during an analysis sequence.

         8.5.5  Step 7.6.9.2  requires  that  all  succeeding standards in  an
     analysis  sequence   must  fall within  the daily  retention  time   window
     established by the first  standard of the sequence.
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     8.6  To  establish  the  ability  to  generate  acceptable  accuracy  and
precision, the analyst must perform the following operations.

          8.6.1  A  quality  (QC)  check sample  concentrate  is  required
     containing each analyte  of interest.  The QC check sample concentrate may
     be  prepared from  pure  standard  materials  or purchased  as  certified
     solutions.   If  prepared  by  the  laboratory,  the  QC  check  sample
     concentrate  must  be made  using  stock standards  prepared  independently
     from those used for calibration.

               8.6.1.1  The  concentration of the QC  check  sample  concentrate
          is  highly  dependent  upon  the  analytes  being  investigated.
          Therefore,  refer  to Method  3500,  Section  8.0  for  the  required
          concentration of the  QC  check  sample concentrate.

          8.6.2  Preparation  of QC check  samples

               8.6.2.1  Volatile  organic  analytes  (Methods 8010,  8020,  and
          8030) - The QC  check  sample is  prepared  by adding 200 uL  of the QC
          check sample concentrate (Step  8.6.1) to  100 ml of water.

               8.6.2.2  Semivolatile organic  analytes  (Methods 8040,  8060,
          8080, 8090,  8100,  and 8120)  -  The  QC  check  sample is  prepared by
          adding  1.0  ml of the QC  check sample  concentrate  (Step  8.6.1) to
          each of four 1-L aliquots  of water.

          8.6.3  Four aliquots  of the well-mixed  QC check sample are analyzed
     by  the  same procedures  used to  analyze  actual  samples  (Section  7.0 of
     each of  the methods).   For  volatile organics,  the  preparation/analysis
     process is purge-and-trap/gas chromatography.  For semivolatile organics,
     the  QC  check samples must undergo  solvent  extraction  (see Method 3500)
     prior to chromatographic analysis.

          8.6.4  Calculate the  average  recovery  (x) in  ug/L, and the standard
     deviation of the recovery  (s) in ug/L, for each  analyte of  interest using
     the four results.

          8.6.5  For  each analyte  compare  s and  x with   the  corresponding
     acceptance criteria  for precision  and  accuracy, respectively,  given the
     QC  Acceptance  Criteria  Table  at  the end of  each  of  the  determinative
     methods.   If s and  x for all  analytes of  interest meet the acceptance
     criteria,  the  system performance  is acceptable and analysis  of actual
     samples  can  begin.   If  any  individual s exceeds  the  precision limit or
     any  individual x falls  outside the  range for accuracy,  then the system
     performance is unacceptable for that analyte.

     NOTE:  The large number  of analytes  in each  of the QC Acceptance Criteria
            Tables  present  a  substantial probability  that  one or  more  will
            fail  at least one  of  the acceptance criteria when all  analytes of
            a given method are determined.
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         8.6.6  When one or more of the  analytes tested  fail  at  least  one  of
    the  acceptance criteria,  the analyst  must proceed according  to  Step
    8.6.6.1 or 8.6.6.2.

              8.6.6.1   Locate  and correct the source of the problem and repeat
         the test for  all  analytes of interest beginning with Step 8.6.2.

              8.6.6.2    Beginning with  Step 8.6.2,   repeat  the test  only  for
         those  analytes that  failed  to meet  criteria.    Repeated  failure,
         however, will  confirm a general  problem with the measurement system.
         If this  occurs,  locate and  correct  the  source  of the  problem  and
         repeat the test  for  all compounds of  interest beginning with  Step
         8.6.2.

    8.7  The laboratory must,  on an ongoing basis,  analyze a reagent blank and
a matrix  spiked replicate for  each analytical   batch  (up to a maximum of  20
samples/batch)  to assess  accuracy.    For  soil  and  waste samples where
detectable  amounts  of organics  are  present,  replicate samples  may  be
appropriate in place of spiked  replicates.   For laboratories analyzing one  to
ten samples per month,  at  least  one spiked sample per month  is required.

         8.7.1   The  concentration of the  spike   in  the  sample should  be
    determined as follows:

              8.7.1.1   If,  as  in compliance monitoring, the concentration  of a
         specific analyte  in the sample is  being checked against  a regulatory
         concentration  limit,  the  spike  should be at that  limit  or 1  to  5
         times  higher  than the  background  concentration determined  in  Step
         8.7.2, whichever  concentration would be larger.

              8.7.1.2    If the concentration of  a specific  analyte  in a water
         sample is not being checked against a limit specific to that analyte,
         the spike  should  be  at the  same  concentration as the  QC  reference
         sample  (Step  8.6.2)   or 1 to  5 times  higher  than the  background
         concentration determined in Step 8.7.2, whichever concentration would
         be larger.  For other matrices, the recommended spiking concentration
         is 20 times the PQL.

              8.7.1.3    For  semivolatile  organics,  it may not be  possible  to
         determine the background concentration  levels  prior to  spiking (e.g.
         maximum holding times  will be exceeded).   If this  is the  case,  the
         spike concentration should be  (1) the regulatory concentration limit,
         if any; or, if none (2) the  larger of  either 5 times higher than the
         expected   background  concentration  or  the  QC   reference  sample
         concentration  (Step  8.6.2).    For other  matrices,  the  recommended
         spiking concentration is 20 times the PQL.

         8.7.2   Analyze  one  unspiked  and one   spiked  sample  aliquot  to
    determine percent  recovery of each of the spiked compounds.

              8.7.2.1   Volatile organics  -  Analyze  one 5-mL sample aliquot  to
         determine  the  background concentration  (B)  of each  analyte.    If
         necessary, prepare a  new QC reference sample concentrate (Step 8.6.1)

                                 8000  - 11                       Revision  1
                                                                December  1987
-------
         appropriate  for the background concentration in the sample.   Spike a
         second  5-mL  sample aliquot with  10  uL of  the QC  reference  sample
         concentrate  and analyze  it to  determine  the concentration  after
         spiking (A)  of each analyte.  Calculate each percent recovery (p) as
         100(A - B)%/T,  where  T  is  the  known true value  of the spike.

              8.7.2.2   Semivolatile organics  - Analyze one  sample aliquot
         (extract of  1-L sample)  to determine  the background concentration (B)
         of each  analyte.   If necessary,  prepare  a  new QC  reference  sample
         concentrate  (Step 8.6.1) appropriate  for the background concentration
         in the  sample.   Spike a second 1-L sample  aliquot with 1.0 ml of the
         QC reference sample  concentrate and  analyze  it  to  determine the
         concentration  after spiking  (A)  of each  analyte.    Calculate  each
         percent recovery  (p)  as  100(A  -  B)%/"T,  where  T  is the  known  true
         value of the spike.

         8.7.3  Compare  the percent  recovery  (p) for each  analyte in a water
    sample  with the  corresponding  criteria  presented  in the  QC Acceptance
    Criteria  Table  found at  the end  of  each of  the  determinative methods.
    These  acceptance criteria  were calculated to  include an  allowance for
    error  in  measurement of both  the background  and  spike concentrations,
    assuming a spike  to background  ratio  of 5:1.  This error will be  accounted
    for to the  extent that  the analyst's spike to background ratio approaches
    5:1.   If spiking was  performed  at  a concentration  lower than  the QC
    reference sample  concentration  (Step 8.6.2), the analyst must use either
    the  QC acceptance  criteria  presented  in the  Tables,  or optional  QC
    acceptance  criteria  calculated  for the specific  spike concentration.  To
    calculate optional  acceptance  criteria for  the  recovery of  an analyte:
    (1)  Calculate  accuracy  (x')   using  the equation  found  in  the  Method
    Accuracy  and  Precision  as a Function  of  Concentration  Table  (appears at
    the  end  of  each  determinative  method),  substituting  the  spike
    concentration (T)  for C;  (2)  calculate overall  precision  (S') using the
    equation in  the same Table,  substituting x'  for x; (3) calculate  the  range
    for recovery at the spike concentration as (100x'/T) ± 2.44(100S'/T)%.

         8.7.4   If  any  individual   p falls outside  the  designated range for
    recovery, that   analyte has failed  the  acceptance criteria.  A check
    standard containing each analyte that  failed the  criteria must  be analyzed
    as described in Step 8.8.

    8.8  If any  analyte  in  a water  sample fails the acceptance criteria for
recovery in  Step 8.7, a  QC reference  standard containing  each analyte that
failed must be prepared and analyzed.

NOTE;  The frequency for the required analysis of a QC reference standard will
      depend  upon the  number of  analytes being  simultaneously  tested, the
      complexity of the  sample matrix,  and the performance of the  laboratory.
      If the entire list of analytes given  in  a  method must be measured in the
      sample  in Step 8.7,  the  probability that the analysis  of  a  QC  check
      standard will  be required  is  high.   In  this  case  the QC check standard
      should be routinely analyzed  with the spiked  sample.
                                 8000 - 12                       Revision  1
                                                                 December  1987
-------
         8.8.1   Preparation of the  QC  check sample  -  For volatile organics,
    add 10 uL of the QC check sample concentrate  (Step  8.6.1  or 8.7.2) to 5 ml
    of water.   For  semivolatile  organics,  add 1.0 ml  of the QC check sample
    concentrate (Step  8.6.1  or 8.7.2)  to  1  L of water.  The QC check sample
    needs only  to  contain the analytes  that failed criteria in  the  test in
    Step  8.7.    Prepare  the  QC check  sample  for  analysis  following  the
    guidelines  given in Method 3500  (e.g. purge-and-trap,  extraction, etc.).

         8.8.2   Analyzed the  QC  check  sample to  determine the concentration
    measured (A) of each analyte. Calculate  each  percent recovery  (ps) as 100
    (A/T)%,  where T is the true value of  the  standard concentration.

         8.8.3   Compare the  percent  recovery (ps) for  each  analyte with the
    corresponding QC  acceptance  criteria  found  in   the  appropriate Table in
    each of the methods.  Only analytes that failed  the  test  in Step 8.7 need
    to be compared  with these  criteria.   If the  recovery of  any such analyte
    falls outside  the designated range,  the  laboratory performance for that
    analyte is  judged  to  be  out  of  control,  and  the  problem must  be
    immediately identified and corrected.  The result  for that analyte in the
    unspiked  sample  is  suspect and  may not  be   reported for  regulatory
    compliance purposes.

     8.9  As part of  the  QC program for the laboratory, method accuracy for
each matrix  studied must  be assessed and  records must be maintained.   After
the analysis of five  spiked  samples  (of the  same matrix  type) as in Step 8.7,
calculate the  average  percent  recovery  (p) and  the   standard  deviation of the
percent recovery (sp).  Express  the  accuracy assessment  as a percent recovery
interval from p - 2sp to  p + 2sp.   If p = 90% and sp  =  10%,  for example, the
accuracy interval is expressed as 70-110%.   Update the  accuracy  assessment for
each analyte  on a  regular basis (e.g.  after  each   five  to  ten new accuracy
measurements).

     8.10  To determine acceptable accuracy and precision limits  for surrogate
standards the following procedure should  be performed.

          8.10.1  For each sample analyzed, calculate  the percent  recovery of
     each surrogate in the sample.

          8.10.2  Once a  minimum of thirty  samples  of  the  same  matrix have
     been analyzed,  calculate  the average percent  recovery  (p) and standard
     deviation  of the percent recovery  (s)  for each  of  the surrogates.

          8.10.3  For a given  matrix,  calculate  the upper  and  lower control
     limit for method performance for each  surrogate  standard.   This should be
     done as follows:

               Upper Control  Limit  (UCL)  =  p  + 3s
               Lower Control  Limit  (LCL)  =  p  - 3s

          8.10.4  For aqueous and soil  matrices,  these  laboratory  established
     surrogate  control limits  should,  if  applicable,  be compared  with  the
     control limits  listed  in  Tables  A  and  B  of Methods  8240  and  8270,


                                 8000 - 13                      Revision 1
                                                                December 1987
-------
     respectively.    The  limits given  in these methods  are multi-laboratory
     performance based limits  for  soil  and  aqueous samples,  and therefore, the
     single-laboratory  limits established in  Step  8.10.3 must  fall  within
     those given in Tables  A and B for  these matrices.

          8.10.5  If recovery  is not  within limits, the following is required.

               •  Check  to be  sure there are  no  errors in  calculations,
                  surrogate solutions  and internal  standards.    Also,  check
                  instrument performance.

               •  Recalculate  the  data  and/or  reanalyze the extract if any of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the  sample if none of the above are
                  a problem or flag the data as  "estimated  concentration."

          8.10.6  At  a  minimum,  each  laboratory  should  update  surrogate
     recovery limits on a matrix-by-matrix  basis, annually.

     8.11  It  is  recommended  that  the  laboratory  adopt  additional  quality
assurance practices for use with this method.  The specific  practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples.   Field duplicates may  be  analyzed  to assess the precision  of the
environmental measurements.   When doubt exists over  the  identification  of  a
peak on  the  chromatogram,  confirmatory techniques  such as  gas chromatography
with a dissimilar column, specific element  detector,  or mass spectrometer must
be used.  Whenever  possible,  the  laboratory should analyze  standard reference
materials and participate in relevant performance evaluation studies.

9.0  METHOD PERFORMANCE

     9.1  The  method detection   limit  (MDL)  is  defined  as  the  minimum
concentration  of  a  substance  that can  be  measured and  reported  with 99%
confidence that the value is above zero.   The  MDL concentrations listed in the
referring analytical  methods were  obtained using water.  Similar results were
achieved  using  representative wastewaters.   The  MDL actually  achieved  in  a
given  analysis will  vary  depending  on  instrument  sensitivity  and  matrix
effects.

     9.2  Refer to  the determinative  method  for  specific  method  performance
information.

10.0  REFERENCES

     1.  U.S.  EPA  40 CFR  Part  136,  "Guidelines Establishing  Test Procedures
for  the Analysis  of Pollutants  Under the Clean  Water  Act;   Final  Rule and
Interim Final Rule and Proposed Rule,"  October 26,  1984.

     2.  U.S. EPA 40  CFR Part  136, Appendix B.  "Guidelines Establishing Test
Procedures  for  the Analysis  of Pollutants Under  the Clean Water Act;  Final
Rule and Interim Final Rule and Proposed Rule,"  October 26,  1984.


                                  8000  -  14                      Revision 1
                                                                December 1987
-------
     3.  U.S. EPA Contract Laboratory Program, Statement of Work  for  Organic
Analysis,  July 1985,  Revision.

     4.  Rohrbough,  W.G.;  et  al.  Reagent Chemicals,  American  Chemical  Society
Specifications,  7th  ed.; American Chemical Society: Washington,  DC, 1986.

     5.  1985  Annual  Book   of  ASTM  Standards.  Vol.   11.01;  "Standard
Specification for Reagent  Water"; ASTM:  Philadelphia, PA, 1985;  D1193-77.
                                 8000  -  15                       Revision 1
                                                                December 1987
-------
                                             METHOD  BOOO

                                         GAS  CHBQ.MATOGPUPHY
    7.1
          Refer to
     oeterninatJve
        •atnod  for
        extract ion
        proceOure
    7.3
                           7.4.3
    Select internet
   standards heving
  similar behavior to
compounds of Interest
           Befer
         to deter-
   •Inetlve metnoa
   for cleanup ena
       separet ion
       procedures
                             7.4.3.2
   7.4.2.1
           Prepare
      calibrat Ion
     •tandaros for
    eacn oaramater
      of interest
        Prepare
      calibrat ion
       standards
    CstaDllsn gas
    chrometograon
operating parameters:
 prepare cellDretlon
      stsnoaros
                             7.4.3.3
                                                                              7.4.2
  Inject calibration
  standard:  prepare
  calibration curve
or calibration factor
          In)ect
       calibration
        • tanoards:
      calculate RF
                             7.4.3.4
                                                                                 7.4.2.3
    Verify Morking
     CalIbrat ion
    curve aacn day
                             Verify working
                               calIbrat ion
                               Curve or PF
                                eacn day
                                                        7 .5
                                Calculate
                             retention  tlmo
                                  windows
                                                          o
                                              8000 -  16
                                                        Revision  1
                                                        December  1987
-------
                METHOD BOOO

             GAS CHROMATOGRAPH

                 (Continued)
7.6.1 Use
3810 or 3820
•s screening
tecnn.to.uo.
If n«c«s*ary


7.6.11 Introduce
1 compounds
into gas cnro-
•atograpri by
Our ae -ana -trap
(Method 5030)


Volatile ^ 7.6.1 X^emivolctl !•
^r Type ot ^^


7.6.1
Introduce
comoounas into
gas cnromato-
graph by direct
Injection

7.6.4
mxtr
• Olv
i
recc


Inject
• •mo le
•act using
rent flucn
.ecnnlquc;
>rd volume


                            Dilute extract
                            •nd reanalyze
 Is peak
tlon prevented by
  interference?
                                                     7.6.8
                                                           Cal Ibrate
                                                            system
                                                         Immedlately
                                                           prior to
                                                           analyses
                                                     7.6.9
                                                           Establish
                                                            dally
                                                      retention  time
                                                        windows  for
                                                        each analyte
                                                      7.7
                                                              Oo
   chromatography
         system
      maintenance
       If needed
                                                   7.8
      Calculate
  concentration of
eacn analyte.  using
appropriate formula
for matrix and tyoe
    of standard
                                                    (      Stop       j
                     8000  - 17
       Revision 1
       December 1987
-------
                                 METHOD 8010B

              HALQGENATED  VOLATILE  ORGANICS BY GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method  8010  is  used to  determine the  concentration of  various
volatile  halogenated  organic  compounds.    The  following  compounds  can  be
determined by this method:
Appropriate Technique
Compound Name
Allyl chloride
Benzyl chloride
Bi s (2-chl oroethoxy)methane
Bis(2-chloroisopropyl) ether
Bromoacetone
Bromobenzene
Brotnodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chl oroacetaldehyde
Chlorobenzene
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chl oromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Di bromochl oromethane
1 , 2-Di bromo-3-chl oropropane
Dibromomethane
1 , 2-Di chl orobenzene
1, 3 -Di chlorobenzene
1,4-Dichlorobenzene
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1, 2-Di chl oroethene
Dichloromethane
1, 2-Di chl oropropane
l,3-Dichloro-2-propanol
cis-l,3-Dichloropropene
trans - 1 , 3 -Di chl oropropene
CAS No."
107-05-1
100-44-7
111-91-1
39638-32-9
598-31-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
108-90-7
75-00-3
107-07-03
110-75-8
67-66-3
544-10-5
74-87-3
107-30-2
126-99-8
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
96-23-1
10061-01-5
10061-02-6
Purge-and-Trap
b
PP
PP
b
PP
b
b
b
b
b
b
b
b
PP
b
b
pc
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
Direct
Injection
b
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
b
pc
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
                                  8010B - 1
   Revision 2
November 1992
-------
                                                     Appropriate Technique
                                                                      Direct
Compound Name                        CAS No.a       Purge-and-Trap     Injection
Epichlorhydrin
Ethyl ene di bromide
Methyl iodide
1, 1 ,2,2-Tetrachloroethane
1,1,1 , 2-Tetrachl oroethane
Tetrachloroethene
1,1 , 1-Tri chl oroethane
1 , 1 , 2-Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
Vinyl Chloride
106-89-8
106-93-4
74-88-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
PP
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a  Chemical Abstract Services Registry Number
b  Adequate response using this technique
pp Poor purging efficiency, resulting in high EQLs
pc Poor chromatographic performance.

       1.2   Table  1 indicates compounds that may be analyzed  by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantitation limit for other matrices.


2.0    SUMMARY OF METHOD

       2.1   Method  8010   provides  gas  chromatographic  conditions  for  the
detection of halogenated volatile organic compounds.  Samples can be introduced
into the GC using direct injection or purge-and-trap (Method 5030).  Ground water
samples must be analyzed using Method 5030.   A temperature program is  used  in the
gas chromatograph to separate the organic compounds.  Detection is achieved by
a electrolytic conductivity detector (HECD).

       2.2   The method provides an optional  gas chromatographic column that may
be helpful in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation.


3.0    INTERFERENCES

       3.1   Refer  to  Methods  5030 and  8000.

       3.2   Samples  can  be  contaminated  by  diffusion  of  volatile  organics
(particularly  chlorofluorocarbons and  methylene  chloride)  through  the  sample
container  septum during  shipment  and  storage.    A  trip blank  prepared from
organic-free reagent water  and carried through  sampling and  subsequent storage
and handling can serve as  a check on such contamination.


                                   8010B -  2                        Revision  2
                                                                 November 1992
-------
4.0   APPARATUS AND MATERIALS

      4.1    Gas chromatograph

             4.1.1  Gas chromatograph  -  analytical  system  complete with  gas
      chromatograph suitable for on-column injections or purge-and-trap sample
      introduction and all required accessories,  including detector, analytical
      columns, recorder, gases, and syringes.   A  data system for measuring peak
      heights and/or  peak areas is  recommended.

             4.1.2  Columns

                   4.1.2.1    Column 1 - 8 ft  x  0.1  in.  ID stainless steel  or
             glass  column  packed with 1% SP-1000 on  Carbopack-B  60/80  mesh  or
             equivalent.

                   4.1.2.2    Column 2 - 6 ft  x  0.1  in.  ID stainless steel  or
             glass  column  packed with chemically bonded  n-octane on Porasil-C
             100/120 mesh  (Durapak)  or equivalent.

             4.1.3  Detector  -  Electrolytic  conductivity  (HECD).

      4.2    Sample  introduction  apparatus,   refer  to   Method   5030  for  the
appropriate equipment for sample introduction purposes.

      4.3    Syringes, 5 ml  Luerlok  glass hypodermic and a 5 ml,  gas-tight with
shutoff valve.

      4.4    Volumetric  flask,   Class  A,  Appropriate sizes with  ground  glass
stoppers.

      4.5    Microsyringe, 10 and 25 juL with a 0.006 in.  ID needle  (Hamilton 702N
or equivalent) and a  100 pi.

      4.6    Analytical balance  - 0.0001  g.


5.0   REAGENTS

      5.1    Reagent  grade  chemicals shall  be  used in  all  tests.    Unless
otherwise  indicated,  it   is  intended  that  all reagents  shall  conform to  the
specifications of the Committee on  Analytical  Reagents of the American Chemical
Society, where such  specifications  are available.   Other  grades  may be  used,
provided it is first ascertained that the reagent  is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2    Organic-free  reagent water.  All  references  to  water  in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3    Methanol, CH3OH.  Pesticide quality or  equivalent.  Store away from
other solvents.

      5.4    Stock standards - Stock solutions may be prepared from pure standard
materials  or purchased  as  certified solutions.    Prepare  stock  standards  in

                                   8010B  -  3                         Revision 2
                                                                 November 1992
-------
methanol using assayed liquids or gases,  as appropriate.  Because of the toxicity
of some  of  the organohalides,  primary dilutions of  these  materials  should be
prepared in a hood.

            5.4.1  Place about  9.8 ml  of methanol in  a 10 ml tared ground glass
      stoppered volumetric  flask.   Allow  the  flask to stand,  unstoppered, for
      about 10 minutes until all  alcohol-wetted surfaces have dried.  Weigh the
      flask to the nearest  0.0001 g.

            5.4.2  Add  the assayed reference material,  as described below.

                   5.4.2.1    Liquids.  Using  a 100 juL syringe,  immediately add
            two or more drops  of assayed reference material to  the flask; then
            reweigh.   The liquid must fall directly into  the  alcohol  without
            contacting  the  neck of  the  flask.

                   5.4.2.2    Gases.  To  prepare standards for any  compounds
            that   boil   below   30°C   (e.g.   bromomethane,    chloroethane,
            chloromethane,   dichlorodifluoromethane,  trichlorofluoromethane,
            vinyl  chloride),  fill  a  5  ml valved  gas-tight syringe with the
            reference  standard to  the 5.0 ml mark.   Lower the needle  to 5 mm
            above  the  methanol  meniscus.    Slowly  introduce  the  reference
            standard  above  the surface  of the  liquid.  The heavy gas  rapidly
            dissolves  in the methanol.  This may also be accomplished by using
            a lecture  bottle  equipped  with  a  Hamilton Lecture Bottle Septum
            (#86600).   Attach  Teflon tubing to the  side-arm  relief  valve and
            direct a gentle stream  of gas  into the methanol meniscus.

            5.4.3  Reweigh,  dilute to  volume,  stopper, and then  mix by inverting
      the flask several  times.  Calculate the concentration in milligrams per
      liter (mg/L) from the net gain in weight.  When  compound purity is assayed
      to be  96%  or  greater,  the  weight  may  be  used  without  correction to
      calculate the concentration of the stock standard.  Commercially prepared
      stock standards may be used at any concentration  if they  are certified by
      the manufacturer  or by an independent source.

            5.4.4  Transfer the stock standard solution into  a bottle with a
      Teflon  lined screw-cap.  Store, with minimal  headspace,  at -10°C  to  -20°C
      and protect  from  light.

            5.4.5  Prepare  fresh  standards  every 2  months, for gases  or for
      reactive compounds such as  2-chloroethyl  vinyl  ether.   All  other standards
      must  be replaced after  6 months,  or  sooner  if comparison with check
      standards indicates a problem.

      5.5   Secondary   dilution  standards.  Using   stock   standard  solutions,
prepare  secondary  dilution  standards in  methanol,   as  needed,  containing the
compounds of  interest, either singly or  mixed  together.  The secondary dilution
standards should be prepared at concentrations such  that the aqueous calibration
standards  prepared  in   Section  5.6  will  bracket   the  working range   of the
analytical system.  Secondary  dilution standards should be  stored with minimal
headspace for volatiles and  should be checked frequently for signs of degradation
or evaporation, especially  just  prior to preparing  calibration  standards  from
them.

                                   8010B - 4                         Revision 2
                                                                 November  1992
-------
       5.6    Calibration   standards.     Prepare   calibration   standards   in
organic-free reagent water from the secondary dilution of the stock standards,
at a minimum of five concentrations.  One of the concentrations should be at a
concentration  near,  but  above,  the  method  detection  limit.    The  remaining
concentrations should  correspond  to the expected  range  of  the concentrations
found  in  real  samples or should define the  working range  of the GC.   Each
standard should contain each analyte for detection  by this method (e.g. some or
all of  the  compounds  listed in Table 1 may be  included). In order to prepare
accurate aqueous  standard solutions, the following precautions must  be observed.

             5.6.1  Do  not inject more  than  20 ^l  of alcoholic standards into
       100 ml of water.

             5.6.2  Use  a 25   jut-  Hamilton  702N   microsyringe  or  equivalent
       (variations  in   needle  geometry  will  adversely  affect  the ability  to
      deliver  reproducible volumes of methanolic standards into water).

             5.6.3  Rapidly  inject  the   alcoholic  standard   into  the  filled
      volumetric flask.  Remove the  needle  as  fast  as possible after injection.

             5.6.4  Mix  aqueous  standards by  inverting  the flask three times only.

             5.6.5  Fill the  sample syringe from the standard  solution contained
       in the expanded  area  of  the flask (do  not use  any solution contained in
      the neck of the  flask).

             5.6.6  Never  use pipets to  dilute or  transfer samples or aqueous
      standards.

             5.6.7  Aqueous standards are not stable  and should  be discarded after
      one hour, unless properly  sealed  and  stored.  The aqueous standards can
      be stored up to  24  hours, if held  in sealed  vials with zero  headspace.

      5.7    Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must  select  one or more internal standards that
are similar in analytical behavior to  the compounds  of  interest.   The analyst
must further demonstrate  that  the measurement of  the internal  standard is not
affected by method or  matrix interferences.   Because of these limitations,  no
internal standard  can  be suggested  that is  applicable  to  all samples.   The
compounds recommended for use  as surrogate  spikes  (Section 5.8) have been used
successfully as internal  standards,  because of their generally unique retention
times.

            5.7.1  Prepare  calibration  standards   at   a   minimum   of  five
      concentrations for  each  analyte of interest as described in Section 5.5.

            5.7.2  Prepare a spiking solution containing each  of the  internal
      standards using  the procedures described in Sections 5.4 and 5.5.  It is
      recommended  that  the secondary  dilution  standard be prepared  at  a
      concentration of  15  ng/^L of  each  internal  standard  compound.    The
      addition of  10  /uL   of this standard  to  5.0 ml of  sample or  calibration
      standard would be equivalent to 30 jug/L.
                                  8010B  - 5                         Revision 2
                                                                 November 1992
-------
            5.7.3  Analyze  each  calibration  standard according to Section 7.0,
      adding  10 pi  of  internal  standard  spiking solution  directly  to  the
      syringe.

      5.8   Surrogate   standards   -   The   analyst  should  monitor  both  the
performance of  the analytical  system  and  the effectiveness of  the  method in
dealing  with  each  sample  matrix   by spiking   each  sample,   standard,  and
organic-free reagent water blank with surrogate halocarbons.  A combination of
bromochloromethane, bromochlorobenzene and bromofluorobenzene  is  recommended to
encompass the  range  of temperature  program  used  in this method.   From stock
standard solutions prepared as in Section 5.4, add  a volume to  give  750 ^g of
each surrogate  to  45 ml of  organic-free  reagent water  contained in a 50 ml
volumetric flask,  mix,  and dilute  to volume for  a  concentration of  15  ng/^L.
Add 10 juL of this surrogate spiking solution directly into the  5 mL syringe with
every  sample  and  reference  standard  analyzed.    If  the  internal  standard
calibration procedure is used,  the  surrogate  compounds may be added directly to
the internal standard spiking solution (Section 5.7.2).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the  introductory material  to  this  Chapter, Organic  Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1    Volatile compounds are introduced into the gas chromatograph using
either direct injection or purge-and-trap (Method 5030).  Method 5030 may be used
directly on  ground  water samples or  low-concentration  contaminated soils and
sediments.  For medium-concentration  soils  or sediments, methanolic extraction,
as described in Method  5030,  may  be necessary prior to purge-and-trap analysis.

      7.2    Gas  chromatographic  conditions (Recommended)

             7.2.1  Column 1:

             Helium  flow  rate = 40 mL/min
             Temperature  program:
                   Initial  temperature =   45°C, hold for 3 minutes
                   Program =                45°C to 220°C at 8°C/min
                   Final  temperature  =     220°C, hold for 15 minutes.

             7.2.2  Column 2:

             Helium  flow  rate = 40 mL/min
             Temperature  program:
                   Initial  temperature =   50°C, hold for 3 minutes
                   Program =                50°C to 170°C at 6°C/min
                   Final  temperature  =     170°C, hold for 4 minutes.

      7.3    Calibration. The procedure for internal or external  calibration may
be used.  Refer to Method 8000 for a description of each of these  procedures. Use


                                   8010B -  6                         Revision  2
                                                                  November 1992
-------
Table 1 and Table 2 for guidance on  selecting the lowest point  on the calibration
curve.

             7.3.1  Calibration must take place using the same sample introduction
      method that will be used to analyze actual samples (see Section 7.4.1).

      7.4    Gas chromatographic  analysis

             7.4.1  Introduce volatile compounds into the gas chromatograph using
      either Method  5030  (purge-and-trap)  or  the direct  injection method (see
      Section 7.4.1.1).  If  the internal standard calibration  technique is used,
      add  10 nl of  internal  standard to the sample  prior to  purging.

                   7.4.1.1     In very limited applications (e.g. aqueous process
             wastes)  direct  injection  of the sample onto the GC  column  with a
             10 p,L  syringe may be appropriate.   The detection  limit is very high
             (approximately  10,000  M9/L)  therefore,  it is only permitted where
             concentrations  in excess of 10,000 M9/L are expected or for water-
             soluble  compounds that do not purge.   The  system  must be calibrated
             by direct  injection  (bypassing the purge-and-trap device).

             7.4.2  Method  8000 provides instructions on the  analysis sequence,
      appropriate  dilutions, establishing daily retention   time  windows,  and
      identification criteria.  Include a mid-concentration standard after each
      group  of 10 samples in  the analysis sequence.

             7.4.3  Table  1  summarizes  the  estimated retention times  on the two
      columns for a  number  of organic  compounds  analyzable  using this method.
      An example of  the separation achieved by Column  1 is shown in Figure 1.

             7.4.4  Record the sample volume purged or injected and the resulting
      peak sizes (in area units or peak heights).

             7.4.5  Refer   to  Method   8000   for  guidance  on  calculation  of
      concentration.

             7.4.6  If analytical interferences are suspected,  or for the purpose
      of confirmation, analysis using  the second GC column is recommended.

             7.4.7  If the  response  for  a peak  is off-scale,  prepare  a dilution
      of the sample with organic-free reagent  water.   The dilution must  be
      performed on a second  aliquot of  the sample which has been properly sealed
      and  stored prior to use.


8.0   QUALITY CONTROL

      8.1    Refer  to Chapter One for  specific quality control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control  to  ensure the
proper operation of the purge-and-trap device  is covered in  Method 5030.

      8.2    Quality  control required  to validate  the GC system  operation  is
found in Method 8000.
                                   8010B  -  7                         Revision 2
                                                                 November 1992
-------
            8.2.1  The  quality control  check sample concentrate  (Method  8000)
      should contain each analyte of interest at a concentration of 10 mg/L in
      methanol.

            8.2.2  Table 3 indicates the calibration and QC acceptance criteria
      for this method.  Table 4 gives method accuracy and precision as functions
      of  concentration for  the  analytes  of interest.   The contents  of both
      Tables should be used to  evaluate  a laboratory's  ability to perform and
      generate acceptable data by this method.

      8.3   Calculate  surrogate  standard  recovery  on  all  samples,  blanks, and
spikes.  Determine  if recovery  is within limits (limits  established by performing
QC procedure outlined  in Method 8000).

            8.3.1  If recovery  is not within limits, the following is required:

                   •     Check   to  be  sure  that  there   are   no   errors  in
            calculations, surrogate  solutions  and internal  standards.   Also,
            check  instrument performance.

                   •      Recalculate  the  data and/or  re-analyze  the  sample if
            any of the above checks reveal a problem.

                   •     Re-extract  and re-analyze  the sample  if none of the
            above  are  a problem or flag the data as "estimated concentration".


9.0   METHOD PERFORMANCE

      9.1   This method was  tested by 20 laboratories using organic-free reagent
water, drinking water,  surface water, and three industrial wastewaters spiked at
six concentrations over  the range 8.0-500  ng/L.   Single  operator precision,
overall  precision,  and  method  accuracy were  found to be directly related to the
concentration of the  analyte,  and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 4.

      9.2   The accuracy and precision obtained will be determined by the sample
matrix,  sample introduction technique,  and by the calibration procedure used.


10.0  REFERENCES

1.    Bellar, T.A.; Lichtenberg, J.J.  Jj. Amer.  Water Works Assoc. 1974, 66(12).
      pp. 739-744.

2.    Bellar,  T.A.;  Lichtenberg, J.J.,  Semi-Automated Headspace  Analysis of
      Drinking  Waters  and  Industrial  Waters  for  Purgeable  Volatile  Organic
      Compounds, Measurement of Organic Pollutants  in  Water and Wastewater; Van
      Hall, Ed.; ASTM  STP 686, pp 108-129,  1979.

3.    "Development and Application of Test Procedures for Specific Organic Toxic
      Substances  in  Wastewaters: Category  11  -  Purgeables and  Category 12  -
      Acrolein,  Acrylonitrile,   and  Dichlorodifluoromethane";  report  for EPA
      Contract 68-03-2635 (in preparation).

                                  8010B  - 8                        Revision  2
                                                                 November  1992
-------
      U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
      Analysis of Pollutants Under the Clean Water Act:  Final  Rule and Interim
      Final Rule and Proposed Rule", October 26, 1984.

5.     "EPA Method  Validation Study  23,  Method 601  (Purgeable  Halocarbons)";
      Report for EPA Contract 68-03-2856 (in preparation).

5.     Gebhart, J.E., S.V. Lucas, S.J. Naber, A.M.  Berry,  T.H.  Danison and H.M.
      Burkholder, "Validation of SW-846 Methods 8010, 8015, and 8020";  Report
      for  EPA Contract  68-03-1760,  Work  Assignment  2-15;    US  EPA,  EMSL-
      Cincinnati, 1987.
                                  8010B - 9                         Revision 2
                                                                 November 1992
-------
                       TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
           FOR HALOGENATED VOLATILE ORGANICS
Compound
Ally chloride ^
Benzyl chloride 'c
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bromobenzene
Bromodichloromethane
Bromoform*
Bromomethane
Carbon tetrachloride
Chi oroacetal dehyde*
Chlorobenzene*
Chloroethane
Chloroform
1-Chlorohexane ^
2-Chloroethyltvinyl ether
Chloromethane* ^
Chloromethyl methyl ether
4-Chlorotoluene
Dibromochloromethane
l,2-Dibromo-3-chloropropane*
Dibromomethane
1,2-Di chlorobenzene*
1,3-Di chlorobenzene*
1,4-Di chlorobenzene*
l,4-Dichloro-2-butene
Dichlorodifluoromethane '
1,1-Dichloroethane^
1,2-Di chloroethane^
1,1-Dichloroethene f
trans-l,2-Dichloroethene
Dichloromethane
1,2-Dichloropropane* ^
trans -1,3-Dichloropropene
Ethyl ene di bromide t
1,1,2 , 2-Tetrachl oroethane^
1,1,1 , 2-Tetrachl oroethane
Tetrachloroethene*
1 , 1 , 1 -Tri chl oroethane^
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane^
1,2,3-Trichlorppropane
Vinyl Chloride
CAS
Registry
Number
107-05-1
100-44-7
111-91-1
39638-32-9
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
108-90-7
75-00-3
67-66-3
544-10-5
110-75-8
74-87-3
107-30-2
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
10061-02-5
106-93-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
Retention Time
(minutes)
Column 1 Column 2
10.17
30.29
38.60
34.79
29.05
15.44
21.12
2.90
14.58
(b)
25.49
5.18
12.62
26.26
19.23
1.40
8.88
34.46
18.22
28.09
13.83
37.96
36.88
38.64
23.45
3.68
11.21
13.14
10.04
11.97
7.56
16.69
16.976
19.59
23.12
21.10
23.05
14.48
18.27
17.40
9.26
22.95
3.25
(b)
(b)
(b)
(b)
(b)
14.62
19.17
7.05
11.07
(b)
18.83
8.68
12.08
(b)
(b)
5.28
(b)
(b)
16.62
(b)
14.92
23.52
22.43
22.33
(b)
(b)
12.57
15.35
7.72
9.38
10.12
16.62
16.60
(b)
(b)
21.70
14.97
13.10
18.07
13.12
(b)
(b)
5.28
Method
Detection
Limit3
(M9/L)
(b)
(b)
(b)
(b)
(b)
0.002
0.020
0.030
0.003
(b)
0.001
0.008
0.002
(b)
0.130
0.010
(b)
(b)
(b)
0.030
(b)
(b)
(b)
(b)
(b)
(b)
0.002
0.002
0.003
0.002
(b)
(b)
0.340
(b)
0.010
(b)
0.001
0.003
0.007
0.001
(b)
(b)
0.006
                       8010B - 10
   Revision 2
November 1992
-------
                                   TABLE 1.
                                   Continued
a = Using purge-and-trap method (Method 5030)
b = Not determined
* = Appendix VIII compounds
c = Demonstrated very erratic results when tested by purge-and-trap
d = See Section  4.10.2  of Method  5030  for guidance on  selection  of trapping
    material
e = Estimated retention time
                                   TABLE 2.
             DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
                             FOR VARIOUS MATRICES3
               Matrix                              Factor6
               Ground water                             10
               Low-concentration soil                   10
               Water miscible liquid waste             500
               High-concentration soil and sludge     1250
               Non-water miscible waste               1250
               Sample EQLs are highly matrix-dependent.  The EQLs listed herein
               are provided for guidance and may not always be achievable.

