-------
3.1.4.2.3 Nitric Acid, 0.1 N. With stirring, add 6.3 ml of concen-
trated HN03 (70 percent) to a flask containing approximately 900 ml of water.
Dilute to 1000 ml with water. Mix well. The reagent shall contain less than
2 ng/ml of each target metal.
3.1.4.2.4 Hydrochloric Acid (HC1), 8 N. Make the desired volume of
8 N HC1 in the following proportions. Carefully with stirring, add 690 ml of
concentrated HC1 to a flask containing 250 ml of water. Dilute to 1000 ml
with water. Mix well. The reagent shall contain less than 2 ng/ml of Hg.
3.1.4.3 Glassware Cleaning Reagents.
3.1.4.3.1 Nitric Acid, Concentrated. Fisher ACS grade or equiva-
lent.
3.1.4.3.2 Water. To conform to ASTM Specifications D1193-77,
Type II.
3.1.4.3.3 Nitric Acid, 10 Percent (V/V). With stirring, add 500 ml
of concentrated HN03 to a flask containing approximately 4000 ml of water.
Dilute to 5000 ml with water. Mix well. Reagent shall contain less than 2
ng/ml of each target metal.
3.1.4.4 Sample Digestion and Analysis Reagents.
3.1.4.4.1 Hydrochloric Acid, Concentrated.
3.1.4.4.2 Hydrofluoric Acid, Concentrated.
3.1.4.4.3 Nitric Acid, Concentrated. Baker Instra-analyzed or
equivalent.
3.1.4.4.4 Nitric Acid, 50 Percent (V/V). With stirring, add 125 ml
of concentrated HN03 to 100 ml of water. Dilute to 250 ml with water. Mix
well. Reagent shall contain less than 2 ng/ml of each target metal.
3-14
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3.1.4.4.5 Nitric Acid. 5 Percent (V/V). With stirring, add 50 ml
of concentrated HN03 to 800 ml of water. Dilute to 1000 ml with water. Mix
well. Reagent shall contain less than 2 ng/ml of each target metal.
3.1.4.4.6 Water. To conform to ASTM Specifications D1193-77,
Type II.
3.1.4.4.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution.
See EPA Method 7470 for preparation.
3.1.4.4.8 Stannous Chloride. See Method 7470.
3.1.4.4.9 Potassium Permanganate, 5 Percent (W/V). See
Method 7470.
3.1.4.4.10 Sulfuric Acid, Concentrated.
3.1.4.4.11 Nitric Acid, 50 Percent (V/V).
3.1.4.4.12 Potassium Persulfate, 5 Percent (W/V). See Method 7470.
3.1.4.4.13 Nickel Nitrate, Ni(N03)2. 6H20.
3.1.4.4.14 Lanthanum, Oxide, La203.
3.1.4.4.15 AAS Grade Hg Standard, 1000 Mg/ml.
3.1.4.4.16 AAS Grade Pb Standard, 1000 pg/ml.
3.1.4.4.17 AAS Grade As Standard, 1000 jig/ml.
3.1.4.4.18 AAS Grade Cd Standard, 1000 pg/ml.
3.1.4.4.19 AAS Grade Cr Standard, 1000
3-15
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3.1.4.4.20 AAS Grade Sb Standard, 1000
3.1.4.4.21 AAS Grade Ba Standard, 1000 A»g/ml.
3.1.4.4.22 AAS Grade Be Standard, 1000
3.1.4.4.23 AAS Grade Cfj. Standard, 1000 jig/ml.
3.1.4.4.24 AAS Grade Mn Standard, 1000 ng/ml.
3.1.4.4.25 AAS Grade Ni Standard, 1000 /*g/ml.
3.1.4.4.26 AAS Grade P Standard, 1000 jig/ml.
3.1.4.4.27 AAS Grade Se Standard, 1000 jig/ml.
3.1.4.4.28 AAS Grade Ag Standard, 1000 Mg/ml.
3.1.4.4.29 AAS Grade Tl Standard, 1000 jig/ml.
3.1.4.4.30 AAS Grade Zn Standard, 1000 ^g/ml.
3.1.4.4.31 AAS Grade Al Standard, 1000 /ig/ml.
3.1.4.4.32 AAS Grade Fe Standard, 1000 jig/ml.
3.1.4.4.33 The metals standards may also be made from solid
chemicals as described in EPA Method 200.7. EPA SW-846 Method 7470 or
Standard Methods for the Analysis of Water and Wastewater. 15th Edition,
Method 303F should be referred to for additional information on mercury
standards.
