v>EPA
United States
Environmental Protection
Agency
Office of Water and
Watte Management
Washington. DC 20460
SW - 846
Revision A
August 8.1980
Solid Waste
Test Methods
for Evaluating Solid Waste
Physical/Chemical Methods
Technical
U pdate
-------
SW- 846a
Technical
Update
The enclosed material, SW-846.af updates the manual "Test Methods for
Evaluating Solid Waste" (SW-846). It is the first in a continuing
series of "Technical Updates" to be issued as corrections, or additional
methodologies and procedures become available.
Insert these pages in your manual to replace like-numbered pages or
add as new pages where appropriate. The date of issue is printed in
the upper righthand corner. Changes made on a page in that revision
(but not those made in past revisions) are double-underlined. For
easy and precise reference, the sequential number of each change is
given in a footnote.
The Office of Solid Waste thanks those in both the public and private
sectors who have made suggestions for improvement of this manual. We
encourage additional comments and suggestions, which may be made by
telephone or in writing. Conments should be sent to:
Manager, Waste Analysis Program
Office of Solid Waste
U.S. EPA (WH-565)
Washington, D.C. 20460
(202-755-9187)
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U.S. Environmental Protection Agency
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Revision A 8/8/80 5.3-3
seal, a thermove11 and temperature regulating device , a
heating device (mantle, hot plate, or bath), and a specimen
support system. A typical resin flask set up for this type
test is shown in figure 1.
2. The supporting device and container should not be
affected by or cause contamination of the waste under test.
3. The method of supporting the coupons will vary with
the apparatus used for conducting the test but should be
designed to Insulate the coupons from each other physically
and electrically and to insulate the coupons from any metallic
container or other device used in the test. Some common
support materials include: glass, fluorocarbon or coated metal.
4. The shape and form of the coupon support should assure free
con'tact with the waste.
Test Procedure
1. Assemble the test apparatus as described the "Equipment"
section above.
2. Fill the container with the appropriate amount of waste.
(See #5 under the "Precautions and Comments" section.)
3. Begin agitation at a rate sufficient to insure that
the liquid is kept well mixed and homogeneous.
4. Using the heating device bring the temperature of
.the waste to 55° C (130° F).
5. If the anticipated corrosion rate is moderate (i.e.,
<.2S4 mmpy)*. the test should be run for at leat 200 hours to
insure adequate weight loss to permit accurate results to be
obtained. If the corrosion rate is low (i.e., <.Q254 mmpy)**,
* Change #1
** Change #2
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5.3-4
then the test duration should be on the order of 2000 hours.
in cases where the anticipated corrosion rate Is completely
unknown, Initial testing should be performed using a 200
hour duration.
6. In order to accurately determine the amount of material
lost to corrosion, the coupons have to be cleaned after
immersion and prior to weighing. The cleaning procedure
should remove all products of corrosion while removing a
minimum of sound metal. Cleaning methods can be divided
into three general categories: mechanical, chemical and
electrolytic.
Mechanical cleaning includes scrubbing, scraping, brushing
and ultrasonic procedures. Scrubbing with a bristle brush
and mild abrasive is the most popular of these methods; the
others are used In cases of heavy corrosion as a first step
in removing heavily encrusted corrosion products prior to
scrubbing. Care should be taken to avoid removing sound metal.
Chemical cleaning implies the removal of material from
the surface of the coupon by dissolution in an appropriate
solvent. Solvents such as acetone, dichloromethane, and
alcohol are used to remove oil, grease or resinous materials,
and are used prior to immersion to remove the products of corrosion.
Solutions suitable for removing corrosion from the steel
coupon are:
Solution Soaking Time Temperature
20% NaOH + 200g/l zinc dust 5 min Bo'iling
or
Cone. HC1 + 50g/l SnCl2 + 20g/l SB-^s Until clean Cold
-------
5.3-5
Electrolytic cleaning should be proceeded by scrubbing
to remove loosely adhering corrosion products. One method of
electrolytic cleaning that can be employed is:
Solution
Anode
Cathode
Cathode current density
Inhibitor
Temperature
Exposure Period
50 g/1 H2S04
Carbon or lead
Steel coupon
20 amp/cm2 (129 amp/In2)
2 cc organic inhibitor/liter
74°C (165°F)
3 minutes
Kote: Precautions must be taken to insure good electrical
contact with the coupon, to avoid contamination of the cleaning
solution with easily reducible metal ions, and to insure
that inhibitor decomposition has not occurred. Instead of
using a proprietary inhibitor, 0.5 g/1 or either diorthotolyl
thiourea or qulnolin ethlodide can be used.