               EQL = [Method  detection  limit  (Table  1)]  X [Factor (Table 2)].
               For non-aqueous samples, the factor is on a wet-weight basis.
                                  8010B - 11                        Revision 2
                                                                 November 1992
-------
                                   TABLE 3.
                    CALIBRATION  AND QC ACCEPTANCE CRITERIA8
Range Limit
for Q for S
Analyte
Bromodi chloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chl oroethane
2-Chloroethylvinyl ether
Chloroform
Chloromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1,2-Di chl oroethene
Dichloromethane
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans - 1 , 3 -Di chl oropropene
1,1,2, 2 -Tetrachl oroethane
Tetrachl oroethene
1 , 1 , 1-Tri chl oroethane
1 , 1 , 2-Tri chl oroethane
Tri chl oroethene
Tri chl orof 1 uoromethane
Vinyl chloride
(M9/L) (M9/L)
15.2-24.8
14.7-25.3
11.7-28.3
13.7-26.3
14.4-25.6
15.4-24.6
12.0-28.0
15.0-25.0
11.9-28.1
13.1-26.9
14.0-26.0
9.9-30.1
13.9-26.1
16.8-23.2
14.3-25.7
12.6-27.4
12.8-27.2
15.5-24.5
14.8-25.2
12.8-27.2
12.8-27.2
9.8-30.2
14.0-26.0
14.2-25.8
15.7-24.3
15.4-24.6
13.3-26.7
13.7-26.3
4.3
4.7
7.6
5.6
5.0
4.4
8.3
4.5
7.4
6.3
5.5
9.1
5.5
3.2
5.2
6.6
6.4
4.0
5.2
7.3
7.3
9.2
5.4
4.9
3.9
4.2
6.0
5.7
Q = Concentration measured in QC check sampl
Range
for x
(M9/L)
10.7-32.0
5.0-29.3
3.4-24.5
11.8-25.3
10.2-27.4
11.3-25.2
4.5-35.5
12.4-24.0
D-34.9
7.9-35.1
1.7-38.9
6.2-32.6
11.5-25.5
11.2-24.6
13.0-26.5
10.2-27.3
11.4-27.1
7.0-27.6
10.1-29.9
6.2-33.8
6.2-33.8
6.6-31.8
8.1-29.6
10.8-24.8
9.6-25.4
9.2-26.6
7.4-28.1
8.2-29.9
e, in /ug/L.
Range
P,ePs

42-172
13-159
D-144
43-143
38-150
46-137
14-186
49-133
D-193
24-191
D-208
7-187
42-143
47-132
51-147
28-167
38-155
25-162
44-156
22-178
22-178
8-184
26-162
41-138
39-136
35-146
21-156
28-163

s = Standard deviation of four recovery measurements, in jitg/L.
X = Average recovery
P, P = Percent recovery
S
D = Detected; result
for four recovery measurements, in Mg/L.
measured.
must be greater



than zero.
a     Criteria from 40 CFR Part 136 for Method 601  and were calculated  assuming
      a QC check  sample concentration  of  20 /itg/L.
                                  8010B - 12
   Revision 2
November 1992
-------
                                TABLE 4.
      METHOD ACCURACY AND PRECISION AS  FUNCTIONS OF CONCENTRATION8
Analyte
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1, 4 -Di chlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
Di chloromethane
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropeneb
1 , 1 ,2,2-Tetrachloroethane
Tetrachl oroethene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(M9/L)
1.12C-1.02
0.96C-2.05
0.76C-1.27
0.98C-1.04
l.OOC-1.23
0.99C-1.53
l.OOC
0.93C-0.39
0.77C+0.18
0.94C+2.72
0.93C+1.70
0.95C+0.43
0.93C-0.09
0.95C-1.08
1.04C-1.06
0.98C-0.87
0.97C-0.16
0.91C-0.93
l.OOC
l.OOC
l.OOC
0.95C+0.19
0.94C+0.06
0.90C-0.16
0.86C+0.30
0.87C+0.48
0.89C-0.07
0.97C-0.36
Single analyst
precision, s '
(M9/L)
0.11X+0.04
0.12X+0.58
0.28X+0.27
0.15X+0.38
0.15X-0.02
0.14X-0.13
0.20X
0.13X+0.15
0.28X-0.31
0.11X+1.10
0.20X+0.97
0.14X+2.33
0.15X+0.29
0.08X+0.17
0.11X+0.70
0.21X-0.23
0.11X+1.46
0.11X+0.33
0.13X
0.18X
0.18X
0.14X+2.41
0.14X+0.38
0.15X+0.04
0.13X-0.14
0.13X-0.03
0.15X+0.67
0.13X+0.65
Overall
precision,
S' (M9/L)
0.20X+1.00
0.21X+2.41
0.36X+0.94
0.20X+0.39
0.18X+1.21
0.17X+0.63
0.35X
0.19X-0.02
0.52X+1.31
0.24X+1.68
0.13X+6.13
0.26X+2.34
0.20X+0.41
0.14X+0.94
0.15X+0.94
0.29X-0.04
0.17X+1.46
0.21X+1.43
0.23X
0.32X
0.32X
0.23X+2.79
0.18X+2.21
0.20X+0.37
0.19X+0.67
0.23X+0.30
0.26X+0.91
0.27X+0.40
x' =


sr'=

S' =


C  =

X  =
      Expected recovery for one or more measurements of a sample containing
      a concentration of C, in /jg/L.

      Expected  single analyst  standard deviation  of  measurements  at  an
      average concentration of x, in M9/L.

      Expected  interlaboratory  standard  deviation  of  measurements  at  an
      average concentration found of x, in /xg/L.

      True value for the concentration, in
      Average  recovery  found  for  measurements  of  samples  containing  a
      concentration of C, in
a From 40 CFR Part 136 for Method 601.

b
  Estimates  based upon the performance in a single  laboratory.
                               8010B - 13
                                                                 Revision 2
                                                              November 1992
-------
                 FIGURE 1.
      GAS CHROMATOGRAM OF HALOGENATED VOLATILE ORGANICS

! 6
  i
fl *
            !
•   »
i
UjLjUUUUU
                            5
                            6

         10 17  14
                10  1« TO 77  74


                NCTf WTIOM TIMC IMIMUTHI
                                 37  34
                8010B - 14
                         Revision 2
                       November 1992
-------
                            METHOD 8010B
        HALOGENATED VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
    7.2  Set
chxomatographlc
  c ond i 11 on*
 7 . 3  Calibrate
   (refer  co
 Method tOO 0)
7.4.x  Introduce
• amp1 e  into GC
   by  d i r «c c
 7.4.2  Follow
  Method  «000
   sequence,
     etc.
7.4.4  Record
volume  purged
     o r
injected,and
      sizes.
                        7.4 6  Analy ze
                        • ample  u» i no
                           B a ccnd  QC
                           column.
                        7.4.7  Diluce
                           ••cond
                         all QUO t  of
                           & amp1e.
                             8010B - 15
                                     Revision 2
                                  November 1992
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                                Method 8011

         1.2-DIBROMOETHANE AND 1.2-DIBROMO-3-CHLOROPROPANE IN WATER
                  BY  MICROEXTRACTION AND GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION

    1.1  This  method is  applicable to  the determination  of  the  following
compounds in drinking water and ground water:

                                         Chemical Abstracts Service
         Analvte                              Registry Number

    1,2-Dibromoethane (EDB)                      106-93-4
    l,2-Dibromo-3-chloropropane (DBCP)             96-12-8

    1.2  For compounds other than the above mentioned  analytes,  or  for other
matrices,  the  laboratory  must  demonstrate  the  usefulness  of the  method  by
collecting  precision  and  accuracy data  on  actual  samples  and provide
qualitative  confirmation  of results by  gas  chromatography/mass spectrometry
(GC/MS).

    1.3  The experimentally determined method detection limits  (MDL) for  EDB
and DBCP were  calculated to be 0.01 ug/L.   The method has been  shown  to  be
useful  for  these  analytes  over  a  concentration  range  from approximately 0.03
to  200  ug/L.    Actual  detection   limits  are  highly  dependent  upon  the
characteristics  of the  gas  chromatographic  system,  sample  matrix,  and
calibration.

    1.4  This  method is  restricted to  use  by  or  under  the  Supervision  of
analysts  experienced  in  the  use  of gas   chromatography  and  in  the
interpretation of gas chromatograms.  Each analyst must demonstrate the ability
to generate  acceptable results with this method  using the procedure described
in Step 8.2.

    1.5  1,2-Dibromoethane  and  1,2-Dibromo-3-chloropropane  have been
tentatively  classified as  known or  suspected human  or mammalian carcinogens.
Pure standard materials  and stock  standard solutions of these compounds  should
be handled  in  a  hood.   A  NIOSH/MESA approved toxic gas  respirator  should  be
worn when the analyst handles high concentrations of these toxic compounds.

2.0 SUMMARY OF METHOD

    2.1  Thirty five mL of  sample are extracted with 2 mL of  hexane.   Two  uL
of the  extract are  then  injected  into a gas  chromatograph equipped with  a
linearized   electron  capture detector for separation  and  analysis.  Aqueous
matrix spikes are extracted and  analyzed in an identical manner as the samples
in order to compensate for  possible  extraction losses.

    2.2  The extraction  and  analysis  time  is  30  to  50  minutes per  sample
depending upon  the analytical  conditions chosen.   See Table 1 and Figure  1.


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    2.3  Confirmatory evidence is obtained using a different  column  (Table  1).

3.0 INTERFERENCES

    3.1  Impurities  contained  in the  extracting  solvent  (hexane)  usually
account for the majority of the analytical problems.   Reagent blanks should be
analyzed on each  new bottle of  hexane  before  use.   Indirect daily checks on
the  hexane are  obtained  by  monitoring  the calibration  and reagent blanks.
Whenever  an  interference  is  noted  in the  method or  instrument  blank,  the
laboratory should reanalyze the hexane.   Low level  interferences  generally  can
be removed  by distillation  or column chromatography however, it is generally
more economical to obtain  a new source of hexane  solvent.   Interference-free
hexane is defined as containing  less than 0.01  ug/L of  the analytes.  Protect
interference-free hexane   by  storing  it in  an  area  known  to be  free of
organochlorine solvents.

    3.2  Several  instances of  accidental  sample  contamination  have been
attributed to diffusion of  volatile  organics through the  septum  seal  into  the
sample  bottle during  shipment and  storage.    Field  blanks  must be  used to
monitor for this problem.

    3.3  This liquid/liquid extraction technique extracts  a wide  boiling range
of non-polar  organic  compounds and,  in addition, extracts some  polar organic
compounds.

    3.4  EDB  at low  concentrations  may  be masked by very  high  levels of
dibromochloromethane  (DBCM), a common  chlorinated  drinking water contaminant,
when using the confirmation column.

4.0 APPARATUS AND MATERIALS

    4.1  Microsyringe  -  10, 25,  and 100 uL with a  2  in x 0.006  in  needle
    4.1   Microsyringe -  10,  2
(Hamilton 702N or equivalent).

    4.2   Gas Chromatograph
         4.2.1  The GC  must  be capable of temperature programming  and  should
    be  equipped  with  a linearized  electron  capture detector and a capillary
    column splitless injector.

         4.2.2  Two gas chromatography columns are recommended.   Column  A is  a
    highly efficient column that provides separations for EDB and DBCP without
    interferences from  trihalomethanes.   Column  A should  be  used as  the
    primary  analytical  column  unless  routinely occurring  analytes are  not
    adequately resolved.   Column B  is  recommended  for use as  a confirmatory
    column when  GC/MS  confirmation  is  not  available.   Retention times for EDB
    and DBCP on  these columns are presented in Table 1.

         4.2.3   Column  A  - 0.32 mm i.d.  x 30  m fused silica  capillary with
    dimethyl silicone mixed phase (Durawax-DX 3, 0.25 urn film, or equivalent).
    The linear velocity of the helium carrier gas is established at  25 cm/sec.
    The column temperature is programmed  to hold at 40°C  for 4 minutes, then
    increase to  190°C  at 8°C/min,   and  hold  at  190°C for  25  minutes  or  until

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    all  expected  compounds  have  eluted.    Injector  temperature:   200°C.
    Detector temperature:  290°C.  See Figure 1 for a sample chromatogram and
    Table 1 for retention data.

         4.2.4  Column B  (confirmation  column)  - 0.32  mm  i.d. x  30  m fused
    silica capillary  with  methyl  polysiloxane phase  (DB-1,  0.25  urn film, or
    equivalent).  The linear velocity of the  helium  carrier gas  is  established
    at 25  cm/sec.   The column temperature is programmed to  hold  at 40°C for
    4  minutes,  then  increase  to 270°C  at  10°C/min, and  hold at  270"C  for
    10 minutes  or until  all  expected  compounds  have  eluted.   Injector
    temperature:   200°C.   Detector temperature:   290°C.    See Table  1  for
    retention data.

5.0 REAGENTS

    5.1  Hexane, €5^4.  UV grade (Burdick and Jackson #216 or  equivalent).

    5.2  Methyl  alcohol,  CH30H.   Demonstrated  to  be  free of analytes.

    5.3  Sodium chloride, NaCl .   Pulverize a  batch  of NaCl  and place it  in a
muffle furnace  at room  temperature.   Increase  the  temperature to 400°C  for
30 minutes.  Place it in  a bottle and cap.

    5.4  1,2-Dibromoethane (99%),  C2H4Br2, (Aldrich  Chemical  Company).
    5.5  l,2-Dibromo-3-chloropropane  (99.4%),  CsHsB^Cl ,   (AMVAC  Chemical
Corporation, Los Angeles,  California).

    5.6  ASTM Type II Water (ASTM D1193-77  (1983)). All  references to water in
the method  refer  to  ASTM  Type  II unless otherwise  specified.  Must be free of
interferents at the method detection limit (MDL) of the analytes of interest.
ASTM Type II water is further purified by any  of the following techniques:

         5.6.1  Water may be generated  by  passing  tap water  through a carbon
    filter  bed containing  about  453 g of  activated  carbon  (Calgon  Corp.,
    Filtrasorb-300 or equivalent).

         5.6.2  A water purification  system  (Millipore  Milli-Q  Plus with the
    Organex-Q cartridge or equivalent) may  be  used  to  generate water.

         5.6.3  Water may also  be  prepared by boiling  water  for 15 minutes.
    Subsequently, while  maintaining  the temperature  at   90"C,  bubble  a
    contaminant-free inert gas through the  water for 1 hour. While it is  still
    hot, transfer the water to a narrow-mouth  screw-cap  bottle and seal with a
    Teflon  lined septum and cap.

    5.7  Stock  standards  -  These  solutions  may  be  purchased  as  certified
solutions or prepared from pure standards using  the following  procedures:

         5.7.1  Place  about  9.8  ml of  methanol   into  a  10-mL  ground  glass
    stoppered  volumetric  flask.   Allow  the flask  to  stand,  unstoppered, for
    about 10 minutes and weigh to the nearest  0.1 mg.


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         5.7.2  Use a  25-uL  syringe and  immediately add  two  or more  drops
    ( ~ 10  uL)  of  standard  to  the  flask.   Be  sure  that the  standard  falls
    directly into the  alcohol without contacting the neck of the flask.

         5.7.3  Reweigh,  dilute  to volume,  stopper,  then mix by inverting the
    flask  several  times.   Calculate  the  concentration  in  micrograms  per
    microliter from the net  gain  in  weight  (approximately 1000 ug/L).

         5.7.4  Store   stock  standards  in  15-mL  bottles equipped  with  PTFE
    lined screw-caps.   Stock standards  are  stable  for at least four weeks when
    stored at 4eC and  away from  light.

    5.8  Intermediate standard  - Use  stock  standards  to  prepare  an
intermediate  standard  that  contains both  analytes  in methanol.    The
intermediate standard  should be  prepared  at a  concentration  that can be easily
diluted to prepare aqueous calibration  standards that will bracket the working
concentration range.   Store  the  intermediate  standard  with minimal  headspace
and  check  frequently   for  signs  of deterioration or  evaporation, especially
just before  preparing  calibration standards.   The storage time described for
stock standards also applies to  the  intermediate standard.

    5.9  Quality control  (QC)  reference sample - Prepare  a QC reference sample
concentrate  at  0.25  ug/mL of both  analytes from standards  from  a  different
source than the standards used for the  stock standard.

    5.10 Reagent grade inorganic chemicals  shall be used in all tests. Unless
otherwise indicated, it is intended that all  inorganic reagents shall conform
to the specifications  of the Committee on  Analytical Reagents of  the American
Chemical  Society, where such specifications are available. Other grades may be
used, provided  it is   first  ascertained  that  the reagent  is  of  sufficiently
high  purity to  permit  its use  without lessening   the  accuracy of  the
determination.

    5.11 Check  standard  -  Add  an  appropriate  volume  of the  intermediate
standard to  an  aliquot of  water  in  a  volumetric flask.   Do not add less than
20 uL  of an  alcoholic intermediate standard  to the water  or  poor precision
will  result.   Use a  25-uL microsyringe  and  rapidly  inject  the  alcoholic
intermediate standard  into the  expanded  area  of the almost filled volumetric
flask.   Remove the needle  as  quickly as  possible  after injection.   Mix by
inverting the flask several  times.  Discard the contents  contained in the neck
of the flask.  Aqueous calibration standards should be prepared every 8 hours.

6.0 SAMPLE COLLECTION, PRESERVATION, AND  STORAGE

    6.1  See the introductory material  to this chapter,  Organic Analytes, Step
4.1.

7.0 PROCEDURE

    7.1  Calibration

         7.1.1  At least  five  calibration  standards are  needed.   One should
    contain  EDB and DBCP at a concentration near,  but greater than,  the method

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detection limit  (Table  1) for  each compound.   The others  should  be at
concentrations that bracket the range  expected  in  samples.   For example,
if the MDL  is 0.01 ug/L, and a sample expected to contain  approximately
0.10  ug/L  is  to be  analyzed,  aqueous  calibration standards  should be
prepared at concentrations of 0.03 ug/L, 0.05 ug/L, 0.10 ug/L, 0.15 ug/L,
and 0.20 ug/L.

     7.1.2  Analyze each calibration standard and tabulate peak height or
area  response  versus  the  concentration  in the  standard.    Prepare  a
calibration  curve  for  each  compound.  Alternatively,  if  the  ratio of
response  to   concentration  (calibration  factor) is  a constant  over  the
working  range  (<  10%  relative standard  deviation),  linearity  can be
assumed and the  average  ratio or  calibration  factor can  be used in place
of a calibration curve.

7.2  Sample preparation

     7.2.1  Remove  samples and  standards  from  storage and  allow them to
reach room temperature.

     7.2.2  For  samples and  field blanks  contained  in  40-mL  bottles,
remove the  container  cap.  Discard  a 5-mL volume  using  a 5-mL transfer
pipet.  Replace the container  cap  and  weigh  the  container with contents to
the  nearest  0.1 g  and  record  this  weight for  subsequent  sample volume
determination.

     7.2.3  For  calibration  standards,  check  standards,  QC  reference
samples,  and  blanks,  measure  a  35-mL  volume   using  a 50-mL  graduated
cylinder and transfer it to  a  40-mL sample  container.

7.3  Extraction

     7.3.1  Remove the container cap and  add 7 g of NaCl to  all  samples.

     7.3.2  Recap the sample  container and  dissolve the NaCl  by  shaking by
hand for about 20 seconds.

     7.3.3  Remove  the  cap and using  a  transfer  pipet,  add  2.0  mL of
hexane.  Recap and shake vigorously by hand  for  1 minute.  Allow the water
and  hexane  phases  to  separate.   If stored  at  this  stage,   keep  the
container upside down.

     7.3.4  Remove  the  cap and carefully  transfer a  sufficient  amount
(0.5-1.0 mL)  of the hexane  layer into a  vial  using  a  disposable glass
pipet.

     7.3.5  Transfer the  remaining  hexane phase,  being  careful  not to
include any of the  water  phase, into  a second vial.   Reserve this second
vial  at 4°C for reanalysis if  necessary.
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    7.4  Analysis

         7.4.1   Transfer  the first  sample  vial  to  an  autosampler set  up  to
    inject  2.0  uL  portions  into  the  gas chromatograph  for analysis.
    Alternately,  2  uL portions  of  samples,  blanks  and  standards may  be
    manually injected,  although  an  auto  sampler is strongly recommended.

    7.5  Determination  of  sample volume

         7.5.1   For samples and field blanks, remove the  cap from the sample
    container.  Discard the remaining sample/hexane mixture.   Shake  off the
    remaining few drops using short, brisk wrist movements. Reweigh the empty
    container with  original  cap and  calculate  the net  weight of  sample  by
    difference  to  the  nearest  0.1  g.   This  net weight  is  equivalent to the
    volume of water extracted.

    7.6  Calculations

         7.6.1   Identify  EDB and DBCP in the sample chromatogram by comparing
    the retention time  of  the suspect peak  to retention times generated by the
    calibration standards  and the check  standard.

         7.6.2   Use the calibration  curve  or calibration  factor  to  directly
    calculate the uncorrected concentration (C-j) of  each  analyte in the sample
    (e.g. calibration factor x response).

         7.6.3   Calculate  the sample  volume  (Vs)  as equal  to  the net sample
    weight:

         Vs (ml) = gross weight  (grams)  - bottle tare (grams)

         7.6.4   Calculate  the corrected  sample concentration  as:

         Concentration  (ug/L) =  Ci  x 35
                                     VS

         7.6.5   Report  the results  for the  unknown samples  in ug/L.  Round the
    results to  the nearest 0.01  ug/L or  two significant figures.

8.0 QUALITY CONTROL

    8.1  Each laboratory that uses  this  method is required  to operate  a formal
quality control program.

         8.1.1   The  laboratory  must  make  an  initial  determination of the
    method detection limits and  demonstrate the  ability to  generate acceptable
    accuracy and precision with  this method.  This is established  as described
    in Step 8.2.

         8.1.2   In recognition  of  laboratory advances that  are  occurring in
    chromatography, the laboratory  is permitted  certain options to  improve the
    separations  or  lower  the cost of  measurements.    Each time such  a


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    modification is made to the method,  the analyst is required to repeat the
    procedure in Steps 7.1  and  8.2.

         8.1.3  The laboratory  must  analyze a reagent and calibration blank to
    demonstrate that  interferences  from the  analytical  system are  under
    control  every  twenty  samples or  per  analytical  batch whichever  is  more
    frequent.

         8.1.4  The laboratory  must, on  an ongoing basis, demonstrate through
    the  analyses  of QC  reference samples  and  check  standards that  the
    operation of the measurement system is in control.   The frequency of the
    check standard analyses  is equivalent  to  5% of  all  samples  or  every
    analytical batch, whichever  is  more frequent.  On  a weekly basis, the QC
    reference sample must  be run.

    8.2  To  establish the  ability to achieve low  detection limits  and generate
acceptable  accuracy  and  precision, the  analyst must  perform  the following
operations:

         8.2.1  Prepare seven samples each at a concentration of 0.03 ug/L.

         8.2.2  Analyze the samples  according   to  the  method beginning  in
    Section  7.0.

         8.2.3  Calculate  the  average concentration  (X)  in  ug/L  and  the
    standard  deviation  of  the concentrations (s)  in ug/L, for  each analyte
    using the seven  results.   Then  calculate the MDL at 99% confidence level
    for seven replicates as 3.143s.

         8.2.4  For  each  analyte  in an  aqueous matrix sampler, X  must be
    between  60%  and  140%  of the true value.   Additionally, the  MDL may not
    exceed  the  0.03 ug/L  spiked concentration.    If both  analytes  meet the
    acceptance criteria, the system performance   is acceptable and analysis of
    actual  samples can  begin.    If  either analyte  fails  to  meet a criterion,
    repeat  the  test.    It  is  recommended  that  the laboratory  repeat  the MDL
    determination on a regular  basis.

    8.3  The  laboratory must demonstrate  on  a  frequency  equivalent  to  5% of
the sample load  or once per analytical batch, whichever  is more frequent, that
the measurement  system  is   in  control by  analyzing a check standard  of both
analytes at  0.25 ug/L.

         8.3.1  Prepare a  check  standard  (0.25  ug/L)  by  diluting  the
    intermediate standard with  water to  0.25 ug/L.

         8.3.2  Analyze the sample according  to  Section 7.0 and calculate the
    recovery for each analyte.    The recovery must  be between  60% and 140% of
    the expected  value  for  aqueous  matrices.  For non-aqueous  matrices,  the
    U.S. EPA will set criteria  after more  interlaboratory data are gathered.

         8.3.3  If  the recovery  for  either  analyte  falls outside  the
    designated range, the  analyte fails  the acceptance criteria.   A second
    calibration  verification standard  containing  each analyte that failed must

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    be analyzed.   Repeated  failure,  however, will confirm  a  general  problem
    with  the  measurement  system.    If this occurs,  locate and  correct  the
    source of the problem and  repeat  the test.

    8.4  On a  weekly  basis,  the laboratory  must demonstrate the  ability to
analyze a QC reference sample.

         8.4.1  Prepare a QC reference sample at 0.10 ug/L by diluting the QC
    reference sample concentrate  (Step  5.9).

         8.4.2  For each analyte in  an aqueous matrix, the  recovery  must be
    between 60% and 140% of  the expected value.   When either analyte fails the
    test, the analyst must repeat the test only for that analyte which failed
    to meet the  criteria.   Repeated  failure,  however,  will  confirm a general
    problem with  the  measurement system or  faulty  samples  and/or standards.
    If this occurs,  locate  and  correct the source of  the  problem and repeat
    the test.  For  non-aqueous matrices, the  U.S.  EPA will  set criteria after
    more interlaboratory data  are gathered.

    8.5  Instrument  performance  -  Check the  performance of  the  entire
analytical  system daily using data  gathered from  analyses  of  blanks,
standards, and replicate samples.

         8.5.1  Peak  tailing  significantly  in  excess  of  that shown  in  the
    chromatogram (Figure 1)  must  be corrected.   Tailing  problems are generally
    traceable to active sites  on  the  GC column  or to  the detector  operation.

         8.5.2  Check  the precision  between replicate  analyses.   A properly
    operating  system  should  perform with  an  average  relative  standard
    deviation  of less  than  10%.   Poor  precision is  generally  traceable to
    pneumatic leaks, especially  at  the injection port.

9.0 METHOD PERFORMANCE

    9.1  Single laboratory accuracy and precision at  several concentrations in
tap water are presented in Table  2.   The method  detection  limits are presented
in Table 1.

    9.2  In a  preservation  study extending  over a 4 week period,  the  average
percent  recoveries  and  relative  standard deviations presented in Table 3  were
observed for  reagent water  (acidified),  tap  water  and  ground  water.   The
results  for  acidified and  non-acidified  samples  were not  significantly
different.

10.0  REFERENCES

1.  Optimization of Liquid-Liquid Extraction Methods for Analysis of Orqanics
    in Water. EPA-600/S4-83-052,  1984.

2.  Henderson, J.E.; Peyton,  G.R.;  Glaze,  W.H.  Identification  and Analysis of
    Organic Pollutants  in Water; Keith, L.H.,  Ed; Ann Arbor Sci.: Ann Arbor,
    MI;  1976.


                                 8011 - 8                        Revision  0
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3.  Richard J.J.;  Junk,  G.A.  Journal AWWA 1977, 69, 62.

4.  Handbook for Analytical  Quality  Control  in  Water  and  Wastewater
    Laboratories,  EPA-600/4-79-019,  U.S.  Environmental  Protection  Agency.
    Environmental  Monitorning and  Support Laboratory, Cincinnati, OH, 1979.

5.  Budde, W.L.; Eichelberger,  J.W.  Organic Analyses Using Gas Chromatography-
    Mass Spectormetrv;  Ann Arbor Science: Ann Arbor, MI; 1978.

6.  Glaser, J.A.;  et al.  Environmental Science and Technology 1981, 15, 1426.

7.  Methods  for the  Determination of Organic Compounds in  Finished Drinking
    Water  and  Raw Source Water;  U.S.  Environmental  Protection  Agency.
    Environmental  Monitoring  and Support Laboratory, Cincinnati, OH, 1986.

8.  Rohrbough,  W.G.;  et  al.  Reagent  Chemicals. American  Chemical  Society
    Specifications. 7th  ed.;  American  Chemical Society: Washington, DC, 1986.

9.  1985 Annual  Book  of ASTM  Standards. Vol.  11.01;  "Standard Specification
    for Reagent  Water";  ATSM:  Philadelphia, PA, 1985; D1193-77.

10.  Methods  for the  Determination of Organic Compounds in  Finished Drinking
    Water and Raw  Source  Water; U.S.  Environmental  Protection  Agency.  Office
    of  Research  and  Development.  Environmental  Monitoring  and  Support
    Laboratory.   ORD Publication Offices of Center for Environmental Research
    Information:  Cincinnati,  OH 1986.
                                8011 - 9                        Revision  0
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                                  TABLE 1.
               CHROMATOGRAPHIC  CONDITIONS  AND  METHOD  DETECTION
                LIMITS  (MDL)  FOR  1,2-DIBROMOETHANE  (EDB)  AND
                     l,2-DIBROMO-3-CHLOROPROPANE (DBCP)
Analyte
Retention Time, Minutes
  Column A    Column B
                 MDL (ug/L)
EDB

DBCP
   9.5

  17.3
 8.9

15.0
0.01

0.01
Column A:  Durawax-DX 3

Column B:  DB-1
                                  TABLE 2.
                  SINGLE LABORATORY ACCURACY AND PRECISION
                        FOR EDB AND DBCP IN TAP WATER

Number
of
Analyte Samples
EDB 7
7
7
DBCP 7
7
7

Spike
Level
(ug/L)
0.03
0.24
50.0
0.03
0.24
50.0

Average
Recovery
(*)
114
98
95
90
102
94
Relative
Standard
Deviation
(%)
9.5
11.8
4.7
11.4
8.3
4.8
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                                  TABLE 3.
                     ACCURACY AND PRECISION AT 2.0 ug/L
                         OVER A 4-WEEK STUDY PERIOD


Analyte
EDB




DBCP






Matrixl
RW-A
GW
GW-A
TW
TW-A
RW-A
GW
GW-A
TW
TW-A

Number
of Samples
16
15
16
16
16
16
16
16
16
16
Average
Accuracy
(% Recovery)
104
101
96
93
93
105
105
101
95
94
Relative
Std. Dev.
(%)
4.7
2.5
4.7
6.3
6.1
8.2
6.2
8.4
10.1
6.9
^Matrix Identities
    RW-A = Reagent water at pH 2
    GW = Ground water, ambient pH
    GW-A = Ground water at pH 2
    TW = Tap water, ambient pH
    TW-A = Tap water at pH 2
                                 8011 - 11
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                   FIGURE 1.
SAMPLE CHROMATOGRAM FOR EXTRACT OF WATER SPIKED
        AT  0.114 ug/L WITH EDB AND DBCP
                              COLUMN:   Fused $111ca capillary
                              LIQUID PHASE:  Durawax-DX3
                              FILM THICKNESS:  0.25 urn
                              COLUMN DIMENSIONS:   30 M x 0.317 im ID
                                  I
10  la   14   16   16
       TIME (MIN)
                                 20   22   24   2ft   28   30
                   8011 - 12
                                          Revision 0
                                          December 1987
-------
                                          METHOD  8011
            1,2-DIBROMOMETHANE  AND  l,2-DIBROMO-3-CHLOROPROPANE  IN WATER
                       BY MICROEXTRACTION  AND GAS  CHROMATOGRAPHY
 C  *"•  )
  7.1 C«libr»t«
iaitriMit: propiro
 calibration car**
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                                        T.3.5 Pit r«ulid«r
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                                            8011  - 13
                                           Revision
                                           December
               0
               1987
-------
                                METHOD 8015

                      NONHALOGENATED VOLATILE ORGANICS
1.0  SCOPE AND APPLICATION

     1.1  Method  8015  is used  to determine  the  concentration of  various
nonhalogenated volatile  organic  compounds.   Table  1  indicates  the compounds
that may be investigated by this  method.

2.0  SUMMARY OF METHOD

     2.1  Method  8015  provides  gas  chromatographic  conditions  for  the
detection of  certain  nonhalogenated  volatile  organic  compounds.   Samples may
be analyzed  using  direct injection or purge-and-trap  (Method  5030).   Ground
water samples must be analyzed by Method 5030.  A temperature program is used
in the  gas  chromatograph  to separate the  organic  compounds.    Detection  is
achieved by a flame ionization detector  (FID).

     2.2  If  interferences  are  encountered,  the method  provides  an  optional
gas chromatographic column that may be helpful in resolving the analytes from
interferences that may occur and  for  analyte confirmation.

3.0  INTERFERENCES

     3.1  Refer to Method 5030 and  8000.

     3.2  Samples  can  be contaminated  by  diffusion  of volatile  organics
(particularly chlorofluorocarbons and methylene chloride)  through  the sample
container septum during  shipment and storage.   A  field sample  blank prepared
from reagent  water and  carried  through  sampling  and  subsequent  storage  and
handling can serve as  a check on  such contamination.

4.0  APPARATUS AND MATERIALS

     4.1  Gas chromatograph

          4.1.1  Gas  Chromatograph  -  Analytical  system  complete with  gas
     chromatograph suitable for on-column injections or purge-and-trap sample
     introduction and  all  required accessories,  including  detectors,  column
     supplies, recorder,  gases,  and  syringes.  A data  system  for measuring
     peak heights and/or peak areas is recommended.

          4.1.2  Columns

               4.1.2.1  Column 1  -  8  ft x 0.1  in i.d. stainless steel  or glass
          column  packed with  1%  SP-1000  on  Carbopack-B  60/80  mesh  or
          equivalent.
                                  8015  -  1                       Revision 1
                                                                December 1987
-------
               4.1.2.2   Column  2  -  6  ft x 0.1 in i.d. stainless steel or glass
          column packed with n-octane on Porasil-C  100/120  mesh  (Durapak)  or
          equivalent.

          4.1.3  Detector -  Flame ionization  (FID).

     4.2  Sample  introduction  apparatus  -  Refer  to  Method  5030 for  the
appropriate equipment  for sample  introduction purposes.

     4.3  Syringes - A 5-mL Luerlok glass  hypodermic  and  a  5-mL,  gas-tight
with shutoff valve.

     4.4  Volumetric  flasks -  10-,  50-,  100-,  500-,  and  1,000-mL with  a
ground-glass stopper.

     4.5  Microsyringes - 10- and 25-uL with a 0.006-in i.d. needle  (Hamilton
702N or equivalent)  and a 100-uL.

5.0  REAGENTS

     5.1  Reagent grade chemicals shall  be  used  in all tests. Unless  otherwise
indicated,  it  is  intended  that  all  reagents shall  conform to  the
specifications  of  the  Committee  on  Analytical  Reagents  of the  American
Chemical Society, where such specifications  are  available. Other grades may be
used,  provided  it is  first  ascertained  that the  reagent  is  of sufficiently
high  purity to  permit  its  use without  lessening  the  accuracy of  the
determination.

     5.2  ASTM Type II  Water  (ASTM D1193-77  (1983)).  All  references to water
in the method refer to ASTM Type II unless  otherwise  specified.

     5.3  Stock standards - Stock solutions  may  be prepared  from pure standard
materials  or purchased as  certified  solutions.    Prepare  stock  standards  in
methanol using assayed liquids.

          5.3.1  Place about 9.8 mL of  methanol  in a  10-mL tared ground-glass-
     stoppered volumetric flask.   Allow  the  flask to stand, unstoppered,  for
     about 10 minutes  or until all alcohol-wetted surfaces have dried.  Weigh
     the flask to the nearest 0.1 mg.

          5.3.2  Using a 100-uL syringe, immediately add two or more drops of
     assayed reference material  to the  flask;  then reweigh.  The liquid must
     fall directly into the alcohol without  contacting the neck of the flask.

          5.3.3  Reweigh, dilute to volume,  stopper,  and then mix by  inverting
     the flask  several  times.   Calculate the concentration in micrograms per
     microliter (ug/uL) from the net gain in weight.  When  compound  purity is
     assayed to  be 96% or  greater, the weight may be used without correction
     to  calculate the concentration  of the  stock standard.   Commercially
     prepared  stock  standards  may be  used  at any concentration  if they are
     certified by the manufacturer or by an  independent  source.
                                  8015 - 2                       Revision  1
                                                                 December  1987
-------
          5.3.4  Transfer the  stock  standard solution  into  a bottle  with  a
     Teflon lined screw-cap.   Store, with minimal headspace, at -10°C to -20°C
     and protect from light.

          5.3.5  Standards must  be replaced after  6 months,  or  sooner if
     comparison with check standards indicates a problem.

     5.4  Secondary dilution  standards - Using stock standard solutions, pre-
pare in  methanol  secondary dilution  standards,  as needed, that  contain  the
compounds  of  interest,  either  singly  or  mixed  together.   The  secondary
dilution standards should be prepared at concentrations such that the aqueous
calibration standards prepared in  Step  5.5 will  bracket the working range of
the analytical  system.    Secondary dilution  standards should be  stored with
minimal headspace for volatiles and should be checked frequently for signs of
degradation  or evaporation,  especially  just prior to  preparing  calibration
standards from them.

     5.5  Calibration standards -  Calibration standards  at a  minimum of five
concentration levels are  prepared in water from the secondary dilution of the
stock standards.  One of the  concentration  levels should  be at a concentration
near,  but  above,  the  method  detection  limit.   The  remaining  concentration
levels should correspond to the expected range of concentrations found in real
samples or  should  define the working  range  of the GC.   Each standard should
contain each  analyte for detection by  this  method (e.g.  some or  all  of the
compounds listed  in  Table 1  may be included).   In order to prepare accurate
aqueous standard solutions,  the following precautions  must  be observed:

          5.5.1  Do  not  inject more than  20 uL of  alcoholic  standards into
     100 ml of water.

          5.5.2  Use  a  25-uL Hamilton  702N  microsyringe or  equivalent
     (variations  in needle  geometry  will  adversely  affect  the  ability to
     deliver reproducible volumes  of methanolic  standards  into water).

          5.5.3  Rapidly inject   the  alcoholic   standard into  the  filled
     volumetric flask.   Remove the  needle as  fast as possible after  injection.

          5.5.4  Mix aqueous   standards  by  inverting  the flask  three times
     only.

          5.5.5  Fill the sample syringe from the  standard solution contained
     in the expanded area of the flask  (do not  use any solution contained in
     the neck of the flask).

          5.5.6  Never  use pipets  to  dilute  or  transfer  samples  or aqueous
     standards.

          5.5.7  Aqueous  standards are  not  stable  and should be  discarded
     after  1 hour,  unless properly sealed  and  stored.   The aqueous standards
     can be stored up  to 24 hours,  if  held  in  sealed vials   with  zero
     headspace.
                                  8015  - 3                       Revision 1
                                                                December 1987
-------
     5.6  Internal  standards (if internal  standard  calibration  is  used)  -  To
use this approach,  the analyst  must  select  one or more internal standards that
are similar in analytical behavior to the compounds of interest.  The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences.  Because of these limitations,  no
internal standard can be suggested that  is  applicable to all  samples.

          5.6.1  Prepare calibration   standards at  a  minimum  of  five
     concentration levels for each parameter of interest as described in Step
     5.5.

          5.6.2  Prepare a  spiking  solution containing  each  of the internal
     standards using  the procedures described in  Steps  5.3  and 5.4.   It  is
     recommended that  the  secondary  dilution standard  be  prepared  at  a
     concentration  of  15  ug/mL of each  internal  standard  compound.   The
     addition of  10  uL of  this  standard  to 5.0 ml of  sample or calibration
     standard would be equivalent to 30  ug/L.

          5.6.3  Analyze each  calibration  standard  according to Section 7.0,
     adding  10 uL  of  internal  standard  spiking  solution  directly  to the
     syringe.

     5.7  Surrogate  standards  -  The  analyst   should  monitor  both  the
performance of the  analytical  system and  the effectiveness  of the method in
dealing  with  each  sample matrix by  spiking  each  sample,  standard,  and water
blank with  one or  two surrogate compounds recommended to encompass the range
of  temperature  program used in  this method.   From  stock  standard  solutions
prepared  as in Step  5.3,  add  a volume  to give 750 ug of each surrogate to
45  ml  of  water  contained  in  a 50-mL  volumetric  flask,  mix,  and  dilute to
volume  for  a  concentration  of  15 ng/uL.   Add 10 uL of this  surrogate  spiking
solution directly  into the  5-mL  syringe with every  sample  and  reference
standard  analyzed.   If  the  internal  standard  calibration  procedure is  used,
the surrogate compounds may be added directly to the  internal  standard  spiking
solution  (Step 5.6.2).

     5.7  Methanol, CHsOH.  Pesticide quality or equivalent.   Store  away from
other solvents.

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See  the introductory  material  to this  Chapter,  Organic  Analytes,
Step 4.1.

7.0  PROCEDURE

     7.1  Volatile compounds are introduced  into the gas chromatograph either
by  direct  injection or  purge-and-trap (Method 5030).  Method  5030 may  be used
directly  on ground water samples or  low-level  contaminated   soils and
sediments.   For medium-level  soils or  sediments,  methanolic extraction,  as
described in Method 5030, may be necessary prior to purge-and-trap analysis.

     7.2  Gas chromatography conditions  (Recommended)


                                  8015 - 4                       Revision 1
                                                                 December 1987
-------
          7.2.1  Column 1 - Set helium gas flow at 40 mL/min flow  rate.   Set
     column  temperature  at 45°C  for 3  minutes; then  program  an 8'C/min
     temperature rise to 220°C  and hold for 15 minutes.

          7.2.2  Column 2 - Set helium gas flow at 40 mL/min flow  rate.   Set
     column  temperature  at 50°C  for  3 minutes;  then  program  a 6°C/min
     temperature rise to 170°C  and hold for 4 minutes.

     7.3  Calibration  -  Refer to  Method  8000 for  proper calibration
techniques.

          7.3.1  Calibration  must  take  place using  the   same  sample
     introduction method that will be used to analyze  actual  samples (see  Step
     7.4.1).

          7.3.2  The procedure  for  internal  or external  calibration may  be
     used.    Refer  to Method  8000  for a  description  of  each  of  these
     procedures.

     7.4  Gas chromatographic analysis

          7.4.1  Introduce  volatile compounds into the gas chromatograph using
     either  Method  5030  (purge-and-trap  method) or  the  direct  injection
     method.    If the  internal  standard  calibration  technique  is used,   add
     10 uL of internal  standard  to the sample prior to purging.