3.1.4.4.34 Mercury Standards and Quality Control Samples. Prepare
fresh weekly a 10 /ig/ml intermediate mercury standard by adding 5 ml of 1000
/ig/ml mercury stock solution to a 500-ml volumetric flask; dilute with
3-16
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stirring to 500 ml by first carefully adding 20 ml of 15 percent HN03 and then
adding water to the 500-ml volume. Mix well. Prepare a 200 ng/ml working
mercury standard solution fresh daily: add 5 ml of the 10 jig/ml intermediate
standard to a 250-ml volumetric flask and dilute to 250 ml with 5 ml of 4
percent KMn04, 5 ml of 15 percent HN03, and then water. Mix well. At least
six separate aliquots of the working mercury standard solution should be used
to prepare the standard curve. These aliquots should contain 0.0, 1.0, 2.0,
3.0, 4.0, and 5.0 ml of the working standard solution containing 0, 200, 400,
600, 800, and 1000 ng mercury, respectively. Quality control samples should
be prepared by making a separate 10 pg/ml- standard and diluting until in the
range of the calibration.
3.1.4.4.35 ICAP Standards and Quality Control Samples. Calibration
standards for ICAP analysis can be combined into four different mixed standard
solutions as shown below.
MIXED STANDARD SOLUTIONS FOR ICAP ANALYSIS
Solution Elements
I As, Be, Cd, Mn, Pb, Se, Zn
II Ba, Cu, Fe
III Al, Cr, Ni
IV Ag, P, Sb, Tl
Prepare these standards by combining and diluting the appropriate volumes of
the 1000 /ig/ml solutions with 5 percent nitric acid. A minimum of one
standard and a blank can be used to form each calibration curve. However, a
separate quality control sample spiked with known amounts of the target metals
in quantities in the midrange of the calibration curve should be prepared.
Suggested standard levels are 25 ng/ml for Al, Cr, and Pb, 15 Mg/n»l for Fe,
and 10 Mg/ml for the remaining elements. Standards containing less than 1
jig/ml of metal should be prepared daily. Standards containing greater than 1
of metal should be stable for a minimum of 1 to 2 weeks .
3.1.4.4.36 Graphite Furnace AAS Standards. Antimony, arsenic,
cadmium, lead, selenium, and thallium. Prepare a 10 /*g/ml standard by adding
1 ml of 1000 Mg/ml standard to a 100-ml volumetric flask. Dilute with
stirring to 100 ml with 10 percent nitric acid. For graphite furnace AAS, the
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standards must be matrix matched. Prepare a 100 ng/ml standard by adding 1 ml
of the 10 A*g/ml standard to a 100-ml volumetric flask and dilute to 100 ml
with the appropriate matrix solution. Other standards should be prepared by
dilution of the 100 ng/ml standards. At least five standards should be used
to make up the standard curve. Suggested levels are 0, 10, 50, 75, and 100
ng/ml. Quality control samples should be prepared by making a separate 10
Mg/ml standard and diluting until it is in the range of the samples. Stan-
dards containing less than 1 pg/ml of metal should be prepared daily.
Standards containing greater than 1 Mg/ml of metal should be stable for a
minimum of 1 to .2 weeks*
3.1.4.4.37 Matrix Modifiers.
3.1.4.4.37.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of
Ni(N03)2 . 6H20 in approximately 50 ml of water in a 100-ml volumetric flask.
Dilute to 100 ml with water.
3.1.4.4.37.2 Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of
the 1 percent nickel nitrate solution from Section 4.4.37.1 above to 100 ml
with water. Inject an equal amount of sample and this modifier into the
graphite furnace during AAS analysis for As.
3.1.4.4.37.3 Lanthanum. Carefully dissolve 0.5864 g of La2°3 in 10
ml of concentrated HN03 and dilute the solution by adding it with stirring to
approximately 50 ml of water, and then dilute to 100 ml with water. Mix well.