Whatever treatment is employed to clean the coupons, its
effect in removing sound metal should be determined using a
blank (i.e., a coupon that has not been exposed to the waste).
The blank should be cleaned along with the test coupon and
its waste loss subtracted from that calculated for the test
coupons*
7. After corroded specimens have been cleaned and dried,
they are reweighed. The weight loss is employed as the
principal measure of corrosion. Use of weight loss as a
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Revision A 8/8/80 5.3-6
measure of corrosion required making the assumption that
all weight loss has been due to generalized corrosion
and not localized pitting. In order to determine the
corrosion rate for purpose of this requlation, the following
formula is used:
Corrosion Rate (mmpy) » (weight loss) (11.145)*
(area) (time)==-
where weight loss is In milligrams, area In square
centimeters, time in hours, and corrosion rate in
millimters per year (mmpy).
* Change #3
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7.2-5
Table 7.2-1
APPROVED FILTER HOLDERS
Vacuum Filters
Manufacturer
Size
Model No
Comments
Nalgene
500 ml
Systems
Millipore
142 mm
45-0045
p
Nuclepore
Millipore
ressure Filters
Nuclepore
Micro Filtration
47 mm
4 7 mm
142 mm
142 mm
410400
XX10 047 00
420800
302300
YT30 142 HW
Disposable plastic unit,
includes prefilter and
filter pads, and reservoir
Should only be used when
solution is to be analyzed
for inorganic constituents
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Revision A 8/8/80 7.2-6
Table 7.2-2
APPROVED FILTRATION MEDIA
Filter
Type
Supplier
Filter To Be Used
For Aqueous Systems*
Filter To Be Used
For Organic Systems*
Coarse
Pref liter
Medium
Pref ilters
Fine
Pref ilters
Fine
Filters
(0.45um)
Gelman
Nuclepore
Millipore
Nuclepore
Millipore
Nuclepore
Millipore
Gelman
Pall
Nuclepore
Millipore
Selas
J_
210907
211707
AP25 042 00
AP25 127 50
211705
AP20 042 00
AP20 124 50
210903
211703
APIS Q42 OQttt
API 5 124 50
60173
60177
N704750tttt
NX14225
111107
112007
HAWP 047 00
HAWP 142 50
83485-02
83486-02
J_
210907
211707
AP25 042 00
AP25 127 00
211705
AP20 042 00
AP20 124 50
210903
211703
APIS 042 OfHtt
AP15 1?4 SO
60540
60544
181107
182007
FHLP 047 00
FHLP 142 00
83485-02
83486-02
t
tt
Change #4
Change #5
ttt Chenge #6
tttt Change #7
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8.01-4
3. Stock standards - prepare stock standard solutions In
methyl alcohol using assayed liquids or gas cylinders
as appropriate. Because of the toxicity of many of
the compounds being analyzed, primary dilutions of these
materials should be prepared in a hood . A NIOSH/MESA
approved toxic gas respirator should be used when
the analyst handles high concentrations of such
materials.
a. Place about 9.8 ml of methyl alcohol into a 10 ml
ground glass stoppered volumetric flask. Allow
about 10 minutes or until all alcohol wetted surfaces
have dr
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Revision A 8/8/80 8.01-5
c. Reveigh, dilute to volume, stopper, then nix by
by inverting the flask several tines. Transfer the
standard solution to a 15 ml screw cap bottle with a
teflon cap liner.
d. Calculate the concentration in mg/1 from the net
gain in weight.
e. Store stock standards at A.OeC.* Prepare fresh standards
weekly for the 4 compounds whose BP £ 30° C. All other
standards must be replaced with fresh standards each
month.
Calibration
1. Using stock standards, prepare secondary dilution standards
in methyl alcohol that contains the compounds of interest,
eitner singly or mixed together.
2. Assemble necessary gas chromatographic apparatus and establish
operating parameters equivalent to those indicated in the
Procedure section. By injecting secondary standards, adjust
the sensitivity of the analytical system for each compound
being analyzed so as detect _<_ 1 ug.
Quality Controls
1. Before processing any samples, the analyst should dally
demonstrate through the analysis of an organic-free water
or solvent blank that the entire analytical system is
interference free.
^. Standard quality assurance practices should be used with
this method. Field replicates should be collected to
validate the precision of the sampling technique.
* Change #8
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8.04-3
4. Gas chromatograph - Analytical system complete with
programmable gas chromatograph suitable for on-column
injection and all required accessories, including FID or
HSD, column supplies, recorder and gases. A data system
for measuring peak area is recommended.