               7.4.1.1   Direct  injection  -  In  very limited  applications (e.g.
          aqueous process wastes),  direct  injection of the  sample  into the GC
          system with  a  10-uL syringe  may  be appropriate.    One   such
          application is for verification of the alcohol  content of an aqueous
          sample prior to determining if the sample is ignitable (Methods  1010
          or  1020).   In this  case,  it is suggested that direct injection be
          used. The detection  limit  is  very high (approximately 10,000 ug/L);
          therefore, it  is only permitted when  concentrations  in excess  of
          10,000 ug/L are expected  or for water-soluble  compounds  that do not
          purge.  The system must be calibrated by direct injection (bypassing
          the purge-and-trap device).

          7.4.2  Follow  Step   7.6  in Method  8000 for  instructions on   the
     analysis  sequence,  appropriate  dilutions,  establishing daily  retention
     time windows, and  identification  criteria.   Include  a  mid-level  standard
     after each group of 10 samples in the analysis sequence.

          7.4.3  Record the sample volume purged or injected and the resulting
     peak sizes (in area units  or peak heights).

          7.4.4  Calculation of concentration is covered  in  Step 7.8 of Method
     8000.

          7.4.5  If analytical  interferences are suspected,  or for  the purpose
     of confirmation,  analysis  using the second GC column is recommended.
                                 8015 - 5                       Revision  1
                                                                December  1987
-------
          7.4.6  If the response for a  peak is off-scale, prepare a dilution
     of the  sample  with water.  The  dilution must be  performed  on a second
     aliquot of the sample which has been properly sealed and stored prior to
     use.

8.0  QUALITY CONTROL

     8.1  Refer to  Chapter One  for  specific  quality  control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control to  ensure the
proper operation of the purge-and-trap  device is  covered in  Method 5030.

     8.2  Mandatory quality  control  to  validate  the GC  system operation is
found in Method 8000,  Step 8.6.

     8.3  Calculate surrogate  standard  recovery on  all  samples,  blanks, and
spikes.    Determine  if recovery  is within  limits  (limits established by
performing QC procedure outlined in Method 8000,  Step 8.10).

          8.3.1  If recovery is not within limits,  the following is  required:

               •  Check  to  be sure  there  are  no  errors  in  calculations,
                  surrogate  solutions,  and  internal   standards.   Also,  check
                  instrument performance.

               •  Recalculate the data and/or  reanalyze the  extract  if any of
                  the above checks  reveal a problem.

               •  Reextract and reanalyze the  sample  if none of the  above are
                  a problem or flag the data as "estimated concentration."

9.0  METHOD PERFORMANCE

     9.1  The accuracy and precision obtained will  be determined by  the sample
matrix, sample introduction technique,  and calibration procedures  used.

     9.2  Specific  method  performance  information  will  be provided  as it
becomes available.

10.0 REFERENCES

1.   Bellar,  T.A., and J.J.  Lichtenberg,  Determining  Volatile  Organics at
     Microgram-per-Liter  Levels  by Gas  Chromatography,  J.  Amer.  Water  Works
     Assoc., 66(12), pp. 739-744 (1974).

2.   Bellar, T.A.,  and  J.J.  Lichtenberg,  Semi-Automated  Headspace Analysis of
     Drinking  Waters  and Industrial  Waters  for  Purgeable Volatile  Organic
     Compounds, in  Van  Hall,  ed.,  Measurement of Organic Pollutants  in  Water
     and Wastewater, ASTM STP 686,  pp.  108-129, 1979.

3.   Development and Application of Test Procedures for Specific Organic  Toxic
     Substances in  Wastewaters:   Category  11  -  Purgeables  and Category  12  -
     Acrolein,  Acrylonitrile,  and  Dichlorodifluoromethane,  Report for  EPA
     Contract 68-03-2635  (in preparation).

                                  8015 - 6                       Revision 1
                                                                 December 1987
-------
4.   Rohrbough,  W.G.;  et  al.  Reagent Chemicals,  American Chemical  Society
     Specifications, 7th ed.; American Chemical  Society:  Washington, DC,  1986.

5.   1985 Annual  Book  of ASTM Standards.  Vol.  11.01;  "Standard  Specification
     for Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
                                  8015 -  7                       Revision  1
                                                                 December  1987
-------
            TABLE 1.
NONHALOGENATED VOLATILE ORGANICS
   Diethyl ether
   Ethanol
   Methyl ethyl ketone (MEK)
   Methyl isobutyl ketone (MIBK)
             8015  -  8                        Revision 1
                                            December 1987
-------
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                                                8015  -  9
                           Revision  1
                           December  1987
-------
                                 METHOD 8020A

               AROMATIC VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method  8020  is  used to  determine the  concentration of  various
aromatic volatile organic compounds.   The following compounds can be determined
by this method:
                                                   Appropriate Technique
                                                                    Direct
Compound Name                        CAS  No.a       Purge-and-Trap  Injection
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Toluene
Xylenes
a Chemical Abstract
b adequate response
71-43-2
108-90-7
95-50-1
541-73-1
106-46-7
100-41-4
108-88-3

Services Registry Number.
by this technique.
b
b
b
b
b
b
b
b


b
b
b
b
b
b
b
b


      1.2   Table 1 lists the method detection limit for each target analyte in
organic-free reagent water.  Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
2.0   SUMMARY OF METHOD

      2.1   Method 8020 provides chromatographic conditions for the detection of
aromatic volatile compounds.  Samples can be introduced into the GC using direct
injection  or purge-and-trap  (Method 5030).    Ground water  samples  must  be
determined  using Method  5030.    A  temperature  program  is  used  in  the  gas
chromatograph to  separate  the  organic  compounds.   Detection is  achieved  by a
photo-ionization detector (PID).

      2.2   If interferences are encountered,  the method provides an optional gas
chromatographic column that may be  helpful in  resolving  the  analytes  from the
interferences and for analyte confirmation.


3.0   INTERFERENCES

      3.1   Refer to Method 5030  and 8000.
                                  8020A  -  1                         Revision 1
                                                                 November 1992
-------
      3.2   Samples  can  be  contaminated by  diffusion  of volatile  organics
(particularly chlorofluorocarbons  and  methylene chloride) through  the  sample
container septum during shipment and storage.  A field sample blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1   Gas Chromatograph  -  Analytical  system  complete  with  gas
      chromatograph suitable for on-column injections or purge-and-trap sample
      introduction  and all  required accessories,  including  detectors,  column
      supplies, recorder, gases,  and syringes.  A data system for measuring peak
      heights and/or peak areas is recommended.

            4.1.2   Columns

                   4.1.2.1    Column 1:   6 ft x 0.082 in ID  #304 stainless steel
            or  glass  column packed with 5%  SP-1200  and  1.75%  Bentone-34  on
            100/120 mesh  Supelcoport,  or equivalent.

                   4.1.2.2    Column 2:  8  ft x 0.1  in  ID stainless  steel  or
            glass   column packed  with  5% l,2,3-Tris(2-cyanoethoxy)propane  on
            60/80  mesh Chromosorb W-AW, or equivalent.

            4.1.3   Detector -  Photoionization  (PID)  (h-Nu  Systems,  Inc. Model
      PI-51-02  or equivalent).

      4.2   Sample  introduction   apparatus  -  Refer  to  Method  5030  for  the
appropriate equipment for sample  introduction purposes.

      4.3   Syringes - A  5 ml Luerlok glass hypodermic  and a 5 ml, gas-tight with
shutoff valve.

      4.4   Volumetric flask,  Class A  -  Appropriate sizes with  ground glass
stoppers.

      4.5   Microsyringe - 10 and 25 /uL with a 0.006 in ID needle  (Hamilton 702N
or equivalent)  and  a  100 /iL.

      4.6   Analytical balance - 0.0001 g.


5.0   REAGENTS

      5.1   Organic-free reagent water.  All  references to  water  in  this method
refer to  organic-free reagent  water, as  defined  in  Chapter One.

      5.2   Methanol  (CH3OH) -  pesticide  quality or equivalent.  Store  away from
other solvents.


                                   8020A - 2                        Revision  1
                                                                  November 1992
-------
      5.3   Stock standards - Stock solutions may be prepared from pure standard
materials  or  purchased as  certified solutions.   Prepare stock  standards  in
methanol  using  assayed  liquids.    Because  of  the toxicity  of benzene  and
1,4-dichlorobenzene, primary dilutions of these  materials  should be prepared in
a hood.

            5.3.1  Place about  9.8 ml of  methanol  in a 10 ml tared ground glass
      stoppered volumetric flask.  Allow the  flask to  stand,  unstoppered,  for
      about 10 min or until all alcohol wetted surfaces have dried.   Weigh the
      flask to the nearest 0.0001 g.

            5.3.2  Using a 10 juL syringe, immediately add two or more drops of
      assayed reference material to  the  flask;  then reweigh.   The liquid must
      fall directly into the alcohol  without contacting the neck of the flask.

            5.3.3  Reweigh, dilute to volume, stopper,  and then mix by inverting
      the  flask  several times.   Calculate the concentration  in milligrams  per
      liter (mg/L) from the net gain  in weight.  When compound purity is assayed
      to  be  96%  or greater,  the  weight  may be  used  without  correction  to
      calculate the concentration of  the  stock standard.  Commercially prepared
      stock standards may be used at  any  concentration if  they are certified by
      the manufacturer or by an independent source.

            5.3.4  Transfer the  stock standard  solution  into  a Teflon-sealed
      screw-cap bottle.  Store,  with  minimal headspace,  at 4°C and protect from
      light.

            5.3.5  All  standards must be  replaced after 6 months, or sooner if
      comparison with check standards indicates a problem.

      5.4   Secondary  dilution  standards:    Using  stock  standard  solutions,
prepare in methanol secondary dilution standards,  as  needed,  that contain  the
compounds of interest,  either singly  or mixed  together.  The secondary dilution
standards should be prepared at concentrations such that  the aqueous calibration
standards  prepared in  Section  5.4   will  bracket  the  working  range  of  the
analytical system.  Secondary dilution standards should be stored with minimal
headspace for volatiles and should be  checked frequently for signs of degradation
or evaporation, especially just  prior to preparing calibration standards from
them.

      5.5   Calibration standards:   Calibration standards at  a minimum of five
concentrations are  prepared  in  organic-free reagent water from the secondary
dilution  of  the  stock standards.   One of  the  concentrations  should be at  a
concentration  near,  but  above,  the  method  detection  limit.    The  remaining
concentrations should correspond to the expected range of concentrations found
in real samples  or  should define the working range of  the GC.   Each standard
should contain each analyte for detection by this method (e.g., some or all  of
the compounds listed in the target analyte list may be included).  In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.

            5.5.1  Do  not  inject more than  20 ^L  of alcoholic  standards into
      100 mL  of organic-free reagent  water.

                                  8020A  -  3                         Revision  1
                                                                 November 1992
-------
            5.5.2  Use  a  25   /uL  Hamilton  702N  microsyringe  or  equivalent
      (variations  in  needle  geometry will  adversely affect  the  ability  to
      deliver reproducible volumes of methanolic standards into water).

            5.5.3  Rapidly  inject  the   alcoholic  standard  into  the  filled
      volumetric flask.   Remove the needle as fast as possible after injection.

            5.5.4  Mix aqueous  standards by inverting the flask three  times only.

            5.5.5  Fill  the sample syringe from the standard solution contained
      in the expanded area of  the  flask  (do not  use  any  solution contained in
      the neck of the flask).

            5.5.6  Never use pipets  to  dilute  or transfer  samples  or aqueous
      standards.

            5.5.7  Aqueous standards  are not stable and should be discarded after
      1 hr, unless  properly sealed and  stored.   The  aqueous standards can be
      stored up to 24 hr, if held in sealed vials with zero headspace.

      5.6   Internal standards (if internal  standard  calibration is  used):   To
use this approach, the analyst must select one  or more internal  standards that
are similar in  analytical  behavior to the compounds  of interest.   The analyst
must further demonstrate that  the  measurement of  the  internal  standard is  not
affected by method  or matrix  interferences.  Because  of  these  limitations,  no
internal  standard  can   be suggested that  is  applicable  to  all  samples.
Alpha,alpha,alpha-trifluorotoluene has been  used successfully as  an  internal
standard.

            5.6.1  Prepare  calibration   standards   at  a  minimum  of  five
      concentrations for each parameter of interest as described in Section 5.5.

            5.6.2  Prepare a spiking  solution containing  each  of the  internal
      standards using the procedures described  in Sections 5.3  and 5.4.  It is
      recommended  that   the  secondary  dilution  standard  be  prepared  at  a
      concentration of 15 mg/L  of each internal  standard compound.  The addition
      of 10 fj.1 of this  standard  to  5.0  ml of sample  or  calibration  standard
      would be equivalent to 30 M9/L.

            5.6.3  Analyze each calibration standard  according  to Section 7.0,
      adding  10 /A of  internal  standard  spiking  solution  directly  to  the
      syringe.

      5.7   Surrogate standards:  The analyst should monitor both the performance
of the analytical  system  and the effectiveness of the method in dealing with each
sample matrix by spiking each  sample, standard,  and organic-free reagent water
blank with surrogate compounds (bromochlorobenzene,  bromofluorobenzene, 1,1,1-
trifluorotoluene,  fluorobenzene,  and difluorobenzene are  recommended)  which
encompass the range of the temperature program used in  this method.  From stock
standard solutions  prepared as  in  Section 5.3, add a  volume  to  give 750 ^g of
each  surrogate  to 45 mL of organic-free reagent water  contained  in  a  50 mL
volumetric flask,  mix,  and dilute to volume for a concentration  of 15 ng//iL.
Add 10 /itL of this surrogate spiking solution directly into the 5 mL syringe with

                                   8020A  -  4                         Revision  1
                                                                 November 1992
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every  sample  and  reference  standard  analyzed.    If  the  internal  standard
calibration procedure is used,  the surrogate  compounds may  be added directly to
the internal standard spiking solution  (Section 5.6.2).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Volatile compounds  are introduced into the gas  chromatograph either
by direct injection  or  purge-and-trap  (Method 5030).  Method 5030 may be used
directly on  ground  water samples or  low-concentration  contaminated soils and
sediments.  For medium-concentration soils  or sediments, methanolic extraction,
as described in Method 5030,  may be  necessary prior  to purge-and-trap analysis.
Method 5030 also provides guidance on the analysis of aqueous miscible and non-
aqueous miscible liquid wastes  (see Section  7.4.1.1 below).

      7.2   Gas chromatography conditions  (Recommended):

            7.2.1  Column 1:

            Carrier gas (He)  flow rate:  36  mL/min
            For lower boiling compounds:
                   Initial  temperature:  50°C,  hold for 2  min;
                   Temperature program:  50°C to 90°C  at  6°C/min,  hold until
                                         all compounds  have eluted.
            For higher boiling range of compounds:
                   Initial  temperature:  50°C,  hold for 2  min;
                   Temperature program:  50°C to 110°C  at  3°C/min,  hold until
                                         all compounds  have eluted.

            Column  1  provides  outstanding  separations  for a wide  variety of
      aromatic hydrocarbons.   Column 1 should be used as the primary analytical
      column because of its unique ability to resolve para-, meta-, and ortho-
      aromatic isomers.

            7.2.2  Column 2:

            Carrier gas (He)  flow rate:  30  mL/min
            Initial  temperature:         40°C,  hold for 2  min;
            Temperature program:         40°C to 100°C  at  2°C/min,  hold until
                                         all compounds  have eluted.

            Column 2, an extremely  high polarity column,   has been  used for a
      number of years to resolve aromatic  hydrocarbons  from alkanes in complex
      samples.  However,  because resolution between some  of  the aromatics is not
      as efficient as with Column 1, Column  2 should be used as a confirmatory
      column.
                                   8020A -  5                         Revision 1
                                                                 November 1992
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      7.3   Calibration:  Refer to Method 8000 for proper calibration techniques.
Use Table 1  and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.

            7.3.1  Calibration must take place using the same sample introduction
      method that will be used  to analyze actual samples  (see Section 7.4.1).

            7.3.2  The procedure  for  internal  or external calibration  may be
      used.   Refer to  Method 8000 for a description of each of these procedures.

      7.4   Gas chromatographic  analysis:

            7.4.1  Introduce volatile compounds into the gas chromatograph using
      either Method 5030  (purge-and-trap method) or the direct injection method.
      If the  internal standard  calibration technique  is used,  add 10 nl of
      internal standard to the  sample prior to purging.

                   7.4.1.1    Direct injection:   In very  limited applications
            (e.g., aqueous  process wastes), direct  injection of the sample into
            the  GC  system with  a  10 /xL  syringe  may  be  appropriate.   The
            detection  limit is very high (approximately 10,000 fj.g/1)', therefore,
            it is only permitted when  concentrations in excess of  10,000  p.g/1
            are expected  or for water  soluble compounds that do not purge.   The
            system must be calibrated  by direct  injection (bypassing the purge-
            and-trap device).

                   Non-aqueous  miscible wastes may  also be  analyzed by direct
            injection   if the concentration of  target  analytes  in  the  sample
            falls within  the calibration range.   If dilution  of  the sample is
            necessary, follow the guidance for High Concentration  samples in
            Method 5030A, Section 7.3.3.2.

            7.4.2  Method 8000  provides instructions on  the  analysis sequence,
      appropriate dilutions, establishing  daily  retention  time windows,  and
      identification criteria.   Include a mid-concentration standard after each
      group of 10 samples in  the analysis sequence.

            7.4.3  Table  1 summarizes the estimated retention  times and detection
      limits for a number of organic compounds  analyzable  using  this method.  An
      example of  the  separation  achieved  by  Column 1 is  shown in  Figure 1.
      Figure 2 shows an example  of the separation achieved using Column 2.

            7.4.4  Record the sample volume purged or injected and the resulting
      peak sizes (in area units  or peak heights).

            7.4.5  Calculation  of concentration is covered in Method 8000.

            7.4.6  If  analytical  interferences are suspected,  or for the purpose
      of confirmation, analysis  using the second GC column is recommended.

            7.4.7  If  the response for a  peak  is off scale,  prepare a dilution
      of the sample with  organic-free reagent  water.  The dilution must be


                                  8020A  -  6                         Revision 1
                                                                 November 1992
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      performed on a second aliquot of the sample which has been properly sealed
      and stored prior to use.


8.0   QUALITY CONTROL

      8.1   Refer to  Chapter  One for specific  quality  control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.

      8.2   Quality control required to validate the GC system operation is found
in Method 8000.

            8.2.1  The quality control check  sample  concentrate (Method 8000)
      should contain  each parameter  of interest at  a concentration of 10 mg/L
      in methanol.

            8.2.2  Table 3 indicates  the  calibration  and QC acceptance criteria
      for this method.  Table 4 gives method accuracy  and precision  as functions
      of concentration  for the  analytes of  interest.   The contents  of both
      Tables should be  used to evaluate  a  laboratory's  ability to perform and
      generate acceptable data by this method.

      8.3   Calculate surrogate  standard recovery on all  samples,  blanks, and
spikes.  Determine if recovery is  within limits (limits established by performing
QC procedure outlined in Method 8000).

            8.3.1  If recovery is not within limits,  the following  is required.

                   •    Check  to  be  sure   that  there   are   no   errors  in
                        calculations,   surrogate   solutions   and   internal
                        standards.  Also, check instrument performance.

                   •    Recalculate the data and/or reanalyze the extract  if any
                        of the above  checks reveal  a  problem.

                   •    Reextract and reanalyze the sample  if none  of the above
                        are  a   problem  or  flag   the  data   as   "estimated
                        concentration".
9.0   METHOD PERFORMANCE

      9.1   This method was tested by 20 laboratories using organic-free reagent
water, drinking water,  surface water, and three industrial wastewaters spiked at
six concentrations over the range 2.1  -  500  Mg/L.   Single  operator precision,
overall precision, and method  accuracy were found to be directly related to the
concentration of the  parameter and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 4.

      9.2   The accuracy and precision obtained will  be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.


                                  8020A  - 7                         Revision 1
                                                                 November 1992
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10.0  REFERENCES

1.    Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
      pp. 739-744, 1974.

2.    Bellar, T.A., and J.J.  Lichtenberg,  "Semi-Automated Headspace Analysis of
      Drinking  Waters  and  Industrial  Waters for Purgeable  Volatile Organic
      Compounds", in Van Hall  (ed.),  Measurement of Organic Pollutants in Water
      and Wastewater, ASTM STP 686, pp. 108-129,  1979.

3.    Dowty, B.J., S.R. Antoine, and J.L.  Laseter,  "Quantitative and Qualitative
      Analysis of Purgeable Organics by High Resolution Gas Chromatography and
      Flame  lonization  Detection",  in Van  Hall,  ed., Measurement  of Organic
      Pollutants in Water and Wastewater.  ASTM STP 686,  pp.  24-35,  1979.

4.    Development and Application  of Test  Procedures for Specific Organic Toxic
      Substances  in Wastewaters.   Category 11 -   Purgeables  and  Category 12 -
      Acrolein,  Acrylonitrile,  and Dichlorodifluoromethane.   Report  for EPA
      Contract 68-03-2635 (in preparation).

5.    "EPA Method Validation  Study 24, Method 602 (Purgeable Aromatics)", Report
      for EPA Contract 68-03-2856 (in preparation).

6.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
      Final Rule and Proposed Rule", October 26,  1984.
                                   8020A - 8                        Revision  1
                                                                 November  1992
-------
                                  TABLE 1.
            CHROMATOGRAPHIC  CONDITIONS  AND METHOD  DETECTION  LIMITS
                        FOR AROMATIC VOLATILE ORGANICS



Compound
Benzene
Chlorobenzeneb
1,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl Benzene
Toluene
Xylenes
Retention
(min)

Col. 1
3.33
9.17
16.8
18.2
25.9
8.25
5.75

time


Col. 2
2.75
8.02
16.2
15.0
19.4
6.25
4.25

Method
detection
limit3
(M9/L)
0.2
0.2
0.3
0.4
0.4
0.2
0.2

a Using purge-and-trap method (Method 5030).
b Chlorobenzene and m-xylene may co-elute on some columns,
                                  TABLE 2.
             DETERMINATION  OF  ESTIMATED  QUANTITATION  LIMITS  (EQLs)
                             FOR VARIOUS MATRICES3
      Matrix
Factor
      Ground water
      Low-concentration soil
      Water miscible liquid waste
      High-concentration soil  and sludge
      Non-water miscible waste
  10
  10
 500
1250
1250
   a  Sample EQLs  are highly matrix  dependent.   The  EQLs listed  herein  are
      provided for guidance and may not always be achievable.
   b  EQL =  [Method detection  limit  (Table  1)]  X [Factor  (Table 2)].
      non-aqueous samples, the factor is on a wet-weight basis.
                     For
                                  8020A  - 9
              Revision 1
           November 1992
-------
                             TABLE 3.
                      QC  ACCEPTANCE  CRITERIA8
Range Limit Range
for Q for s for x
Parameter (M9/L) (M9/L) (M9/L)
Benzene 15.4-24.6 4.1 10.0-27.9
Chlorobenzene 16.1-23.9 3.5 12.7-25.4
1,2-Dichlorobenzene 13.6-26.4 5.8 10.6-27.6
1,3-Dichlorobenzene 14.5-25.5 5.0 12.8-25.5
1,4-Dichlorobenzene 13.9-26.1 5.5 11.6-25.5
Ethylbenzene 12.6-27.4 6.7 10.0-28.2
Toluene 15.5-24.5 4.0 11.2-27.7
Q = Concentration measured in QC check sample, in /xg/L.
s = Standard deviation of four recovery measurements, in
x = Average recovery for four recovery measurements, in ju
P, Ps = Percent recovery measured.
D = Detected; result must be greater than zero.
a Criteria from 40 CFR Part 136 for Method 602, and were calcul
Range
P P
' rs

39-150
55-135
37-154
50-141
42-143
32-160
46-148

M9/L.



ated assuming
as check  sample concentration  of 20  p.g/1.    These criteria  are  based
directly upon the method performance data  in  Table  4.   Where necessary,
the limits for recovery have been broadened to  assure applicability of the
limits to concentrations below those used to develop Table 1.
                            8020A - 10
   Revision 1
November 1992
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                                   TABLE 4.
          METHOD ACCURACY AND PRECISION AS  FUNCTIONS  OF  CONCENTRATION


Parameter
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1, 4 -Di chlorobenzene
Ethyl benzene
Toluene
Accuracy, as
recovery, x'
(M9/L)
0.92C+0.57
0.95C+0.02
0.93C+0.52
0.96C-0.04
0.93C-0.09
0.94C+0.31
0.94C+0.65
Single analyst
precision, s '
(M9/L)
0.09X+0.59
0.09X+0.23
0.17X-0.04
O.lBx-0.10
O.lSx+0.28
0.17X+0.46
0.09X+0.48
Overall
precision,
S' (M9/L)
0.21X+0.56
0.17x+0.10
0.22X+0.53
0.19X+0.09
0.20X+0.41
0.26X+0.23
O.lSx+0.71
            Expected  recovery  for  one  or   more  measurements  of  a  sample
            containing concentration C, in p.g/1.

            Expected single  analyst  standard deviation of  measurements  at an
            average concentration of x, in
S'


c

x
Expected interlaboratory standard deviation  of measurements at an
average concentration found of x,  in M9/L.

True value for the concentration,  in jug/L.

Average recovery  found for  measurements  of samples  containing a
concentration of C, in M9/L.
                                  8020A - 11
                                                        Revision 1
                                                     November 1992
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                   Figure  1
Chromatogram of Aromatic  Volatile Organics
            (column  1 conditions)
                               Cofamn: B*SM200/1.7S%B«ntofw34
                               Profram: 60°C-2 Mlnutti. 6°C/Min. to 90°C
                               Detector: Photoionintion
                               Sample: 0.40 jif/l Standard Mixture
           8       10       12      14

            RETENTION TNIC (MINUTES)
16
18
20
                  8020A - 12
             Revision  1
         November  1992
-------
                   Figure 2
Chromatogram of Aromatic  Volatile Organics
            (column 2 conditions)
                    Cohimn: 1% UJ-Trw (2-CyanoMtoxy)
                          on Chromo«of»-W
                           4QOC-2 MinwtM 2°C/Min. to 10QOC
                    famoto: 2.0MI/I Sundcrd Mixturt
                     12         1f

          MfTtimOM TlMi (MtNUTIS)
20
24
                  8020A - 13
              Revision  1
          November 1992
-------
                         METHOD 8020A
       AROMATIC VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
7,2 «nt  «»•
                          8020A - 14
   Revision 1
November 1992
-------
                                 METHOD 8021A

               HALOGENATED VOLATILES  BY  GAS  CHROMATOGRAPHY  USING
            PHOTOIONIZATION AND ELECTROLYTIC CONDUCTIVITY DETECTORS
                    IN  SERIES;  CAPILLARY  COLUMN  TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 8021  is  used to determine volatile organic  compounds  in a
variety of solid waste matrices.  This method  is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic  liquors,  acid liquors,  waste  solvents,  oily wastes,  mousses,  tars,
fibrous  wastes,  polymeric  emulsions,   filter  cakes,  spent  carbons,  spent
catalysts, soils, and sediments.  The following compounds can be determined by
this method:
Analyte
CAS No.'
  Appropriate Technique
                  Direct
Purge-and-Trap    Injection
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butylbenzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Hi bromomethane
1,^-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-l,2-Dichloroethene
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
135-98-8
98-06-6
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-59-4
156-60-5
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
                                   8021A  -  1
                               Revision 1
                            November 1992
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Analyte
CAS No.!
  Appropriate Technique
                  Direct
Purge-and-Trap    Injection
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
cis-l,3-dichloropropene
trans-l,3-dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p- I sopropyl toluene
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1,2-Tetrachl oroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1 -Tri chl oroethane
1 , 1 , 2 -Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1 , 2 , 4-Tri methyl benzene
1, 3, 5-Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
78-87-5
142-28-9
590-20-7
563-58-6
10061-01-5
10061-02-6
100-41-4
87-68-3
98-82-8
99-87-6
75-09-2
91-20-3
103-65-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
87-61-6
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
95-63-6
108-67-8
75-01-4
95-47-6
108-38-3
106-42-3
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a Chemical Abstract Services Registry Number.
b Adequate response by thi
pp Poor purging efficiency
i Inappropriate technique
s technique.
resulting in high EQLs.
for this analyte.






pc Poor chromatographic behavior.
       1.2    Method detection limits (MDLs) are compound dependent and  vary with
purging  efficiency and  concentration.    The MDLs  for selected  analytes  are
presented  in Table 1.   The  applicable  concentration  range  of  this method  is
compound  and  instrument dependent  but  is   approximately  0.1  to 200  jug/L.
Analytes  that are  inefficiently  purged  from water will  not be detected when
present at low concentrations,  but they can be measured with  acceptable accuracy
and  precision  when present  in  sufficient  amounts.   Determination  of some
structural  isomers  (i.e. xylenes)  may be  hampered by  coelution.
                                   8021A - 2
                               Revision  1
                            November  1992
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       1.3    The  estimated  quantitation  limit  (EQL)  of Method  8021A  for  an
individual compound  is approximately 1  /xg/kg (wet weight)  for  soil/sediment
samples, 0.1 mg/kg  (wet  weight)  for wastes,  and 1 ng/l  for  ground water (see
Table 3).  EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the detector.

       1.4    This method  is  recommended for use only by analysts experienced in
the measurement of purgeable organics at the  low  /ig/L level  or by experienced
technicians under the close supervision of a qualified analyst.

       1.5    The toxicity or carcinogenicity of chemicals used in this method has
not been  precisely  defined.   Each  chemical  should be treated as  a potential
health  hazard,  and  exposure  to these  chemicals  should be  minimized.   Each
laboratory is responsible for maintaining  awareness of OSHA regulations regarding
safe  handling  of chemicals used in  this  method.   Additional references  to
laboratory safety are available for the information of the  analyst (references
4 and 6).

       1.6    The  following  method  analytes have  been  tentatively  classified as
known or suspected human or mammalian carcinogens: benzene, carbon tetrachloride,
1,4-dichlorobenzene,    1,2-dichloroethane,    hexachloro-butadiene,   1,1,2,2-
tetrachloroethane,    1,1,2-trichloroethane,    chloroform,   1,2-dibromoethane,
tetrachloroethene,  trichloroethene,  and vinyl chloride.  Pure standard materials
and stock standard  solutions of these compounds  should be handled in a hood.  A
NIOSH/MESA approved  toxic gas respirator should be  worn when the analyst handles
high concentrations of these toxic compounds.


2.0   SUMMARY OF METHOD

      2.1    Method   8021  provides  gas  chromatographic  conditions  for  the
detection of halogenated and aromatic volatile organic compounds.   Samples can
be analyzed using direct injection or purge-and-trap (Method  5030).   Ground water
samples must be analyzed using Method 5030  (where applicable).   A temperature
program  is used  in  the gas chromatograph  to separate the  organic compounds.
Detection is achieved  by a  photoionization detector  (PID)  and an  electrolytic
conductivity detector (HECD) in series.

      2.2    Tentative  identifications are obtained by  analyzing standards under
the same conditions  used for samples and comparing  resultant GC retention times.
Confirmatory information can be gained by comparing the relative  response from
the two detectors.   Concentrations of the identified components are measured by
relating the response produced for that compound to the response  produced by a
compound that is used as an internal standard.


3.0    INTERFERENCES

      3.1    Refer to Methods 5030 and 8000.

      3.2    Samples  can  be contaminated by diffusion  of volatile  organics
(particularly chlorofluorocarbons and  methylene chloride)  through the sample
container  septum  during shipment  and  storage.   A  trip  blank prepared  from


                                  8021A  - 3                         Revision 1
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organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.
      3.3   Sulfur dioxide is a potential  interferant  in the analysis for vinyl
chloride.
4.0   APPARATUS AND MATERIALS
      4.1   Sample  introduction  apparatus  -  Refer to  Method  5030 for  the
appropriate equipment for sample introduction purposes.
      4.2   Gas  Chromatograph  - capable of temperature  programming; equipped
with variable-constant differential flow controllers, subambient oven controller,
photoionization and electrolytic conductivity detectors connected with a short
piece of uncoated capillary tubing, 0.32-0.5 mm ID, and data system.
            4.2.1  Column -  60  m x 0.75 mm ID VOCOL wide-bore capillary column
      with 1.5 urn  film  thickness  (Supelco Inc., or  equivalent).
            4.2.2  Photoionization  detector  (PID)  (Tracer   Model   703,   or
      equivalent).
            4.2.3  Electrolytic conductivity detector (HECD) (Tracer Hall Model
      700-A, or equivalent).
      4.3   Syringes -  5 ml glass  hypodermic with  Luer-Lok tips.
      4.4   Syringe valves  - 2-way with  Luer ends  (Teflon or  Kel-F).
      4.5   Microsyringe -  25  /xL  with  a  2 in. x 0.006  in. ID,  22° bevel needle
(Hamilton #702N or equivalent).
      4.6   Microsyringes - 10, 100 /uL.
      4.7   Syringes -  0.5, 1.0,  and 5 ml, gas tight with shut-off  valve.
      4.8   Bottles -  15 ml, Teflon lined with screw-cap or crimp top.
      4.9   Analytical  balance -  0.0001  g.
      4.10  Refrigerator.
      4.11  Volumetric  flasks, Class A  - Appropriate  sizes  with ground glass
stoppers.

5.0   REAGENTS
      5.1   Reagent  grade  inorganic  chemicals  shall  be used  in  all  tests.
Unless  otherwise  indicated,  it is  intended that  all  inorganic reagents shall
conform  to  the  specifications  of  the  Committee on  Analytical  Reagents of the
American Chemical Society, where such specifications are available. Other grades

                                   8021A - 4                         Revision  1
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may be used, provided it is first ascertained that the reagent is of sufficiently
high  purity  to  permit  its  use  without  lessening  the  accuracy  of  the
determination.

      5.2   Organic-free  reagent water.  All  references  to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Methanol, CH3OH - Pesticide quality or equivalent, demonstrated to
be free of analytes.  Store away from other solvents.

      5.4   Vinyl chloride, (99.9% pure),  CH2=CHC1.  Vinyl chloride is available
from  Ideal  Gas  Products,  Inc., Edison,  New Jersey  and  from Matheson,  East
Rutherford, New Jersey, as well  as  from  other  sources.   Certified  mixtures of
vinyl chloride in nitrogen at 1.0 and  10.0 ppm  (v/v) are available from several
sources.

      5.5   Stock standards  - Stock solutions may either be prepared from pure
standard materials or purchased  as certified solutions.   Prepare stock standards
in methanol using  assayed liquids or  gases,  as appropriate.  Because  of the
toxicity of some of the organohalides, primary dilutions of these materials of
the toxicity should be prepared in a hood.

      NOTE: If  direct  injection is  used,  the solvent system of standards must
            match that  of the  sample.    It  is  not necessary to prepare high
            concentration aqueous mixed standards when using direct injection.

            5.5.1 Place about 9.8 ml  of methanol  in a 10 ml tared ground glass
      stoppered  volumetric flask.   Allow  the flask to stand, unstoppered, for
      about 10 minutes until  all alcohol-wetted surfaces have dried.  Weigh the
      flask to  the  nearest 0.1 mg.

            5.5.2 Add  the assayed  reference  material, as described  below.

                  5.5.2.1    Liquids:  Using a  100 jttL syringe, immediately add
            two or  more drops of assayed  reference material to the flask; then
            reweigh.   The liquid must fall directly  into  the alcohol  without
            contacting the neck of the flask.

                  5.5.2.2    Gases:   To  prepare standards  for  any compounds
            that    boil   below   30°C    (e.g.    bromomethane,   chloroethane,
            chloromethane,   dichlorodifluoromethane,   trichlorofluoromethane,
            vinyl chloride),  fill  a  5 ml valved gas-tight syringe with the
            reference  standard  to the 5.0 ml mark.  Lower  the needle  to 5 mm
            above   the  methanol  meniscus.    Slowly  introduce  the  reference
            standard above  the  surface of the  liquid.  The heavy  gas  rapidly
            dissolves in  the methanol.  This may also be accomplished by using
            a  lecture  bottle equipped with  a  Hamilton Lecture  Bottle  Septum
            (#86600).   Attach  Teflon  tubing to the  side-arm relief valve and
            direct  a gentle  stream of  gas into  the methanol meniscus.

            5.5.3 Reweigh, dilute to volume,  stopper,  and then mix by inverting
      the  flask  several times.   Calculate the  concentration in  milligrams per
      liter (mg/L) from the net  gain in weight.   When compound purity is assayed
      to  be 96%  or greater, the  weight  may  be  used  without correction  to

                                  8021A  - 5                         Revision 1
                                                                 November 1992
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      calculate the concentration of the stock standard.  Commercially prepared
      stock standards may be used at any concentration if they are certified by
      the manufacturer or by an independent source.

            5.5.4  Transfer  the stock standard  solution  into a bottle  with a
      Teflon lined screw-cap or crimp top.  Store, with minimal headspace, at -
      10°C to  -20°C and  protect from light.

            5.5.5  Prepare  fresh stock standards  every  two months  for  gases.
      Reactive compounds such as 2-chloroethyl vinyl ether and styrene may need
      to  be prepared more frequently.  All  other standards must  be replaced
      after six months.   Both gas and liquid standards must be monitored closely
      by  comparison  to  the  initial  calibration  curve and by  comparison to QC
      reference samples.   It may be necessary  to replace the  standards more
      frequently if either check exceeds a 25% difference.

      5.6   Prepare   secondary  dilution   standards,   using   stock  standard
solutions, in methanol, as needed, that contain the compounds of interest, either
singly or mixed together.  The secondary dilution standards should be prepared
at concentrations such that the aqueous calibration standards prepared in Section
5.7 will  bracket the  working range of the analytical system.  Secondary dilution
standards should be  stored with  minimal headspace  for  volatiles and should be
checked frequently  for signs of degradation or evaporation,  especially just prior
to preparing calibration standards from them.

      5.7   Calibration standards, at a minimum of five concentration levels are
prepared in organic-free reagent water from the  secondary dilution of the stock
standards.  One of the concentration levels should be  at a concentration near,
but above, the method detection limit. The remaining concentration levels should
correspond to  the  expected range of  the concentrations found in real  samples or
should define  the  working range  of the  GC.   Standards  (one or  more)  should
contain each analyte  for detection by this method (e.g. some or all of the target
analytes  may  be included).    In  order  to prepare accurate  aqueous standard
solutions, the following precautions must be  observed.

      NOTE: Prepare calibration solutions for use with direct injection analyses
            in  water at  the  concentrations required.

            5.7.1  Do not inject more than 20  /xL  of alcoholic  standards into
      100 ml of water.

            5.7.2  Use  a 25   /xL Hamilton   702N  microsyringe  or   equivalent
      (variations  in needle  geometry will  adversely affect  the  ability to
      deliver reproducible volumes  of methanolic standards into water).

            5.7.3  Rapidly  inject   the  alcoholic  standard  into   the  filled
      volumetric flask.  Remove the needle  as fast  as possible after  injection.

            5.7.4  Mix aqueous standards by inverting the  flask  three times.

            5.7.5  Fill  the  sample syringe from  the standard solution contained
      in  the expanded  area  of the  flask  (do  not use  any solution contained in
      the  neck  of  the flask).


                                   8021A  -  6                          Revision  1
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             5.7.6  Never use pipets  to  dilute or transfer  samples  or aqueous
      standards.

             5.7.7  Aqueous  standards are not stable and should be discarded after
      one  hour,  unless  properly  sealed  and stored.   The aqueous standards can
      be stored  up to 12 hours,  if held in  sealed vials with zero headspace.

      5.8    Internal  standards   -   Prepare  a  spiking  solution  containing
fluorobenzene  and  2-bromo-l-chloropropane  in  methanol , using  the  procedures
described in Sections 5.5 and 5.6. It is recommended that the  secondary dilution
standard be  prepared  at a concentration  of 5 mg/L of  each  internal  standard
compound.   The addition of  10 /xL of such  a  standard  to 5.0 ml  of  sample or
calibration standard would be equivalent to 10
      5.9    Surrogate   standards   -   The   analyst   should  monitor  both  the
performance  of  the analytical  system  and  the effectiveness of  the  method in
dealing with each  sample matrix by  spiking  each  sample,  standard,  and reagent
blank with two or more surrogate compounds.  A combination of bromochloromethane,
2-bromo-l-chloropropane, 1,4-dichlorobutane and bromochlorobenzene is recommended
to encompass the  range  of  the  temperature program used in  this  method.   From
stock standard solutions prepared  as in Section 5.5,  add a  volume  to give 750 M9
of each surrogate  to 45 ml of  organic-free  reagent water  contained  in a 50 mL
volumetric flask,  mix,  and dilute to  volume for a concentration of  15 ng/^L.
Add 10 ML of this  surrogate spiking solution directly into  the 5 ml syringe with
every  sample and  reference  standard  analyzed.    If the  internal  standard
calibration procedure is used,  the surrogate  compounds may be added directly to
the internal standard spiking solution (Section 5.8).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    See  the  introductory  material to this chapter,  Organic  Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap  (Method 5030).  Method  5030  may be used
directly on ground  water samples or low-concentration contaminated  soils  and
sediments.   For medium-concentration  soils or sediments,  methanolic extraction,
as described in Method  5030, may  be necessary prior to purge-and-trap analysis.