Inject an equal amount of sample and this modifier into the graphite furnace
during AAS analysis for Pb.
3.1.5 Procedure
3.1.5.1 Sampling. The complexity of this method is such that, to
obtain reliable results, testers and analysts should be trained and experi-
enced with the test procedures, including source sampling, reagent preparation
and handling, sample handling, analytical calculations, reporting, and
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descriptions specifically at the beginning of and throughout Section 3.1.4 and
all other sections of this methodology.
3.1.5.1.1 Pretest Preparation. Follow the same general procedure
given in Method 5, Section 4.1.1, except that, unless particulate emissions
are to be determined, the filter need not be desiccated or weighed. All
sampling train glassware should first be rinsed with hot tap water and then
washed in hot soapy water. Next, glassware should be rinsed three times with
tap water, followed by three additional rinses with water. All glassware
should then be soaked in a 10 percent (V/V) nitric acid solution for a minimum
of 4 hours, rinsed three times with water, rinsed a final time with acetone,
and allowed to air dry. All glassware openings where contamination can occur
should be covered until the sampling train is assembled for sampling.
3.1.5.1.2 Preliminary Determinations. Same as Method 5, Section
4.1.2.
3.1.5.1.3 Preparation of Sampling Train. Follow the same general
procedures given in Method 5, Section 4.1.3, except place 100 ml of the nitric
acid/hydrogen peroxide solution (Section 3.1.4.2.1) in each of the two
HN03/H202 impingers as shown in Figure 3.1-1 (normally the second and third
impingers), place 100 ml of the acidic potassium permanganate absorbing
solution (Section 3.1.4.2.2) in each of the two permanganate impingers as
shown in Figure A-l, and transfer approximately 200 to 300 g of preweighed
silica gel from its container to the last impinger. Alternatively, the silica
gel may be weighed directly in the impinger just prior to train assembly.
Several options are available to the tester based on the sampling
requirements and conditions. The use of an empty first impinger can be
eliminated if the moisture to be collected in the impingers will be less than
approximately 100 ml. If necessary, use as applicable to this methodology the
procedure described in Section 7.1.1 of EPA Method 101A, 40 CFR Part 61,
Appendix B, to maintain the desired color in the last permanganate impinger.
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Retain for reagent blanks volumes of the nitric acid/hydrogen
peroxide solution per Section 3.1.5.2.9 of this method and of the acidic
potassium permanganate solution per Section 3.1.5.2.10. These reagent blanks
should be labeled and analyzed as described in Section 3.1.7. Set up the
sampling train as shown in Figure 3.1-1, or if mercury analysis is not to be
performed in the train, then it should be modified by removing the two
permanganate impingers and the impinger preceding the permanganate impingers.
If necessary to ensure leak-free sampling train connections and prevent
contamination Teflon tape or other non-contaminating material should be used
instead of silicone grease..
Precaution: Extreme care should be taken to prevent
contamination within the train. Prevent the mercury
collection reagent (acidic potassium permanganate) from
contacting any glassware of the train which is washed and
analyzed for Mn. Prevent hydrogen peroxide from mixing
with the acidic potassium permanganate.
Mercury emissions can be measured, alternatively, in a separate
train which measures only mercury emissions by using EPA Method 101A with the
modifications described below (and with the further modification that the
permanganate containers shall be processed as described in the Precaution in
Section 3.1.4.2.2 and the Note in Section 3.1.5.2.5 of this methodology).
This alternative method is applicable for measurement of mercury emissions,
and it may be of special interest to sources which must measure both mercury
and manganese emissions.
[Section 7.2.1 of Method 101A shall be modified as follows after the
250 to 400-ml KMn04 rinse:
To remove any precipitated material and any
residual brown deposits on the glassware follow-
ing the permanganate rinse, rinse with approxi-
mately 100 ml of deionized distilled water, and
add this water rinse carefully assuring transfer
3-20
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of all loose precipitated materials from the
three permanganate impingers into the permangan-
ate Container No. 1. If no visible deposits
remain after this water rinse, do not rinse with
8 N HC1. However, if deposits do remain on the
glassware after this water rinse, wash the
impinger surfaces with 25 ml of 8 N HC1, and
place the wash in a separate sample container
labeled Container No. l.A. containing 200 ml of
water as follows. Place 200 ml of water in a
sample container labeled Container No. l.A.