5. Supelcoport 80/100 mesh coated with 1% SP-1240 DA in
1.8 meter long 2 mm ID glass column (Column 1) or Chromosorb
V-AWDMCS 80/100 mesh coated with 5% OV-17 packed in a 1.8
meter long X mm ID glass column (Column 2).
6. Syringes - 5 ml glass hypodermic with Luerlok tip (2each).
7. Micro syringe - 10, 25, 100 ul.
8. 2-way syringe valve with Luer ends (3 each).
9. Syringe - 5 ml gas tight with shut-off valve.
10. Bottle - 15 ml screw-cap, with teflon cap liner.
11. Kuderna-Danish apparatus (K-D) [Kontes K-570000 or equivalent]
with 3 ball Snyder column.
12. Water bath - heated with concentric ring cover capable
of temperature control (+ 2°C). The bath should be used
in a hood.
13. Chromatographic column - 10mm ID by 100mm length with
teflon stopcock.
14. Reaction vial - 20 ml with teflon - lined cap.
Reagents
1. 2 - propanol - pesticide quality or equivalent
2. Stock standards - prepare stock standard solutions at
a concentration of 1.0 ug/ul by dissolving 0.100 grams
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Revision A 8/8/80 8.04-
of assayed reference material in pesticide quality 2-propanol
and diluting to volume in a 100 ml ground glass stopped
volumetric flask. The stock solution is transferred to
ground glass stoppered reagent bottles, stored In a refrigera-
tor, end checked frequently for signs of degradation or
evaporation, especially just prior to preparing working stan-
dards from then.
3. PFB derivative reagents:
a. Hexane and toluene - pesticide quality or equivalent
b. Sodium sulfate - (ACS) granular, anhydrous (purified
by heating at 400°C for 4 hours in a shallow tray).
c. Potassium carbonate - (ACS) powdered.
d. Silica gel - (ACS) 100/200 mesh, grade 923; activated
at 130°C and stored in a desslcator.
e. Pentafluorobenzyl bromide - 97% minimum purity.
f. 1,4,7,10,13,16-Hexaoxacylooctadecene (18
crown 6) - 98% minimum purity.
E. Preparation of derlvitiztng reagent! Add 1 ml pentafluro-
benzil bromide and 1 gm of the 18 crown 6 ether to a 50 ml
volumetric flask and dilute to volume with 2-propanol.
Prepare fresh weekly.*
Calibration
1. Dsing stock standards, prepare secondary dilution standards
in 2-propanol that contain the compounds of interest, either
singly or mixed together.
2. Assemble necessary gas chromatographlc apparatus and
establish operating parameters equivalent to those in the
* Change #9
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8.04-5
"procedure section." By injecting secondary standards
adjust the sensitivity limit and the linear range of the
analytical system for each compound being analyzed for to
a sensitivity of £ 1 ug (2X background).
Quality Control
1. Before processing any samples the analyst should demon-
strate through the analysis of an organic - free water
or solvent blank that the entire analytical system is
interference free.
2. Standard quality assurance practices should be used with
this method. Field replicates should be collected to vali-
date the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the accuracy of
the analysis. Where doubt exists over the identification
of a peak on the gas chromatogram confirmatory techniques
such as mass spectroscopy should be used.
3. The analyst should maintain constant surveillance of both
the performance of the analytical system and the effective-
ness of this method in dealing with each sample matrix by
spiking each sample with known amounts of the compounds
the waste is being analyzed for and using these spiked
samples readjust the sensitivity of the instrument such
that 1 ug/gm of sample can be readily detected (see Quality
Control).
Flame lonization Gas Chromatography Procedure
1. Assemble gas chromatograph with column 1 and Flame lonization
Detector (apparatus section).
2. .Set nitrogen carrier gas at 30 ml/min flow rate.
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8.04-6
3. Set column temperature at 80°C at injection and program
to immediately rise at 8°C/min to 150°C.
Derivatizatlon and Electron Capture Gas Chromatography Procedure
1. Pipet a 1.0 ml aliquot of the 2-propanol solution of standard
or sample extract into a glass reaction vial. Add 1.0 ml
derivatization reagent. This is a sufficient amount of
reagent to derivatize a solution whose total phenolic
content does not exceed 0.3 mg/ml.
2. Add about 3 mg of potassium carbonate to the solution and
shake gently.
3. Cap the mixture and heat for 4 hours at 80°C in a hot
water bath.
4. Remove the solution from the hot water bath and allow it
to cool.
5. Add 10 ml hexane to the reaction vial and shake vigorously
for one minute. Add 3.0 ml of distilled deionized water
to the reaction vial and shake for two minutes.
6. Decant organic layer into a concentrator tube and cap with
a glass stopper.