      7.2   Gas chromatography conditions (Recommended)

            7.2.1 Set   up  the   gas   chromatograph  system   so   that   the
      photoionization  detector  (PID)   is   in  series  with  the  electrolytic
      conductivity detector (HECD).
                                  8021A  - 7                         Revision 1
                                                                 November 1992
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            7.2.2 Oven  settings:

            Carrier gas (Helium) Flow rate:     6 mL/min.
            Temperature program
                  Initial  temperature:    10°C,  hold for 8 minutes at
                  Program:                10°C to 180°C  at  4°C/min
                  Final temperature:      180°C,   hold   until    all   expected
                                          compounds have eluted.

            7.2.3 The carrier gas flow is augmented  with an additional 24 ml of
      helium flow before entering the  photoionization  detector.   This make-up
      gas is necessary to ensure optimal response from both detectors.

            7.2.4 These halogen-specific systems eliminate misidentifications
      due to non-organohalides which are coextracted during the purge step.  A
      Tracer Hall Model  700-A detector  was used to gather the single laboratory
      accuracy  and   precision data  presented  in  Table   2.    The  operating
      conditions used to collect these data are:

            Reactor tube:                       Nickel,  1/16 in OD
            Reactor temperature:                810°C
            Reactor base temperature:           250°C
            Electrolyte:                        100% n-Propyl  alcohol
            Electrolyte flow rate:              0.8 mL/min
            Reaction gas:                       Hydrogen at 40 mL/min
            Carrier gas plus make-up gas:       Helium at 30 mL/min

            7.2.5 A sample chromatogram  obtained with this column is presented
      in  Figure  5.   This  column was  used  to develop  the  method performance
      statements in Section  9.0.  Estimated  retention  times  and MDLs that can
      be  achieved under these conditions  are  given  in  Table  1.   Other columns
      or  element specific detectors may be used if the requirements of Section
      8.0 are met.

      7.3   Calibration  -   Refer   to   Method  8000  for   proper  calibration
techniques.   Use Table  1 and  especially  Table 2  for guidance  on selecting the
lowest point on the  calibration curve.

            7.3.1 Calibration must take place  using the same sample introduction
      method that will be used to analyze actual samples (see Section 7.4.1).

            7.3.2 The  procedure for internal  or external calibration  may be
      used.  Refer to Method  8000 for a description of each  of these procedures.

      7.4   Gas  chromatographic  analysis

            7.4.1 Introduce  volatile compounds into the  gas chromatograph using
      either Method 5030 (purge-and-trap method)  or  the  direct injection method
      (see Section 7.4.1.1).   If the internal  standard calibration technique is
      used, add  10 fj,L of internal standard to the sample prior  to purging.

                  7.4.1.1     Direct injection -  In very  limited applications
            (e.g. aqueous  process wastes)  direct injection of the sample into
            the  GC  system with  a  10  p.1 syringe  may be  appropriate.   The

                                  8021A - 8                         Revision 1
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             detection limit is very high (approximately 10,000 M9/L), therefore,
             it  is only permitted where concentrations in excess of 10,000 p.g/1
             are expected or for water-soluble compounds that do not purge.  The
             system must be calibrated by direct  injection  (bypassing the purge-
             and-trap device).

             7.4.2  Follow  Section 7.6  in  Method 8000 for  instructions  on the
      analysis  sequence,  appropriate dilutions,  establishing  daily  retention
      time windows, and identification  criteria.   Include a mid-concentration
      standard  after each group of 10 samples in the analysis sequence.

             7.4.3  Table  1  summarizes the estimated retention  times on the two
      detectors for a number of organic  compounds  analyzable using this method.

             7.4.4  Record the  sample volume purged or injected and the resulting
      peak sizes (in area units or peak heights).

             7.4.5  Calculation of concentration  is covered in Method 8000.

             7.4.6  If analytical interferences are suspected, or for the purpose
      of confirmation, analysis using a second GC column  is recommended.

             7.4.7  If the  response for a peak is off-scale, prepare a  dilution
      of  the sample with  organic-free  reagent water.   The dilution  must be
      performed on a second aliquot of the sample which has been properly sealed
      and stored prior to use.


8.0   QUALITY CONTROL

      8.1    Refer  to  Chapter One for specific  quality  control  procedures and
Method 8000 for gas chromatographic procedures.   Quality control  to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.

      8.2    Quality  control  required to  validate the GC  system  operation is
found in Method 8000.

             8.2.1  The  quality control  reference  sample  (Method  8000)  should
      contain  each  parameter  of  interest at  a concentration of 10  mg/L in
      methanol.

             8.2.2  Table 2  gives  method accuracy and precision  as functions of
      concentration for the analytes of interest.

      8.3    Calculate  surrogate  standard  recovery on all  samples,  blanks, and
spikes.  Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000).

             8.3.1  If recovery is  not within limits, the following is  required.

                   •     Check to be sure  there  are  no  errors  in  calculations,
                        surrogate solutions and  internal standards.  Also check
                        instrument performance.


                                  8021A - 9                         Revision 1
                                                                 November 1992
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                        Recalculate the data and/or reanalyze the extract if any
                        of the above checks  reveal  a problem.

                        Reextract and reanalyze  the  sample if none of the above
                        are  a   problem   or  flag  the  data   as   "estimated
                        concentration".
9.0   METHOD PERFORMANCE

      9.1   Method detection limits for these analytes have been calculated from
data collected by spiking organic-free reagent water  at  0.1  jug/L.   These data
are presented in Table 1.

      9.2   This  method  was tested in a  single  laboratory using organic-free
reagent water spiked at 10 /xg/L.   Single laboratory precision and accuracy data
for each detector are presented for the method analytes in Table 2.


10.0  REFERENCES

1.    Volatile Organic Compounds  in Water by Purge-and-Trap Capillary Column Gas
      Chromatographv   with   Photoionization  and   Electrolytic   Conductivity
      Detectors in Series. Method 502.2; U.S. Environmental Protection Agency.
      Environmental   Monitoring   and  Support   Laboratory:   Cincinnati,   OH,
      September,  1986.

2.    The Determination of Halogenated Chemicals  in  Water by  the Purge and Trap
      Method,  Method  502.1;  Environmental  Protection  Agency,  Environmental
      Monitoring  and Support Laboratory:  Cincinnati, Ohio  45268,  September,
      1986.

3.    Volatile Aromatic and Unsaturated Organic Compounds in  Water by Purge and
      Trap Gas  Chromatographv, Method 503.1;  Environmental Protection Agency,
      Environmental   Monitoring  and  Support  Laboratory:  Cincinnati,  Ohio,
      September,  1986.

4.    Glaser, J.A.;  Forest, D.L.; McKee, G.D.; Quave, S.A.; Budde, W.L. "Trace
      Analyses for Wastewaters"; Environ. Sci. Technol.  1981, 15, 1426.

5.    Bellar, T.A.;  Lichtenberg,  J.J. The  Determination  of  Synthetic Organic
      Compounds in Water bv Purge and Sequential  Trapping Capillary Column Gas
      Chromatography;  U.S.  Environmental  Protection  Agency,  Environmental
      Monitoring  and  Support Laboratory: Cincinnati,  Ohio, 45268.
                                  8021A - 10                        Revision  1
                                                                 November 1992
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                               TABLE  1.

CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL) FOR
  VOLATILE ORGANIC COMPOUNDS ON PHOTOIONIZATION DETECTION (PID) AND
      HALL  ELECTROLYTIC  CONDUCTIVITY DETECTOR  (HECD) DETECTORS
Analyte
Dichlorodifl uoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methylene Chloride
trans-l,2-Dichloroethene
1,1-Dichloroethane
2,2-Dichloropropane
cis-1, 2 -Di chloroethane
Chloroform
Bromochl oromethane
1,1,1 -Tri chloroethane
1,1-Dichloropropene
Carbon Tetrachloride
Benzene
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodichl oromethane
Dibromomethane
Toluene
1 , 1 , 2 -Tri chl oroethane
Tetrachl oroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
Chlorobenzene
Ethyl benzene
1,1,1 , 2-Tetrachl oroethane
m-Xylene
p-Xylene
o-Xylene
Styrene
Isopropyl benzene
Bromoform
1,1,2 , 2-Tetrachl oroethane
1,2,3-Trichloropropane
PID
Ret. Time3
minute
_b
-
9.88
-
-
-
16.14
-
19.30
-
-
23.11
-
-
-
25.21
-
26.10
-
27.99
-
-
-
31.95
-
33.88
-
-
-
36.56
36.72
-
36.98
36.98
38.39
38.57
39.58
-
-
-
HECD
Ret. Time
minute
8.47
9.47
9.93
11.95
12.37
13.49
16.18
18.39
19.33
20.99
22.88
23.14
23.64
24.16
24.77
25.24
25.47
-
26.27
28.02
28.66
29.43
29.59
-
33.21
33.90
34.00
34.73
35.34
36.59
-
36.80
-
-
-
-
-
39.75
40.35
40.81
PID
MDL
M9/L


0.02



NDC

0.05


0.02



0.02

0.009

0.02



0.01

0.05



0.003
0.005

0.01
0.01
0.02
0.01
0.05



HECD
MDL
M9/L
0.05
0.03
0.04
1.1
0.1
0.03
0.07
0.02
0.06
0.07
0.05
0.01
0.02
0.01
0.03
0.02
0.01

0.03
0.01
0.006
0.02
2.2

ND
0.04
0.03
0.03
0.8
0.01

0.005





1.6
0.01
0.4
                             8021A  - 11
   Revision 1
November 1992
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                                   TABLE 1.
                                  (Continued)
Analyte
   PID
Ret.  Time8
  minute
  HECD       PID
Ret.  Time    MDL
 minute
                                                                        HECD
                                                                         MDL
n-Propylbenzene                   40.87
Bromobenzene                      40.99
1,3,5-Trimethylbenzene            41.41
2-Chlorotoluene                   41.41
4-Chlorotoluene                   41.60
tert-Butylbenzene                 42.92
1,2,4-Trimethylbenzene            42.71
sec-Butyl benzene                  43.31
p-Isopropyltoluene                43.81
1,3-Dichlorobenzene               44.08
1,4-Dichlorobenzene               44.43
n-Butylbenzene                    45.20
1,2-Dichlorobenzene               45.71
l,2-Dibromo-3-Chloropropane
1,2,4-Trichlorobenzene            51.43
Hexachlorobutadiene               51.92
Naphthalene                       52.38
1,2,3-Trichlorobenzene            53.34

Internal Standards
  Fluorobenzene                   26.84
  2-Bromo-l-chloropropane
                41.03

                41.45
                41.63
                 44.11
                 44.47

                 45.74
                 48.57
                 51.46
                 51.96

                 53.37
                 33.08
             0.004
             0.006
             0.004
             ND
             0.02
             0.06
             0.05
             0.02
             0.01
             0.02
             0.007
             0.02
             0.05

             0.02
             0.06
             0.06
             ND
0.03

0.01
0.01
0.02
0.01

0.02
3.0
0.03
0.02

0.03
    Retention times determined  on  60 m  x  0.75 mm  ID
    Program:  Hold at 10°C for 8 minutes, then  program
    hold until  all  expected compounds have  eluted.

    Dash (-)  indicates detector does not respond.

    ND = Not  determined.
                     VOCOL capillary  column.
                     at  4°C/min  to  180°C,  and
                                  8021A  -  12
                                   Revision 1
                                November 1992
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                   TABLE 2.
SINGLE LABORATORY ACCURACY AND PRECISION DATA
   FOR VOLATILE ORGANIC COMPOUNDS IN WATERd
Photoionization
Detector
lalyte
inzene
"omobenzene
"omochloromethane
-omodichloromethane
"omoform
"omomethane
-Butyl benzene
*c-Butyl benzene
srt-Butyl benzene
arbon tetrachloride
ilorobenzene
iloroethane
iloroform
iloromethane
-Chlorotoluene
-Chlorotoluene
,2-Dibromo-3-chloropropane
i bromochl oromethane
,2-Dibromoethane
ibromomethane
,2-Dichlorobenzene
,3-Dichlorobenzene
,4-Dichlorobenzene
i chl orodi f 1 uoromethane
,1-Dichloroethane
,2-Dichloroethane
,1-Dichloroethene
is-1,2 Dichloroethene
rans-l,2-Dichloroethene
,2-Dichloropropane
,3-Dichloropropane
,2-Dichloropropane
,1-Dichloropropene
thyl benzene
exachl orobutadi ene
sopropyl benzene
-Isopropyltoluene
Recovery,3
%
99
99
-
-
-
-
100
97
98
-
100
-
-
-
NDC
101
-
-
-
-
102
104
103
-
-
-
100
ND
93
-
-
-
103
101
99
98
98
Standard
Deviation
of Recovery
1.2
1.7
-
-
-
-
4.4
2.6
2.3
-
1.0
-
-
-
ND
1.0
-
-
-
-
2.1
1.7
2.2
-
-
-
2.4
ND
3.7
-
-
-
3.6
1.4
9.5
0.9
2.4
Hall Electrolytic
Conductivity Detector
Standard
Recovery,3 Deviation
% of Recovery
_b
97
96
97
106
97
-
-
-
92
103
96
98
96
97
97
86
102
97
109
100
106
98
89
100
100
103
105
99
103
100
105
103
-
98
-
-

2.7
3.0
2.9
5.5
3.7
-
-
-
3.3
3.7
3.8
2.5
8.9
2.6
3.1
9.9
3.3
2.7
7.4
1.5
4.3
2.3
5.9
5.7
3.8
2.9
3.5
3.7
3.8
3.4
3.6
3.4
-
8.3
-
-
                  8021A - 13
   Revision 1
November 1992
-------
                                         TABLE 2.
                                        (Continued)
Analyte
Photoionization
Detector
Standard
Recovery,8 Deviation
% of Recovery
Hall Electrolytic
Conductivity Detector
Standard
Recovery,3 Deviation
% of Recover
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichl oroethane
1,1,2-Trichl oroethane
Trichl oroethene
Tr i chl orof 1 uoromethane
1,2,3-Trichloropropane
1, 2, 4-Trimethyl benzene
1, 3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
-
102
103
104
-
-
101
99
106
104
-
-
100
-
-
99
101
109
99
100
99
-
6.3
2.0
1.4
-
-
1.8
0.8
1.9
2.2
-
-
0.78
-
-
1.2
1.4
5.4
0.8
1.4
0.9
97
-
-
-
99
99
97
-
98
102
104
109
96
96
99
-
-
95
-
-
~
2.8
-
-
-
2.3
6.8
2.4
-
3.1
2.1
3.4
6.2
3.5
3.4
2.3
-
-
5.6

-
~
    Recoveries  and standard  deviations  were determined  from  seven samples  and  spiked a
    10  fxg/L of each analyte. Recoveries were determined by internal  standard method. Interna
    standards were:  Fluorobenzene  for PID,  2-Bromo-l-chloropropane for HECD.
b   Detector  does  not  respond.

c   ND  =  Not  determined.
    This  method  was  tested
    reference  8).
in a  single laboratory  using water  spiked at  10 jug/L  (se
                                        8021A - 14
                                              Revision  1
                                           November  1992
-------
                      TABLE 3.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
                FOR VARIOUS MATRICES3
  Matrix                              Factor6
  Ground water                             10
  Low-concentration soil                   10
  Water miscible liquid waste             500
  High-concentration soil and sludge     1250
  Non-water miscible waste               1250
  Sample EQLs are highly matrix dependent.  The EQLs listed herein
  are provided for guidance and may not always be achievable.

  EQL = [Method detection limit  (Table  1)]  X  [Factor (Table 2)].
  For non-aqueous samples,  the factor is on a wet-weight basis.
                     8021A - 15                        Revision 1
                                                    November 1992
-------
   FIGURE 1.
PURGING DEVICE
      MWAT 11 «i IP*

       CM * OAUQC STMNGC NUOLI

      • MMOO

         MM OO
  8021A  -  16
   Revision  1
November  1992
-------
                          FIGURE 2.
TRAP PACKINGS AND CONSTRUCTION  TO INCLUDE DESORB CAPABILITY
         PACKING OCTA*.
CONSTRUCTION OCTA*
                         8021A - 17
                        Revision 1
                     November 1992
-------
                              FIGURE 3.
                 PURGE-AND-TRAP SYSTEM -  PURGE MODE
CAWVCROAS
R.OW
UOUK) iNJfCTION

    - COLUMN OVtN
                                     JW-
                                                TO
                                                             COLUMN
                                                 ANALYTICAL COLUMN
                               OPTIONAL 4*OKT COLUMN
                               SCLCCHON VALVC
                                        TIUI»MLCT
SlCVt
                                 PUAGING
                                 0€VC€
             NOTt
             ALL UNCS aCTWCEN
             AND oc SHOULD ac
             TOWX
                              8021A -  18
                              Revision 1
                           November 1992
-------
                             FIGURE 4.
          SCHEMATIC  OF  PURGE-AND-TRAP DEVICE - DESORB MODE
CAfMfftGAft
                              OPTIONAL
                              SCLfCDON VALVf
COLUMN OVEN

         CONFWMATOftV COLUMN


        TO DETECTOR


      ^-ANALYTICAL COLUMN

     COLUMN
                                              NOTf:
                                              AU UNCS iCTWUW
                                              AND QC IMOUVO K NtATO
                                              TO arc
                             8021A  -  19
                       Revision  1
                    November  1992
-------
     4T1*
-------
                             METHOD 8021A
 HALOGENATED VOLATILES BY GAS CHROMATOGRAPHY USING PHOTOIONIZATION
         AND ELECTROLYTIC  CONDUCTIVITY DETECTORS  IN SERIES:
                      CAPILLARY COLUMN TECHNIQUE
    7.2  Sat
chr oraatographic
  conditions.
 7,3  Refer  to
  Method  8000
      for
  calibration
  technique s.
7.4.1  Introduce
*a«pl»  into  QC
 us Ing  direct
 inj ec t i on   or
purge-and-trap .
 7.4.4  Record
 sample  volume
  introduced
  into  GC  and
  peak  sizes .
                           7.4.5  Refer
                             to Method
                             8000  for
                          calculati ons.
                            7.4.6  Are
                           analy tic al
                           Interfax ence
                           suspec t ed?
 Reanaly z e
s amp 1e  u i ng
 second  GC
  column.
                                                     Dilute  and
                                                      r*an*lyce
                                                       second
                                                     aliquot   of
                                                       samp1e.
                              8021A - 21
                                                                 Revision  1
                                                              November 1992
-------
                                METHOD 8030

                   ACROLEIN. ACRYLONITRILE. ACETONITRILE
1.0  SCOPE AND APPLICATION

    1.1  Method 8030 is used  to  determine  the concentration of the following
three volatile organic  compounds:

         Acrolein (Propenal)
         Acrylonitrile
         Acetonitrile

    1.2  Table 1 lists chromatographic conditions and method detection limits
for acrolein and acrylonitrile in reagent water.  Table 2 lists the practical
quantitation limit (PQL)  for other matrices.

2.0  SUMMARY OF METHOD

    2.1  Method 8030 provides gas chromatographic conditions for the detection
of the three volatile organic compounds.  Samples can  be analyzed  using direct
injection  or  purge-and-trap  (Method  5030).    Ground water  samples  must be
analyzed  using  Method  5030.   A temperature  program  is  used  in  the gas
chromatograph  to separate  the organic  compounds.  Detection is achieved by a
flame ionization detector (FID).

    2.2  The method  provides  an  optional  gas  chromatographic column that may
be helpful in resolving the analytes  from interferences that may occur and for
analyte confirmation.

3.0  INTERFERENCES

    3.1  Refer to Methods 5030 and 8000.

    3.2  Samples  can  be  contaminated  by diffusion of   volatile  organics
(particularly  chlorofluorocarbons  and  methylene chloride)  through the sample
container septum during  shipment  and  storage.  A field sample blank prepared
from reagent  water  and  carried  through  sampling and subsequent  storage and
handling can serve as a check on  such  contamination.

4.0  APPARATUS AND MATERIALS

    4.1  Gas chromatograph

         4.1.1  Gas  Chromatograph  -  Analytical  system  complete with gas
    chromatograph suitable  for on-column  injections  or purge-and-trap sample
    introduction  and all  required accessories,  including  detectors,  column
    supplies, recorder,  gases, and syringes.   A data system  for measuring peak
    height and/or peak  area is recommended.
                                  8030 -  1                       Revision 1
                                                                December 1987
-------
         4.1.2  Columns

              4.1.2.1  Column  1  - 10 ft x 2 mm  i.d.  stainless  steel  or  glass
         packed with Porapak-QS  (80/100 mesh) or equivalent.

              4.1.2.2  Column  2  - 6  ft  x  0.1  in  i.d.  stainless  steel  or  glass
         packed with Chromosorb  101  (60/80 mesh) or equivalent.

         4.1.3  Detector -  Flame ionization (FID).

    4.2  Sample  introduction  apparatus  - Refer to  Method  5030  for the
appropriate equipment  for sample introduction purposes.

    4.3  Syringes - A 5-mL  Luerlok glass hypodermic and a 5-mL,  gas-tight with
shutoff valve.

    4.4  Volumetric flasks  -  10-,  50-,  100-, 500-, and 1,000-mL with a ground-
glass stopper.

    4.5  Microsyringes - 10- and  25-uL with a 0.006  in  i.d.  needle (Hamilton
702N or equivalent) and  a 100-uL.

5.0  REAGENTS

    5.1 .Reagent grade chemicals shall  be used in all tests.  Unless otherwise
indicated,   it  is  intended  that all   reagents  shall  conform  to  the
specifications  of the  Committee  on  Analytical  Reagents  of the  American
Chemical Society, where  such  specifications are  available. Other grades may be
used,  provided  it is first  ascertained  that  the reagent  is  of sufficiently
high  purity to  permit  its use without  lessening  the  accuracy  of  the
determination.

    5.2  ASTM Type II Water (ASTM D1193-77  (1983)). All references to water in
the method refer to ASTM Type II unless otherwise  specified.

    5.3  Stock standards - Stock  solutions may be prepared from pure standard
materials  or purchased  as certified solutions.   Prepare  stock  standards  in
water   using assayed  liquids.   Because  acrolein  and  acrylonitrile  are
lachrymators,  primary dilutions of these  compounds  should be prepared  in  a
hood.

         5.3.1  Place about  9.8 ml of water  in  a  10-mL tared ground-glass-
    stoppered volumetric flask.   For  acrolein  standards  the  water  must  be
    adjusted to  pH  4-5 using  hydrochloric  acid (1:1)  or  sodium hydroxide
    (ION), if necessary.  Weigh  the  flask to the nearest  0.1 mg.

         5.3.2  Using a  100-uL  syringe,  immediately  add  two  or more drops of
    assayed  reference material  to the  flask;  then reweigh.   The liquid must
    fall directly  into the water without  contacting the neck of the flask.

         5.3.3  Reweigh, dilute  to volume, stopper,  and then mix by inverting
    the flask several  times.    Calculate  the  concentration  in  micrograms per
    microliter (ug/uL)  from the net gain  in weight.   When compound purity is

                                  8030  -  2                       Revision 1
                                                                December 1987
-------
    assayed to be 96% or greater,  the  weight may be used without correction to
    calculate the concentration of the stock standard.  Commercially prepared
    stock standards may be used at any concentration  if they are certified by
    the manufacturer or by an independent  source.

         5.3.4  Transfer  the stock standard  solution into  a bottle  with  a
    Teflon lined screw-cap.  Store, with minimal headspace, at 4°C and protect
    from light.

         5.3.5  Prepare fresh standards daily.

    5.4  Secondary  dilution standards  -  Using  stock  standard  solutions,
prepare  in  water secondary  dilution  standards, as  needed,  that  contain  the
compounds  of  interest,  either singly  or mixed  together.   The  secondary
dilution standards should be prepared  at concentrations such that the aqueous
calibration standards prepared  in Step 5.5  will bracket  the working range of
the analytical  system.    Secondary dilution  standards should be  stored  with
minimal headspace for volatiles and should be checked frequently for signs of
degradation or evaporation,  especially just  prior  to  preparing  calibration
standards from them.

    5.5  Calibration standards  -  Calibration  standards at a  minimum  of  five
concentration levels are prepared in  water from the  secondary dilution of the
stock standards.  One of the  concentration  levels should be at a concentration
near,  but  above, the  method detection limit.   The  remaining  concentration
levels should correspond to the expected range of concentrations found in  real
samples or  should define  the working  range of the GC.   Each standard should
contain  each   analyte  for detection  by  this  method.   In order  to  prepare
accurate  aqueous  standard  solutions,  the  following  precautions must  be
observed.

         5.5.1  Use  a  25-uL  Hamilton   702N  microsyringe or  equivalent
    (variations  in  needle geometry  will  adversely  affect  the  ability  to
    deliver reproducible volumes of standards into water).

         5.5.2  Never  use pipets to  dilute or  transfer  samples  or  aqueous
    standards.

         5.5.3  These standards must be prepared daily.

    5.6  Internal standards  (if internal  standard  calibration is  used)  -  To
use this approach,  the analyst must select  one or more  internal standards  that
are similar in analytical behavior to  the compounds  of interest.   The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences.  Because of these limitations, no
internal standard can be suggested that is  applicable  to all  samples.

         5.6.1  Prepare  calibration  standards  at a  minimum  of  five
    concentration levels for each parameter of  interest  as described  in  Step
    5.5.
                                  8030 - 3                       Revision 1
                                                                December 1987
-------
         5.6.2  Prepare a  spiking solution  containing  each of  the internal
    standards using  the  procedures described  in  Steps 5.3  and  5.4.   It is
    recommended that  the  secondary  dilution  standard  be  prepared  at  a
    concentration  of  15  ug/mL of  each  internal  standard  compound.   The
    addition of  10 uL of  this standard to  5.0  ml of  sample  or calibration
    standard would  be equivalent to 30  ug/L.

         5.6.3  Analyze each  calibration standard according to  Section  7.0,
    adding  10  uL  of  internal  standard  spiking solution  directly  to the
    syringe.

    5.7  Surrogate  standards - The analyst  should  monitor both  the performance
of the analytical  system and  the effectiveness of the method in dealing  with
each sample matrix by  spiking each sample, standard,  and reagent water  blank
with  one or  two surrogate compounds  (e.g.  compounds  similar in  analytical
behavior to the  analytes of interest but which are not  expected to  be  present
in the sample)  recommended  to encompass the range of the temperature  program
used in  this method.   From stock standard  solutions  prepared as in Step  5.3,
add a volume to give  750 ug of each surrogate to 45 ml of water contained  in a
50-mL  volumetric  flask,  mix,  and  dilute  to  volume  for a  concentration of
15 ng/uL.  Add 10 uL  of this surrogate  spiking  solution  directly into the  5-mL
syringe  with  every sample  and reference standard analyzed.   If the internal
standard calibration procedure  is  used,  the  surrogate  compounds  may be  added
directly to the internal  standard spiking solution (Step 5.6.2).

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

    6.1  See the introductory material  to this  chapter,  Organic Analytes,  Step
4.1.

7.0  PROCEDURE

    7.1  Volatile compounds are  introduced into  the  gas chromatograph  either
by direct injection or purge-and-trap  (Method 5030).   Method 5030 may  be  used
directly on  ground  water  samples  or low-level  contaminated  soils and
sediments.    For high-level  soils or  sediments, methanolic  extraction, as
described in Method 5030,  may be necessary  prior to purge-and-trap analysis.

    7.2  Gas chromatography conditions  (Recommended)

         7.2.1  Column 1 -  Set helium  gas  flow at 30  mL/min flow  rate.  Set
    column  temperature at HO'C  for  1.5  minutes;  then  heat as   rapidly as
    possible to  150°C and hold for 20 minutes.

         7.2.2  Column 2 -  Set helium  gas  flow at 40  mL/min flow  rate.  Set
    column  temperature at 80eC  for 4  minutes;  then program  at  50°C/min to
    120eC and hold for 12 minutes.

    7.3  Calibration - Refer to Method  8000 for proper calibration techniques.
Use Table 1 and  especially Table  2  for guidance on selecting the  lowest point
on the calibration curve.
                                  8030 - 4                       Revision  1
                                                                 December  1987
-------
         7.3.1  Calibration must take place using  the same sample introduction
    method that will be used to analyze actual  samples (see Step 7.4.1).

         7.3.2  The  procedure  for  internal or  external  calibration may  be
    used.  Refer to Method 8000 for a description  of each of these procedures.

    7.4  Gas chromatographic analysis

         7.4.1  Introduce volatile compounds into the  gas chromatograph  using
    either Method 5030 (purge-and-trap method)  or  the direct injection method.
    If the  internal  standard  calibration  technique  is used, add  10  uL of  the
    internal standard to the sample prior to purging.

              7.4.1.1  Direct  injection  -  In very limited  applications  (e.g.
         aqueous process wastes),  direct  injection  of the  sample  into the  GC
         system with a 10 uL  syringe  may  be  appropriate.   The  detection  limit
         is  very high  (approximately  10,000  ug/L);  therefore,  it is  only
         permitted  when  concentrations  in excess  of 10,000  ug/L  are expected
         or for water-soluble compounds that do not  purge.  The system must be
         calibrated by direct injection (bypassing the purge-and-trap device).

         7.4.2  Follow  Step  7.6  of Method 8000  for  instructions on  the
    analysis  sequence,  appropriate  dilutions,  establishing  daily  retention
    time windows,  and  identification criteria.   Include  a  mid-level  standard
    after each group of 10 samples in the analysis sequence.

         7.4.3  Table 1 summarizes the estimated  retention times and detection
    limits  for  a number  of organic  compounds analyzable using  this method.
    Figure  1  illustrates the  chromatographic  separation  of acrolein and  of
    acrylonitrile using Column 1.

         7.4.4  Record the sample volume  purged or  injected and the resulting
    peak sizes (in area units or peak heights).

         7.4.5  Calculation of concentration is covered  in  Step 7.8 of Method
    8000.

         7.4.6  If  analytical  interferences  are suspected,  or  for the purpose
    of confirmation, analysis using the second  GC  column  is recommended.

         7.4.7  If the response for a peak is off-scale,  prepare a dilution of
    the sample with water.  The dilution must be performed on a second aliquot
    of the sample which has been properly sealed and stored prior to use.

8.0  QUALITY CONTROL

    8.1  Refer  to  Chapter  One  for  specific  quality  control   procedures  and
Method 8000 for gas chromatographic procedures. Quality  control to ensure  the
proper operation of the purge-and-trap device is covered  in Method 5030.

    8.2  Procedures to check the GC system operation are  found  in Method  8000,
Step 8.6.


                                  8030 - 5                       Revision  1
                                                                 December  1987
-------
         8.2.1  The quality  control  check  sample concentrate  (Method  8000,
    Step 8.6) should contain each parameter of interest at a concentration of
    25 ug/mL in water.

         8.2.2  Table  3 indicates the  calibration  and  QC acceptance criteria
    for this method.   Table  4  gives single laboratory  accuracy and precision
    for the analytes of interest.  The contents of both Tables should be used
    to evaluate a laboratory's  ability to perform  and generate acceptable data
    by this method.

    8.3  Calculate  surrogate  standard recovery on  all  samples,  blanks,  and
spikes.    Determine if  recovery  is  within  limits (limits  established  by
performing QC procedure outlined  in  Method 8000, Step 8.10).

         8.3.1  If recovery is  not within limits,  the following is required.

         •  Check to be  sure there are no  errors  in  calculations,  surrogate
            solutions  and  internal   standards.   Also,  check instrument
            performance.

         •  Recalculate the  data and/or  reanalyze the  extract if any  of the
            above checks  reveal a problem.

         •  Reextract   and  reanalyze the sample  if none  of the above  are a
            problem or  flag the data as "estimated  concentration."

9.0  METHOD PERFORMANCE

    9.1  In  a  single  laboratory,  the  average recoveries  and  standard
deviations  presented  in  Table  4  were  obtained  using  Method 5030.   Seven
replicate samples were  analyzed at  each spike  level.

    9.2  The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique,  and  by  the  calibration procedure used.

10.0 REFERENCES

1.   Bellar, T.A.  and  J.J.  Lichtenberg,  J.  Amer.  Water Works Assoc., 66(12).
     pp. 739-744, 1974.

2.   Bellar, T.A.  and  J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
     Drinking  Waters   and  Industrial   Waters  for  Purgeable Volatile Organic
     Compounds," in Van Hall, ed.,  Measurement of Organic Pollutants in Water
     and Wastewater, ASTM STP 686,  pp. 108-129,  1979.

3,   Development and Application  of Test Procedures for Specific Organic Toxic
     Substances  in Wastewaters, Category  11: Purgeables  and  Category  12:
     Acrolein,  Acrylonitrile, and  Dichlorodifluoromethane,  Report  for  EPA
     Contract 68-03-2635 (in preparation).

4.   Going,  J., et  al.,   Environmental  Monitoring  Near  Industrial  Sites -
     Acrylonitrile, Office of Toxic Substances, U.S. EPA, Washington, DC,  EPA
     560/6-79-003, 1979.

                                 8030 - 6                       Revision 1
                                                                December 1987
-------
5.   U.S. EPA  40  CFR Part  136,  "Guidelines  Establishing Test  Procedures  for
     the Analysis  of Pollutants  Under the  Clean  Water Act;  Final Rule  and
     Interim Final  Rule and Proposed Rule," October 26,  1984.

6.   Provost, L.P.  and R.S.  Elder,  "Interpretation  of  Percent  Recovery Data,"
     American Laboratory, 15, pp. 58-63, 1983.

7.   Kerns,  E.H.,  et al.  "Determination of Acrolein and Acrylonitrile in Water
     by  Heated Purge and Trap  Technique,"  U.S.  Environmental  Protection
     Agency, Environmental Monitoring and Support Laboratory,  Cincinnati, Ohio
     45268,  1980.

8.   "Evaluation of Method 603,"  Final  Report  for  EPA  Contract 68-03-1760 (in
     preparation).

9.   Rohrbough, W.G.; et  al.  Reagent Chemicals,  American Chemical  Society
     Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.

10.  1985 Annual Book of ASTM Standards. Vol.  11.01;  "Standard Specification
     for Reagent Water";  ASTM:  Philadelphia,  PA, 1985;  D1193-77.
                                  8030 - 7                       Revision 1
                                                                 December 1987
-------
                                  TABLE 1.
           CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION  LIMITS
                         Retention time (min)           Method  detection
Compound                 Col.  1        Col.  2            limit3 (ug/L)
Acrolein
Acrylonitrile
10.6
12.7
8.2
9.8
0.7
0.5
^Based on using purge-and-trap,  Method 5030.
                                  TABLE 2.
                   DETERMINATION  OF  PRACTICAL QUANTITATION
                     LIMITS (PQL) FOR VARIOUS MATRICES*
                         Matrix                    Factor0
                 Ground water                         10
                 Low-level soil                       10
                 Water tniscible liquid waste         500
                 High-level soil and sludge         1250
                 Non-water miscible waste           1250
                 a Sample  PQLs  are  highly  matrix-dependent.
                   The  PQLs  listed  herein  are provided  for
                   guidance and may not always be achievable.

                 b PQL = [Method detection limit (Table 1)] X
                   [Factor  (Table  2)].   For  non-aqueous
                   samples,  the factor  is on a  wet-weight
                   basis.
                                  8030 - 8                       Revision 1
                                                                 December 1987
-------
                                  TABLE 3.
                  CALIBRATION AND QC ACCEPTANCE CRITERIA*


Parameter
Range
for Q
(ug/L)
Limit
for S
(ug/L)
Range
for x
(ug/L)
Range
P, PS
(%)
Acrolein
Acrylonitrile
45.9-54.1
41.2-58.8
4.6
9.9
42.9-60.1
33.1-69.9
88-118
71-135
Q = Concentration measured in QC check sample, in ug/L.
S = Standard deviation of four recovery measurements, in ug/L.
x = Average recovery for four recovery measurements, in ug/L.
P, Ps = Percent recovery measured.

a Criteria from 40 CFR Part  136  for  Method  603  and were calculated assuming a
  QC check sample concentration of 50 ug/L.
                                  TABLE 4.
                  SINGLE LABORATORY ACCURACY AND PRECISION


Parameter
Acrolein





Acrylonitrile





Spike
cone.
(ug/L)
5.0
50.0
5.0
50.0
5.0
100.0
5.0
50.0
20.0
100.0
10.0
100.0
Average
recovery
(ug/L)
5.2
51.4
4.0
44.4
0.1
9.3
4.2
51.4
20.1
101.3
9.1
104.0
Standard
deviation
(ug/L)
0.2
0.7
0.2
0.8
0.1
1.1
0.2
1.5
0.8
1.5
0.8
3.2
Average
percent
recovery
104
103
80
89
2
9
84
103
100
101
91
104

Sample
matrix3
AW
AW
POTW
POTW
IW
IW
AW
AW
POTW
POTW
IW
IW
      = ASTM Type II water.
 POTW = Prechlorination secondary  effluent  from a municipal  sewage treatment
        plant.
 IW   = Industrial wastewater containing an unidentified acrolein reactant.
                                  8030 - 9
Revision 1
December 1987
-------
                    Figure 1.
Gas chromatogram of acroleln  and acrylonltrlle.
 Column: Porapak-QS
 Program. 110°C for 1.5 mm. rapidly
         haatad to 150«C
 Oat actor: Flama lonization
 I
1.5
 r
30
 T
45
 I
60
 i
7.5
• I
9.0
 i
10.5
  i
120
  i
135
                                                     150
                 RETENTION TIME.
                       8030 -  10
        Revision 1
        December 1987
-------
                                               METHOD 8030
                                ACROLEIN,  ACRYLONITRILE,  ACETONITRILE
  C
Start
 7. J
  Introduce compounds
        Into gas
   chromatograph by
  direct injection or
    purge-and-trap
     (Method 5030)
    7.2
0
                                                       7.4.4
                                                     Record
                                                volume  purged
                                              or Injected  ana
                                                  peax  sites
       Set gas
    chromatogreph
      condlt Ion
                                                       7.4.5
                                                   Calculate
                                                concentratIon
                                                (Section  7.8.
                                                 Method 80OO)
    7.3
      CalIbrete
      (re f cr to
     Method 6000)
7.4.1
  Introduce  volatile
  compounds  into  gas
   cnromatogreon  tsy
    Method  5030 or
   direct  Injection
   7. 4.2
          Follow
       Section  7.6
    In  Method 8000
      for  analyst*
    sequence, etc.
                                                                                7.4.6
                                                                        Analyze using
                                                                          second GC
                                                                           column
                                                                                7.4.7
                                                                        Dilute  cecond
                                                                          a 1 lauot  or
                                                                            sample
      o
                                               8030  - 11
                                                                           Revision  1
                                                                           December  1987
-------
                                  METHOD 8031

                      ACRYLONITRILE BY GAS CHROMATOGRAPHY
  .0   SCOPE AND APPLICATION

      1.1   Method 8031 is used to determine the concentration of acrylonitrile
 n water.  This method may also be applicable to other matrices.  The following
 :ompounds can be determined by this method:
      Compound Name                                         CAS No.'
      Acrylonitrile                                         107-13-1
      a  Chemical  Abstract Services Registry Number.

      1.2   The estimated quantitation limit of Method 8031 for determining the
:oncentration of acrylonitrile in water is approximately 10
      1.3   This method  is restricted to  use  by or under  the  supervision of
analysts  experienced in  the use  of gas  chromatographs and  skilled  in  the
interpretation of gas chromatograms.   Each  analyst must demonstrate the ability
;o generate acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   A measured sample volume is micro-extracted with methyl tert-butyl
ether.   The extract  is  separated  by gas  chromatography and measured  with  a
Nitrogen/Phosphorus detector.


3.0   INTERFERENCES

      3.1   Method  interferences  may be caused by contaminants  in  solvents,
reagents, glassware, and  other sample processing hardware  that leads to discrete
artifacts and/or elevated baselines in gas chromatograms.  All of these materials
must be  routinely demonstrated to be free from interferences under the conditions
of the analysis by running laboratory reagent blanks.

      3.2   Samples can be  contaminated by diffusion of volatile organics around
the septum  seal  into the  sample during handling and  storage.   A  field blank
should  be  prepared from organic-free  reagent  water  and carried  through  the
sampling and sample handling  protocol to serve as a check  on  such contamination.

      3.3   Contamination by  carryover can occur whenever  high-concentration and
low-concentration  samples  are sequentially  analyzed. To  reduce  carryover,  the
sample  syringe  must be  rinsed  out between  samples with  solvent.  Whenever an

                                   8031 -  1                         Revision  0
                                                                 November 1992
-------
unusually concentrated  sample is  encountered,  it should  be followed  by  the
analysis of solvent to check for cross contamination.