Wash the impinger walls and stem with the HC1 by
turning the impinger on its side and rotating it
so that the HC1 contacts all inside surfaces.
Use a total of only 25 ml of 8 N HC1 for rinsing
all permanganate impingers combined. Rinse the
first impinger, then pour the actual rinse used
for the first impinger into the second impinger
for its rinse, etc. Finally, pour the 25 ml of
8 N HC1 rinse carefully with stirring into Con-
tainer No. l.A. Analyze the HC1 rinse sepa-
rately by carefully diluting with stirring the
contents of Container No. l.A. to 500 ml with
deionized distilled water. Filter (if neces-
sary) through Whatman 40 filter paper, and then
analyze for mercury according to Section 7.4,
except limit the aliquot size to a maximum of
10 ml. Prepare and analyze a water diluted
blank 8 N HC1 sample by using the same procedure
as that used by Container No. l.A., except add 5
ml of 8 N HC1 with stirring to 40 ml of water,
and then dilute to 100 ml with water. Then
analyze as instructed for the sample from Con-
tainer No. l.A. Because the previous separate
permanganate solution rinse (Section 7.2.1) and
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water rinse (as modified in these guidelines)
have the capability to recover a very high per-
centage of the mercury from the permanganate
impingers, the amount of mercury in the HC1
rinse in Container No. l.A. may be very small,
possibly even insignificantly small. However,
add the total of any mercury analyzed and calcu-
lated for the HC1 rinse sample Container No.
l.A. to that calculated from the mercury sample
from Section,7.3.2..which-contains • the- separate
permanganate rinse (and water rinse as modified
herein) for calculation of the total sample
mercury concentration.
3.1.5.1.4 Leak-Check Procedures. Follow the leak-check procedures
given in Method 5, Section 4.1.4.1 (Pretest Leak-Check), Section 4.1.4.2
(Leak-Checks During the Sample Run), and Section 4.1.4.3 (Post-Test Leak-
Checks) .
3.1.5.1.5 Sampling Train Operation. Follow the procedures given in
Method 5, Section 4.1.5. For each run, record the data required on a data
sheet such as the one shown in Figure 5-2 of Method 5.
3.1.5.1.6 Calculation of Percent Isokinetic. Same as Method 5,
Section 4.1.6.
3.1.5.2 Sample Recovery. Begin cleanup procedures as soon as the
probe is removed from the stack at the end of a sampling period.
The probe should be allowed to cool prior to sample recovery. When
it can be safely handled, wipe off all external particulate matter near the
tip of the probe nozzle and place a rinsed, non-contaminating cap over the
probe nozzle to prevent losing or gaining particulate matter. Do not cap the
probe tip tightly while the sampling train is cooling. This normally causes a
3-22
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vacuum to form in the filter holder, thus causing the undesired result of
drawing liquid from the impingers into the filter.
Before moving the sampling train to the cleanup site, remove the
probe from the sampling train and cap the open outlet. Be careful not to lose
any condensate that might be present. Cap the filter inlet where the probe
was fastened. Remove the umbilical cord from the last impinger and cap the
impinger. Cap off the filter holder outlet and impinger inlet. Use non-
contaminating caps, whether ground-glass stoppers, plastic caps, serum caps,
or Teflon .tape .to .close..these .openings.
Alternatively, the train can be disassembled before the probe and
filter holder/oven are completely cooled, if this procedure is followed:
Initially disconnect the filter holder outlet/impinger inlet and loosely cap
the open ends. Then disconnect the probe from the filter holder or cyclone
inlet and loosely cap the open ends. Cap the probe tip and remove the
umbilical cord as previously described.
Transfer the probe and filter-impinger assembly to a cleanup area
that is clean and protected from the wind and other potential causes of
contamination or loss of sample. Inspect the train before and during disas-
sembly and note any abnormal conditions. The sample is recovered and treated
as follows (see schematic in Figure 3.1-2). Ensure that all items necessary
for recovery of the sample do not contaminate it.
3.1.5.2.1 Container No. 1 (Filter). Carefully remove the filter
from the filter holder and place it in its identified petri dish container.