7. Pack a 10mm ID chromatographlc column with 4.0 grams of
activated silica gel. After settling the silica gel by
tapping the column, add about two grams of anhydrous sodium
sulfate to the top.
8. Pre-elute the column with 6 ml hexane. Discard the eluate
and Just prior to exposure of the sulfate layer to air
pipet onto the column 2.0 ml of the hexane solution that
contains the derivatlzed sample or standard. Elute the
-------
8.04-7
column with 10.0 ml of hexane (Fraction 1) and discard
this fraction. Elute the column, in order with 10.0 ml
15% toluene in hexane (Fraction 2), 10.0 ml 40% toluene
in hexane (Fraction 3), 10.0 ml 75% toluene in hexane
(Fraction 4), and 10.0 ml 15% 2-propanol in toluene (Fraction
5). Elution patterns for the phenolic derivatives are
shown in Table 8.04-2 Fractions nay be combined as desired
depending upon the specific phenols of interest or level
of interferences. Collect the fractions in appropriate
sized K-D apparatus and concentrate each fraction to 10 al.
9. Assemble gas chromatograph with column 2 and HSD (apparatus
sect ion).
10. Using 5% methane/95% argon as the carrier gas adjust flow to
30 ml/min.
11. Set column temperature at 200°C.
12. Inject 2-5ml of the appropriate fraction using the solvent -
flush technique. Smaller (1.0 ml) volumes can be injected
if automatic devices are employed. Record volume injected
to the nearest 0.05 ml and the resulting peak size In area
units. If the peak area exceeds the linear range of the
system dilute the extract and reanalyze.
Calibrate the system immediately prior to conducting any
analyses and recheck as in Quality Control for each type of
waste. Calibration should be done no less frequently than at
the beginning and end of each session.
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8.04-8
Calculations
1. If a response for the contaminant being analyzed for is
greater than 2X background is noted, then the waste does
not meet the criteria for delisting of being fundamentally
different than the listed waste. If a response is not noted,
then prior to concluding that the sample does not contain
the specific contaminant, the analyst must demonstrate, using
spiked samples, that the instrument sensitivity is ^ 1 ug/gm.
2. When duplicate and spiked samples are analyzed, all data
obtained should be reported.
3. If one desires to determine the actual concentration of
the compound in the waste, the method of standard addition
should be used.
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Revision A 8/8/80 8.06-8
d. Just prior to exposure of the sodium sulfate layer to
the air add 40 ml hexane and continue the elutlon at
the rate of 2 ml/minute. This eluate is Traction 1.
Concentrate the fraction by standard K-D technque. No
solvent exchange is necessary. After concentration and
cooling, transfer to a* 10 ml volumetric flask, dilute to
10 ml and analyze by gas chromatography.
e. Next elute the Florisil with 100 ml of 5 percent ethyl
ether/95% hexane (v/v) and concentrate as in step d.
[Fraction 2] .
f. Next, elute with 100 ml of 15% ethyl ether/85% hexane
(v/v) and concentrate Fraction 3 as in step d.
g. Elute with 100 ml of 50% ethyl ether/50% hexane (v/v),
and concentrate, Fraction 4 as in step d.
h. Finally, elute with 100 ml of ethyl ether, and concen-
trate, Fraction 5 as in step d.
Gas Chromatography
1. Assemble gas chromatograph with either Column 1 or 2 (see
Apparatus) .
Column 1 (Supelcoport 100/120 with l.S% SP 2250 + 1.95% SP 2401)
a. Set carrier gas at 60 ml/minute flow rate.
b. Column temperatures will vary from 180°C to 220°C depending
on the compound.
Column 2 (Supelcoport 100/120 with 3Z OV-1)
a. Set carrier gas at 60 ml/min flow rate.
b. Column temperature will vary from 200CC to 220°C depending
on the compound.
* Change #10
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8.06-9
2. Calibrate the system at the beginning and end of an analytical
session by spiking aliquots of the extract with calibration
standards.
3. Inject 2-5 ul of the sample extract or appropriate Florisil
eluate using the solvent-flush technique. Smaller (1.0 ul)
volumes can be injected if automatic devices are employed.
Recorc the volume injected to the nearest 0.05 ul, and the
resulting peak size, in area units.
4. If a response for the contaminant being analyzed for is greater
than 2x background, then the waste does not meet the criteria
for delisting of being fundamentally different than the
listed waste. If a response is not noted, then prior to
concluding that the sample does not contain the specific
contaminant, the analyst must demonstrate, using the spiked
samples, that the method sensitivity is £ 1 ug of compound
per gm of sample.
5. If the peak area measurement is prevented by the presence of
interferences, further cleanup is required.