4.0   APPARATUS AND MATERIALS
      4.1   Gas chromatograph system
            4.1.1 Gas  chromatograph,  analytical  system  complete  with  gas
      chromatograph  suitable  for   on-column   injections   and  all  requirec
      accessories, including detector,  analytical  columns, recorder, gases, anc
      syringes.  A data system for measuring peak heights and/or peak areas is
      recommended.
            4.1.2 Column:   Porapak  Q  -  6 ft.,  80/10  Mesh, glass  column,  or
      equivalent.
            4.1.3 Nitrogen/Phosphorus detector.
      4.2   Materials
            4.2.1 Grab sample bottles - 40 ml VGA bottles.
            4.2.2 Mixing bottles - 90 ml bottle with a Teflon lined cap.
            4.2.3 Syringes - 10 /xL and 50 p.1.
            4.2.4 Volumetric flask (Class A) - 100 ml.
            4.2.5 Graduated cylinder - 50 ml.
            4.2.6 Pipet  (Class A) -  5, 15, and 50 ml.
            4.2.7 Vials  - 10 ml.
      4.3   Preparation
            4.3.1 Prepare all materials to be used as described in Chapter 4 for
      volatile organics.
5.0   REAGENTS
      5.1   Reagent grade chemicals shall  be used in all  tests.  Unless otherwise
indicated, it is intended that all  reagents  shall  conform to  the  specifications
of the Committee on Analytical Reagents of the  American  Chemical  Society, where
such specifications are available. Other grades may be used,  provided it  is first
ascertained that  the  reagent is  of sufficiently high purity to permit  its use
without  lessening the accuracy of the determination.
      5.2   General
            5.2.1 Methanol,  CH3OH -  Pesticide quality, or equivalent.
                                   8031 - 2                         Revision  0
                                                                  November 1992
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      5.2.2 Organic-free reagent water.  All references to water in this
 lethod refer to organic-free reagent water, as defined in Chapter One.

      5.2.3 Methyl  tert-butyl  ether,  CH3Ot-C4H9  -  Pesticide  quality,  or
 equivalent.

      5.2.4 Acrylonitrile, H2C:CHCN, 98%.

 5.3   Stock standard solution

      5.3.1 Stock standard solutions - Can  be prepared from pure standard
 laterials  or  can  be purchased  as certified  solutions.   Commercially
 )repared  stock  standards  can be  used if they are  verified  against EPA
 standards.   If EPA  standards  are not available  for  verification,  then
 standards certified  by  the manufacturer  and verified  against a standard
 lade from pure material is acceptable.

      5.3.2 The stock standard solution  may be  prepared  by volume or by
 veight.   Stock  solutions  must be replaced  after  one year,  or sooner if
 :omparison with the  check standards indicates a problem.

      CAUTION:    Acrylonitrile is toxic.  Standard  preparation should be
                  performed in a laboratory fume hood.

            5.3.2.1     To prepare the stock standard solution by volume:
      inject 10 /-iL  of acrylonitrile (98%) into a 100 ml volumetric flask
      with a syringe.  Make up to volume with methanol.

            5.3.2.2     To prepare the stock standard solution by weight:
      Place about 9.8  ml  of organic-free  reagent water  into  a  10  ml
      volumetric  flask  before weighing the  flask and  stopper.  Weigh the
      flask and record the weight to the  nearest  0.0001 g.  Add two drops
      of pure acrylonitrile,  using  a  50  ^l_ syringe, to  the  flask.   The
      liquid must  fall  directly  into  the water,  without  contacting the
      inside wall  of the  flask.    Stopper  the  flask and  then  reweigh.
      Dilute to volume  with  organic-free reagent water.   Calculate the
      concentration  from the net gain  in weight.

5.4   Working standard solutions

      5.4.1 Prepare  a minimum of 5 working standard solutions that cover
the range  of  analyte concentrations  expected  in the samples.   Working
standards of 20, 40,  60, 80, and 100 /xg/L may be  prepared by injecting 10,
20, 30, 40, and 50 juL of the stock  standard solution prepared in Section
5.3.2.1 into 5 separate  90 ml  mixing bottles containing 40 ml of organic-
free reagent water.

      5.4.2 Inject  15  ml of  methyl  tert-butyl  ether  into  each  mixing
bottle, shake vigorously, and let  stand  5  minutes,  or  until  layers have
separated.

      5.4.3 Remove 5 mL of top layer by pi pet, and place in a 10 ml vial.

      5.4.4 Keep all standard solutions below 4°C until used.

                             8031 - 3                          Revision 0
                                                           November 1992
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6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this chapter,  Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Sample Extraction

            7.1.1 Pour 40 mL of the sample into a 90 mL mixing  bottle.  Pipet 15
      mL of Methyl tert-butyl  ether  into the  mixing bottle.   Shake vigorously
      for about 2 min. and let stand  for about 5 min.  Remove  about 5 mL of the
      top layer and store in a 10 mL vial.

      7.2   Chromatographic Conditions (Recommended)

      Carrier Gas (He) flow rate:   35 mL/min.
      Column Temperature:           180° C,  Isothermal
      Injection port temperature:   250° C
      Detector temperature:         250° C
      Detector Current (DC):        18 volts
      Gases:                        Hydrogen,  3 mL/min;   Air,  290 mL/min.

      7.3   Calibration of GC

            7.3.1 On  a  daily  basis,  inject  3 juL  of methyl  tert-butyl  ether
      directly into the  GC to flush  the system.   Also purge the  system with
      methyl tert-butyl  ether injections  between  injections  of  standards and
      samples.

            7.3.2 Inject  3  /zL of a  sample  blank  (organic-free  reagent  water
      carried through the  sample  storage procedures and extracted  with methyl
      tert-butyl  ether).

            7.3.3 Inject 3 nL of at  least five standard solutions: one should
      be near the detection limit; one should be near, but below, the expected
      concentrations of the analyte; one should be near,  but above, the expected
      concentrations  of   the   analyte.     The  range  of  standard  solution
      concentrations used should not exceed  the working  range  of the GC system.

            7.3.4 Prepare  a  calibration curve using  the peak  areas of the
      standards (retention time of acrylonitrile under the  conditions of Section
      7.2  is  approximately 2.3 minutes).   If the  calibration  curve deviates
      significantly from a straight line,  prepare a new calibration curve with
      the existing standards,  or, prepare new standards and  a new calibration
      curve.   See  Method  8000,  Section 7.4.2,   for  additional   guidance  on
      calibration by the external standard method.

      7.4   Sample Analysis

            7.4.1 Inject   3   jLtL  of  the  sample   extract,   using  the  same
      chromatographic conditions used to prepare  the standard  curve.  Calculate

                                   8031 - 4                         Revision 0
                                                                 November 1992
-------
      the concentration of acrylonitrile in the extract, using the area of the
      peak, against the calibration curve prepared in Section 7.3.4.


3.0   QUALITY CONTROL

      8.1   Refer to Chapter One  and  Method  8000  for specific quality control
Drocedures.

      8.2   Prior  to  preparation of  stock  solutions, methanol  and  methyl
tert-butyl ether reagents should be analyzed gas chromatographically under the
conditions described in Section 7.2, to determine possible interferences with the
acrylonitrile peak.   If the solvent blanks show contamination,  a different batch
of solvents should be  used.
9.0   METHOD PERFORMANCE

      9.1   Method 8031 was tested  in a single laboratory over a period of days.
Duplicate samples and one spiked sample were run for each calculation.   The GC
was calibrated daily.  Results are presented in Table 1.


10.0  REFERENCES

1.    K.L. Anderson,  "The  Determination  of Trace Amounts  of Acrylonitrile in
      Water by Specific Nitrogen Detector Gas Chromatograph", American  Cynamid
      Report No. WI-88-13,  1988.
                                   8031 - 5                         Revision 0
                                                                 November 1992
-------
                        TABLE  1

         SINGLE LABORATORY METHOD PERFORMANCE
                  CONCENTRATION
  SAMPLE          SPIKE (/ig/L)        % RECOVERY
      A                 60                100
      B                 60                105
      C                 40                 86
      D                 40                100
      E                 40                 88
      F                 60                 94

Average                                    96
                        8031  -  6                          Revision 0
                                                      November 1992
-------
                         METHOD  8031
            ACRYLONITRILE BY  GAS  CHROMATOGRAPHY
    Start
  7.1.1   E! ^c t £ a o 1
4 O m 1    of   s a mp 1
   with   methyl
  to - bvityl
       \ /
  •7.2   S
omato&3:
o n d i tion
7.3.1
system
       lviSti   GC
       w±th   3u.l
   l   t-fc>utyl
  ether .
                                          7.3.2    Analyze
                                          3x-il   of  samr>lo
                                                 bl
                                                     \ /
                                            7.3.3-7.3.4
                                              EstatxlisK
                                          !•«.• fe
                                                     with.
                                                     S
                                                    \ /
                                                 7 .  -4   S amp> 1 •
                                                  Analysis
                           8031 - 7
                                                                   Revision 0
                                                                November 1992
-------
                                  METHOD 8032

                       ACRYLAMIDE BY GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method 8032 is used to determine trace amounts of acrylamide monomer
in aqueous  matrices.   This method  may  be applicable to  other  matrices.   The
following compounds can be determined by this method:
      Compound Name                             CAS No.a


      Acrylamide                                79-06-01


      a  Chemical  Abstract Services Registry Number.

      1.2   The method detection limit (MDL) in clean water is 0.032 M9/L-

      1.3   This method  is  restricted  to  use  by,  or  under the supervision of,
analysts  experienced in  the use  of  gas  chromatographs  and  skilled  in  the
interpretation of gas chromatograms.   Each  analyst must demonstrate the ability
to generate acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   Method 8032 is based on bromination of the acrylamide double bond.
The reaction product  (2,3-dibromopropionamide)  is  extracted  from the reaction
mixture with ethyl  acetate,  after salting  out with sodium  sulfate.  The extract
is cleaned up using a Florisil column, and analyzed by gas chromatography with
electron capture detection (GC/ECD).

      2.2   Compound  identification  should  be  supported  by  at  least  one
additional qualitative technique.  Analysis using a second gas chromatographic
column  or  gas  chromatography/mass  spectrometry  may  be used  for  compound
confirmation.


3.0   INTERFERENCES

      3.1   No interference  is observed from sea water or in the presence of 8.0%
of  ammonium  ions  derived from  ammonium  bromide.   Impurities  from  potassium
bromide are removed by the Florisil clean up procedure.
                                   8032 - 1                         Revision 0
                                                                 November 1992
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4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatographic System

            4.1.1 Gas chromatograph suitable for on-column injections with all
      required accessories,  including detector,  analytical  columns,  recorder,
      gases, and syringes.  A data  system for measuring peak heights and/or peak
      areas is recommended.

            4.1.2 Column:   2 m  x  3 mm glass column, 5%  FFAP  (free fatty acid
      polyester) on 60-80 mesh acid washed Chromosorb W,  or equivalent.

            4.1.3 Detector:  electron capture detector.

      4.2   Kuderna-Danish  (K-D) apparatus.

            4.2.1 Concentrator tube -  10  ml graduated (Kontes K-570050-1025 or
      equivalent).  A  ground glass stopper is used  to prevent  evaporation of
      extracts.

            4.2.2 Evaporation  flask  -    500  mL (Kontes   K-570001-500   or
      equivalent).   Attach to  concentrator  tube  with   springs,  clamps,  or
      equivalent.

            4.2.3 Snyder column  -   Three  ball macro  (Kontes  K-503000-0121 or
      equivalent).

            4.2.4 Snyder column  -   Two   ball  micro (Kontes  K-569001-0219 or
      equivalent).

            4.2.5 Springs -  1/2 inch (Kontes K-662750 or equivalent).

      4.3   Separatory funnel - 150 ml.

      4.4   Volumetric flask (Class A) -  100  ml,  with  ground  glass stopper;
25 ml, amber, with ground glass stopper.

      4.5   Syringe - 5 ml.

      4.6   Microsyringes - 5 juL,  100 /iL.

      4.7   Pipets (Class A).

      4.8   Glass column (30 cm x  2 cm).

      4.9   Mechanical shaker.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all tests.  Unless otherwise
indicated,  it is intended that all  reagents shall conform to the specifications
of the Committee on Analytical  Reagents of the  American Chemical Society, where
such  specifications  are  available.  Other grades may be used,  provided it is

                                    8032 -  2                         Revision  0
                                                                 November  1992
-------
first ascertained that the reagent is of sufficiently high purity to  permit  its
use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined  in Chapter One.

      5.3   Solvents

            5.3.1 Ethyl acetate, C2H5C02C2H5.  Pesticide quality,  or equivalent.

            5.3.2 Diethyl ether,  C2H5OC2H5.   Pesticide quality,  or equivalent.
      Must  be  free  of  peroxides as  indicated  by  test strips  (EM  Quant,   or
      equivalent).   Procedures  for  removal  of peroxides are provided with  the
      test strips.  After cleanup, 20 ml of ethyl alcohol preservative must be
      added to each liter of ether.

            5.3.3 Methanol, CH3OH.  Pesticide quality, or equivalent.

            5.3.4 Benzene, C6H6.   Pesticide  quality,  or equivalent.

            5.3.5 Acetone, CH3COCH3.   Pesticide quality, or equivalent.

      5.4   Saturated bromine water.   Prepare by shaking organic-free reagent
water with bromine and allowing to stand for  1  hour,  in the  dark,  at 4°C.   Use
the aqueous phase.

      5.5   Sodium sulfate (anhydrous, granular), Na2S04.   Purify by  heating at
400°C for 4 hours in a shallow tray, or by  precleaning  the sodium sulfate with
methylene chloride.   If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed,  demonstrating that there is no interference from
the sodium sulfate.

      5.6   Sodium thiosulfate, Na2S203, 1 M aqueous  solution.

      5.7   Potassium bromide, KBr, prepared  for infrared analysis.

      5.8   Concentrated hydrobromic acid,  HBr,  specific gravity 1.48.

      5.9   Acrylamide  monomer,  H2C:CHCONH2,  electrophoresis  reagent  grade,
minimum 95% purity.

      5.10  Dimethyl phthalate, C6H4(COOCH3)2, 99.0% purity.

      5.11  Florisil (60/100 mesh):   Prepare Florisil by activating at 130°C  for
at least 16 hours.  Alternatively, store Florisil in an  oven at  130°C.  Before
use, cool the Florisil  in a desiccator.   Pack 5 g of  the Florisil, suspended in
benzene, in a glass column (Section 4.8).

      5.12  Stock standard solutions

            5.12.1      Prepare a stock standard solution of  acrylamide monomer
      as specified in Section 5.12.1.1.  When compound  purity  is assayed to be
      96% or greater, the weight can be used without  correction to calculate  the


                                   8032 - 3                          Revision 0
                                                                 November 1992
-------
      concentration of the stock  standard.  Commercially prepared standards can
      be used at any concentration  if they are certified by the manufacturer or
      by an independent source.

                  5.12.1.1    Dissolve   105.3  mg  of  acrylamide  monomer  in
            organic-free reagent  water  in a 100 mL volumetric flask, and dilute
            to the mark with  organic-free reagent water. Dilute the solution of
            acrylamide monomer so  as  to obtain  standard  solutions containing
            0.1 - 10 mg/L of acrylamide monomer.

      5.13  Calibration standards

            5.13.1      Dilute the acrylamide stock solution with organic-free
      reagent water to  produce standard  solutions  containing 0.1-5  mg/L of
      acrylamide.  Prior to injection the calibration standards are reacted and
      extracted in the same manner as  environmental  samples (Section 7).

      5.14  Internal standards

            5.14.1      The suggested  internal  standard is dimethyl phthalate.
      Prepare  a  solution containing 100 mg/L  of dimethyl  phthalate  in ethyl
      acetate.  The concentration of dimethyl phthalate in the sample extracts
      and calibration standards should  be 4 mg/L.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the  introductory material  to this chapter,  Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Bromination

            7.1.1 Pipet 50 mL  of sample into a 100 mL  glass  stoppered flask.
      Dissolve 7.5 g of potassium bromide into the sample, with stirring.

            7.1.2 Adjust the pH  of  the  solution  with  concentrated hydrobromic
      acid until the pH is between 1 and 3.

            7.1.3 Wrap the flask with aluminum foil in order to exclude light.
      Add 2.5 mL of  saturated bromine water, with  stirring.  Store the flask and
      contents in the dark, at 0°C,  for  at least  1 hour.

            7.1.4 After reacting the  solution  for at  least an hour, decompose
      the excess of  bromine by adding 1 M sodium thiosulfate solution, dropwise,
      until the color of the solution is discharged.

            7.1.5 Add 15 g of sodium sulfate, using a magnetic  stirrer to effect
      vigorous stirring.
                                   8032 - 4                         Revision 0
                                                                 November 1992
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      7.2   Extraction

            7.2.1 Transfer the solution into a  150 mL separatory funnel.  Rinse
      the reaction flask three times  with  1  mL  aliquots of organic-free reagent
      water.  Transfer the rinsings into the separatory funnel.

            7.2.2 Extract the aqueous solution  with two 10 ml portions of ethyl
      acetate for 2 min each, using a mechanical shaker (240 strokes per min).
      Dry the organic phase with 1 g of sodium sulfate.

            7.2.3 Transfer the  organic phase  into  a  25  ml amber  volumetric
      flask.   Rinse the  sodium  sulfate with  three  1.5  ml portions  of ethyl
      acetate and combine the rinsings with the organic phase.

            7.2.4 Add exactly 100 /ug  of dimethyl phthalate to the flask and make
      the solution  up to  the 25  ml  mark  with  ethyl  acetate.   Inject 5  /uL
      portions of this solution into the gas chromatograph.

      7.3   Florisil cleanup:  Whenever  interferences are observed, the samples
should be cleaned up as follows.

            7.3.1 Transfer the dried  extract into a  Kuderna-Danish  evaporator
      with  15  mL of  benzene.   Evaporate the  solvent  at  70°C under  reduced
      pressure, and concentrate the solution to about 3 mL.

            7.3.2 Add 50  mL  of benzene and subject  the solution to  Florisil
      column chromatography at a  flow rate of 3 mL/min.  Elute the column first
      with 50 mL of diethyl ether/benzene  (1:4) at a flow rate of 5 mL/min,  and
      then with  25  mL of  acetone/benzene (2:1)  at  a  flow rate of 2  mL/min.
      Discard all of the  first eluate and the initial  9  mL portion of the second
      eluate,  and use  the  remainder  for  the  determination,  using  dimethyl
      phthalate (4 mg/L) as  an internal standard.

            NOTE: Benzene  is  toxic,  and   should  be  only be  used  under  a
                  ventilated  laboratory hood.

      7.4   Gas chromatographic conditions:

      Nitrogen carrier gas flow rate:     40 mL/min
      Column temperature:                 165°C.
      Injector temperature:               180°C
      Detector temperature:               185°C.
      Injection volume:                    5 juL

      7.5   Calibration:

            7.5.1 Inject 5 ML of  a  sample blank (organic-free reagent water
      carried through all sample storage,  handling,  bromination and  extraction
      procedures).

            7.5.2 Prepare  standard solutions  of acrylamide as  described  in
      Section 5.13.1.  Brominate and extract each  standard solution as described
      in Sections 7.1 and 7.2.
                                   8032 - 5                         Revision 0
                                                                 November 1992
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            7.5.2.1      Inject 5 jiL of each of a minimum of five standard
      solutions:  one should be  near the detection limit; one  should be
      near,  but below, the  expected concentrations of the  analyte;  one
      should be  near,  but  above,  the expected  concentrations of  the
      analyte.

            7.5.2.2      Prepare a calibration curve using the peak areas
      of the standards.   If the calibration  curve deviates significantly
      from a straight  line,  prepare  a new  calibration  curve  with  the
      existing  standards,  or,  prepare  new standards and a new calibration
      curve.   See Method  8000, Section 7.4.3, for additional guidance on
      calibration by the  internal standard  method.

            7.5.2.3      Calculate the response factor  for each standard
      according to Equation 1.

                  (Ps)  (Mis)
            RF  = -               Equation 1
            RF    =     Response factor
            Ps    =     Peak height of acryl amide
            Mis    =     Amount of internal  standard injected (ng)
            P1s    =     Peak height of internal  standard
            MA    =     Amount of acryl amide injected (ng)

      7.5.3 Calculate the mean response factor according to Equation 2.

            n
            I  RF
            i=1
      RF = -                        Equation 2
      RF    =     Mean response factor
      RF    =     Response factors from standard analyses (calculated in
                  Equation 1)
      n     =     Number of analyses

7.6   Gas chromatographic analysis:

      7.6.1 Inject  5 /LtL  portions  of each  sample  (containing  4  mg/L
internal  standard)   into  the  gas  chromatograph.    An  example  GC/ECD
chromatogram is shown in Figure 1.

      7.6.2 The concentration of acrylamide monomer in the sample is given
by Equation 3.

               (PA)  ("is)
      [A] =  - = -             Equation 3
             (P,.)  (RF)  (V,)  (V.)
      [A]   =     Concentration of acrylamide monomer in sample  (mg/L)
      PA    =     Peak height of acrylamide monomer

                             8032 - 6                          Revision  0
                                                           November  1992
-------
            Mis    =     Amount of internal standard injected (ng)
            Vs    =     Total volume of sample (ml)
            P.    =     Peak height of internal standard
            RF    =     Mean response factor from Equation 2
            Vj    =     Injection volume
8.0   QUALITY CONTROL

      8.1   Refer to Chapter One  and  Method  8000  for specific quality control
procedures.


9.0   METHOD PERFORMANCE

      9.1   The  following  performance  data  have  been  generated  under  the
conditions described in this method:

            9.1.1 The calibration curve  for Method 8032 is linear  over the range
      0-5 M9/L of acryl amide monomer.

            9.1.2 The limit of detection for  an aqueous solution is 0.032 M9/L.

            9.1.3 The yields of the  brominated compound are 85.2 + 3.3% and 83.3
      + 0.9%,  at  fortification concentrations of 1.0 and 5.0 /xg/L, respectively.

      9.2   Table 1  provides  the recoveries of acrylamide  monomer  from river
water, sewage effluent, and sea water.

      9.3   The recovery of the bromination  product as a  function of the amount
of  potassium  bromide  and  hydrobromic  acid  added  to the  sample is  shown  in
Figure 2.

      9.4   The effect of the reaction time on the recovery of the bromination
product is shown  in  Figure  3.  The yield was  constant when the  reaction time was
more than 1 hour.

      9.5   Figure 4 shows  the recovery of the bromination product as a function
of the initial pH from 1  to 7.35.  The yield was constant within this pH range.
The use of conventional buffer solutions,  such as sodium acetate - acetic acid
solution or phosphate solution, caused a significant decrease in yield.


10.0  REFERENCES

1.    Hashimoto,   A.,   "Improved  Method for  the  Determination  of  Acrylamide
      Monomer in Water by Means of Gas-Liquid Chromatography with an Electron-
      capture Detector," Analyst, 101:932-938, 1976.
                                   8032 - 7                         Revision 0
                                                                 November 1992
-------











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                                   Figure 1
Typical gas  chromatograms of  the bromination  product  obtained  from  aqueous
acrylamide monomer solution:

   A.   Untreated
   B.   With  Florisil  cleanup
   BL.   Chromatogram of blank,  concentrated five-fold before gas chromatographic
        analysis.
Peaks:

   1.
   2.
   4-7.
2,3-Di bromopropi onami de
Dimethyl phthalate
Impurities from potassium bromide
Sample size = 100 ml; acrylamide monomer = 0.1 M9
                                   8032 - 9
                                                        Revision 0
                                                     November 1992
-------
                                 Figure 2
                    100
                 *
                 £
                 o
                 o
                      0     5    10    15    2$    23

                          Amount of K8r/g per SO ml
                      |	[___^_|	!	f     ,
                      0     2    4     6     8     10

                         Amount of H8r/ml ptr 50 ml
Effect of  (A)  potassium bromide  and  (B) hydrobromic  acid  on  the  yield of
bromination.   Sample  size = 50 ml; acrylamide monomer =  0.25  M9
                                  8032  -  10
   Revision 0
November 1992
-------
                                   Figure 3
                     100
                   «  so
                                                     24
Effect of reaction time on the bromination.  Reaction conditions:

   50 ml of sample;
   0.25 /tig of acrylamide monomer;
   7.5 g of potassium bromide;
   2.5 ml of saturated bromine water

Extraction conditions:

   15 g of sodium sulfate;
   extraction at pH  2;
   solvent = 10 ml of ethyl  acetate (X2)
                                   8032  -  11
   Revision 0
November 1992
-------
                                  Figure 4
               |  50
               o
                       o   o
                       i    1     i
                                               i     (
                   012345671

                                      pH
Effect of initial  pH on  the bromination.  Reaction and extraction conditions as
in Figure 3.  The pH was adjusted to below 3 with concentrated hydrobromic acid,
and to 4-5  with  dilute hydrobromic acid.  Reaction  at pH 6 was  in  distilled
water. pH  7.35 was  achieved  by careful addition  of dilute sodium  hydroxide
solution.  The  broken line shows the result obtained by the use of sodium acetate
- acetic acid buffer solution.
                                   8032  -  12
   Revision 0
November 1992
-------
                                            METHOD 8032
                             ACRYLAMIDE  BY  GAS CHROMATOGRAPHY
       7.1 Bromination
            i
7.1 .1 Dissolve 7.5 gr. KBr into
50 ml. sample in flask
            i
 7.1. 2 Adjust sola pH with
 concentrated HBr to between
 1 and 3.
            i
 7.1 .3 Wrap soln. flask with
 aluminum. Add 2.5 ml. satd.
 bromine water, stir, store at
 0 C for 1 hr.
            i
7.1. 4 Add 1 M sodium
thiosulfate dropwise to flask to
decompose excess bromine.
  7. 1. 5 Add 1 5 gr. sodium
  sulfate, and stir.
                                                                                       *
                                                                                 7.2 Extraction
             I
  7.2.1 Transfer flask soin. to
  sep. funnel along with rinses.
7.2.2 Extract soln. twice w/etnyl
acetate. Dry organic phase
using sodium sulfate.
 7.2.3 Transfer organic phase
 and rinses into amber
 glass flask.
  7.2.4 Add 1 00 ug. dimethyl
  phthalate to flask, dilute to
  mark. Inject 5 ul. into GC.
                                                                              7.3 Fkxisil Cleanup
             I
                                                                         7.3.1 Transfer dried extract to
                                                                         K-D assembly w/benzene.
                                                                         Concentrate to 3 ml. at 70 C
                                                                         under reduced pressure.
                                                                          7.3.2 Add 50 ml. benzene to
                                                                          solution. Pass soln. through
                                                                          Fkxisil column. Bute with
                                                                          diethyl ether/benzene, then
                                                                          acetone/benzene.  Collect
                                                                          the second ekition train (toss
                                                                          initial 9 ml.) for analysis.
                                              8032  -  13
                   Revision 0
               November  1992
-------
         METHOD  8032
          continued
        7.4 GC Conditions
               I
         7.5 Calibration
               I
   7.5.1 Inject 5 ul. sample blank.
               I
  7.5.2 Brominate and extract std.
  solns. similar to the samples.
  .1 Inject 5 ul. of each of the
    minimum 5 stds.
  .2 Plot peak are vs. [ ].
  .3 Calculate response factor
    (RF) for each (].
               I
   7.5.3 Calculate mean RF from
   eqn. 2.
               I
         7.6 GC Analysis
               I
 7.6.1 Inject 5 ul. sample containing
 internal std. into GC.
               I
7.6.2 Calculate acrylamide monomer
concentration in sample using
eqn. 3.
          8032  -  14
    Revision  0
November  1992
-------
                                METHOD 8040

                                  PHENOLS
1.0 SCOPE AND APPLICATION

    1.1 Method 8040 is  used  to  determine the concentration of various phenolic
compounds.   Table  1  indicates  compounds  that  may be analyzed by  this  method
and lists  the method detection limit  for  each compound  in  water.   Table  2
lists the practical quantitation limit  (PQL) for all matrices.

2.0 SUMMARY OF METHOD

    2.1 Method 8040 provides gas chromatographic conditions  for  the  detection
of phenolic  compounds.   Prior to  analysis,  samples  must be  extracted  using
appropriate techniques  (see Chapter Two for guidance).   Both  neat  and diluted
organic  liquids  (Method  3580, Waste  Dilution)  may  be  analyzed by  direct
injection.  A 2- to 5-uL  sample is  injected into a gas chromatograph  using  the
solvent flush  technique, and compounds  in  the GC effluent are detected by  a
flame ionization detector  (FID).

    2.2 Method  8040  also  provides for the  preparation  of pentafluorobenzyl-
bromide  (PFB)  derivatives,  with  additional  cleanup  procedures  for  electron
capture  gas chromatography.   This  is to  reduce detection limits of some
phenols and to aid the  analyst  in  the elimination of interferences.

3.0 INTERFERENCES

    3.1 Refer to Methods 3500,  3600, and 8000.

    3.2 Solvents,  reagents,  glassware,  and other sample  processing  hardware
may  yield  discrete  artifacts and/or  elevated  baselines   causing
misinterpretation of gas  chromatograms.   All  these  materials  must  be
demonstrated  to be  free  from interferences,  under  the conditions of  the
analysis,  by analyzing  calibration and  reagent blanks.   Specific  selection of
reagents and purification of solvents by distillation in all-glass  systems  may
be required.

    3.3  Interferences  coextracted  from samples  will  vary considerably from
source to  source,  depending upon  the  waste being sampled.   Although general
cleanup techniques are  recommended as  part  of this method, unique  samples  may
require additional  cleanup.

4.0 APPARATUS AND MATERIALS

    4.1 Gas chromatograph

         4.1.1  Gas  Chromatograph  -  Analytical  system  complete  with  gas
    chromatograph  suitable   for  on-column   injections and all   required
    accessories, including  detectors,  column  supplies,  recorder,  gases,  and
    syringes.  A data system for  measuring peak  areas and/or peak heights is
    recommended.

                                  8040  - 1                       Revision 1
                                                                December 1987
-------
         4.1.2  Columns

               4.1.2.1  Column for underivatized  phenols - 1.8 m x 2.0 mm i.d.
          glass column packed with 1% SP-1240DA on Supelcoport 80/100 mesh or
          equivalent.

               4.1.2.2  Column for derivatized  phenols  -  1.8 m  x 2  mm i.d.
          glass column  packed with  5%  OV-17 on  Chromosorb  W-AW-DMCS 80/100
          mesh  or equivalent.

          4.1.3 Detectors  -  Flame  ionization   (FID)  and  electron  capture
     (ECD).

     4.2  Reaction  vial -  20-mL,  with Teflon lined cap.

     4.3  Volumetric  flask - 10-, 50-, and 100-mL, ground-glass stopper.

     4.4  Kuderna-Danish  (K-D) apparatus

          4.4.1 Concentrator tube - 10-mL, graduated (Kontes  K-570050-1025 or
     equivalent).    Ground-glass stopper  is  used to prevent  evaporation of
     extracts.

          4.4.2 Evaporation  flask  -  500-mL   (Kontes  K-570001-500  or
     equivalent).   Attach  to concentrator tube with springs.

          4.4.3 Snyder  column  -  Three  ball macro  (Kontes  K-503000-0121 or
     equivalent).

          4.4.4 Snyder  column  -  Two  ball  micro  (Kontes  K-569001-0219 or
     equivalent).

     4.5  Boiling chips -  Solvent extracted, approximately 10/40 mesh  (silicon
carbide or equivalent).

     4.6  Water bath -  Heated,  with   concentric  ring  cover,  capable of
temperature control  (+ 5°C).  The bath should be  used in a hood.

     4.7  Microsyringe -  10-uL.

     4.8  Syringe -  5-mL.

5.0  REAGENTS

     5.1  Reagent grade chemicals shall  be used in all tests.  Unless otherwise
indicated,  it  is  intended  that  all  reagents  shall  conform  to  the
specifications of  the   Committee on  Analytical Reagents  of the  American
Chemical Society, where such specifications are available. Other grades may be
used, provided it  is first ascertained that the reagent is  of  sufficiently
high  purity  to permit  its  use  without  lessening  the  accuracy of  the
determination.
                                 8040 - 2                       Revision 1
                                                                December 1987
-------
     5.2  ASTM Type II Water (ASTM D1193-77 (1983)). All references  to  water
in the method refer to ASTM Type  II unless otherwise specified.

     5.3  Hexane,  CH3(CH2)4CH3.   Pesticide quality or equivalent.

     5.4  2-Propanol,  (CH3)2CHOH.  Pesticide quality or equivalent.

     5.5  Toluene,  CeHsCHs.   Pesticide quality or equivalent.
     5.6  Derivatization  reagent  -  Add 1  ml pentafluorobenzyl  bromide  and  1  g
18-crown-6-ether to  a  50-mL  volumetric  flask and  dilute  to  volume with
2-propanol.   Prepare fresh weekly.   This  operation  should  be carried  out  in  a
hood.   Store at 4°C  and protect from light.

          5.6.1  Pentafluorobenzyl   bromide (alpha-Bromopentafluorotoluene),
              .  97% minimum purity.
     NOTE:  This chemical  is  a lachrymator.

          5.6.2  18-crown-6-ether  (1,4,7,10,13,16-Hexaoxacyclooctadecane)  -
     98% minimum purity.

     NOTE:  This chemical  is  highly toxic.

     5.7  Potassium carbonate (Powdered), K2C03.

     5.8  Stock standard  solutions

          5.8.1  Prepare  stock  standard  solution  at  a concentration  of
     1.00  ug/uL by  dissolving 0.0100  g of  assayed reference  material  in
     2-propanol and  diluting  to  volume  in  a 10-mL volumetric  flask.   Larger
     volumes can  be  used at  the convenience  of the analyst.  When  compound
     purity is  assayed to  be 96% or greater,  the weight  can  be  used without
     correction to  calculate  the  concentration  of  the  stock standard.
     Commercially prepared stock  standards can be used at any concentration if
     they are certified by the manufacturer or by an independent source.

          5.8.2  Transfer  the stock standard  solutions  into  bottles  with
     Teflon lined  screw-caps.   Store at 4°C  and  protect from light.   Stock
     standards  should be  checked  frequently for  signs  of  degradation  or
     evaporation,  especially just  prior  to preparing  calibration  standards
     from them.

          5.8.3  Stock standard solutions must  be  replaced  after  one  year,  or
     sooner if comparison  with check standards indicates a problem.

     5.9  Calibration standards - Calibration  standards at a  minimum  of five
concentration   levels should be  prepared through dilution of the  stock
standards with  2-propanol.   One  of  the  concentration  levels  should  be  at  a
concentration  near,  but  above,  the method  detection  limit.   The  remaining
concentration levels  should correspond to the expected range of concentrations
found  in  real  samples  or  should  define  the  working  range  of  the GC.


                                 8040 - 3                       Revision 1
                                                                December 1987
-------
Calibration solutions  must  be  replaced  after  six  months,  or sooner,  if
comparison with check standards  indicates a  problem.

     5.10 Internal  standards  (if internal standard calibration  is  used)  -  To
use this approach,  the analyst must  select one or more internal standards that
are similar in analytical behavior to the compounds of interest.   The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix  interferences.   Because of these limitations,  no
internal standard can be suggested that  is applicable to all  samples.

          5.10.1 Prepare calibration  standards at  a  minimum  of  five
     concentrations for each analyte as  described  in Step 5.9.

          5.10.2 To each calibration standard,  add a known constant amount of
     one or more internal standards, and dilute  to  volume with 2-propanol.

          5.10.3 Analyze each calibration standard  according  to Section 7.0.

     5.11 Surrogate standards -  The analyst should monitor the performance of
the  extraction,  cleanup   (if  necessary),  and  analytical  system  and the
effectiveness of the method  in dealing  with  each sample matrix by spiking each
sample,  standard,  and  water  blank with  phenolic   surrogates  (e.g.
2-fluorophenol  and 2,4,6-tribromophenol) recommended to encompass the  range of
the  temperature program used in  this method.   Method 3500,  Step  5.3.1.1,
details  instructions  on the preparation   of  acid surrogates.    Deuterated
analogs of  analytes  should  not  be used as   surrogates  for gas chromatographic
analysis due to coelution problems.

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See  the  introductory  material to this  chapter,  Organic Analytes,
Step 4.1.   Extracts  must be stored  under refrigeration and analyzed within 40
days of extraction.

7.0  PROCEDURE

     7.1  Extraction

          7.1.1  Refer to Chapter Two for guidance on  choosing the appropriate
     extraction procedure.   In general,  water samples  are extracted  at a  pH of
     less than or equal to  2 with methylene  chloride,  using  either Method 3510
     or 3520.   Solid samples are extracted  using  either Method 3540  or  3550.
     Extracts  obtained  from application of  either Method  3540 or 3550 should
     undergo Acid-Base Partition Cleanup, using  Method 3650.

          7.1.2  Prior to gas chromatographic analysis, the  extraction solvent
     must be  exchanged to   2-propanol.   The exchange  is  performed during the
     micro  K-D  procedures  listed  in   all   of  the  extraction methods.   The
     exchange  is performed  as follows:

               7.1.2.1  Following concentration of the extract  to  1  mL  using
          the  macro-  Snyder column, allow the apparatus to cool and drain for
          at least 10 minutes.

                                  8040  - 4                        Revision 1
                                                                 December 1987
-------
               7.1.2.2   Increase  the  temperature of  the hot  water bath to
          95-100°C.   Remove  the  Snyder column  and  rinse the  flask and  its
          lower joint into the concentrator tube with 1-2 ml  of 2-propanol.  A
          5-mL syringe   is  recommended for this  operation.   Add  one or  two
          clean boiling chips to  the concentrator tube and attach a  two  ball
          micro-Snyder  column.   Prewet the column by  adding  about 0.5 ml of
          2-propanol to the top.  Place the K-D apparatus on  the water bath so
          that the concentrator  tube is partially immersed in  the hot water.
          Adjust  the   vertical  position  of  the apparatus  and the  water
          temperature,  as required, to complete concentration  in 5-10 minutes.
          At the  proper rate of distillation  the  balls  of  the column  will
          actively  chatter,   but  the  chambers  will  not flood.    When  the
          apparent volume  of  liquid  reaches  2.5 ml,  remove the  K-D  apparatus
          and allow it  to  drain  and cool for  at least  10 minutes.   Add an
          additional 2  ml of  2-propanol, add one or two clean  boiling chips to
          the concentrator tube, and resume concentrating as  before.   When the
          apparent volume  of  liquid  reaches  0.5 ml,  remove the  K-D  apparatus
          and allow it  to drain and cool for at least 10 minutes.

               7.1.2.3   Remove  the  micro-Snyder  column  and  rinse its  lower
          joint  into  the concentrator  tube  with  a  minimum  amount of
          2-propanol.    Adjust the  extract  volume  to  1.0 ml.   Stopper  the
          concentrator tube and  store  refrigerated  at   4"C  if further
          processing will  not be  performed immediately.   If  the extract  will
          be stored longer than  two  days,  it should be transferred to a  vial
          with a Teflon lined screw-cap.   If the extract  requires no further
          derivatization  or cleanup,  proceed  with  gas   chromatographic
          analysis.

     7.2  Gas chromatography  conditions (Recommended)

          7.2.1  Column for  underivatized  phenols -  Set  nitrogen gas  flow at
     30 mL/min  flow  rate.    Set  column temperature  at 80°C and  immediately
     program an 8°C/min temperature rise  to  150°C;  hold  until  all  compounds
     have eluted.

          7.2.2  Column for derivatized phenols - Set 5% methane/95%  argon gas
     flow at 30 mL/min  flow rate.  Set column temperature at  200°C isothermal.

     7.3  Calibration  -  Refer  to Method  8000  for  proper  calibration
techniques.   Use Table  1 and  especially Table  2  for  guidance  on selecting the
lowest point on the calibration curve.

          7.3.1  The  procedure for  internal  or  external  calibration may be
     used for the  underivatized  phenols.    Refer to  Method 8000  for a
     description  of  each of these procedures.    If derivatization of  the
     phenols is required, the method of external calibration  should be used by
     injecting five or  more  levels  of calibration  standards that have  also
     undergone derivatization and cleanup prior to instrument  calibration.

     7.4  Gas chromatographic analysis
                                 8040 - 5                       Revision  1
                                                                December  1987
-------
     7.4.1  Refer to Method 8000.   If the internal standard calibration
technique is used, add 10 uL of internal standard to the sample prior to
injection.

     7.4.2  Phenols are to be determined on a gas  chromatograph equipped
with a flame  ionization  detector  according  to the conditions listed for
the  1% SP-1240DA  column  (Step  7.2.1).   Table  1  summarizes estimated
retention times and sensitivities that should be achieved by this method
for  clean  water  samples.   Practical  quantitation  limits  for  other
matrices are list in Table 2.

     7.4.3  Follow  Step  7.6  in  Method  8000 for  instructions on  the
analysis  sequence,  appropriate  dilutions,  establishing  daily retention
time windows, and identification criteria.  Include a mid-level standard
after each group of 10 samples  in  the analysis sequence.

     7.4.4  An example of a GC/FID  chromatogram  for  certain phenols is
shown  in  Figure 1.   Other packed or  capillary  (open-tubular) columns,
chromatographic conditions, or detectors may be used if the  requirements
of Step 8.2 are met.

     7.4.5  Record  the sample  volume injected  and the  resulting peak
sizes (in area units or peak heights).

     7.4.6  Using either  the  internal  or external calibration procedure
(Method 8000), determine  the identity and quantity of each component peak
in the  sample chromatogram which corresponds to  the  compounds used for
calibration  purposes.   See Step 7.8  of Method  8000 for  calculation
equations.

     7.4.7  If peak detection using  the  SP-1240DA column with the flame
ionization detector is prevented by interferences,  PFB  derivatives  of the
phenols  should  be  analyzed on  a gas  chromatograph  equipped  with an
electron capture detector  according  to the  conditions  listed for the 5%
OV-17 column  (Step  7.2.2).   The derivatization  and cleanup  procedure is
outlined in  Steps  7.5   through  7.6.    Table 3  summarizes  estimated
retention times  for derivatives  of some  phenols  using the conditions of
this method.