Acid-washed polypropylene or Teflon coated tweezers or clean, disposable
surgical gloves rinsed with water and dried should be used to handle the
filters. If it is necessary to fold the filter, make certain the particulate
cake is inside the fold. Carefully transfer the filter and any particulate
matter or filter fibers that adhere to the filter holder gasket to the petri
dish by using a dry (acid-cleaned) nylon bristle brush. Do not use any metal-
containing materials when recovering this train. Seal the labeled petri dish.
3-23
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PiotwLinw
Rinse win
•MtOM
BnMhlMf
Front Hal ol
FMsr Housing
Brush «Mi
nonmstattc brush
FAac Support
•ndBMklWI
(Empty*
O^f HNIIOQ
oltosl)
2nd A 3rd
lmpng«n
(Empty) «Mi
(AddNwtKMnOj)
OJ
I
ro
brush and
wtmacstoM
Chock knar to SM
Hpsrttauujftt
rwnovod: If not.
rops*l stop above
Iram support
OOflfttd IMM2SM
•Adptanbi
OINnMricwU
OINnMcadd
IN
Empty «w
contonls
Empty «w
oontflnts Into
UsllmpkigM
Wwghlor
moMura
contents
I I
Empty to Empty to
knpingsfNo.4 hnpingsn
contents Into Nos. SAe
oonloMslnto
OINnMcodd
(MNnMcadd
100 mL
0.1NHNO3
FH
AR f
(2) 0)
BH
(4)
0 IN HN03
(SA)
• Number In parantosss Mfc
•r numbM
4305 9/90
Figure 3.1-2 Sample recovery scheme.
-------
3.1.5.2.2 Container No. 2 (Acetone Rinse). NOTE: Perform Section
3.1.5.2.2 only if determination of particulate emissions are desired in
addition to metals emissions. If only metals emissions are desired, skip
Section 3.1.5.2.2 and go to Section 3.1.5.2.3. Taking care to see that dust
on the outside of the probe or other exterior surfaces does not get into the
sample, quantitatively recover particulate matter and any condensate from the
probe nozzle, probe fitting (plastic such as Teflon, polypropylene, etc.
fittings are recommended to prevent contamination by metal fittings; further,
if desired, a single glass piece consisting of a combined probe tip and probe
liner may be used., but such a-single glass-piece is not a requirement of this
methodology), probe liner, and front half of the filter holder by washing
these components with 100 ml of acetone and placing the wash in a glass
container. Note: The use of exactly 100 ml is necessary for the subsequent
blank correction procedures. Distilled water may be used instead of acetone
when approved by the Administrator and shall be used when specified by the
Administrator; in these cases, save a water blank and follow the
Administrator's directions on analysis. Perform the acetone rinses as
follows: Carefully remove the probe nozzle and clean the inside surface by
rinsing with acetone from a wash bottle and brushing with a nonmetallic brush.
Brush until the acetone rinse shows no visible particles, after which make a
final rinse of the inside surface with acetone.
Brush and rinse the sample-exposed, inside parts of the fitting with
acetone in a similar way until no visible particles remain.
Rinse the probe liner with acetone by tilting and rotating the probe
while squirting acetone into its upper end so that all inside surfaces will be
wetted with acetone. Allow the acetone to drain from the lower end into the
sample container. A funnel may be used to aid in transferring liquid washings
to the container. Follow the acetone rinse with a nonmetallic probe brush.
Hold the probe in an inclined position, squirt acetone into the upper end as
the probe brush is being pushed with a twisting action through the probe; hold
a sample container underneath the lower end of the probe, and catch any
acetone and particulate matter which is brushed through the probe three times
or more until none remains in the probe liner on visual inspection. Rinse the
3-25
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brush with acetone, and quantitatively collect these washings in the sample
container. After the brushing, make a final acetone rinse of the probe as
described above.
It is recommended that two people clean the probe to minimize sample
losses. Between sampling runs, keep brushes clean and protected from contami-
nation.
Clean the inside of the front half of the filter holder by rubbing
the surfaces with a nonmetallic nylon bristle brush and rinsing with acetone.