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8.08-6
preparation and measurement steps. Where doubt exists over
the Identification of a peak on the chromatogram, confirmatory
techniques such as mass spectroscopy should be used.
Cleanup and Separation
Cleanup procedures are used to extend the sensitivity of a
method by minimizing or eliminating interferences that mask or
otherwise disfigure the gas chromatographic response to the
pesticides and PCB's. The Florisil column allows for a select
fractlonatlon of the compounds and will eliminate polar materials.
Elemental sulfur interferes with the electron capture gas chro-
matography of certain pesticides but can be removed by the
techniques described below.
Florisil Column Cleanup:
1. Add a weight of Florisil, (nominally 21g,) predetermined by
calibration to a chromatographic column. Settle the Florisil
by tapping the column. Add sodium sulfate to the top of the
Florisil to form a layer 1-2 cm deep. Add 60 ml of hexane to
wet and rinse the sodium sulfate and Florisil. Just prior to
exposure of the sodium sulfate to air, stop the elution of the
hexane by closing the stopcock on the chromatography column.
Discard the eluate.
2. Adjust the sample extract volume to 10 ml and transfer it from
the K-D concentrator tube to the Florisil column. Rinse the
tube twice with 1-2 ml hexane, adding each rinse to the column.
3. Place a 500 ml K-D flask and clean concentrator tube under the
chromatography column. Drain the column Into the flask until
the sodium sulfate layer is nearly exposed. Elute the column
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Revision A 8/8/80 8.08-5
with 200 ml of 6% ethyl ether in hexane (Fraction 1) using a
drip rate of about 5 ml/min. Remove the K-D flask and set
aside for later concentration.
4. Elute the column again, using 200 ml of 15% ethyl ether in
hexane (Fraction 2), into a second K-D flask. Perform the
third elution using 200 ml of 50% ethyl ether/hexane (V/V).*
(Fraction 3). The elution patterns for the pesticides and
PCB's are shown in Table 8.08-2.
5. Concentrate the eluates by standard K-D techniques, substi-
tuting hexane for the glassware rinses and using the water
hath at about 85CC. Adjust final volume to 10 ml with hexane.
Analyze by gas chromatography.
6. Elemental sulfur will usually elute entirely in Fraction 1.
To remove sulfur interference from this fraction or the
original extract, pipet 1.00 ml of the concentrated extract
into a clean concentrator tube or Teflon-sealed vial. Add 1-3
drops of mercury and seal. Agitate the contents of the vial
for 15-30 seconds. Place the vial in an upright position on
a reciprocal laboratory shaker for 2 hours. Analyze by gas
chromatography.
Gas Chromatography
Table 8.08.1 summarizes some recommended gas chromatographic
column materials, operating conditions for the instrument, and
some estimated retention times. Examples of the separations
achieved by these columns are shown in Figures 8.08-1 through
* Change
-------
8.49-6
Method of Standard Additions
In this method, equal volumes of sample are added
to a delonized distilled water blank and to three stan-
dards containing different known amounts of the test
element. The final volume of the blank and of the stan-
dards must be the same so that the interfering substance
is present in the same amount. The absorbance of each
solution is determined and then plotted on the vertical
axis of a graph with the concentrations of the standard
plotted on the horizontal axis. When the resulting line
is extrapolated back to zero absorbance, the point of
interception of the abscissa is the concentration of the
unknown. The abscissa on the left of the ordinate is
scaled the same as on right side, but in the opposite
direction from the ordinate. An example of a plot so
obtained is shown below:
Zero
Absorbance ^X*
Lx^
1 Cone, of
Sample
9
O
c
A
h_
8
A
<
X"
/
^r
^*
.x*^
^^^
^/^
/
\
r i
, i
Concentration
i
Addn 0 Addn 1 Addn 2 Addn 5
No Addn Addn of 50% Addn of 100% Addn of 150%
of Expected of Expected of Expected
Amount Amount Amount
Figure 8.49-1
PLOT OF METHOD OF STANDARD ADDITIONS
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Revision A 8/8/80 8.49-
Note: For this method to be valid, the plot must be linear.
The slope of this line should not differ by more than 20%
from the slope of the standard solutions. The effect of the
assumed interference must not change as the proportion of
sample to standard changes.
Solids, Sludges and Slurries
Solids, sludges and slurries may be analyzed by these
methods by weighing out suitable portions and digesting as
described for each metal. The material is then filtered
through a 0.45 micron filter while washing down the sides of
the beaker and rinsing the filter with distilled deionlzed
water. The filtrate is then made up to a suitable volume
and analyzed in the ususal manner. Results can be related
back to the original sample weight and reported as mg/kg.