     7.4.8  Figure  2  shows a GC/ECD  chromatogram  of  PFB derivatives of
certain phenols.

     7.4.9  Record  the  sample  volume  injected  and  the  resulting  peak
sizes  (in area units or peak heights).

     7.4.10    Determine the identity and quantity of  each  component  peak
in  the  sample chromatogram which  corresponds to  the  compounds used for
calibration purposes.  The  method  of external calibration should be  used
(see  Method  8000  for guidance).   The  concentration  of  the  individual
compounds in  the sample is calculated as follows:

     Concentration (ug/L) = [(A)(Vt)(B)(D)]/[(Vi)(X)(C)(E)]


                             8040 - 6                       Revision  1
                                                            December  1987
-------
     where:

       A = Mass of underivatized phenol  represented by area of peak in sample
           chromatogram,  determined from  calibration  curve  (see  Method  8000
           Step 7.4.2),  ng.

      Vt = Total  amount of  column eluate  or  combined  fractions  from which V^
           was taken,  uL.

       B = Total  volume of hexane added  in Step 7.5.5, ml.

       D = Total  volume of 2-propanol  extract prior to derivatization, ml.

      Vi = Volume injected,  uL.

       X = Volume  of  water extracted,  ml,  or weight  of  nonaqueous sample
           extracted,  g,  from Step 7.1.   Either the dry  or wet  weight of the
           nonaqueous sample  may  be  used,  depending  upon  the  specific
           application of the  data.

       C = Volume of  hexane sample  solution  added to cleanup  column (Method
           3630,  Step  7.2),  ml.

       E = Volume of 2-propanol  extract  carried through derivatization in Step
           7.5.1, ml.

     7.5  Derivatization  -  If interferences  prevent measurement  of peak area
during  analysis  of the  extract  by  flame  ionization  gas  chromatography,  the
phenols  must  be  derivatized  and  analyzed   by   electron  capture  gas
chromatography.

          7.5.1  Pipet a 1.0-mL  aliquot  of  the   2-propanol  stock  standard
     solution or of the sample extract into a glass reaction vial.  Add 1.0 ml
     derivatization reagent (Step 5.3).   This amount of reagent is sufficient
     to derivatize  a  solution whose  total  phenolic  content does  not exceed
     0.3 mg/mL.

          7.5.2  Add approximately 3 mg  of potassium carbonate to the  solution
     and shake gently.

          7.5.3  Cap  the  mixture and  heat it  for 4  hours at 80°C  in  a hot
     water bath.

          7.5.4  Remove the solution  from  the  hot  water  bath and allow it to
     cool.

          7.5.5  Add  10  ml  hexane to  the  reaction vial  and shake vigorously
     for  1  minute.   Add 3.0 ml water  to the reaction  vial  and  shake for
     2 minutes.

          7.5.6  Decant  the organic  layer into a concentrator tube  and cap
     with a glass stopper.  Proceed with cleanup procedure.


                                  8040 - 7                      Revision 1
                                                                December 1987
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     7.6  Cleanup

          7.6.1  Cleanup of the derivatized extracts takes place using Method
     3630 (Silica Gel Cleanup), in which specific instructions for cleanup of
     the derivatized phenols appear.

          7.6.2  Following column cleanup, analyze  the  samples using GC/ECD,
     as described starting in Step 7.4.7.

8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific  quality control  procedures.
Quality control to validate sample extraction  is  covered in Method 3500 and in
the extraction method used.   If extract cleanup  was performed, follow the QC
in Method 3600 and in the specific cleanup method.

     8.2  Procedures  to check  the  GC  system  operation are  found  in Method
8000, Step 8.6.

          8.2.1  The  quality  control  check sample  concentrate (Method 8000,
     Step 8.6) should contain each  analyte of interest at a  concentration of
     100 ug/mL in 2-propanol.

          8.2.2  Table 4  indicates the  calibration  and  QC acceptance  criteria
     for  this method.    Table 5  gives  method accuracy  and  precision as
     functions of concentration for the analytes.  The  contents of both Tables
     should be used to evaluate a laboratory's ability  to perform and  generate
     acceptable data by this method.

     8.3  Calculate  surrogate standard recovery  on  all  samples,  blanks,  and
spikes.   Determine if  the  recovery is within limits  (limits established by
performing QC procedures outlined in Method 8000, Step  8.10).

          8.3.1  If recovery  is not within limits,  the  following  is  required.

               •   Check  to  be sure  there are  no  errors   in calculations,
                  surrogate  solutions  and  internal standards.   Also,  check
                  instrument performance.

               •   Recalculate the data  and/or reanalyze the extract if any of
                  the above checks reveal  a problem.

               •   Reextract and reanalyze the sample if none  of the above are
                  a problem or flag the data as "estimated concentration."

9.0  METHOD PERFORMANCE

     9.1  The  method was tested  by  20  laboratories   using  water,  drinking
water,   surface   water,  and  three industrial  wastewaters  spiked at  six
concentrations over the  range 12 to  450 ug/L.    Single operator  precision,
overall  precision,  and  method  accuracy were  found  to  be directly related to
the  concentration  of the  analyte and  essentially  independent of  the sample


                                  8040  - 8                       Revision  1
                                                                 December  1987
-------
matrix.    Linear  equations  to describe these relationships for  a flame
ionization detector are presented in Table 5.

     9.2  The accuracy and  precision  obtained  will  be affected by the  sample
matrix, sample-preparation technique,  and calibration procedures used.

10.0  REFERENCES

1.    Development  and Application of  Test  Procedures  for Specific  Organic
      Toxic Substances in Wastewaters.   Category 3  - Chlorinated  Hydrocarbons
      and  Category 8  -   Phenols.    Report for  EPA  Contract  68-03-2625  (in
      preparation).

2.    U.S. EPA  40  CFR  Part  136, "Guidelines  Establishing Test  Procedures  for
      the  Analysis  of Pollutants  Under  the  Clean Water  Act;  Final  Rule  and
      Interim Final Rule and Proposed Rule,"  October 26,  1984.

3.    "Determination  of  Phenols  in  Industrial  and Municipal  Wastewaters,"
      Report for EPA Contract 68-03-2625 (in  preparation).

4.    "EPA Method Validation  Study Test  Method  604  (Phenols),"  Report  for  EPA
      Contract  68-03-2625 (in preparation).

5.    Kawarahara,  F.K.  "Microdetermination  of Derivatives of  Phenols  and
      Mercaptans by Means of  Electron Capture  Gas  Chromatography,"  Analytical
      Chemistry, 40, 1009,  1968.

6.    Provost,  L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
      American  Laboratory,  lj>,  pp.  58-63, 1983.

7.    Burke,  J.A.  "Gas  Chromatography for  Pesticide Residue  Analysis;  Some
      Practical  Aspects,"  Journal   of the Association of Official  Analytical
      Chemists,  48, 1037, 1965.

8.    Rohrbough,  W.G.; et  al.   Reagent  Chemicals.  American Chemical  Society
      Specifications,  7th  ed.; American Chemical  Society: Washington,  DC,
      1986.

10.   1985 Annual  Book of ASTM  Standards.  Vol.  11.01; "Standard Specification
      for  Reagent Water"; ASTM:  Philadelphia, PA, 1985; D1193-77.
                                  8040 - 9                       Revision 1
                                                                 December 1987
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                                  TABLE 1.
               FLAME IONIZATION GAS CHROMATOGRAPHY OF PHENOLS
                                                                  Method
                                         Retention time          Detection
Compound                                    (minutes)          limit (ug/L)


2-sec-Butyl-4,6-dinitrophenol (DNBP)
4-Ch1oro-3-methylphenol                        7.50                  0.36
2-Chlorophenol                                 1.70                  0.31
Cresols (methyl phenols)
2-Cyclohexyl-4,6-dinitrophenol
2,4-Dichlorophenol                             4.30                  0.39
2,6-Dichlorophenol
2,4-Dimethylphenol                             4.03                  0.32
2,4-Dinitrophenol                             10.00                 13.0
2-Methyl-4,6-dinitrophenol                    10.24                 16.0
2-Nitrophenol                                  2.00                  0.45
4-Nitrophenol                                 24.25                  2.8
Pentachlorophenol                             12.42                  7.4
Phenol                                         3.01                  0.14
Tetrachlorophenols
Trichlorophenols
2,4,6-Trichlorophenol                          6.05                  0.64
                                    TABLE 2.
                     DETERMINATION OF  PRACTICAL QUANTITATION
                       LIMITS  (PQL) FOR VARIOUS MATRICES*
    Matrix                                                    Factor*3
Ground water                                                     10
Low-level soil by sonication with GPC cleanup                   670
High-level soil and sludges by sonication                    10,000
Non-water miscible waste                                    100,000
     aSample  PQLs  are  highly  matrix-dependent.    The PQLs  listed  herein are
     provided for guidance and may not always be achievable.

     bpQL =  [Method detection limit  (Table  1)] X [Factor  (Table 2)].   For non-
     aqueous samples, the factor  is  on a wet-weight basis.
                                  8040 - 10                      Revision  1
                                                                 December  1987
-------
                                  TABLE 3.
           ELECTRON CAPTURE GAS CHROMATOGRAPHY OF PFB DERIVATIVES
Parent compound
Retention
  time
  (min)
                     Method
                    detection
                   limit (ug/L)
4-Chloro-2-methylphenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
    4.8
    3.3
    5.8
    2.9
   46.
   36.
    9.1
   14.0
   28.8
    1.8
    7.0
.9
.6
                       1.8
                       0.58
                       0.68
                       0.63
                       0.77
                       0.70
                       0.59
                       2.2
                       0.58
                                  8040  -  11
                       Revision 1
                       December 1987
-------
                                    TABLE 4.
                            QC ACCEPTANCE CRITERIA*


Parameter
4-Chloro-3 -methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachl orophenol
Phenol
2, 4, 6-Trichl orophenol
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
s = Standard deviation of four recovery
x = Average recovery for
P, Ps = Percent recovery
four recovery
measured.
Limit
for s
(ug/L)
16.6
27.0
25.1
33.3
25.0
36.0
22.5
19.0
32.4
14.1
16.6
measurements
measurements,

Range
for x
(ug/L)
56.7-113.4
54.1-110.2
59.7-103.3
50.4-100.0
42.4-123.6
31.7-125.1
56.6-103.8
22.7-100.0
56.7-113.5
32.4-100.0
60.8-110.4
, in ug/L.
in ug/L.

Range
P, PS
(*)
99-122
38-126
44-119
24-118
30-136
12-145
43-117
13-110
36-134
23-108
53-119



    aCriteria from 40 CFR  Part  136 for Method 604.  These  criteria are based
directly upon the  method performance data  in  Table 5.  Where  necessary,  the
limits for recovery have been broadened  to  assure  applicability of the limits
to concentrations below those used to develop Table 5.
                                  8040 - 12
Revision 1
December 1987
-------
                             TABLE 5.
   METHOD ACCURACY AND PRECISION AS FUNCTIONS  OF  CONCENTRATION3


Parameter
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Accuracy, as
recovery, x'
(ug/L)
0.87C-1.97
0.83C-0.84
0.81C+0.48
0.62C-1.64
0.84C-1.01
0.80C-1.58
0.81C-0.76
0.46C+0.18
0.83C+2.07
0.43C+0.11
0.86C-0.40
Single analyst Overall
precision, sr' precision,
(ug/L)
O.llx-0.21
0.18x+0.20
0.17x-0.02
0.30X-0.89
0.15X+1.25
0.27X-1.15
O.lBx+0.44
0.17x+2.43
0.22X-0.58
0.20X-0.88
O.lOx+0.53
S' (ug/L)
0.16x+1.41
0.21X+0.75
0.18x+0.62
0.25X+0.48
0.19x+5.85
0.29X+4.51
0.14x+3.84
0.19x+4.79
0.23X+0.57
0.17x+0.77
0.13X+2.40
x'  = Expected  recovery for  one  or more  measurements  of  a  sample
      containing a concentration of C,  in  ug/L.

sr' = Expected  single  analyst  standard deviation  of  measurements at  an
      average concentration of x, in ug/L.

S'  = Expected  interlaboratory  standard deviation  of  measurements at  an
      average concentration found of x,  in  ug/L.

C   = True value for the concentration,  in  ug/L.

x   = Average recovery found for measurements  of  samples  containing a
      concentration of C, in ug/L.

aFrom 40 CFR Part 136 for Method 604.
                            8040 - 13
Revision 1
December 1987
-------
          Figure 1.

Gas chromttogrtm of phenol*.
    Column: 1% SP-12400 A on Supclcoport
    Program: 80°C 0 Minutes 8°/Minuti to 150°C
    Otttctor: Flamt lomzation
 8       12      16      20

  RETENTION TIME (MINUTES)
24
28
             8040  -  14
               Revision 1
               December 1987
-------
                        Figure 2.
         Gas chromitogram of PFB derivttivw of phtnols.
                   Column: 5% OV-17 on Otromoiorb W-AW
                   Twnptrnurv: 200°C
                   Otttctor: Electron Capture
J
   &
  A_
            8      12     16    20     24
               RETENTION TIME (MINUTES)
28
32
                        8040  - 15
        Revision  1
        December  1987
-------
                                             METHOD 8040
                                                PHENOLS
C
 7.1.1  Chooie
        appro-
 priate extrect-
  ion procedure
     (refer to
    Chapter 2)
                                                                           7.3. l
                           U«e  method of
                       external cellbretion
                        by  injecting >/- 5
                      level*  of calibration
                           standards
 7.1.2
        exchange
        extract-
  Ion solvent to
     2-propanol
    during micro
  K-O procedures
  7.2
     Set ges
  chromatography
   conditions
  7.3
        Befer  to
     Method 0000
     for proper
     eel ibratIon
     techniques
      Is
der ivetizetion
  of  phenols
  required?
  Perform GC
analysis (see
 Method 8000)
Analyze using
   GC/FIO
    0
                                              8040  - 16
                             Revision 1
                             December 1987
-------
          METHOD 8040
           (Continued)
                           Cleenup using
                            Method 3630
        Record
   •emple volume
    Injected end
     peek sizes
  7.4.10  Oetei—
          nine
    identity end
     quentity of
         eecn
  component peek
  7.4.10
   Prepere
derivetlzet ion
                           7.4.7
 Anelyze  PFB
 oerivetives
using GC/ECO
    Celculete
  concentration
f     Stop      J
             8040 - 17
                      Revision  1
                      December  1987
-------
                                  METHOD 8061

               PHTHALATE ESTERS BY CAPILLARY GAS CHROMATOGRAPHY
                   WITH ELECTRON CAPTURE DETECTION (GC/ECD)
1.0   SCOPE AND APPLICATION

      1.1   Method 8061 is used to determine the identities and concentrations
of various phthalate esters  in liquid, solid and sludge matrices.  The following
compounds can be determined by this method:
      Compound Name                                           CAS No.'
      Benzyl benzoate  (I.S.)                                 120-51-4
      Bis(Z-ethylhexyl) phthalate                             117-81-7
      Butyl benzyl phthalate                                   85-68-7
      Di-n-butyl phthalate                                     84-74-2
      Diethyl phthalate                                        84-66-2
      Dimethyl phthalate                                      131-11-3
      Di-n-octyl phthalate                                    117-84-0


      a  Chemical  Abstract Services Registry Number.

      1.2   Table  1  lists the  method detection limits  (MDL)  for  the  target
analytes in a water matrix.  The MDLs for the components of a  specific sample may
differ  from those listed in Table 1 because  MDLs  depend  on  the nature  of
interferences in the  sample  matrix.   Table  2  lists the estimated quantitation
limits  (EQL) for other matrices.

      1.3   When this method is used to  analyze for any  or all  of the  target
analytes, compound identification should be supported by at least one additional
qualitative technique.  This method describes  conditions for parallel column,
dual electron capture detector  analysis which  fulfills the  above requirement.
Retention time  information obtained on two  megabore  fused-silica open tubular
columns is given in Table  1.  Alternatively, gas chromatography/mass spectrometry
could be used for compound confirmation.

      1.4   The  following compounds,  bis(2-n-butoxyethyl)   phthalate,  bis(2-
ethoxyethyl) phthalate, bis(2-methoxyethyl)  phthalate, bis(4-methyl-2-pentyl)
phthalate,  diamyl  phthalate,   dicyclohexyl   phthalate,  dihexyl   phthalate,
diisobutyl  phthalate, dinonyl phthalate,  and  hexyl  2-ethylhexyl  phthalate can
also be analyzed by this method and may be used as  surrogates.

      1.5   This method is  restricted to use  by  or under  the  supervision  of
analysts  experienced  in  the use  of gas  chromatographs and  skilled  in  the
interpretation of gas  chromatograms.  Each analyst must demonstrate the ability
to generate acceptable results with this  method.
                                   8061 - 1          •               Revision 0
                                                                 November 1992
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2.0   SUMMARY OF METHOD

      2.1   A measured volume  or  weight of sample (approximately  1  liter  for
liquids,  10  to 30  grams  for  solids  and  sludges) is  extracted  by  using  the
appropriate sample  extraction  technique specified in Methods 3510,  3540,  and
3550.   Method  3520 is not  recommended  for the extraction of aqueous  samples
because the longer chain esters (dihexyl  phthalate, bis(2-ethylhexyl) phthalate,
di-n-octyl phthalate,  and dinonyl phthalate) tend to adsorb to the glassware and
consequently, their extraction recoveries  are <40 percent.  Aqueous samples are
extracted at a  pH  of  5 to  7, with methylene chloride,  in a  separatory funnel
(Method 3510).  Alternatively, particulate-free aqueous samples could be filtered
through membrane disks that  contain C^-bonded silica.  The phthalate esters are
retained by the silica and,  later eluted with  acetonitrile.   Solid samples are
extracted with  hexane/acetone  (1:1)  or methylene chloride/acetone  (1:1)  in  a
Soxhlet extractor (Method 3540) or with an ultrasonic extractor  (Method 3550).
After  cleanup,  the extract  is analyzed  by gas chromatography with  electron
capture detection (GC/ECD).

      2.2   The  sensitivity  of Method  8061  usually  depends on  the level  of
interferences rather than on instrumental limitations.   If interferences prevent
detection of the analytes, cleanup of the  sample extracts is necessary.   Either
Method 3610 or  3620  alone or follqwed  by  Method 3660, Sulfur Cleanup, may be used
to eliminate interferences in the analysis.  Method 3640,  Gel Permeation Cleanup,
is applicable for samples that contain high amounts of lipids and  waxes.


3.0    INTERFERENCES

      3.1   Refer to Methods 3500, 3600, and 8000.

      3.2   Interferences coextracted from the  samples  will  vary  considerably
from waste to waste.  While general cleanup techniques  are referenced or provided
as part of this method, unique samples may  require  additional cleanup approaches
to achieve desired  sensitivities for the target analytes.

      3.3   Glassware  must   be scrupulously  clean.     All  glassware  require
treatment in a muffle  furnace at 400  °C for 2 to 4  hrs,  or thorough rinsing with
pesticide-grade solvent, prior to use.  Refer to Chapter 4,  Section 4.1.4, for
further details regarding the cleaning of glassware. Volumetric glassware should
not be heated  in a  muffle furnace.

       If Soxhlet extractors  are baked in the muffle furnace, care must be taken
to ensure  that they are  dry (breakage may result  if any water  is left in the
side-arm).  Thorough rinsing with  hot tap water, followed by deionized water and
acetone  is  not an  adequate  decontamination procedure.   Even after  a  Soxhlet
extractor was refluxed with  acetone  for  three days, with daily solvent changes,
the  concentrations  of bis(2-ethylhexyl) phthalate were as high as 500 ng per
washing.  Storage of glassware in  the laboratory introduces contamination, even
if the glassware is wrapped  in aluminum foil.   Therefore, any glassware used in
Method 8061 should  be  cleaned  immediately prior to use.

       3.4   Florisil and alumina may be  contaminated with phthalate esters and,
therefore,  use  of  these   materials  in  sample  cleanup should   be  employed
cautiously.  If these materials are used, they must be obtained packaged  in glass

                                   8061 - 2                         Revision  0
                                                                  November 1992
-------
(plastic  packaging  will contribute  to  contamination with  phthalate  esters).
Washing of these  materials  prior to use with the  solvent(s)  used  for elution
during extract cleanup was found helpful, however, heating at 320 °C for Florisil
and  210  °C for  alumina is  recommended.   Phthalate  esters were detected  in
Florisil cartridge method blanks  at  concentrations ranging  from 10  to 460 ng,
with 5 phthalate  esters in  the 105 to 460 ng range.  Complete removal  of the
phthalate esters  from Florisil cartridges does  not seem possible, and  it  is
therefore desirable  to  keep the  steps  involved  in  sample preparation  to  a
minimum.

      3.5   Paper thimbles and filter paper must be exhaustively washed with the
solvent that will  be  used in  the sample extraction.   Soxhlet  extraction of paper
thimbles and filter paper for  12 hrs with fresh solvent should be repeated for
a minimum of three times.   Method  blanks  should  be obtained before  any of the
precleaned thimbles or  filter  papers are used.  Storage of precleaned thimbles
and  filter  paper in  precleaned  glass  jars covered  with  aluminum  foil  is
recommended.

      3.6   Glass wool  used  in  any step  of sample  preparation  should  be  a
specially treated pyrex  wool,  pesticide grade, and must  be  baked  at 400°C for
4 hrs. immediately prior to  use.

      3.7   Sodium sulfate must be obtained packaged in glass (plastic packaging
will contribute to contamination with phthalate esters),  and  must be purified by
heating at 400 °C  for 4  hrs.  in a shallow tray, or by precleaning with methylene
chloride (Section 5.3).   To  avoid  recontamination,  the precleaned material must
be  stored in  glass-stoppered glass  bottles,  or  glass  bottles covered  with
precleaned aluminum foil.  The storage period should not exceed two weeks.  To
minimize contamination,  extracts  should be dried directly  in  the  glassware  in
which they are collected by  adding  small  amounts of precleaned sodium sulfate
until an excess of free flowing material is noted.

      3.8   The presence of  elemental sulfur  will  result  in large  peaks which
often mask the  region of the  compounds eluting  before  dicyclohexyl  phthalate
(Compound No. 14) in  the gas chromatograms shown  in Figure  1.   Method 3660  is
suggested for removal of sulfur.

      3.9   Waxes and  lipids can  be removed  by  Gel  Permeation Chromatography
(Method 3640).  Extracts containing high concentrations of lipids are viscous,
and may even solidify at room  temperature.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatography

            4.1.1 Gas  chromatograph,  analytical  system  complete  with  gas
      chromatograph  suitable  for  on-column and  split/splitless injections and
      all  required   accessories,   including  detector,   analytical   columns,
      recorder, gases, and syringes.  A data system for measuring peak heights
      and/or peak areas is recommended.
                                   8061 - 3                         Revision 0
                                                                 November 1992
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                  4.1.1.1     Eight inch injection tee (Supelco,  Inc.,  Catalog
            No. 2-3665, or equivalent)  or glass Y splitter for megabore columns
            (J&W Scientific,  "press-fit", Catalog No. 705-0733, or equivalent).

            4.1.2 Columns

                  4.1.2.1     Column 1, 30 m x 0.53 mm ID, 5% phenyl/95% methyl
            silicone fused-silica open  tubular column (DB-5, J&W Scientific, or
            equivalent), 1.5 jum film thickness.

                  4.1.2.2     Column 2,  30  m x  0.53 mm  ID,   14%  cyanopropyl
            phenyl  silicone  fused-silica open  tubular  column  (DB-1701,  J&W
            Scientific, or equivalent), 1.0  jum film thickness.

            4.1.3 Detector - Dual electron capture detector (ECD)

      4.2   Glassware, see Methods 3510, 3540, 3550, 3610, 3620, 3640, and 3660
for specifications.

      4.3   Kuderna-Danish (K-D) apparatus.

            4.3.1 Concentrator tube - 10 ml  graduated (Kontes  K-570050-1025 or
      equivalent).  A  ground  glass stopper  is used to  prevent evaporation of
      extracts.

            4.3.2 Evaporation flask  -  500 ml  (Kontes K-570001-500  or  equiva-
      lent).  Attach to concentrator tube with springs,  clamps, or equivalent.

            4.3.3 Snyder  column  - Three ball macro (Kontes  K-503000-0121  or
      equivalent).

            4.3.4 Snyder  column  -  Two ball  micro  (Kontes   K-569001-0219  or
      equivalent).

            4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.4   Boiling chips, approximately 10/40 mesh.  Heat to 400  °C for 30 min,
or Soxhlet-extract with methylene chloride prior to use.

      4.5   Water  bath,  heated,  with  concentric  ring  cover,  capable  of
temperature control (± 2°C).


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be  used  in all tests.   Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society, where
such specifications are available.  Other grades may be  used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water. All references  to water  in this method
refer to organic-free reagent water, as defined in Chapter One.

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      5.3   Sodium sulfate (granular, anhydrous), Na2S04.  Purify by heating at
400 "C for 4 hours in a shallow tray,  or by precleaning the sodium sulfate with
methylene chloride.   If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating  that there is no interference from
the sodium sulfate.

      5.4   Solvents:

            5.4.1 Hexane, C6HU  -  Pesticide quality, or equivalent.

            5.4.2 Methylene chloride, CH2C12 -  Pesticide quality, or equivalent.

            5.4.3 Acetone, CH3COCH3 -  Pesticide  quality,  or equivalent.

            5.4.4 Acetonitrile, CH3CN - HPLC  grade.

            5.4.5 Methanol, CH3OH - HPLC grade.

            5.4.6 Diethyl Ether,  C2H5OC2Hr -  Pesticide quality,  or equivalent.
      Must be  free  of peroxides,  as indicated  by  test  strips (EM  Quant,  or
      equivalent).   Procedures  for removal of peroxides  are  provided with the
      test strips.  After cleanup, 20 mL of ethyl alcohol preservative must be
      added to each liter of ether.

      5.5   Stock standard solutions:

            5.5.1 Prepare  stock  standard  solutions   at  a   concentration  of
      1000 mg/L by dissolving 0.0100 g of assayed reference material in hexane,
      and diluting to volume in a 10 mL  volumetric flask.  When compound purity
      is assayed  to  be  96 percent or greater, the  weight can be  used without
      correction  to  calculate  the  concentration  of  the  stock  standard.
      Commercially  prepared  stock  standard  solutions  can   be  used  at  any
      concentration  if  they  are  certified  by  the   manufacturer   or  by  an
      independent source.

            5.5.2 Transfer the  stock  standard solutions  into glass  vials with
      Teflon lined screw-caps  or crimp  tops.   Store  at  4 °C and  protect from
      light.  Stock  standard solutions should be checked periodically  by gas
      chromatography for  signs  of  degradation or evaporation, especially just
      prior to preparation of calibration standards.

            5.5.3 Stock standard solutions must be replaced  after 6 months,  or
      sooner if comparison with check standards indicates a  problem.

      5.6   Calibration  standards:  Calibration  standards are  prepared at  a
minimum of five concentrations for each parameter of interest through dilution
of the stock standard solutions with hexane.   One of the concentrations should
be at  a concentration near, but above,  the method detection limit.  The remaining
concentrations should correspond to the expected range of concentrations found
in real  samples,  or  should define  the  working  range  of the  GC.   Calibration
solutions must be replaced  after 1 to 2 months, or sooner if comparison with
calibration verification standards indicates  a problem.
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      5.7   Internal standards (if internal standard calibration is used):  To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to  the  compounds  of interest.   The analyst
must further demonstrate that the measurement  of the internal  standard is not
affected by method or matrix interferences.  Benzyl benzoate has been tested and
found appropriate for Method 8061.

            5.7.1 Prepare a spiking  solution  of benzyl benzoate  in  hexane at
      5000 mg/L.   Addition of 10 nl of this solution to 1 ml of sample extract
      is recommended.  The spiking concentration of the  internal  standard should
      be kept constant  for  all  samples and calibration  standards.   Store the
      internal standard  spiking  solution at 4  °C in glass  vials  with Teflon
      lined screw-caps  or crimp  tops.   Standard  solutions should  be replaced
      when ongoing QC (Section 8) indicates a problem.

      5.8   Surrogate standards: The analyst should monitor the performance of
the extraction, cleanup  (when used), analytical  system,  and the  effectiveness of
the method in dealing  with each  sample  matrix by  spiking each sample, standard,
and blank with surrogate compounds.  Three surrogates may be used for Method 8061
in  addition to  those  listed  in  Section  1.4:  diphenyl  phthalate,  diphenyl
isophthalate, and dibenzyl  phthalate.   However, the compounds listed in Section
1.4 are recommended.

            5.8.1 Prepare a  surrogate  standard  spiking  solution,  in acetone,
      which contains  50 ng//xL of each compound.   Addition of  500 /jL of this
      solution to 1 L  of water or 30 g  solid sample is equivalent to 25 jug/L of
      water or 830  /ug/kg of  solid  sample.   The  spiking  concentration of the
      surrogate standards may be  adjusted  accordingly,  if the final  volume of
      extract  is  reduced  below 2 ml  for water samples or  10 ml  for  solid
      samples.  Store  the surrogate spiking solution at 4 °C in  glass vials with
      Teflon  lined  screw-caps or crimp  tops.   The  solution must  be replaced
      after 6 months,  or sooner if ongoing QC (Section 8) indicates problems.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to this  chapter,  Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Extraction:

            7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
      extraction procedure.  In general, water samples  are  extracted  at  a pH of
      5 to  7  with methylene  chloride  in  a  separatory funnel  (Method  3510).
      Method  3520  is  not  recommended  for the extraction of  aqueous  samples
      because  the  longer  chain  esters  (dihexyl  phthalate  bis(2-ethylhexyl)
      phthalate, di-n-octyl phthalate, and dinonyl  phthalate) tend to adsorb to
      the   glassware  and  consequently,  their   extraction   recoveries  are
      <40 percent.   Solid  samples are  extracted with  hexane/acetone (1:1) or
      methylene chloride/acetone  (1:1)  in a Soxhlet extractor (Method 3540) or
      with  an  ultrasonic  extractor  (Method  3550).    Immediately   prior to

                                   8061  - 6                          Revision 0
                                                                 November  1992
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extraction,  spike  500 nl  of  the  surrogate  standard spiking  solution
(concentration = 50 ng//iL) into 1 L aqueous sample or 30 g solid sample.

      7.1.2 Extraction   of   particulate-free   aqueous    samples   using
C18-extraction disks  (optional):

            7.1.2.1     Disk preconditioning: Place the C18-extraction disk
      into the filtration apparatus  and  prewash  the disk with 10 to 20 ml
      of acetonitrile. Apply vacuum to pull  the  solvent through the disk.
      Maintain vacuum to  pull air through for 5 min.   Follow with 10 ml of
      methanol.   Apply vacuum  and pull  most  of  the methanol  through the
      disk.  Release vacuum before the disk gets dry.  Follow with 10 ml
      organic-free reagent water.  Apply vacuum and pull most of the water
      through the disk.  Release the vacuum before the disk gets dry.

            7.1.2.2     Sample preconcentration: Add 2.5 mL of methanol to
      the  500 ml  aqueous sample in  order  to get  reproducible  results.
      Pour the  sample into  the filtration apparatus.  Adjust  vacuum so
      that it takes  approximately  20 min to process  the  entire sample.
      After all  of the sample has passed through the membrane disk, pull
      air through the disk for  5 to 10 min. to remove any residual  water.

            7.1.2.3     Sample elution:  Break the vacuum and place the tip
      of the filter base into the test tube that is contained inside the
      suction flask.  Add 10 ml of acetonitrile  to the graduated funnel,
      making sure  to  rinse  the walls of the graduated funnel  with  the
      solvent.  Apply  vacuum to pass  the  acetonitrile  through the membrane
      disk.

            7.1.2.4     Extract concentration  (if necessary): Concentrate
      the  extract to  2 mL or less,  using either the micro Snyder  column
      technique  (Section  7.1.2.4.1)  or  nitrogen  blowdown  technique
      (Section 7.1.2.4.2).

                  7.1.2.4.1    Micro  Snyder Column Technique

                        7.1.2.4.1.1  Add  one or two  clean boiling chips to
                  the concentrator tube  and attach a two ball micro Snyder
                  column.  Prewet the column by adding about  0.5  mL of
                  acetonitrile to the top of  the  column.   Place the K-D
                  apparatus   in a  hot  water  bath  (15-20 °C  above  the
                  boiling point of the solvent)  so that the concentrator
                  tube is partially  immersed in  the hot  water and  the
                  entire lower  rounded surface of the flask is bathed with
                  hot  vapor.   Adjust   the  vertical  position  of  the
                  apparatus   and the  water temperature, as  required,  to
                  complete the concentration  in  5-10  minutes.   At  the
                  proper rate of distillation the balls of  the column will
                  actively chatter, but  the chambers will not flood.  When
                  the apparent  volume of liquid reaches 0.5 mL, remove the
                  K-D apparatus from the water bath and allow it to drain
                  and cool for at least 10 minutes.   Remove  the  Snyder
                  column and rinse the flask and its lower joints  with
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                                                           November 1992
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                        about 0.2 ml  of solvent and  add to  the  concentrator
                        tube.   Adjust  the  final  volume to  1.0-2.0 ml  with
                        solvent.

                        7.1.2.4.2   Nitrogen Slowdown Technique

                              7.1.2.4.2.1 Place the concentrator tube in a warm
                        water bath  (approximately  35 °C)   and evaporate  the
                        solvent   volume  to  the  required  level using a  gentle
                        stream of clean, dry nitrogen (filtered through a column
                        of activated carbon).

                              CAUTION:    Do not use plasticized tubing between
                                          the carbon trap and the sample.

                              7.1.2.4.2.2 The internal  wall  of the tube must be
                        rinsed down several  times with acetonitrile during the
                        operation.   During evaporation, the  solvent  level in the
                        tube must be positioned to prevent water from condensing
                        into the sample  (i.e., the solvent level should be below
                        the level of  the water  bath).   Under normal  operating
                        conditions,  the  extract  should  not be  allowed to become
                        dry.

      7.2   Solvent Exchange: Prior to Florisil  cleanup or  gas chromatographic
analysis, the methylene chloride  and methylene chloride/acetone extracts obtained
in Section 7.1.1 must  be  exchanged  to hexane,  as  described  in Sections 7.2.1
through 7.2.3.   Exchange is not  required for the acetonitrile extracts obtained
in Section 7.1.2.4.

            7.2.1 Add one or two clean boiling chips to the flask and attach a
      three ball Snyder column.  Concentrate the extract as described in Section
      7.1.2.4.1, using  1  ml of  methylene chloride to prewet  the  column,  and
      completing the concentration  in 10-20 minutes.  When  the apparent volume
      of liquid reaches 1-2 ml,  remove the K-D apparatus from the water bath and
      allow it to drain and cool for at least 10 minutes.

            7.2.2 Momentarily remove the Snyder column, add 50 ml of hexane, a
      new boiling  chip,  and attach  the macro Snyder column.   Concentrate the
      extract as described in Section  7.1.2.4.1,  using  1  ml of hexane to prewet
      the  Snyder  column,   raising  the  temperature  of the  water  bath,  if
      necessary,   to   maintain   proper   distillation,  and   completing   the
      concentration  in 10-20 minutes.   When the  apparent  volume  of  liquid
      reaches 1-2 ml_,  remove  the K-D  apparatus  and allow it to drain and cool
      for at least 10 min.

            7.2.3 Remove the  Snyder column  and rinse  the flask  and  its lower
      joint into the concentrator tube with 1 to 2 ml hexane.  A 5 ml syringe is
      recommended  for  this operation.  Adjust the  extract  volume  to 2 ml for
      water samples,  using either  the micro  Snyder column  technique (Section
      7.1.2.4.1) or nitrogen  blowdown technique (Section 7.1.2.4.2),  or 10 ml
      for solid  samples.   Stopper  the concentrator tube and  store  at  4 °C if
      further processing will be performed immediately.  If  the extract will be


                                    8061 - 8                         Revision 0
                                                                 November 1992
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stored for two days or  longer,  it  should  be  transferred  to a glass vial
with  a Teflon  lined  screw-cap  or  crimp top.   Proceed  with the  gas
chromatographic analysis.

7.3   Cleanup/Fractionation:

      7.3.1 Cleanup may  not be  necessary  for extracts  from a relatively
clean  sample   matrix.      If  polychlorinated  biphenyls   (PCBs)   and
organochlorine pesticides are known to be present in the sample, use the
procedure outlined in Methods 3610  or  3620.   When  using  column cleanup,
collect  Fraction  1  by  eluting with  140 ml  (Method  3610)   or  100 ml
(Method 3620) of  20-percent diethyl ether in hexane.  Note that,  under
these  conditions,  bis(2-methoxyethyl)   phthalate,   bis(2-ethoxyethyl)
phthalate, and bis(2-n-butoxyethyl) phthalate are not recovered from the
Florisil  column.  The elution patterns and compound recoveries are given
in Table 3.

      7.3.2 Methods 3610 and  3620  also describe  procedures  for  sample
cleanup  using  Alumina   and  Florisil  Cartridges.    With   this  method,
bis(2-methoxyethyl)   phthalate,   bis(2-ethoxyethyl)   phthalate,    and
bis(2-n-butoxyethyl) phthalate are recovered quantitatively.

7.4   Gas chromatographic conditions (recommended):

      7.4.1 Column 1 and Column 2 (Section 4.1.2):

      Carrier gas (He) =            6 mL/min.
      Injector temperature =        250 °C.
      Detector temperature =        320 °C.
      Column temperature:
            Initial temperature =   150 °C, hold for 0.5 min.
            Temperature  program =   150  °C  to  220  °C  at  5  "C/min.,
                                    followed  by  220  °C  to 275 °C  at 3
                                    0C/min.
            Final temperature =     275 °C hold for 13  min.

      7.4.2 Table  1  gives  the  retention times and MDLs  that can  be
achieved by this  method  for the  16  phthalate esters.   An example  of the
separations achieved with the DB-5 and DB-1701 fused-silica open tubular
columns is shown  in Figure 1.

7.5   Calibration:

      7.5.1 Refer to Method 8000 for proper calibration techniques.  Use
Tables  1   and  2  for  guidance  on  selecting the  lowest  point on  the
calibration curve.

      7.5.2 The  procedure  for internal  or external  calibration may  be
used.   Refer  to  Method 8000  for  the   description  of  each   of  these
procedures.
                             8061 - 9                         Revision 0
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      7.6   Gas chromatographic analysis:

            7.6.1 Refer to Method 8000.   If  the  internal  standard calibration
      technique is used, add 10 /itL  of  internal  standard  solution at 5000 mg/L
      to the sample prior to injection.

            7.6.2 Follow Method 8000 for instructions on the analysis sequence,
      appropriate dilutions,  establishing daily  retention  time  windows,  and
      identification criteria.

            7.6.3 Record the  sample volume  injected and  the resulting  peak
      areas.

            7.6.4 Using  either  the  internal   or  the  external  calibration
      procedure (Method 8000),  determine the identity and the quantity of each
      component  peak  in  the  sample chromatogram  which corresponds  to  the
      compounds used for calibration purposes.

            7.6.5 If the response of a peak exceeds the working  range  of the
      system, dilute the extract and reanalyze.

            7.6.6 Identify compounds in the  sample  by  comparing  the retention
      times of the peaks in the sample  chromatogram with those of the peaks in
      standard  chromatograms.     The  retention  time  window  used  to  make
      identifications  is based  upon  measurements  of  actual  retention  time
      variations over the course of  10  consecutive injections.  Three times the
      standard  deviation  of the  retention  time  can be  used  to  calculate  a
      suggested window size.


8.0   QUALITY CONTROL

      8.1   Refer  to  Chapter  One  for specific  quality control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized.  If extract cleanup was  performed,  follow the QC
specified in Method 3600 and in the specific cleanup method.

      8.2   Quality control  required to evaluate  the GC system operation is found
in Method 8000.

            8.2.1 The  quality  control  check sample  concentrate  (Method 8000)
      should contain the test compounds at 5 to 10 nq/p.1.

      8.3   Calculate the recoveries of the surrogate compounds for all samples,
method blanks, and method spikes.  Determine if the recoveries are  within limits
established by performing QC procedures outlined in Method 8000.

            8.3.1 If the  recoveries are not within  limits,  the  following are
      required:

                  8.3.1.1     Make  sure  there  are no  errors in  calculations,
            surrogate  solutions and  internal standards.  Also check instrument
            performance.


                                   8061 -  10                        Revision  0
                                                                  November  1992
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                  8.3.1.2     Recalculate the data and/or reanalyze the extract
            if any of the above checks reveal a problem.

                  8.3.1.3     Reextract and reanalyze the sample  if none of the
            above are a problem,  or flag  the  data  as  "estimated concentration."

      8.4   An  internal  standard  peak area  check must be  performed  on  all
samples.  The internal  standard must be evaluated  for acceptance by determining
whether the measured area  for the  internal  standard deviates  by more than 30
percent from  the average  area  for  the  internal  standard  in  the calibration
standards.  When the internal standard  peak area is outside  that  limit,  all
samples that fall outside the QC criteria must be reanalyzed.

      8.5   GC/MS confirmation:  Any compounds confirmed  by two columns may also
be confirmed by GC/MS if the concentration  is sufficient for detection by GC/MS
as determined by the laboratory-generated detection  limits.