Rinse each surface three times or more if needed to remove visible particu-
late. Make a final rinse of the brush and filter holder. After all acetone
washings and particulate matter have been collected in the sample container,
tighten the lid on the sample container so that acetone will not leak out when
it is shipped to the laboratory. Mark the height of the fluid level to
determine whether or not leakage occurred during transport. Label the
container clearly to identify its contents.
3.1.5.2.3 Container No. 3 (Probe Rinse). Keep the probe assembly
clean and free from contamination as described in Section 3.1.5.2.2 of this
method during the 0.1 N nitric acid rinse described below. Rinse the probe
nozzle and fitting probe liner, and front half of the filter holder thoroughly
with 100 ml of 0.1 N nitric acid and place the wash into a sample storage
container. Note: The use of exactly 100 ml is necessary for the subsequent
blank correction procedures. Perform the rinses as applicable and generally
as described in Method 12, Section 5.2.2. Record the volume of the combined
rinse. Mark the height of the fluid level on the outside of the storage
container and use this mark to determine if leakage occurs during transport.
Seal the container and clearly label the contents. Finally, rinse the nozzle,
probe liner, and front half of the filter holder with water followed by
acetone and discard these rinses.
3.1.5.2.4 Container No. 4 (Impingers 1 through 3, HN03/H202
Impingers and Moisture Knockout Impinger, when used, Contents and Rinses).
Due to the potentially large quantity of liquid involved, the tester may place
3-26
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the impinger solutions from impingers 1 through 3 in more than one container.
Measure the liquid in the first three impingers volumetrically to within 0.5
ml using a graduated cylinder. Record the volume of liquid present. This
information is required to calculate the moisture content of the sampled flue
gas. Clean each of the first three impingers, the filter support, the back
half of the filter housing, and connecting glassware by thoroughly rinsing
with 100 ml of 0.1 N nitric acid using the procedure as applicable and
generally as described in Method 12, Section 5.2.4. Note: The use of exactly
100 ml of 0.1 N nitric acid rinse is necessary for the subsequent blank
correction procedures. Combine the rinses, and impinger solutions, measure and
record the volume. Mark the height of the fluid level on the outside of the
container to determine if leakage occurs during transport. Seal the container
and clearly label the contents.
3.1.5.2.5 Container Nos. 5A, 5B, and 5C. 5A (0.1 N HN03) , 5B
(KMn04/ H2S04 absorbing solution), and 5C (8 N HC1 rinse and dilution). (As
described previously at the end of Section 3.1.3.1.5 of this method, if
mercury is not being measured in this train, then impingers 4, 5, and 6, as
shown in Figure A-l, are not necessary and may be eliminated.) Pour all the
liquid, if any, from the impinger which was empty at the start of the run and
which immediately precedes the two permanganate impingers (normally impinger
No. 4) into a graduated cylinder and measure the volume to within 0.5 ml.
This information is required to calculate the moisture content of the sampled
flue gas. Place the liquid in Sample Container No. 5A. Rinse the impinger
(No. 4) with 100 ml of 0.1 N HN03 and place this into Container No. 5A.
Pour all the liquid from the two permanganate impingers into a
graduated cylinder and measure the volume to within 0.5 ml. This information
is required to calculate the moisture content of the sampled flue gas. Place
this KMnOA absorbing solution stack sample from the two permanganate impingers
into Container No. 5B. Using 100 ml total of fresh acidified potassium
permanganate solution, rinse the two permanganate impingers and connecting
glass pieces a minimum of three times and place the rinses into Container No.
5B, carefully ensuring transfer of all loose precipitated materials from the
two impingers into Container No. 5B. Using 100 ml total of water, rinse the
3-27
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permanganate impingers and connecting glass pieces a minimum of three times,
and place the rinses into Container 5B, carefully ensuring transfer of all
loose precipitated material, if any, from the two impingers into Container No.
5B. Mark the height of the fluid level on the outside of the bottle to
determine if leakage occurs during transport. See the following note and the
Precaution in Paragraph 3.1.4.2.2 and properly prepare the bottle and clearly
label the contents.
Note: Due to the potential reaction of the potassium
permanganate with the acid, there may be pressure buildup
in the sample storage bottles. These bottles shall not be
completely filled and shall be vented to relieve potential
excess pressure. Venting is required. A No. 70-72 hole
drilled in the container cap and Teflon liner has been
used.