Samples Containing oils, greases, or waxes*
Samples of listed and non-listed wastes may contain sub-
stantial amounts of organic materials. These organics can be
in the form of oils, greases, or waxes. The general HN03 diges
tion, as given in this manual, will not be vigorous enough to
remove organics when analyzing for metals. In order to overcome
this deficiency, the metals analysis may be performed in
groups, whea organics are present.
The first group: (Direct Aspiration Method)
Ba, Cd, Cr, Pb, and Ag
The second group: (Wet Digestion Method)
AS, Hg, (Se), Cd, Cr, Ag, (Pb), and (Ba)
* Change # 15
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Revision A 8/8/80 8.49-E
Scope
Elements of the first group can be determined directly by
by dissolving the organic portion of the waste in an apporpriate
organic solvent and proceeding with atomic absorption using a
direct aspiration technique. To determine the elements of the
second group the waste is subjected to a wet digestion procedure,
followed by subsequent analysis as specified in this manual.
There is some overlap between these two groups of metals
and the analyst may chose either method for determining those
elements common to both groups.
To analyze for metals in oil, grease, or wax containing
wastes, the following methods apply:
I. Analysis of wastes containing oil, grease, or wax of the
== elemets ba, ca, cr, pt>, and Ag.
A. Reagents
1. Cyclohexane ultra high purity grade
2. Mthylisobutylketone
3. p-Xylene
B. Procedure
1. Weigh out a 100 gm representative sample of the waste
or extract. Separate the phases, if more than one
phase is present, and weigh eacn phase.
2. The metals in the organioc phase can be determined
by diluting with a solvent (specified in the reagents
section or other appropriate solvent) and preceding
with atomic absorption by direct aspiration as given
in this manual. Record metal concentrations taking
any dilutions into account.
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Revision A 8/8/80 8.49-°
3. Metals in the aqueous phase are determined by the pro-
cedures in this manual. (Sections 8.50 thru 8.60)
4. Report concentrations for the metals as the weighted
average for both the organic and aqueous phases.
II. Analysis of oil, grease or wax containing wastes for the
"e"Iemenfs~'A8';Hg, (Se)t C3T, Cr, Ag, (Pb), ana (Ba) ~~~
A. Reagents
1. Concentrated Nitric Acid ultra high purity
2. Concentrated Sulfuric Acid
3. Hydrogen Peroxide (30%)
4. Cnecentrated Hydrochloric Acid " "
B. Apparatus
Digestion flask, 250 ml flat bottom boiling flask with
S 24/40 joint, 300 mm Allihin condenser filled to 50 mm
with Rashing rings and glass beads, and heating mantle.
Kjeldahl flask 300 ml, ground glass stoppered.
C. Procedure
1. weigh out a 100 gm representative sample of the waste
or extract. Separate the phases, if more than one is
present, and weigh each phase.
2. Weigh 2.0 gms of the organic phase into the digestion
or Kjeldahl flask. Add 10 ml T^SO^ and a 6 mm glass
bead. Swirl flask to mix the contents.
3. If using a Kjeldahl flask approximately 3/4 of the neck
of the flask should be cooled by air by directing an
air stream against the neck of the flask. If using
the flask and condenser apparatus, connect the Allihin
condenser and circulate cooling water.
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Revision A 8/8/80 8.49-10
4. Heat flask gently and continue heating until dense
white fumes appear. While boiling, cousiously add
1 nl HN(>3 dropwise to oxidize the organic material.
This may be done through the condenser. When the
HN03 has boiled off and dense white fumes reappear
repeat the treatment with an additional 1 ml of HN(>3.
Continue the addition of HNOg in 1 ml inceraents
until the digestion, mixture is no darker than a
straw color, indicating that almost all the organic
matter has been oxidized.
5. Cool the flask slightly and add 0.5 ml (dropwise) of
H202- Heat until dense white fumes appear, and while
boiling coutlously add 1 ml of ENO^ dropwise. When the
HH03 has boiled off and dense white fumes reappear
repeat the treatment with H202 and HN03 until the
digestion mixture is colorless, at which time the
organic material will be completely oxidized. Four
treatments will usually suffice. The total amount of
H202 used should be noted.
6. When oxidation is complete, allow the flask to cool,
wash down the mouth, neck/condenser with a small
volume of distilled water (5 ml) and mix the contents.
Continue heating to the appearence of dense white
fumes•
7. Cool and dilute to a total volume of 25 ml. Precede
with determination of metals as given in this manual.