            8.5.1 The GC/MS would  normally require a minimum concentration of 10
      ng/juL in the final extract  for each single-component compound.

            8.5.2 The sample extract and  associated blank should be analyzed by
      GC/MS as per Section  7.0 of Method 8270.  Normally, analysis of a blank is
      not required for confirmation  analysis, however, analysis for phthalates
      is  a  special  case because  of the  possibility for sample  contamination
      through septum punctures,  etc.

            8.5.3 A reference standard of the compound must also be analyzed by
      GC/MS.   The  concentration  of  the  reference standard  must  be at  a
      concentration that would demonstrate  the ability to confirm the phthalate
      esters identified by GC/ECD.

      8.6   Include a mid-concentration calibration standard after each group of
20 samples  in   the  analysis  sequence.    The   response   factors   for  the
mid-concentration calibration must be within  + 15  percent of the average values
for the multiconcentration calibration.

      8.7   Demonstrate  through  the analyses  of  standards  that  the  Florisil
fractionation scheme  is reproducible.  When using the fractionation schemes given
in Methods 3610  or 3620,  batch-to-batch  variations  in the composition  of  the
alumina or  Florisil  material may  cause  variations  in  the  recoveries  of  the
phthalate esters.


9.0   METHOD PERFORMANCE

      9.1   The MDL is defined in Chapter One.  The MDL concentrations listed in
Table 1 were  obtained  using  organic-free  reagent water.    Details  on  how to
determine MDLs are given in Chapter One.   The MDL actually  achieved  in a given
analysis  will  vary,  as  it  is dependent  on  instrument  sensitivity  and  matrix
effects.

      9.2   This method  has been tested in a single laboratory  by using different
types of  aqueous samples and  solid  samples which  were  fortified  with  the test
compounds at two  concentrations.   Single-operator precision,  overall  precision,

                                   8061 -  11                         Revision 0
                                                                 November 1992
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and method  accuracy were  found  to  be  related  to the  concentration  of  the
compounds and  the type  of  matrix.    Results  of the  single-laboratory method
evaluation are presented in Tables 6 and 7.

      9.3   The accuracy and  precision  obtained  is  determined by  the sample
matrix,  sample preparation  technique,  cleanup  techniques,  and  calibration
procedures used.


10.0  REFERENCES

1.    Glazer, J.A.;  Foerst, G.D.; McKee, G.D.; Quave, S.A.,  and  Budde, W.L.,
      "Trace Analyses  for  Wastewaters," Environ.  Sci. and  Technol.  15: 1426,
      1981.

2.    Lopez-Avila,  V.,  Baldin,  E.,  Benedicto,  J.,  Milanes,  J.,  and Beckert,
      W.F.,  "Application of Open-Tubular Columns to SW-846 GC Methods", EMSL-Las
      Vegas, 1990.

3.    Beckert, W.F. and  Lopez-Avila, V., "Evaluation of SW-846 Method 8060 for
      Phthalate  Esters",  Proceedings  of  Fifth  Annual   Testing  and  Quality
      Assurance Symposium, USEPA, 1989.
                                   8061 - 12                         Revision  0
                                                                  November  1992
-------
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•MOoO^-O-t-J-C-r-cO-l-JCO                                                                                       rt
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                             TABLE 2.
     ESTIMATED QUANTITATION LIMITS (EQL)  FOR VARIOUS  MATRICES3
Matrix                                               Factor6
Groundwater                                                10
Low-concentration soil by ultrasonic extraction          670
  with GPC cleanup
High-concentration soil and sludges by ultrasonic      10,000
  extraction
Non-water miscible waste                              100,000
Sample EQLs are highly matrix dependent.  The EQLs listed herein are
provided for guidance and may not always be achievable.

EQL = [Method detection limit (Table 1)] X [Factor (Table 2)].  For
nonaqueous samples, the factor is on a wet weight basis.
                            8061  -  15                         Revision 0
                                                           November 1992
-------
                                   TABLE 3.
   AVERAGE RECOVERIES OF METHOD 8061 COMPOUNDS USING METHODS 3610 AND 3620
Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-penty1) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Alumina
column8
64.5
62.5
77.0
76.5
89.5
70.5
75.0
67.0
90.5
73.0
87.0
62.5
91.0
84.5
108
71.0
Florisil
column3
40.0
57.0
80.0
85.0
84.5
0
81.5
0
105
74.5
90.0
0
82.0
83.5
115
72.5
Alumina
cartridge6
101
103
104
108
103
64. lc
103
111
101
108
103
108
97.6
97.5
112
97.3
Florisil
cartridge
89.4
97.3
91.8
102
105
78. 3e
94.5
93.6
96.0
96.8
98.6
91.5
97.5
90.5
97.1
105
a 2 determinations; alumina and Florisil chromatography performed according
  to Methods 3610 and 3620, respectively.

b 2 determinations, using 1 g alumina cartridges; Fraction 1 was eluted with
  5 mL of 20-percent acetone in hexane.  40 M9 of each component was spiked
  per cartridge.

c 36.8 percent was recovered by elution with an additional 5 ml of
  20-percent acetone in hexane.

d 2 determinations, using 1 g Florisil cartridges; Fraction 1 was eluted
  with 5 ml of 10-percent acetone in hexane.  40 p,g of each component was
  spiked per cartridge.

e 14.4 percent was recovered by elution with an additional 5 ml of
  10-percent acetone in hexane.
                                   8061  -  16
   Revision 0
November 1992
-------










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                                    Figure  1
                                                                DB-5
                                                                30 m x 0.53 mm 10
                                                                1.5-|im Rim
                          IS
                     v*_>>
                                  6   8
                                  I
                                              11   12 SU-1 SU-2 SU-3
                                                                     16
     LLJ
     -3
                    LJ

                                                      SU-2 SU-3

                                              12   SU-1 15 M 16
                                               13
           DB-1701
           30 mx O.S3 mm ID
           1.0- Jim Film
                                        10
                                           11
                                                14
                                                 J
                     10
    20

TIME (min)
30
40
GC/ECD chromatograms of a composite phthalate  esters standard (concentration
10 ng//nl_  per compound) analyzed on  a  DB-5 and  a DB-1701 fused-silica  open
tubular column.   Temperature program:  150°C (0.5 min hold)  to 220°C at
5°C/min,  then to  275dC  (13 min  hold) at 3°C/min.
                                    8061 - 19
                Revision  0
             November  1992
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                                        METHOD  8061
             PHTHALATE  ESTERS  BY  CAPILLARY GAS  CHROMATOGRAPHY
                  WITH  ELECTRON  CAPTURE  DETECTION  (GC/ECD)
         7.1 Extraction
 7.1.1  Refer to Chapter 2 for
      guidance on choosing
      an extraction procedure.
      Recommendations given.
 7.1.2 Determine spike sample
     recovery and detection limit
     for each new sample matrix
     and a given extraction
     procedure.
 7.1.3 Aqueous sample extraction
      with C18 disks:
      .1 Precondition disks using
        solvent train.
      .2 Concentrate sample
        analytes on disk.
      .3 Bute sample analytes
        with acetonitrile.
      .4 Concentrate extract:
        .1 Mkro-Snvder Column
         Technique
        .2 Nitrogen Slowdown
         Technique
         .1 Evaporate solvent to
           desired level
         .2 Rinse tube walls
           frequently and avoid
           evaporating to dryness.
 7.2 Solvent Exchange to Hexane
 7.2.1 Evaporate extract volume to
 1 -2 ml. using K-D assembly.
7.2.2 Add hexane to K-D assembly
and evaporate to 1 -2 ml.
 7.2.3 Rinse K-D components and
 adjust volume to desired level.
                                                                          7.3 Cleanup/Fractionation
 7.3.1 Cleanup may not be
      necessary for extracts with
      dean sample matrices.
      Fraction collection and
      methods outlined for other
      compd. groups of interest
7.3.2 Fkxteil Cartridge Cleanup
     .1 Check each tot of Ftorisil
       cantidges for analyte
       recovery by editing and
       analyzing a composite std.
     .2 Wash and adjust solvent
       flow through cartridges.
     .3 Place culture tubes or 5 ml.
       vol. flasks for eluate
       collection.
     .4 Transfer appropriate extract
       volume on cartridge.
     .5 Bute the cartridges  and
      dilute to mark on flask.
      Transfer eluate to glass
      vials for concentration.
7.3.3 Collect 2 fractions if PCBs
     and organochkxine pesticides
     are known to be present
                                                                          7.4 Gas Chromatograph
                                                                      7.4.1 SetGC operating parameters.
                                                                      7.4.2 Table 1 and Figure 1 show
                                                                           MDLs and analyte retention
                                                                           times.
                                          8061  -  20
                       Revision  0
                  November  1992
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     METHOD  8061
     (CONTINUED)
        o
       7.5 Calibration
           I
7.5.1  See Method 8000 for
     calibration technique.
7.5.2 Refer to Method 8000 for
     internal/external std.
     procedure.
7.6 GC Analysis
'

7.6.1 Refer to Method 8000.
i
i
7.6.2 Follow Section 7.6 in
Method 8000 for
instructions on analysis
sequence, dilutions,
retention time windows,
and identification criteria.
i

7.6.3 Record injection volume
and sample peak areas.

i
7.6.4 Identify and quantify each
component peak using the
internal or external std.
procedure.
           I
7.6.5 Dilute extracts which
show analyte levels
outside of the calibration
range.


7.6.6 Identify compounds in the
sample by comparing
retention times in the
sample and the standard
chroma tog rams.
i
>
     8061  - 21
    Revision  0
November  1992
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                                METHOD 8070

                                NITROSAMINES
1.0  SCOPE AND APPLICATION

    1.1   This method covers  the  determination of  certain  nitrosamines.  The
following parameters can be determined  by this  method:
Parameter                                               CAS No.
N-Nitrosodimethylamine                                  62-75-9
N-Nitrosodiphenylamine                                  86-30-6
N-Nitrosodi-n-propylamine                              621-64-7


    1.2   This  is  a  gas  chromatographic  (GC)  method  applicable  to  the
determination  of the  parameters  listed above  in municipal  and  industrial
discharges.  When this method is used to analyze unfamiliar samples  for any or
all of the compounds above,  compound  identifications should be supported by at
least one additional  qualitative  technique.  This  method  describes  analytical
conditions for a second  gas  chromatographic column  that can be used to confirm
measurements  made  with  the  primary  column.  Method  8270  provides  gas
chromatograph/mass  spectrometer  (GC/MS)  conditions  appropriate   for  the
qualitative and  quantitative  confirmation  of results  for  N-nitrosodi-n-
propylamine. In order to confirm the  presence of N-nitrosodi-phyenylamine,  the
cleanup procedure specified in  Step  7.3.3 or 7.3.4 must  be  used.  In  order to
confirm  the presence  of N-nitrosodimethylamine  by  GC/MS,  chromatographic
column 1  of this method must  be  substituted  for  the column  recommended in
Method 8270.  Confirmation  of these  parameters using  GC-high  resolution  mass
spectrometry or a Thermal Energy Analyzer is  also recommended practice.

    1.3   The method  detection  limit (MDL)  for  each  parameter is listed in
Table  1.  The  MDL  for  a specific wastewater may  differ from  those  listed,
depending upon the nature of interferences  in the sample matrix. Table 2 lists
the Practical Quantitation Limits (PQLs)  for  various matrices.

    1.4   Any modification of this method, beyond  those  expressly  permitted,
shall be considered  as major modifications  subject  to application and approval
of alternate test procedures.

    1.5   The toxicity or carcinogenicity  of  each  reagent  used in  this method
has  not  been  precisely defined.  However, each  chemical  compound should be
treated as  a potential  health  hazard.  From this  viewpoint,  exposure  to these
chemicals must  be reduced  to  the lowest  possible level  by   whatever means
available. The  laboratory is  responsible  for maintaining  a  current awareness
file  of  OSHA   regulations   regarding the  safe  handling  of the chemicals
specified in this method.  A reference file  of material  data  handling sheets


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                                                                December 1987
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should  also be  made available  to  all  personnel  involved in  the  chemical
analysis.

    1.6  These nitrosamines are  known carcinogens. Therefore, utmost care must
be  exercised  in the  handling  of  these  materials.  Nitrosamine  reference
standards  and  standard  solutions  should  be  handled  and  prepared  in  a
ventilated glove box within a  properly ventilated room.

    1.7   N-Nitrosodiphenylamine  is  reported  to  undergo transnitrosation
reactions.  Care must be  exercised  in  the  heating  or concentrating of solutions
containing this compound in the  presence  of reactive amines.

2.0  SUMMARY OF METHOD

    2.1   A measured volume of sample,  approximately one  liter,  is solvent
extracted with  methylene chloride using  a  separatory  funnel.  The methylene
chloride extract is  washed  with dilute HC1  to remove  free amines, dried, and
concentrated to a volume of 10 ml or  less. Gas chromatographic conditions are
described which permit the  separation  and measurement of the compounds in the
extract after it has been exchanged to methanol.

    2.2  Method 8070 provides  gas  chromatographic conditions for  the detection
of ppb levels of nitrosamines. Prior  to use  of this method,  appropriate sample
extraction  techniques  must be  used.  Both  neat  and  diluted  organic liquids
(Method 3580, Waste Dilution)  may  be  analyzed  by  direct  injection.  A 2- to
5-uL  aliquot  of the extract  is injected into  a  gas  chromatograph (GC) using
the solvent flush technique,  and compounds in the GC  effluent are  detected by
a  nitrogen-phosphorus  detector (NPD)  or a  Thermal  Energy Analyzer  and the
reactive Hall detector.

3.0   INTERFERENCES

    3.1  Refer to Methods 3500,  3600, and 8000.

    3.2    Matrix  interferences  may  be caused by  contaminants that  are
coextracted  from the sample.  The extent  of matrix  interferences will  vary
considerably from source to source, depending  upon the nature and diversity of
the industrial  complex  or  municipality being sampled. The cleanup procedures
(Methods 3610  or 3620)  can be used  to overcome  many  of these  interferences,
but unique  samples  may require additional cleanup  approaches  to  achieve the
MDL listed in Table 1.

    3.3  Nitrosamines contaminate  many types  of products  commonly found in the
laboratory.  The analyst  must  demonstrate  that  no  nitrosamine  residues
contaminate the  sample  or  solvent extract under the  conditions of analysis.
Plastics,  in  particular, must  be  avoided  because  nitrosamines  are commonly
used  as plasticizers and are  easily  extracted from plastic materials. Serious
nitrosamine contamination may  result  at any  time  if consistent quality control
is not practiced.

    3.4  The sensitive and selective  Thermal  Energy Analyzer and  the reductive
Hall  detector  may  be used  in place  of the nitrogen-phosphorus  detector when


                                  8070 - 2                        Revision 0
                                                                 December 1987
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interferences are encountered.  The  Thermal  Energy Analyzer offers the highest
selectivity of the non-mass  spectrometric detectors.

    3.5  Solvents, reagents, glassware, and other sample processing hardware
may  yield  discrete  artifacts  and/or  elevated  baselines  causing
misinterpretation of  gas  chromatograms.  All  these  materials must  be
demonstrated  to be  free  from  interferences,  under  the conditions  of the
analysis,  by analyzing calibration and reagent blanks. Specific selection of
reagents and purification  of solvents by distillation in  all-glass systems may
be required.

    3.6   Interferences  coextracted  from  samples  will  vary considerably from
source to  source,  depending upon the  waste  being  sampled.  Although general
cleanup techniques are recommended  as  part  of  this method, unique samples may
require additional  cleanup.

4.0  APPARATUS AND MATERIALS

    4.1  Kuderna-Danish  (K-D) apparatus

         4.1.1  Concentrator tube -  10-mL,  graduated (Kontes K-570050-1025 or
    equivalent). Calibration must be  checked  at  the volumes  employed  in the
    test.  Ground glass stopper  is used  to prevent evaporation of extracts.

         4.1.2    Evaporation  flask   -  500  ml  (Kontes K-570001-0500  or
    equivalent). Attach  to concentrator tube with springs.

         4.1.3   Snyder column  -  Three ball   macro  (Kontes  K-503000-0121 or
    equivalent).

         4.1.4   Synder column  - Two  ball micro  (Kontes K-569001-0219 or
    equivalent).

    4.2   Boiling  chips  -  Approximately 10/40  mesh.  Heat  to   400°C for
30 minutes or Soxhlet extract with methylene chloride.

    4.3   Water bath  -   Heated,  with  concentric  ring cover,  capable  of
temperature control (± 2°C).  The  bath should be used  in a hood.

    4.4  Balance - Analytical,  capable  of accurately  weighing 0.0001 g.

    4.5  Vials - 10-  to  15-mL,  amber glass with Teflon  lined  screw-cap.

    4.6   Gas  chromatograph  - An analytical system  complete with temperature
programmable gas  chromatograph suitable  for on-column injection and all
required accessories  including  syringes,  analytical  columns, gases,  detector,
and  strip-chart recorder. A data  system is  recommended  for  measuring peak
areas.

         4.6.1   Column 1  - 1.8  m x  4  mm  i.d.  Pyrex  glass,  packed  with
    Chromosorb W AW,  (80/100 mesh)  coated  with 10% Carbowax 20 M/2%  KOH or
    equivalent.  This  column  was  used  to develop  the method  performance


                                 8070  - 3                       Revision 0
                                                                December 1987
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    statements  in  Section 9.0.  Guidelines  for the  use of  alternate  column
    packings are provided in  Step 7.3.2.

         4.6.2   Column  2 -  1.8 m  x  4  mm i.d.  Pyrex glass,  packed with
    Supelcoport (100/120 mesh) coated with 10%  SP-2250.

         4.6.3   Detector  -   Nitrogen-Phosphorus,  reductive Hall  or Thermal
    Energy Analyzer. These detectors have proven effective in the analysis of
    wastewaters for the parameters listed in the scope. A nitrogen-phosphorus
    detector was used to develop the method performance statements in Section
    9.0. Guidelines for  the  use of  alternate  detectors are  provided in Step
    7.3.2.

5.0  REAGENTS

    5.1  Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that  all inorganic reagents shall conform
to the specifications of the  Committee on Analytical  Reagents of the American
Chemical Society,  where such  specifications  are available. Other grades may be
used,  provided  it  is first  ascertained  that  the  reagent  is  of sufficiently
high  purity to  permit  its  use without lessening  the  accuracy of  the
determination.

    5.2  ASTM Type II Water (ASTM D1193-77 (1983)). All  references to water in
the method refer to ASTM Type II unless otherwise specified.

    5.3  Methanol,  CHsOH. Pesticide quality or  equivalent.

    5.4   Stock  standard  solutions  (1000  mg/L)  - Stock standard solutions can
be prepared from pure standard materials  or purchased  as certified solutions.

         5.4.1   Prepare  stock standard solutions  by accurately  weighing
    0.1000  ± 0.0010 g of  pure material. Dissolve the  material  in  pesticide
    quality methanol and dilute to volume in a  100-mL  volumetric flask. Larger
    volumes can be  used at the  convenience of  the  analyst. If compound purity
    is certified at 96% or greater,  the  weight  can be used without correction
    to  calculate  the  concentration  of  the   stock  standard.  Commercially
    prepared  stock standards  can  be used  at  any concentration  if  they are
    certified by the manufacturer or by an independent source.

         5.4.2  Transfer the  stock standard solutions  into  bottles with Teflon
    lined  screw-caps.   Store  at 4°C and protect  from  light.  Stock standard
    solutions  should be  checked  frequently  for signs  of  degradation or
    evaporation, especially just prior to preparing calibration  standards  from
    them.

          5.4.3  Stock standard solutions  must  be replaced  after six months, or
    sooner  if comparison with check standards  indicate a problem.

    5.5   Calibration  standards - A minimum of  five levels should be prepared
through  dilution  of  the  stock  standards  with isooctane.    One  of  the
concentration levels  should  be  at  a  concentration  near, but above, the method


                                  8070 -  4                       Revision  0
                                                                 December  1987
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detection limit.  The remaining concentration levels should correspond to the
expected range  of  concentrations  found  in real samples  or  should  define the
working  range  of  the GC.   Calibration  solutions  must be  replaced  after six
months, or sooner if comparison with  check standards indicates a problem.

    5.6   Internal  standards  (if internal  standard calibration  is  used)  -  To
use this approach,  the analyst must select one  or more internal standards that
are similar in  analytical behavior to the compounds of interest.  The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix  interferences.  Because of these limitations,  no
internal standard can be suggested that  is applicable to  all  samples.

         5.6.1   Prepare calibration  standards  at  a  minimum  of  five
    concentration levels  for  each analyte of  interest  as  described  in Step
    5.5.

         5.6.2  To  each  calibration  standard,  add  a known constant amount  of
    one or more internal  standards, and  dilute  to volume  with  isooctane.

         5.6.3  Analyze each  calibration standard according  to Section 7.0.

    5.7   Surrogate  standards  -  The  analyst should  monitor the performance  of
the  extraction,  cleanup  (when  used),  and  analytical  system  and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample,  standard,  and  reagent  blank  with  one  or two  surrogates  (e.g.
nitrosamines   are not  expected  to be in the  sample) recommended to encompass
the range of the temperature  program used in this  method.   Method 3500, Step
5.3.1.1, details instructions  on  the preparation  of base/neutral  surrogates.
Deuterated  analogs  of  analytes  should  not  be  used  as surrogates  for gas
chromatographic analysis due  to coelution  problems.

6.0  SAMPLE COLLECTION,  PRESERVATION, AND  HANDLING

    6.1  See the introductory material to  this  chapter, Organic Analytes, Step
4.1.    Extracts must  be  stored at 4°C and analyzed  within 40  days  of
extraction.

7.0  PROCEDURE

    7.1  Extraction

         7.1.1  Refer to Chapter Two for  guidance on choosing the appropriate
    extraction  procedure.   In general,  water  samples are  extracted  at  a
    neutral, or as  is,  pH with methylene chloride,  using  either Method 3510 or
    3520.  Solid samples are  extracted using  either Method 3540 or 3550.

         7.1.2  Prior to gas  chromatographic analysis, the extraction solvent
    must be exchanged to  methanol.   The exchange  is performed during the K-D
    procedures  listed  in  all  of the  extraction  methods.   The  exchange  is
    performed as follows.

              7.1.2.1  Following K-D  of  the methylene chloride extract to 1  mL
         using the macro-Snyder column,  allow the apparatus to cool and drain
         for at least 10 minutes.  0.7r.    c                      n  .  .   .
                                  8070 -  5                      Revision 0
                                                                December 1987
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          7.1.2.2    Momentarily  remove the  Snyder  column,  add  50 ml  of
     methanol,  a new boiling chip, and reattach  the  macro-Snyder  column.
     Concentrate the extract using 1  ml of methanol  to  prewet  the Snyder
     column.    Place the  K-D apparatus  on  the  water  bath  so that  the
     concentrator  tube  is  partially immersed in the hot water.   Adjust the
     vertical  position of  the  apparatus  and  the  water temperature,  as
     required,  to  complete concentration  in 5-10 minutes.  At  the proper
     rate of distillation the balls of the column  will  actively chatter,
     but the chambers will not  flood.   When the apparent volume of liquid
     reaches  1  ml,  remove  the K-D  apparatus and allow it to drain and cool
     for at least  10 minutes.   The extract will be handled  differently at
     this  point,  depending  on  whether  or not  cleanup is  needed.   If
     cleanup is not required,  proceed to Step  7.1.2.3.   If  cleanup  is
     needed,  proceed to Step 7.1.2.4.

          7.1.2.3    If  cleanup of  the  extract  is  not  required,  remove the
     Snyder column and  rinse  the flask and  its lower  joint  into  the
     concentrator  tube  with  1-2  ml  of  methanol.   A  5-mL  syringe  is
     recommended  for  this  operation.   Adjust  the extract  volume  to
     10.0 ml.   Stopper  the concentrator tube and  store refrigerated at 4°C
     if  further processing will  not  be   performed  immediately.    If  the
     extract will  be stored longer than two days, it  should be transferred
     to  a vial with  a  Teflon  lined  screw-cap.    Proceed  with  gas
     chromatographic analysis.

          7.1.2.4    If   cleanup  of the  extract  is  required,   remove  the
     Snyder column and  rinse  the flask and  its lower  joint  into  the
     concentrator  tube   with a  minimum amount  of methylene chloride.   A
     5-mL syringe  is recommended for  this operation.   Add a clean boiling
     chip  to  the   concentrator  tube  and   attach  a two  ball  micro-Snyder
     column.   Prewet the column  by adding about 0.5 ml of methanol to the
     top.  Place the micro K-D  apparatus  on the water bath  (80°C) so that
     the concentrator tube is partially immersed  in the hot water.  Adjust
     the vertical  position of the apparatus and the water temperature, as
     required,  to  complete  concentration   in 5-10 minutes.  At  the proper
     rate of distillation the balls of the  column  will  actively chatter,
     but the chambers will not  flood.   When the apparent volume of liquid
     reaches 0.5 mL, remove the  K-D  apparatus and allow it to drain and
     cool for at least  10 minutes.

          7.1.2.5   Remove the micro-Snyder column and rinse the flask and
     its lower  joint into  the concentrator tube  with 0.2  ml  of methylene
     chloride.   Adjust  the extract  volume  to  2.0  ml  and proceed with
     either Method 3610 or 3620.

     7.1.3   If  N-nitrosodiphenyl amine  is  to  be  measured  by  gas
chromatography,  the analyst must  first use  a  cleanup column  to eliminate
diphenylamine interference  (Methods 3610  or 3620).    If N-nitrosodiphenyl-
amine  is  of  no  interest,  the  analyst   may  proceed directly with  gas
chromatographic analysis (Step 7.3).
                              8070  -  6                       Revision 0
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    7.2  Cleanup

         7.2.1  Cleanup procedures  may  not be necessary for a relatively clean
    sample matrix. The cleanup procedure recommended  in  this  method has been
    used for the analysis of various  clean waters and  industrial effluents. If
    particular circumstances demand  the  use  of  an   alternative  cleanup
    procedure, the analyst must determine the elution profile and demonstrate
    that  the  recovery  of  each  compound of  interest is  no  less  than 85%.
    Diphenylamine, if present in  the original  sample extract must be separate
    from  the  nitrosamines  if N-nitrosodiphenylamine  is  to be  determined by
    this method.

         7.2.2   Proceed  with either  Method 3610  or 3620,  using  the 2-mL
    methylene chloride extracts obtained from Step 7.1.2.5.

         7.2.3  Following cleanup, the  extracts  should be  analyzed  by GC, as
    described in the previous paragraphs and in Method 8000.

    7.3  Gas Chromatography

         7.3.1  N-nitrosodiphenylamine  completely reacts  to form diphenylamine
    at  the  normal  operating temperatures  of  a GC  injection port  (200 to
    250°C).  Thus,  N-nitrosodiphenylamine  is  chromatographed  and  detected as
    diphenylamine. Accurate  determination depends on removal  of diphenylamine
    that may be present in the original  extract prior  to  GC (see Step 7.3).

         7.3.2   Table 1  summarizes  the  recommended  operating conditions for
    the gas chromatograph.  This  table  includes  retention times  and  MDLs that
    were  obtained  under  these  conditions.  Examples  of  the   parameter
    separations achieved by these columns are shown in Figures 1 and 2. Other
    packed  columns,  chromatographic  conditions,  or detectors may be used if
    the requirements of Step 8.2  are  met. Capillary  (open-tubular) columns may
    also  be  used if  the  relative  standard deviations  of responses  for
    replicate  injections  are  demonstrated to be  less  than 6% and  the
    requirements of Step 8.2 are  met.

    7.4  Calibration - Refer to Method  8000 for proper calibration techniques.
Use Table 1 and especially Table  2 for guidance on selecting the lowest point
on the calibration curve.

         7.4.1   The  procedure for internal  or  external calibration  may be
    used.   Refer to Method 8000 for a description of each of these procedures.

         7.4.2   If cleanup  is performed on  the samples, the  analyst  should
    process a series  of standards  through  the  cleanup procedure  and then
    analyze  the  samples  by  GC.   This  will  confirm elution patterns  and  the
    absence  of interferents  from  the  reagents.

    7.5  Gas chromatographic analysis

         7.5.1  Refer  to Method  8000.    If the  internal  standard calibration


                                 8070  -  7                       Revision 0
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    technique is used, add  10  uL  of internal  standard to the sample prior to
    injection.

         7.5.2   Follow  Step  7.6  in  Method  8000 for  instructions  on the
    analysis  sequence,  appropriate dilutions,  establishing  daily retention
    time windows,  and  identification  criteria.   Include  a  mid-level  check
    standard after each group of 10 samples in  the  analysis  sequence.

         7.5.3  Examples  of GC/NPD chromatograms for  nitrosamines  are shown in
    Figures 1 and 2.

         7.5.4  Record the sample  volume  injected and  the resulting  peak  sizes
    (in area units or peak heights).

         7.5.5   Using either the  internal  or  external  calibration procedure
    (Method 8000),  determine the identity and quantity of each  analyte  peak in
    the  sample chromatogram.  See  Step  7.8 of Method  8000  for calculation
    equations.

         7.5.6   If  peak detection  and  identification  are  prevented  due to
    interferences,  the hexane extract may  undergo  cleanup using either Method
    3610 or 3620.

8.0  QUALITY CONTROL

    8.1    Refer to  Chapter  One   for  specific  quality  control  procedures.
Quality control to validate sample extraction  is covered in  Method 3500 and in
the extraction method  utilized.   If extract cleanup was  performed,  follow the
QC in Method 3600 and in the specific cleanup method.

    8.2  Procedures to check the GC system operation  are found  in  Method  8000,
Step 8.6.

         8.2.1  The  quality control  (QC)  reference sample concentrate  (Method
    8000,  Step 8.6) should contain each analyte of  interest  at  20  ug/mL.

         8.2.2   Table 3  indicates the calibration  and  QC acceptance criteria
    for this method.  Table 4 gives method accuracy and precision  as functions
    of  concentration  for  the  analytes  of interest.    The  contents   of both
    Tables  should  be used  to  evaluate a laboratory's ability to perform and
    generate acceptable data by this method.

    8.3   Calculate  surrogate  standard  recovery on  all  samples,  blanks, and
spikes.   Determine  if the  recovery is  within limits (limits established by
performing QC procedures outlined  in Method 8000, Step 8.10).

         8.3.1  If recovery is not within limits, the following is required.

               o  Check  to  be  sure there are  no  errors in  calculations,
                  surrogate solutions and  internal  standards.  Also, check
                  instrument performance.
                                  8070 - 8                       Revision 0
                                                                 December 1987
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               o  Recalculate  the  data  and/or  reanalyze  the  extract  if any
                  of the  above checks reveal a problem.

               o  Reextract  and reanalyze the sample  if none  of  the above
                  are  a  problem  or  flag  the  data  as  "estimated
                  concentration."

9.0  METHOD PERFORMANCE

    9.1   This  method has been  tested  for linearity of recovery  from spiked
reagent water and has been demonstrated to be applicable for the concentration
range from 4 x MDL to 1000 x MDL.

    9.2   In  a  single laboratory (Southwest  Research  Institute),  using spiked
wastewater samples,  the  average recoveries presented in Table 2 were obtained.
Each spiked sample was analyzed in triplicate on three separate occasions. The
standard deviation of the percent  recovery is also included in Table 2.

    9.3   The  U.S.   Environmental  Protection Agency is  in  the  process  of
conducting an interlaboratory  method  study to fully define the performance  of
this method.

10.0  REFERENCES

1.   Fed. Regist. 1984,  49,  43234; October 26.

2.   Fine, D.H.;  Lieb, D.;  Rufeh,  R.  "Principle of Operation of  the  Thermal
     Energy Analyzer  for the  Trace  Analysis of Volatile  and  Non-volatile  N-
     nitroso compounds";  Journal of Chromatographv 1975,  107, 351.

3.   Fine,  D.H.; Hoffman,  F.; Rounbehler,  D.P.;  Belcher,  N.M.    N-nitroso
     Compounds  - Analysis  and Formation Lvon;  Walker,  E.A.; Bogovski, P.;
     Griciute,   L.,  Eds.;  International  Agency  for  Research on Cancer  (IARC
     Scientific Publications No. 14), pp  43-50,  1976.

4.   "Determination of Nitrosamines  in  Industrial  and Municipal  Wastewaters";
     Report for EPA Contract 68-03-2606,  in  preparation.

5.   ASTM  Annual  Book  of  Standards.  Part   31;  "Standard Practice for
     Preparation of Sample  Containers  and  for  Preservation"; ASTM:
     Philadelphia, PA, 1980; D3694.

6.   Buglass, A.J.;  Challis,  B.C.;  Osborn, M.R.  N-Nitroso  Compounds  in the
     Environment; Bogovski,  P.; Walker,  E.A., Eds.;  International  Agency for
     Research on Cancer  (IARC  Scientific  Publication No.  9),  pp 94-100, 1974.

7.   Burgess,   E.M.; Lavanish,  J.M.  "Photochemical  Decomposition of  N-
     nitrosamines"; Tetrahedon Letters  1964, 1221.

8.   Druckrey,  H.;   Preussman,  R.;  Ivankovic,  S.;  Schmahl,  D.  "Organotrope
     Carcinogene Wirkungen  bei 65 Verschiedenen  N-Nitroso-Verbindungen an BD-
     Ratten"; Z^ Krebsforsch 1967, 69,  103.

                                  8070  -  9                       Revision  0
                                                                December  1987
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9.    Fiddler,  W. "The  Occurrance  and  Determination  of N-nitroso Compounds";
     Toxicol.  ADD!.  Pharmacol. 1975, 31. 352.

10.  "Carcinogens  -  Working  with  Carcinogens";  Department  of  Health,
     Education,  and  Welfare,  Public  Health  Service,  Center for  Disease
     Control,  National   Institute  for Occupational  Safety  and  Health,
     Publication No. 77-206;  August, 1977.

11.  "OSHA Safety and  Health  Standards, General  Industry";  Occupational Safety
     and Health Administration, OSHA 2206, revised January,  1976  (29CFR1910).

12.  Safety in  Academic  Chemistry Laboratories,  3rd  ed.;  American Chemical
     Society Publication,  Committee on Chemical  Safety,  1979.

13.  Lijinsky,  W.  "How Nitrosamines  Cause  Cancer"; New  Scientist  1977,  73,
     216.

14.  Mirvish,  S.S.  "N-Nitroso compounds:  Their  Chemical and in vivo Formation
     and  Possible  Importance as Environmental  Carcinogens"; J_._ Toxicol.
     Environ.  Health 1977,  3, 1267.

15.  "Reconnaissance of Environmental   Levels of  Nitrosamines  in the Central
     United  States";  U.S.  Environmental  Protection  Agency.  National
     Enforcement Investigations Center, Report No. EPA-330/1-77-001, 1977.

16.  "Atmospheric Nitrosamine Assessment Report";  U.S.  Envirnmental  Protection
     Agency.  Office of Air Quality Planning  and  Standards. Research Triangle
     Park, NC,  1976.

17.  "Scientific and  Technical   Assessment Report  on Nitrosamines";  U.S.
     Environmental  Protection  Agency.  Office  of  Research  and Development.
     Report No. EPA-660/6-7-001, 1976.

18.  Handbook of  Analytical  Quality  Control   in Water and  Wastewater
     Laboratories; U.S.   Environmental Protection  Agency.   Environmental
     Monitoring and Support Laboratory.  ORD  Publication Offices of  Center for
     Environmental  Research  Information:  Cincinnati,  OH, March  1983,  EPA-
     600/4-79-019.

19.  ASTM Annual Book  of  Standards, Part 31; "Standard Practice for Sampling
     Water";  ASTM:  Philadelphia, PA, 1980; D3370.

20.  Methods for Chemical  Analysis of  Water and Wastes;  U.S.  Environmental
     Protection  Agency.  Office  of Research and Development.  Environmental
     Monitoring and Support Laboratory.  ORD  Publication Offices of  Center for
     Environmental  Research  Information:   Cincinnati, OH,  1979;  EPA-
     600/4-79-020.

21.  Burke, J.A. "Gas  Chromatography  for  Pesticide  Residue  Analysis;  Some
     Practical Aspects";  J_.. of the Assoc. of  Official Anal. Chemists 1965, 48,
     1037.


                                 8070 - 10                       Revision 0
                                                                December 1987
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22.  "Method  Detection  Limit and  Analytical  Curve  Studies  EPA  Methods  606,
     607, 608"; U.S. Environmental  Protection Agency. Environmental Monitoring
     and Support  Laboratory, Cincinnati,  OH,  special  letter  report  for  EPA
     Contract 68-03-2606.

23.  Rohrbough,  W.G.;  et al.  Reagent  Chemicals,  American Chemical  Society
     Specifications. 7th ed.; American Chemical  Society: Washington, DC, 1986.

24.  1985 Annual  Book  of ASTM Standards,  Vol.  11.01;  "Standard Specification
     for Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
                                 8070  -  11                       Revision 0
                                                                 December 1987
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                                  TABLE 1.
           CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
                                   Retention Time
                                     (minutes)
Parameter
Column 1  Column 2
    Method
Detection Limit
    (ug/L)
N-Nitrosodimethylamine
N-Nitrosodi-n-propylamine
N-Nitrosodiphenylaminea
4.1
12.1
12. 8°
0.88
4.2
6.4C
0.15
0.46
0.81
Column 1 conditions: Chromosorb W  AW(80/100  mesh)  coated with 10% Carbowax
20 M/2% KOH packed  in a  1.8  m  x  4  mm i.d.  glass column with helium carrier
gas at  a  flow rate of 40  mL/min column temperature  Isothermal,  at 110'C,
except as otherwise indicated.

Column  2  conditions:  Supelcoport  (100/120 mesh)  coated with  10% SP-2250
packed  in  a  1.8 m  x 4  mm i.d. glass  column  with  helium carrier  gas  at a
flow rate  of  40 mL/min  column temperature,  Isothermal  at  120°C,  except as
otherwise indicated.

^Measured as diphenylamine.
bDetermined isothermally at 220°C.
CDetermined isothermally at 210°C.
                                 TABLE 2.
                  SINGLE OPERATOR ACCURACY AND PRECISION


Parameter
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
Average
Percent
Recovery
32
79
61
Standard Spike Number
Deviation Range of
%
3.7
7.1
4.1
(uq/L) Analyses
0.8 29
1.2 29
9.0 29
Matrix
Types
5
5
5
                                  8070 -  12
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                                 December 1987
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             FIGURE  1.
GAS  CHROMATOGRAM OF NITROSAMINES
          Column: 10% Carbowax 20M + 2%
                 KOH on Chromosorb W-AW
          Temperature: J10°
          Detector: Phosphorus/Nitrogen
             2   4  6   8   10  12  14

               Retention time, minute*
             8070  - 13
Revision 0
December 1987
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                            FIGURE 2.
GAS  CHROMATOGRAM OF N-NITROSODIPHENYLAMINE AS  DIPHENYLAMINE
              Column: 10% Carbowax 20M + 2% KOH on
                     Chromosorb W-AW
              Temperature: 220°C.
              Detector: Phosphorus/Nitrogen
                                          
-------
                                     METHOD  8070
                                     NITROSAMINES
                          C   St*rt    J


7.1.1 Chooee
appropriate
extractioa
procedure


7.1.2 Perform
aolveat exchange
• liif aethanol


  7.1.2.4 Perform
aicro'K-D procedure
  ueiAf aothyloao
 chloride; perform
  Method 3610 or
3620;  proceed with
    GC tnalyeie
Tee
                          7.1.2.3 Adjiet
                        extract volue tad
                           proceed *itk
                         aaalyais or etore
                          la appropriate
                              •aaaer
                                                                 lo
                                 7.1.3
                                 Will
                              I-altroaodi-
                             pheaylaiiae be
                               aeaiaredT
                                                   7.1.3 Pirfora
                                                  colua cleaanp
                                                 aalax Method 3610
                                                      or 3620
                                                  7.3.2 lefer to
                                                    Table 1 for
                                                    recoueadod
                                                     operatiai
                                                condition! for the
                                                        GC
                           7.4 lefer to Method
                             8000 for proper
                              calibration
                              techalqaea
                            7.6.1 lefer  to
                            Method 6000  for
                            faldaace oa  OC
                               aaalyeia
                                                7.5.4/7.E.6 teeord
                                                   aaiple Tola**
                                                   injected aad
                                                  reealtiaf peat
                                                   aize; perfom
                                                    appropriate
                                                   calculation
                                                (Method 6000, Step
                                                      7.6)
                                                      Stop
                                       8070  -  15
                                                                  Revision
                                                                  December
0
1987
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                                 METHOD 8080A

            ORGANOCHLORINE  PESTICIDES  AND  POLYCHLORINATED  BIPHENYLS
                             BY  GAS  CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method  8080  is  used to  determine the  concentration of  various
Drganochlorine pesticides and polychlorinated biphenyls (PCBs).  The following
:ompounds can be determined by this method:
      Compound Name
CAS No.'
Aldrin
a-BHC
J0-BHC
S-BHC
y-BHC (Lindane)
Chlordane (technical)
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
4,4'-Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
12789-03-6
72-54-8
72-55-9
50-29-3
60-57-1
959-98-8
33212-65-9
1031-07-8
72-20-8
7421-93-4
76-44-8
1024-57-3
72-43-5
8001-35-2
12674-11-2
1104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
a  Chemical Abstract Services Registry Number.