If no visible deposits remain after the above described water rinse,
do not rinse with 8 N HC1. However, if deposits do remain on the glassware
after this water rinse, wash the impinger surfaces with 25 ml of 8 N HC1, and
place the wash in a separate sample container labeled Container No. 5C
containing 200 ml of water as follows: Place 200 ml of water in a sample
container labeled Container No. 5C. Wash the impinger walls and stem with the
HC1 by turning the impinger on its side and rotating it so that the HC1
contacts all inside surfaces. Use a total of only 25 ml of 8 N HC1 for
rinsing both permanganate impingers combined. Rinse the first impinger, then
pour the actual rinse used for the first impinger into the second impinger for
its rinse. Finally, pour the 25 ml of 8 N HC1 rinse carefully with stirring
into Container No. 5C. Mark the height of the fluid level on the outside of
the bottle to determine if leakage occurs during transport.
3.1.5.2.6 Container No. 6 (Silica Gel). Note the color of the
indicating silica gel to determine whether it has been completely spent and
make a notation of its condition. Transfer the silica gel from its impinger
to its original container and seal. The tester may use a funnel to pour the
silica gel and a rubber policeman to remove the silica gel from the impinger.
3-28
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The small amount of particles that may adhere to the impinger wall need not be
removed. Do not use water or other liquids to transfer the silica gel since
weight gained in the silica gel impinger is used for moisture calculations.
Alternatively, if a balance is available in the field, record the weight of
the spent silica gel (or silica gel plus impinger) to the nearest 0.5 g.
3.1.5.2.7 Container No. 7 (Acetone Blank). If particulate emis-
sions are to be determined, at least once during each field test, place a 100-
ml portion of the acetone used in the sample recovery process into a labeled
container for use in the front-half field reagent blank. Seal the container.
3.1.5.2.8 Container No. 8A (0.1 N Nitric Acid Blank). At least
once during each field test, place 300 ml of the 0.1 N nitric acid solution
used in the sample recovery process into a labeled container for use in the
front-half and back-half field reagent blanks. Seal the container. Container
No. 8B (water blank). At least once during each field test, place 100 ml of
the water used in the sample recovery process into a labeled Container No. 8B.
Seal the container.
3.1.5.2.9 Container No. 9 (5% Nitric Acid/10% Hydrogen Peroxide
Blank). At least once during each field test, place 200 ml of the 5% nitric
acid/10% hydrogen peroxide solution used as the nitric acid impinger reagent
into a labeled container for use in the back-half field reagent blank. Seal
the container.
3.1.5.2.10 Container No. 10 (Acidified Potassium Permanganate
Blank). At least once during each field test, place 100 ml of the acidified
potassium permanganate solution used as the impinger solution and in the
sample recovery process into a labeled container for use in the back-half
field reagent blank for mercury analysis. Prepare the container as described
in Section 3.1.5.2.5.
Note: Due to the potential reaction of the potassium
permanganate with the acid, there may be pressure buildup
in the sample storage bottles. These bottles shall not be
3-29
-------
completely filled and shall be vented to relieve potential
excess pressure. Venting is required. A No. 70-72 hole
drilled in the container cap and Teflon liner has been
used.
3.1.5.2.11 Container No. 11 (8 N HC1 Blank). At least once during
each field test, perform both of the following: Place 200 ml of water into a
sample container. Pour 25 ml of 8 N HC1 carefully with stirring into the 200
ml of water in the container. Mix well and seal the container.
3.1.5.2.12 Container No. 12 (Filter Blank). Once during each field
test, place three unused blank filters from the same lot as the sampling
filters in a labeled petri dish. Seal the petri dish. These will be used in
the front-half field reagent blank.
3.1.5.3 Sample Preparation. Note the level of the liquid in each
of the containers and determine if any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the final
results. A diagram illustrating sample preparation and analysis procedures
for each of the sample train components is shown in Figure 3.1-3.
3.1.5.3.1 Container No. 1 (Filter). If particulate emissions are
being determined, then desiccate the filter and filter catch without added
heat and weigh to a constant weight as described in Section 4.3 of Method 5.