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Revision A 8/8/80 8.49-11
Note: If a percipitate forms add 2ml of concentrated HCL
before diluting to remove the precipitate. If
the precipitate pesists filter or centrifuge the
solution to remove the precipitate, and precede to
determine As, Se, Hg, Cr, and Cd. Ba, Pb, and Ag
may be determined either by the direct aspiration
method or by digestion of a smaller sample.
8. Metals in the aqueous phase, if an aqueous phase was
present, are determined by the procedures in this
manual, sections 8.50 thru 8.60.
9. Report concentration for metals as the weighted average
for both organic and aqueous phases.
Conclusion
The details of the following approved methods are examples
of acceptable techniques. Dilutions and concentrations may
have to be varied to suit the instrument being used. It is
important not to overwhelm the instrument with very high
concentrations above the optimum recommended range. Contami-
nation can result which is difficult to remove. At the same
time, many dilutions introduce error which can be avoided by
some knowledge of the waste beforehand. If nothing is known,
caution is advised.
For additional information the applicable sections of
"Methods for Chemical Analysis of Water and Wastes", EPA
600/4-79-020 (Appendix II of this manual) may be consulted.
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Revision A 8/8/80 8.60-7
Graphite Furnace*
Comment s:
1. It has been reported that the addition of cyanogen iodide
in this procedure does not Interfere in the silver
determination.
2. Samples should be analyzed immediately after collection.
Procedure
1. Standards are prepared by making dilutions to cover the
range 1 - 25ug Ag/llter as described in the direct
aspiration method.
2. Samples are prepared, standard additions made and analyses
are performed as in the direct aspiration method.
Instrument Operation
Wavelength: 328.1 nanometers
Optimum Concentration Range: 1-25 ug/liter.
Lower detection limit: 0.2 ug/liter
Purge gas: Argon
Drying time and temp: 30 sec - 125°C
Ashing time and temp: 30 sec - 400°C
Atomizing time and temp: 10 sec - 2700°C
The conditions listed above are based on a 20 ul
injection; continuous flow purge gas and non-pyrolytic
graphite on a Perkin Elmer model HGA 2100 furnace.
Other equipment will have different requirements. Follow
the manufacturer's manual.
* Change #12 ~~
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8.82-1
Method 8.82
BEADSPACE METHOD
Scope and Application
This method provides a procedure for the extraction of
volatile organic compounds In pastes and solids. The static
headspace technique is a simple method which allows large
numbers of samples to be analyzed in a relatively short period
of time. Because of the large variability and complicated
matrices of waste samples in the solid and paste forms,
detection limits for this method may vary widely among samples.
The method works best for compounds with boiling points less
than 125CC. Due to their low solubility, low molecular
weight compounds can or.ly be detected at high concentrations
or at reduced pressure.
The sensitivity of chis method will depend on the equili-
bria of the various compounds between the vapor and dissolved
phases .
Static Headspace Technique
Summary of Method
The waste is collected in sealed glass containers and
allowed to equilibrate at 90°C. A sample of the headspace
gas is withdrawn with a gas tight syringe for analysis by the
appropriate gas chromatographic method.
Apparatus
1. Gas-tight syringe - 5-cc.
2. Head space standard solutions - Prepare two standard solu-
tions of the compounds being determined at the 50-ng/ul and
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Revision A 8/R/80 8.82-2
250-ng/ul concentrations. Standard solutions should be prepared
using tnethanol, methane, or other appropriate solvent. The
standard solutions should be stored at less than 0°C, then
allowed to warn to room temperature before dosing. Fresh
standards should be prepared weekly. Procedures for preparing
standards are outlined in the Purge and Trap Procedure of this
manual (Method 8.83).
3. Vials, 125 ml "Hypo-Vials" (Pierce Chemical Co., #12995), or
equivalent.
4. Septa, "Tuf-Bond" (Pierce 012720), or equivalent.
5. Seals, aluminum, (Pierce #13214), or equivalent.
6. Crimper, hand, (Pierce #13212), or equivalent.
Procedure*
1. Place 10.0-g each of the well-mixed waste sample into three
separate 125-ml septum seal vials.
2. Dose one sample vial through the septum with 200-ul of the
50-ng/ul standard methanol solution. Label this 1 *ppm spike.
3. Dose a separate (empty) 125 ml septum seal vial with 200 ul of
the 50 ng/ul standard methanol solution. Label this 1 ppm standard.
4. Place the sample, 1 ppm spike, and the 1 ppm standard vials
into a 90°C water bath for 1 hour. Store the remaining sample
vial at 4.0°C for possible future analysis.
5. While maintaining the vials at 90°C withdraw 2 ml of the
headspace gas with a gas tight syringe and analyze by injecting
into a GC, operating under the appropriate conditions for the GC
measurement used. Analyze all three samples in exactly the same
manner.