      1.2   Table  1  lists  the  method  detection  limit  for  each  compound  in
organic-free reagent water.  Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
                                   8080A  -  1
                  Revision 1
               November 1992
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2.0   SUMMARY OF METHOD

      2.1   Method 8080 provides gas chromatographic conditions for the detection
of ppb concentrations of certain organochlorine pesticides and PCBs.   Prior to
the use of this method,  appropriate sample extraction techniques must be used.
Both neat  and diluted organic  liquids (Method 3580,  Waste Dilution)  may  be
analyzed by  direct injection.   A 2  to  5 /xL  sample  is  injected  into  a  gas
chromatograph (GC) using the  solvent  flush technique,  and  compounds  in  the GC
effluent are detected by an electron capture  detector (ECD) or an electrolytic
conductivity detector (HECD).

    --  2.2   The sensitivity of Method  8080 usually depends on the concentration
of  interferences  rather  than on  instrumental  limitations.   If interferences
prevent detection of the  analytes,  Method 8080 may also be performed on samples
that have undergone cleanup.   Method 3620,  Florisil Column  Cleanup, by itself or
followed by Method 3660,  Sulfur Cleanup, may be used to eliminate interferences
in the analysis.


3.0   INTERFERENCES

      3.1   Refer to Methods 3500, 3600,  and  8000.

      3.2   Interferences  by phthalate esters  can  pose   a  major problem  in
pesticide  determinations  when  using   the  electron  capture  detector.    These
compounds  generally  appear  in  the  chromatogram  as  large  late-eluting  peaks,
especially  in  the 15% and  50% fractions  from the  Florisil cleanup.   Common
flexible plastics contain varying amounts  of phthalates.   These phthalates are
easily extracted  or leached  from  such materials during laboratory operations.
Cross contamination of clean glassware  routinely occurs when plastics are handled
during extraction  steps, especially when  solvent-wetted  surfaces  are handled.
Interferences from phthalates can  best  be minimized  by avoiding  contact with any
plastic materials.  Exhaustive cleanup  of reagents and glassware may be required
to  eliminate  background   phthalate  contamination.     The  contamination  from
phthalate  esters  can  be  completely   eliminated  with  a   microcoulometric  or
electrolytic conductivity detector.
4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1 Gas  Chromatograph:    Analytical  system  complete with  gas
      chromatograph  suitable   for  on-column   injections  and  all  required
      accessories,  including detectors, column  supplies,  recorder,  gases,  and
      syringes.  A data system  for measuring peak heights and/or peak areas is
      recommended.
            4.1.2 Columns

                  4.1.2.1
            1.5% SP-2250/1
            or equivalent.
   Column 1:   Supelcoport  (100/120 mesh) coated with
95% SP-2401  packed in  a  1.8 m x 4 mm ID glass column
                                   8080A - 2
                                         Revision 1
                                      November 1992
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                  4.1.2.2     Column 2:  Supelcoport  (100/120 mesh) coated with
            3% OV-1 in a 1.8 m x 4 mm  ID glass column or equivalent.

            4.1.3 Detectors:     Electron   capture   (ECD)   or   electrolytic
      conductivity detector (HECD).

      4.2   Kuderna-Danish (K-D) apparatus:

            4.2.1 Concentrator tube:   10 ml, graduated (Kontes K-570050-1025 or
      equivalent).  A ground-glass stopper is used  to  prevent  evaporation of
      extracts.

            4.2.2 Evaporation   flask:      500   ml   (Kontes  K-570001-500   or
      equivalent).    Attach  to  concentrator   tube  with  springs,  clamps,  or
      equivalent.

            4.2.3 Snyder column:   Three  ball  macro (Kontes K-503000-0121 or
      equivalent).

            4.2.4 Snyder  column:    Two  ball  micro  (Kontes K-569001-0219 or
      equivalent).

            4.2.5 Springs -  1/2 inch  (Kontes K-662750 or equivalent).

      4.3   Boiling chips:  Solvent extracted,  approximately 10/40 mesh (silicon
carbide or equivalent).

      4.4   Water  bath:    Heated,  with  concentric  ring  cover,  capable  of
temperature control (±5°C).   The bath should be used  in  a hood.

      4.5   Volumetric flasks, Class  A:  sizes  as  appropriate with ground-glass
stoppers.

      4.6   Microsyringe:  10 juL.

      4.7   Syringe:  5 ml.

      4.8   Vials:  Glass, 2, 10, and  20 ml capacity with  Teflon-lined screw caps
or crimp tops.

      4.9   Balances:   Analytical,  0.0001 g and Top loading, 0.01 g.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all  tests. Unless otherwise
indicated, it is intended that all  reagents shall  conform to the specifications
of the Committee on Analytical  Reagents of  the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that  the  reagent  is of sufficiently  high purity to permit its use
without lessening the accuracy of the determination.

      5.2   Organic-free reagent water - All references  to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

                                   8080A -  3                         Revision 1
                                                                 November 1992
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      5.3   Solvents

            5.3.1 Hexane, C6H14 - Pesticide quality or equivalent.

            5.3.2 Acetone,  CH3COCH3 - Pesticide quality or equivalent.

            5.3.3 Toluene, C6H5CH3 - Pesticide quality or equivalent.

            5.3.4 Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or equivalent.

      5.4   Stock standard solutions:

            5.4.1 Prepare  stock  standard  solutions  at  a  concentration  of
      1000 mg/L  by  dissolving  0.0100  g  of assayed  reference  material  in
      isooctane and diluting to volume  in  a  10 ml volumetric flask.   A small
      volume of toluene  may be  necessary to  put some pesticides in solution.
      Larger volumes  can be used  at the  convenience of  the  analyst.   When
      compound purity is assayed to be 96% or greater, the weight  can be used
      without correction to calculate the concentration  of the stock standard.
      Commercially prepared stock  standards can be used at any concentration if
      they are certified by the manufacturer  or by an independent source.

            5.4.2 Transfer the  stock standard solutions into vials with Teflon-
      lined screw caps  or crimp tops.   Store  at 4°C and  protect  from light.
      Stock standards should be checked frequently for signs  of degradation or
      evaporation, especially just prior to preparing  calibration  standards from
      them.

            5.4.3 Stock standard solutions must be replaced after one year, or
      sooner if comparison with check standards indicates a problem.

      5.5   Calibration standards:  Calibration standards at  a minimum of five
concentrations for each parameter of interest are prepared through dilution of
the stock standards with  isooctane.  One of  the  concentrations  should be at a
concentration  near,  but  above,  the method  detection limit.    The remaining
concentrations should correspond to the expected range of concentrations found
in real  samples  or should  define  the working range  of  the GC.   Calibration
solutions must be replaced after six months, or sooner, if comparison with check
standards indicates a problem.

      5.6   Internal standards (if internal standard calibration is used):  To
use this approach, the analyst must select one or more internal  standards that
are similar in analytical  behavior to the  compounds  of  interest.  The analyst
must further demonstrate  that the  measurement  of the internal  standard is not
affected by method  or matrix interferences.   Because of  these limitations, no
internal standard can be suggested that is applicable to all  samples.

            5.6.1 Prepare   calibration   standards   at   a  minimum   of  five
      concentrations for each analyte of interest as described in Section 5.5.

            5.6.2 To each calibration standard, add a known constant  amount of
      one or more internal  standards, and dilute to volume with  isooctane.

            5.6.3 Analyze each calibration standard according to Section 7.0.

                                   8080A -  4                         Revision 1
                                                                 November  1992
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      5.7   Surrogate standards:  The analyst  should monitor the performance of
the extraction,  cleanup  (when used), and analytical  system and the effectiveness
of  the  method  in  dealing with each  sample  matrix by  spiking each  sample,
standard,  and organic-free  reagent  water  blank  with pesticide  surrogates.
Because GC/ECD data are much more subject to interference than GC/MS, a secondary
surrogate is  to  be  used when sample  interference  is apparent.   Two  surrogate
standards (tetrachloro-m-xylene (TCMX) and decachlorobiphenyl)  are added to each
sample;   however,  only  one need  be  calculated  for recovery.   Proceed  with
corrective action when both surrogates are out of limits for a sample (Section
8.3). Method  3500 indicates the proper procedure for preparing these surrogates.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to this  chapter, Organic  Analytes,
Section 4.1.   Extracts must be stored under refrigeration and analyzed within 40
days of extraction.


7.0   PROCEDURE

      7.1   Extraction:

            7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
      extraction procedure.    In general,  water  samples   are  extracted  at  a
      neutral, or as  is,  pH with methylene chloride, using either Method 3510 or
      3520.  Solid samples are extracted using Method 3540, 3541, or 3550.

            7.1.2 Prior to gas  chromatographic analysis, the extraction solvent
      must be exchanged  to  hexane.   The exchange  is performed during  the K-D
      procedures listed  in all  of  the extraction  methods.   The  exchange  is
      performed as follows.

                  7.1.2.1     Following K-D of the methylene chloride extract to
            1 mL using the macro-Snyder column, allow the apparatus to cool and
            drain for at least 10 min.

                  7.1.2.2     Increase the temperature  of the hot water bath to
            about 90°C.    Momentarily remove   the Snyder column,  add 50 mL  of
            hexane,  a new boiling chip,  and  reattach the macro-Snyder  column.
            Concentrate  the extract using 1 mL of  hexane to prewet the Snyder
            column.    Place the  K-D  apparatus on the  water  bath  so that the
            concentrator tube is partially immersed in the hot water.   Adjust
            the vertical  position of the apparatus and the water temperature,  as
            required, to complete concentration in 5-10  min. At the proper rate
            of distillation the balls of the  column will  actively chatter, but
            the chambers will  not  flood.   When the apparent volume  of liquid
            reaches  1 mL,  remove the K-D apparatus and allow it to  drain and
            cool for at  least 10 min.

                  7.1.2.3     Remove the Snyder column  and  rinse  the  flask and
            its lower joint into the  concentrator  tube with 1-2  mL of  hexane.
            A 5 mL  syringe  is  recommended  for  this  operation.   Adjust  the
            extract  volume to 10.0 mL. Stopper the concentrator tube and store

                                  8080A  - 5                         Revision 1
                                                                 November  1992
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            refrigerated at 4°C, if  further  processing will not  be  performed
            immediately.  If the extract will  be stored  longer than two days, it
            should be transferred to  a  vial  with a Teflon-lined  screw  cap or
            crimp top.   Proceed  with gas chromatographic analysis  if further
            cleanup is not required.

      7.2   Gas chromatography conditions (Recommended):

            7.2.1 Column 1:

            Carrier gas (5% methane/95% argon) flow rate:    60 mL/min
            Column temperature:                             200°C  isothermal

            When  analyzing  for the  low molecular weight  PCBs (PCB  1221-PCB
      1248), it is advisable to set the oven  temperature to  160°C.

            7.2.2 Column 2:

            Carrier gas (5% methane/95% argon) flow rate:    60 mL/min
            Column temperature:                             200°C  isothermal

            When  analyzing  for the  low molecular weight  PCBs (PCB  1221-PCB
      1248), it is advisable to set the oven  temperature to  140°C.

            7.2.3 When analyzing  for most or all of the  analytes in this method,
      adjust the  oven temperature and  column  gas flow to  provide  sufficient
      resolution for accurate  quantitation of the  analytes.  This will normally
      result in a retention time  of 10 to 12 minutes for 4,4'-DDT,  depending on
      the packed column used.

      7.3   Calibration: Refer to Method 8000 for proper calibration techniques.
Use Table 1  and especially Table 2 for guidance on selecting  the lowest point on
the calibration curve.

            7.3.1 The  procedure  for   internal  or external  calibration  may be
      used.   Refer to  Method 8000 for a description of each of these procedures.

            7.3.2 Because  of   the  low  concentration   of  pesticide  standards
      injected on a GC/ECD, column adsorption may be a problem when the GC has
      not been  used for a  day.  Therefore,  the GC column should  be primed or
      deactivated by injecting a PCB or pesticide standard mixture approximately
      20 times more concentrated  than the mid-concentration standard.  Inject
      this prior to beginning initial or daily calibration.

      7.4   Gas chromatographic analysis:

            7.4.1 Refer to Method 8000.   If  the internal  standard calibration
      technique is used, add  10 nl of internal standard to the sample prior to
      injection.

            7.4.2 Method 8000  provides  instructions on the  analysis sequence,
      appropriate  dilutions,  establishing daily  retention  time  windows,  and
      identification criteria.  Include a mid-concentration  standard after each
      group of  10 samples in  the analysis sequence.

                                   8080A - 6                         Revision  1
                                                                 November  1992
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      NOTE: A 72 hour sequence is not required with this method.

      7.4.3 Examples of  GC/ECD chromatograms  for various pesticides and
PCBs are shown in Figures 1 through 5.

      7.4.4 Prime the column as per Section 7.3.2.

      7.4.5 DDT and endrin  are easily degraded in the injection port if
the injection port or  front  of the column is dirty.  This  is the result of
buildup  of  high  boiling  residue  from sample  injection.    Check  for
degradation problems by injecting  a mid-concentration standard containing
only 4,4'-DDT and endrin.  Look for the degradation products of 4,4'-DDT
(4,4'-DDE and 4,4'-ODD)  and  endrin  (endrin ketone and endrin aldehyde).
If degradation of either  DDT or endrin exceeds  20%,  take corrective action
before proceeding with calibration, by following the GC system maintenance
outlined in of Method 8000.  Calculate percent breakdown as follows:

                          Total DDT degradation peak area (DDE + ODD)
      % breakdown       =	 x 100
      for 4,4'-DDT          Total  DDT peak area (DDT + DDE + ODD)

                          Total endrin degradation peak area
                          (endrin aldehyde + endrin ketone)
      % breakdown       = 	   x 100
      for Endrin           Total  endrin peak area  (endrin +
                           endrin aldehyde + endrin ketone)

      7.4.6 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).

      7.4.7 Using either  the  internal  or  external  calibration procedure
(Method 8000), determine the identity  and quantity  of each component peak
in the  sample chromatogram which  corresponds  to  the  compounds  used for
calibration purposes.

      7.4.8 If peak  detection and  identification  are prevented  due  to
interferences, the hexane extract may need to undergo cleanup using Method
3620.   The  resultant  extract(s)  may  be  analyzed by GC  directly  or may
undergo further cleanup to remove sulfur using Method 3660.

7.5   Cleanup:

      7.5.1 Proceed with  Method 3620,  followed by, if necessary,  Method
3660, using the 10 mL hexane extracts obtained from Section 7.1.2.3.

      7.5.2 Following cleanup, the extracts should be analyzed by GC,  as
described in the previous sections and in Method 8000.

      7.5.3 If only PCBs are to be measured  in a  sample,  the  sulfuric
acid/permanganate  cleanup  (Method  3665),  followed  by  Silica  Cleanup
(Method 3630) or Florisil Cleanup (Method 3620), is recommended.
                             8080A  -  7                         Revision 1
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7.6   Calculations (excerpted from U.S.  FDA,  RAM):

      7.6.1 Calculation of Certain Residues:  Residues which are mixtures
of two or more components  present  problems in measurement.  When they are
found together,  e.g.,  toxaphene  and  DDT, the  problem  of  quantitation
becomes even more difficult.   In  the  following  sections  suggestions are
offered for  handling  toxaphene,  chlordane,  PCB,  DDT, and  BHC.   A 10%
DC-200 stationary phase column was used to obtain the  chromatograms in
Figures 6-9.

      7.6.2 Toxaphene:   Quantitative calculation of toxaphene or Strobane
is difficult,  but reasonable  accuracy  can be  obtained.  To  calculate
toxaphene on  GC/ECD:  (a) adjust sample size so that toxaphene major peaks
are 10-30% full-scale deflection  (FSD);  (b)  inject a toxaphene standard
that is estimated to be within ±10 ng of the sample;  (c)  construct the
baseline of standard toxaphene  between its extremities; and (d) construct
the baseline under the  sample,  using the distances of the peak troughs to
baseline on the standard as a guide (Figures 7, 8, and 9).  This procedure
is made difficult by the fact that the relative heights and widths of the
peaks in  the  sample will  probably not be identical to the  standard.  A
toxaphene standard that has  been  passed through a Florisil  column  will
show a shorter retention time for peak X and an  enlargement of peak Y.

      7.6.3 Toxaphene  and  DDT:   If DDT is present,  it  will  superimpose
itself on toxaphene peak V.   To determine the approximate baseline of the
DDT, draw a line  connecting the trough of peaks U and  V with the trough of
peaks W and X and construct another line parallel to this line which will
just cut  the top  of peak  W  (Figure 61).   This procedure  was tested with
ratios of standard toxaphene-DDT mixtures from 1:10  to 2:1 and the results
of added  and calculated DDT and toxaphene by the "parallel  lines" method
of  baseline  construction  were  within  10% of the  actual values  in all
cases.

            7.6.3.1     A  series of  toxaphene  residues   have  been
      calculated using  total  peak  area for comparison to  the standard and
      also using  area  of  the  last four peaks  only  in  both  sample and
      standard.   The agreement between  the results  obtained  by  the two
      methods  justifies  the use  of  the  latter method  for  calculating
      toxaphene  in  a  sample  where  the  early  eluting  portion   of the
      toxaphene chromatogram is interfered with  by other substances.

            7.6.3.2     The  baseline  for  methoxychlor  superimposed on
      toxaphene (Figure 8b) was constructed by overlaying the samples on
      a toxaphene standard of approximately the same concentration  (Figure
      8a) and  viewing the charts  against a lighted background.

      7.6.4 Chlordane  is   a  technical  mixture  of  at  least  11  major
components   and   30  or   more   minor   ones.     Gas  chromatography-mass
spectrometry  and  nuclear  magnetic resonance  analytical  techniques   have
been  applied  to  the  elucidation  of the chemical structures  of the  many
chlordane constituents.   Figure 9a is a chromatogram of standard chlor-
dane.   Peaks  E and F are  responses to trans- and cis-chlordane,  respec-
tively.   These are the  two major  components  of  technical chlordane,  but
the exact percentage of each in the technical material is not completely

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defined and is not consistent from batch to batch.  Other labelled peaks
in Figure  9a  are  thought  to represent:   A,  monochlorinated  adduct  of
pentachlorocyclopentadiene   with   cyclopentadiene;   B,   coelution   of
heptachlor and a-chlordene; C, coelution of j8-chlordene and  y-chlordene;
D, a chlordane analog; G, coelution of cis-nonachlor and "Compound K," a
chlordane isomer.  The  right "shoulder" of peak  F  is   caused  by trans-
nonachlor.

            7.6.4.1     The GC pattern of a chlordane residue may differ
      considerably from that of the technical standard.  Depending on the
      sample substrate and its history,  residues of chlordane can consist
      of  almost  any  combination  of  constituents  from  the  technical
      chlordane,  plant  and/or  animal  metabolites,  and  products  of
      degradation  caused  by exposure  to  environmental factors  such  as
      water and sunlight.   Only limited  information  is available on which
      residue GC patterns are likely  to  occur in which samples types, and
      even this information may not be applicable to a situation where the
      route of exposure  is  unusual.  For example,  fish exposed to a recent
      spill of  technical  chlordane  will  contain a  residue drastically
      different from  a  fish whose chlordane residue was  accumulated  by
      ingestion  of smaller  fish  or  of vegetation, which  in turn  had
      accumulated  residues  because   chlordane  was  in the water  from
      agricultural runoff.

            7.6.4.2     Because of this inability to predict a chlordane
      residue GC pattern,  it is not possible to prescribe a single method
      for the quantitation of chlordane  residues.  The analyst must judge
      whether or not the residue's GC pattern is sufficiently similar to
      that of a technical chlordane reference material  to use the latter
      as a reference standard for quantitation.

            7.6.4.3     When  the   chlordane  residue does   not  resemble
      technical chlordane, but instead consists primarily of individual,
      identifiable peaks,  quantitate each  peak  separately  against  the
      appropriate reference materials and report the individual residues.
      (Reference  materials  are  available  for  at  least   11  chlordane
      constituents, metabolites or degradation products  which may occur in
      the residue.)

            7.6.4.4     When the GC pattern  of the residue resembles that
      of technical chlordane, quantitate chlordane residues  by comparing
      the total area of  the chlordane chromatogram from peaks A through F
      (Figure  9a)  in  the  sample  versus the same part of  the standard
      chromatogram.  Peak G may be obscured in a  sample  by the presence of
      other  pesticides.     If  G  is   not  obscured,  include  it   in  the
      measurement for both  standard and sample.   If the heptachlor epoxide
      peak is relatively small,  include  it as part of the total chlordane
      area  for  calculation  of  the residue.    If  heptachlor  and/or
      heptachlor  epoxide  are much out  of  proportion  as  in  Figure  6j,
      calculate these separately and  subtract their  areas from total area
      to give a corrected chlordane area.   (Note that octachlor epoxide,
      a metabolite of chlordane,  can easily be mistaken  for heptachlor
      epoxide on a nonpolar GC column.)
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            7.6.4.5     To  measure  the  total  area  of  the  chlordane
      chromatogram, proceed as in Section 7.6.2  on  toxaphene.   Inject an
      amount  of  technical  chlordane  standard  which  will  produce  a
      chromatogram in which peaks  E and F are approximately the same size
      as those  in  the  sample  chromatograms.   Construct  the  baseline
      beneath the  standard  from the beginning of  peak A to the end of peak
      F as  shown in Figure 9a.  Use  the  distance from  the  trough between
      peaks E and  F  to the baseline in the chromatogram of the standard to
      construct the baseline in the chromatogram  of  the sample.  Figure 9b
      shows  how the  presence of toxaphene  causes the  baseline  under
      chlordane to take  an upward angle.   When the  size  of peaks E and F
      in standard  and  sample chromatograms are the same, the distance from
      the  trough  of  the  peaks  to  the  baselines  should  be the  same.
      Measurement  of chlordane area  should be done  by  total  peak area if
      possible.

            NOTE:  A  comparison  has been made  of  the  total  peak  area
                  integration  method and the addition  of  peak heights
                  method for  several samples  containing chlordane.   The
                  peak heights  A,  B,  C,  D,  E,  and F  were measured in
                  millimeters  from peak  maximum of  each to  the baseline
                  constructed  under the total chlordane area  and were then
                  added  together.   These  results   obtained  by  the  two
                  techniques are too close to  ignore this method of "peak
                  height addition" as a  means of calculating chlordane.
                  The technique has  inherent difficulties because not all
                  the peaks are  symmetrical and not  all are present in the
                  same ratio in standard  and  in  sample.  This method does
                  offer a  means of calculating results  if no  means of
                  measuring total area  is practical.

      7.6.5 Polychlorinated biphenyls (PCBs):  Quantitation of residues of
PCB involves problems similar  to those encountered in the quantitation of
toxaphene,  Strobane, and chlordane.  In  each case, the chemical  is made up
of numerous compounds. So the chromatograms are  multi-peak.  Also in each
case, the chromatogram of  the  residue may not match that of the standard.

            7.6.5.1     Mixtures of  PCBs  of various  chlorine contents were
      sold  for many  years  in the  U.S.  by the Monsanto  Co.  under  the
      tradename Aroclor  (1200  series and  1016).  Though these Aroclors are
      no longer marketed, the  PCBs  remain  in  the environment  and  are
      sometimes found as residues in foods, especially fish.

            7.6.5.2     PCB residues are quantitated by comparison to one
      or more of the Aroclor materials,  depending  on the chromatographic
      pattern of the  residue.   A choice must be made as  to which Aroclor
      or mixture of Aroclors will produce a chromatogram most similar to
      that  of  the  residue.  This  may also involve  a judgment about what
      proportion  of the  different  Aroclors  to combine to  produce  the
      appropriate reference material.

            7.6.5.3     Quantitate PCB residues  by comparing total  area or
      height  of residue  peaks  to total  area  of  height  of  peaks   frorr
      appropriate Aroclor(s)  reference materials.   Measure total area or

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            height  response  from common baseline  under  all  peaks.   Use only
            those   peaks   from   the   sample  that   can   be   attributed   to
            chlorobiphenyls.    These  peaks  must  also  be  present  in  the
            chromatogram of the reference materials.  Mixtures of Aroclors may
            be required to provide the best match of GC patterns of sample and
            reference.

            7.6.6 DDT:  DDT found  in  samples  often  consists  of both o,p'- and
      p,p'-DDT.   Residues  of DDE  and  ODD  are also frequently  present.   Each
      isomer of  DDT and  its metabolites should be  quantitated  using  the pure
      standard of that compound and reported as such.

            7.6.7 Hexachlorocyclohexane   (BHC,  from the  former name,  benzene
      hexachloride) :   Technical  grade BHC is  a  cream-colored  amorphous solid
      with a very  characteristic  musty odor;  it consists of a  mixture of six
      chemically distinct isomers and one or more heptachloro-cyclohexanes and
      octachloro-cyclohexanes.

                  7.6.7.1     Commercial  BHC  preparations  may show  a  wide
            variance  in  the  percentage  of individual  isomers  present.   The
            elimination rate of the isomers fed to rats was 3 weeks for the a-,
            y-,  and 6-isomers and 14 weeks for the /3-isomer.   Thus it may be
            possible to have any combination of the various isomers  in different
            food commodities.  BHC found in dairy products usually has a large
            percentage of /3-isomer.

                  7.6.7.2     Individual isomers  (a, 0, y» and 5) were injected
            into   gas   chromatographs  equipped   with   flame   ionization,
            microcoulometric, and electron  capture detectors.  Response for the
            four  isomers  is  very nearly the same whether flame ionization or
            microcoulometric GLC is used.   The a-, y> and 6-isomers show equal
            electron  affinity.   /3-BHC  shows  a much weaker  electron  affinity
            compared to the other isomers.
                  7.6.7.3     Quantitate  each   isomer   (a,   /3,  y>
            separately against a standard of the respective pure isomer, using
            a GC column which separates all  the isomers from one another.


8.0   QUALITY CONTROL

      8.1   Refer  to Chapter  One  for  specific  quality control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized.  If extract cleanup was  performed, follow the QC
in Method 3600 and in the specific cleanup method.

      8.2   Quality control  required to evaluate the GC system operation  is found
in Method 8000.

            8.2.1 The quality  control  check sample concentrate  (Method 8000)
      should  contain  each   single-component   parameter  of  interest  at  the
      following  concentrations  in  acetone  or  other  water  miscible  solvent:
      4,4'-DDD, 10 mg/L; 4,4'-DDT, 10 mg/L;  endosulfan II,  10 mg/L;  endosulfan
      sulfate,  10  mg/L;  endrin,   10 mg/L;  and   any  other  single-component

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      pesticide, 2 mg/L.   If this method is only to  be used to analyze for PCBs,
      chlordane, or toxaphene, the QC  check  sample concentrate  should contain
      the most representative multi-component parameter at a concentration of 50
      mg/L in acetone.

            8.2.2 Table 3 indicates the calibration and QC acceptance criteria
      for this method.  Table 4 gives method accuracy and precision as functions
      of concentration  for  the analytes  of  interest.    The  contents  of  both
      Tables should be used to evaluate a  laboratory's  ability  to perform and
      generate acceptable data by this method.

      8.3   Calculate surrogate standard recovery  on all  samples,  blanks,  and
spikes.   Determine if the  recovery  is within  limits  (limits  established  by
performing QC procedures outlined in Method 8000).

            8.3.1 If recovery is not within limits, the following is required.

                  •     Check to be  sure there  are no  errors  in calculations,
                        surrogate solutions and internal standards.  Also, check
                        instrument performance.

                  •     Recalculate the data and/or reanalyze  the extract if any
                        of the above checks reveal  a problem.

                  •     Reextract and reanalyze the sample if none of the above
                        are  a  problem   or   flag   the  data   as  "estimated
                        concentration".

      8.4   GC/MS confirmation:  Any  compounds confirmed by two columns may also
be confirmed by GC/MS if the concentration  is sufficient for detection by GC/MS
as determined by the laboratory generated detection limits.

            8.4.1 The GC/MS would normally require a minimum concentration of 10
      ng/^L in  the final  extract, for  each single-component compound.

            8.4.2 The pesticide extract and associated blank should be analyzed
      by GC/MS  as per Section 7.0 of Method 8270.

            8.4.3 The  confirmation   may  be  from  the  GC/MS  analysis of  the
      base/neutral-acid extractables extracts (sample and blank).  However,  if
      the  compounds  are  not  detected in  the  base/neutral-acid  extract  even
      though the concentration is high  enough, a GC/MS analysis of the pesticide
      extract should be performed.

            8.4.4 A reference standard of the compound must also  be analyzed by
      GC/MS.   The  concentration  of the reference  standard must  be  at a level
      that  would  demonstrate  the   ability  to  confirm  the  pesticides/PCBs
      identified by GC/ECD.


9.0   METHOD PERFORMANCE

      9.1   The method was tested by  20 laboratories using organic-free reagent
water, drinking water, surface water, and three industrial wastewaters  spiked at

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six concentrations.  Concentrations  used in the study ranged  from 0.5 to 30
for single-component  pesticides  and from 8.5 to 400 /zg/L for multi-component
parameters.  Single operator precision, overall precision, and method accuracy
were found  to  be directly related  to  the concentration  of  the  parameter and
essentially independent of the sample matrix.  Linear equations to describe these
relationships for an electron capture detector are presented in Table 4.

      9.2   The accuracy and  precision obtained will be  determined  by the sample
matrix,   sample-preparation   technique,   optional   cleanup   techniques,   and
calibration procedures used.


10.0  REFERENCES

1.    U.S.  EPA,  "Development and Application of Test  Procedures  for Specific
      Organic  Toxic Substances  in  Wastewaters,  Category 10: Pesticides  and
      PCBs," Report for EPA Contract 68-03-2605.

2.    U.S.  EPA,  "Interim Methods  for  the Sampling  and  Analysis  of Priority
      Pollutants  in  Sediments  and Fish Tissue,"  Environmental  Monitoring and
      Support Laboratory, Cincinnati, OH 45268, October 1980.

3.    Pressley, T.A.,  and J.E.  Longbottom,  "The Determination of Organohalide
      Pesticides and PCBs in Industrial and Municipal Wastewater: Method 617,"
      U.S. EPA/EMSL, Cincinnati, OH, EPA-600/4-84-006,  1982.

4.    "Determination  of  Pesticides and  PCB's  in  Industrial  and  Municipal
      Wastewaters,   U.S.   Environmental   Protection   Agency,"   Environmental
      Monitoring and Support  Laboratory, Cincinnati, OH  45268, EPA-600/4-82-023,
      June 1982.

5.    Goerlitz, D.F. and L.M. Law,  Bulletin for  Environmental Contamination and
      Toxicology, 6, 9, 1971.

6.    Burke, J.A.,  "Gas Chromatography  for  Pesticide  Residue  Analysis;  Some
      Practical Aspects,"  Journal  of  the Association  of Official  Analytical
      Chemists, 48, 1037, 1965.

7.    Webb,  R.G.  and  A.C.  McCall,   "Quantitative  PCB  Standards  for Electron
      Capture Gas Chromatography,"  Journal of Chromatographic Science, 1_1, 366,
      1973.

8.    Millar, J.D.,  R.E.  Thomas and H.J. Schattenberg,  "EPA Method Study 18,
      Method 608: Organochlorine Pesticides and PCBs,"  U.S.  EPA/EMSL, Research
      Triangle Park, NC, EPA-600/4-84-061, 1984.

9.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures  for the
      Analysis of Pollutants Under the Clean Water Act; Final Rule and  Interim
      Final Rule and Proposed Rule," October 26, 1984.

11.   U.S. Food and  Drug  Administration,  Pesticide Analytical  Manual, Vol. 1,
      June 1979.
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12.    Sawyer,  L.D., JAOAC,  56, 1015-1023 (1973),  61 272-281 (1978),  61 282-291
      (1978).

13.    Stewart, J.   "EPA Verification Experiment for Validation of the  SOXTEC* PCB
      Extraction  Procedure";  Oak  Ridge  National Laboratory,  Oak  Ridge,  TN,
      37831-6138;  October 1988.
                                  8080A - 14                         Revision  1
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                                   TABLE 1.
                  GAS CHROMATOGRAPHY OF PESTICIDES AND PCBsa
Analyte
Aldrin
a-BHC
0-BHC
5-BHC
y-BHC (Lindane)
Chlordane (technical)
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Retention
Col. 1
2.40
1.35
1.90
2.15
1.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
e
time (min)
Col. 2
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
e
Method
Detection
limit (MQ/L)
0.004
0.003
0.006
0.009
0.004
0.014
0.011
0.004
0.012
0.002
0.014
0.004
0.066
0.006
0.023
0.003
0.083
0.176
0.24
nd
nd
nd
0.065
nd
nd
nd
aU.S.  EPA.   Method 617.   Organochlorine Pesticides and  PCBs,
Monitoring and Support Laboratory, Cincinnati, Ohio 45268.

e  =  Multiple peak response.

nd = not determined.
Environmental
                                  8080A - 15
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                                  TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs) FOR VARIOUS MATRICES8
        Matrix                                                Factor6
        Ground water                                               10
        Low-concentration soil  by sonication with GPC cleanup     670
        High-concentration soil  and sludges by sonication      10,000
        Non-water miscible waste                              100,000
           Sample EQLs are highly matrix-dependent.  The EQLs listed herein are
           provided for guidance and may not always be achievable.

           EQL - [Method detection  limit  (Table  1)] X  [Factor (Table 2)].  For
           non-aqueous samples, the factor is on a wet-weight basis.
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                                   TABLE 3.
                            QC  ACCEPTANCE CRITERIA3


Analyte
Aldrin
a-BHC
/J-BHC
6-BHC
y-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan
Endosulfan
Endosulfan
Endrin
Heptachlor
Heptachlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
s
X
P, Ps =
D
Test
cone.
(M9/L)
2.0
2.0
2.0
2.0
2.0
50
10
2.0
10
2.0
I 2.0
II 10
Sulfate 10
10
2.0
epoxide 2.0
50
50
50
50
50
50
50
50
Standard deviation of
Average recovery for
Limit
for s
(M9/L)
0.42
0.48
0.64
0.72
0.46
10.0
2.8
0.55
3.6
0.76
0.49
6.1
2.7
3.7
0.40
0.41
12.7
10.0
24.4
17.9
12.2
15.9
13.8
10.4
four recovery
four recovery
Range
for x
(M9/L)
1.08-2.24
0.98-2.44
0.78-2.60
1.01-2.37
0.86-2.32
27.6-54.3
4.8-12.6
1.08-2.60
4.6-13.7
1.15-2.49
1.14-2.82
2.2-17.1
3.8-13.2
5.1-12.6
0.86-2.00
1.13-2.63
27.8-55.6
30.5-51.5
22.1-75.2
14.0-98.5
24.8-69.6
29.0-70.2
22.2-57.9
18.7-54.9
measurements, i
measurements, in
Range
P> Ps
(%)
42-122
37-134
17-147
19-140
32-127
45-119
31-141
30-145
25-160
36-146
45-153
D-202
26-144
30-147
34-111
37-142
41-126
50-114
15-178
10-215
39-150
38-158
29-131
8-127
n M9/L.
M9/L.
Percent recovery measured.
Detected; result must
be greater than zero.
Criteria from 40 CFR Part 136 for Method 608.  These criteria are based directly
upon the method performance data in Table 4.   Where  necessary,  the  limits for
recovery  have  been  broadened to  assure  applicability  of  the  limits  to
concentrations below those used to develop Table 4.
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                                   TABLE 4.
         METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
Analyte
Aldrin
a-BHC
0-BHC
5-BHC
Y-BHC
Chlordane
4, 4' -ODD
4,4'-DDE
4, 4' -DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Accuracy, as
recovery, x'
(M9/L)
0.81C+0.04
0.84C+0.03
0.81C+0.07
0.81C+0.07
0.82C-0.05
0.82C-0.04
0.84C+0.30
0.85C+0.14
0.93C-0.13
0.90C+0.02
0.97C+0.04
0.93C+0.34
0.89C-0.37
0.89C-0.04
0.69C+0.04
0.89C+0.10
0.80C+1.74
0.81C+0.50
0.96C+0.65
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
Single analyst
precision, s '
(M9/L)
0.16X-0.04
0.13X+0.04
0.22X+0.02
0.18x+0.09
0.12X+0.06
0.13X+0.13
0.20X-0.18
0.13X+0.06
0.17x+0.39
0.12X+0.19
O.lOx+0.07
0.41X-0.65
0.13x+0.33
0.20X+0.25
0.06x+0.13
O.lSx-0.11
0.09X+3.20
0.13X+0.15
0.29X-0.76
0.21X-1.93
0.21X-1.93
0.21X-1.93
0.21X-1.93
0.21X-1.93
Overall
precision,
S' (M9/L)
0.20X-0.01
0.23x-0.00
0.33X-0.95
0.25x+0.03
0.22x+0.04
0.18x+0.18
0.27x-0.14
0.28X-0.09
0.31x-0.21
O.lSx+0.16
0.18x+0.08
0.47x-0.20
0.24X+0.35
0.24x+0.25
0.16X+0.08
0.25x-0.08
0.20X+0.22
O.lSx+0.45
0.35x-0.62
O.Slx+3.50
0.31x+3.50
O.Slx+3.50
0.31x+3.50
0.31X+3.50
x'
Sp'
S'


C

x
Expected  recovery  for  one   or  more  measurements  of  a  sample
containing concentration C, in
Expected single  analyst  standard deviation of measurements  at an
average concentration of x, in
Expected interlaboratory standard deviation  of measurements at an
average concentration found of x, in
True value for the concentration, in M9/L-

Average  recovery  found for  measurements  of samples  containing a
concentration of C, in M9/L.
                                  8080A - 18
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                Figure 1
    Gas Chromatogram of  Pesticides
Column: 1.S*922SO«
       1J8% SP-2401 en
Ttmptriturt: 200°C
Droctor: Electron Cwturt
                              I
                               f
               •          12
       KfTINTION TIME (MINUTES)
II
              8080A  -  19
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            Figure 2
 Gas  Chromatogram of Chlordane
Column: 1.S*$P-22SO»
       1.MH S^ 2*01 en Suptieopon
Ttmptraturt 20C°C
        Election CiCturt
   4          I         12

  KCTENTION TIME (MINUTES)
16
          8080A  -  20
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           Figure 3
Gas Chromatogram of Toxaphene
            Column: 1 J% 9 2250*
                   1J5\ SP-2«01 en Sueticoeon
            Twnotrnurt. 200CC
            Orttctof: lltetron
    10       14       II

 NETINTION TIME (MINUTIS)
22
26
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                    Figure 4
       Gas Chromatogram of Aroclor 1254
Column: 1.5\$P22SO*
       1JSV S^ 2«01 en Suo«icoeon
T«motriftift: 200°C
Dtuctor: lltcrron Cwturt
         6         10          U

           KCTINTION TIMf (MINUTES)
II
22
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                         Figure 5
             Gas Chromatogram of Aroclor 1260
   CrtumnM.f«S? 2250*
          1JI% SJ-2401 en Suetlcepon
              200°C
                  Cwturt
I	t	I
              I	f	I	I	I	l     I
                 10       14       11
                MTf NTION TIMI (MINUTU)
22
2t
                         8080A - 23
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                              Figure  6
   J..L
Fig. 0—Baseline construction for some typical gas chromatoftraphic peaks.
•, symmetrical separated Hat baseline; b and c, overlapping flat baseline;
d. separated (pan dots not return to baatllns between peaks); e, separated
sloping baseline; f,  separated (pen goes below  baseline between peaks):
g, «- andY-BHC sloping baaeliae; h, •-.£-. and Y-BHC sloping baseline;
i, chlordane  flat baseline; J.  neptachlor and beptachlor epoxloe super-
imposed  on chlordane;  k, dwir-ahapad peaks, unsymmeulcal peak; U
n,p'-DOT superimposed on tostapbem.
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                       Figure  7
Fig. 7§—Baseline construction for multiple residues with standard
                       toxtphene.
      VI
   rtg.7fr  Pfftllnr coMcructlaa far multiple i»«ldue*»lditaju-
                       8080A  - 25
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                         Figure  8
Fig. ••—Bas«llne construction for multiple rtsUfews: standard toxaphcrw.
                           f«r nitdptt raaiduca: rica bran with BHC,
                           DOT, Md matkoKycalor.
                        8080A  -  26
    Revision  1
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                                      Figure 9
           Flf. 9t~
           construction for multiple residues:  standard chlordane.
Ftf.
cflanmctlat for multiple nti4u*»i  rlct brin wldi chlacttent,
•ad DOT.
                                     8080A  -  27
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                            METHOD 8080A
      ORGANOCHLORINE PESTICIDES AND POLYCHLORINATED BIPHENYLS
                       BY GAS CHROMATOGRAPHY
 7.1.1  ChOO8 e
  appropriate
  extraction
  piocedux•.
     7.1.2
   Bxchang-e
  extraction
  •olvene  to
    h ex* ne.
    7 . 2  Sat
chromatographic
  condi11on B .
 7.3  Rarer  to
  Method  *OOO
  fox  p rope r
  ca1ibrat1on
  techni qu•• .
7.3.2  P r1 ma  o x
deactivate   the
G C column  prior
   to da 1ly
 calibratlon.
                           7 . 5.1   Cleanup
                           u« ing   Merhod
                           3 6 2 O a nd  3 « « O
                           i f  n«c e a s a r y .
                             8080A - 28
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