* Change #13
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Revision A 8/8/80 8.82-!
6. Analyze the I ppm standard and adjust instrument sensitivi-
ty to give a responce of at least 2x the background. Record
retention time and peak area.
7. Analyze the 1 ppm spiked sample in the same manner. Record
RT and peak area.
8. Analyze the undosed sample as in item 7.
9. If a positive responce is noted for the undosed sample, then
the waste has not been demonstrated to be free of the
contaminat of interest and is thus not fundamentally different
than the listed waste. If no response is noted, reinject
the 1 ppm standard to verify the required sensitivity.
Note; Standard quality assurance protocols should be employed,
including blanks, duplicates, and dosed samples, as described
in Section 10.
Bibliography
1. "Interim Methods for the Sampling and Analyses of Priority
Pollutants In Sediments and Pish Tissue," U.S. Environmental
Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268 [19801.
2. "Master Scheme for the Analysis of Organic Compounds in
Water, Part I: State-of-the-Art Review of Analytical
Operations," U.S. Environmental Protection Agency,
Environmental Research Laboratory, Athens, Georgia 30605.
3. "An EPA Manual for Organic Analysis Using Gas Chromatography -
Mass Spectrometry," W.L. Budde and J.W. Eichelberger, U.S.
Environmental Protection Agency, Environmental Monitoring
Support Laboratory, Cincinnati, Ohio, 1979, EPA/600/8-79/006,
Order Number PB-297164.
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8.83-1
Method 8.83
PURGE AND TRAP METHOD
Scope and Application
This method covers a procedure for the extraction of pur-
geable organic compounds from aqueous liquids and free flowing
paste samples prior to gas chromatographlc analysis.
The success of the extraction depends on partitioning
the compounds between the sample phase and gaseous headspace
phases. This partitioning is a function of temperature,
interfacial area, the volatility of the species being analyzed
for, its solubility in the liquid being purged, and the
volatility of the waste matrix. For highly volatile matrices,
direct Injection preceded by dilution, if necessary, should be
used. For pastes, dilution of the sample until It becomes free
flowing is used to insure adequate interfacial area. The
success of this method also depends on the level of interferences
in the sample; results may vary due to the large variability
and complicated matri'ces of solid waste samples.
Summary of Method
An inert gas is bubbled through the sample contained in
a specially-designed purging chamber. This purging transfers
the volatile compounds from the liquid phase to the vapor
phase. The gaseous effluent is then swept through a short
sorbent tube where the organic compounds are trapped. After
purging is completed, the trap is heated and backflushed to
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Revision A 8/8/80 8.84-7
EXTRACTION CONDITIONS cont. (4)
Compound
Tetrachloroethene
Tetrachlorophenol
Toluene
Toluened iamine
Toluene diisocyanate( s )
Toxaphene
Trichloroethane
Trichloroethene(s)
Trichlorofluoromethane
Trichlorophenol(s)
2 ,4,5-TPCSilvex)
Trichloropropane
Vinyl chloride
Vinylidene chloride
1
Xylene
Extraction pH
NA
12
NA
> 11
NA*
5-9 or > 11
NA
NA
NA
12
<7 or > 11
NA
NA
NA
NA
Extraction
Solvent
NA
Methylene Chloride
NA
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
NA
NA
Methylene Chloride
Ethyl Ether or
Methylene Chloride
.NA
NA
NA
NA
* Change #
U.S Environmental Protoction Agency
Reason V, Library
230 South Dearborn Street
Chicago, Illinois 60604
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8.85-1
Method 8.85
SONICATION METHOD
Scope and Application
This method covers a procedure for the extraction of non-
volatile and semi-volatile organic compounds from solids. The
sonicatlon produces solid disruption to ensure Intimate contact
of the sample matrix with the extraction solvent.!
Summary of Method
A weighed- sample of the solid waste is ground, mixed with
the extraction medium, then dispersed into the solvent using
sonication. The resulting solution may then be cleaned up further
or analyzed directly using the appropriate technique (Methods
8.24 through 8.25).
Apparatus
1. Apparatus for Grinding.*t
The necessity for grinding and the choice of grinding
apparatus will depend on the physical and chemical charac-
teristics of the solid waste material in question. Any of
1 The high energy vibrations produced by this method may produce
artifacts and may drive off some semi-volatile compounds.
* Grinding is only necessary If the waste cannot either pass
through a 1-mm standard seive or be extracted through a 1-mm
diameter hole.
t Specific equipment listed in this method are for descriptive
purposes only. Equivalent equipment is available from other
manufactures and laboratory supply companies.
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