For analysis of metals, divide the filter with its filter catch into portions
containing approximately 0.5 g each and place into the analyst's choice of
either individual microwave pressure relief vessels or Parr* Bombs. Add 6 ml
of concentrated nitric acid and 4 ml of concentrated hydrofluoric acid to each
vessel. For microwave heating, microwave the sample vessels for approximately
12-15 minutes in intervals of 1 to 2 minutes at 600 Watts. For conventional
heating, heat the Parr Bombs at 140°C (285°F) for 6 hours. Cool the samples
to room temperature and combine with the acid digested probe rinse as required
in Section 3.1.5.3.3, below.
3-30
-------
Container 3
Acid Probe Rmse
(Labeled FH)
I
to
Container 2
Acetone Probe Rinse
(Labeled AR)
Container 1
filler
(Labeled F)
Container 4
(HNOa/ HaOa) bnpingars
(Labeled BH)
impinger. 4 used)
Containers SA. SB. A 5C
Reduce to dryness
in a tared
Determine residue
weigh! in beaker
Solubize residue
wish cone.
constant weight
_L
Determine Mar
partculete weight
AcirJtytopH2
wit) cone HN03
Aliquot taken
torCVAAS
tor Hg analysis
Fraction 2B
Digeslwittaad
and analyze
torHgbyCVAAS
1
Acidify
remaining
uunptetopH2
wMtconc HNOj
FracaonZA
J.
Reduce volume
to near dryness
and digest win
Divide intoOSg
sections and olgest
each section with
cone. HFandHNOs
Reduce volume to
near dryness and
dgeslwMiHF
and cone.
L
I
InrJvidualy. ttree
separate digestions
and analyses:
digect with acid
and permanganate
at96*Ctor2h
and analyze
torHgbyCVAAS
Fracaons 3A. 38. 3C
Analyze
by (CAP far
1
Analyze by
GFAAS
tor metals1
Filar and dim*
to known volume
ton i
1
1
•
Remove 50 to 100 mL
atiquoitorHg
analysis by CVAAS
Fraction IB
Digest well acid and
pwinanganale at 96*C in
a water bam tor 2 h
i
AnaVzebylCAPIor
target metats
Fraction 1A
Analyze tor
metals by GFAAS1
Fraction 1A
Analyze ahquol tor
Hg using CVAAS
1
Analysis by AAS tor metals found at less turn 2 ug/mL in rJgestato sokKon. if desired Or analyze tor each metal by AAS. if desired.
4305 9/90
Figure 3.1-3 Sample preparation and analysis scheme.
-------
Notes: 1. Suggested microwave heating times are approximate and are
dependent upon the number of samples being digested. Twelve to
15 minute heating times have been found to be acceptable for
simultaneous digestion of up to 12 individual samples. Suffi-
cient heating is evidenced by sorbent reflux within the vessel.
2. If the sampling train uses an optional cyclone, the cyclone
catch should be prepared and digested using the same procedures
described for the filters and combined with the digested filter
samples.
3.1.5.3.2 Container No. 2 (Acetone Rinse). Note the level of
liquid in the container and confirm on the analysis sheet whether leakage
occurred during transport. If a noticeable amount of leakage has occurred,
either void the sample or use methods, subject to the approval of the Adminis-
trator, to correct the final results. Measure the liquid in this container
either volumetrically to ±1 ml or gravimetrically to ±0.5 g. Transfer the
contents to an acid-cleaned, tared 250-ml beaker and evaporate to dryness at
ambient temperature and pressure. If particulate emissions are being deter-
mined, desiccate for 24 hours without added heat, weigh to a constant weight
according to the procedures described in Section 4.3 of Method 5, and report
the results to the nearest 0.1 mg. Redissolve the residue with 10 ml of
concentrated nitric acid and, carefully with stirring, quantitatively combine
the resultant sample including all liquid and any particulate matter with
Container No. 3 prior to beginning the following Section 3.1.5.3.3.
3.1.5.3.3 Container No. 3 (Probe Rinse). The pH of this sample
shall be 2 or lower. If the pH is higher, the sample should be acidified to
pH 2 by the careful addition with stirring of concentrated nitric acid. The
sample should be rinsed into a beaker with water and the beaker should be
covered with a ribbed watchglass. The sample volume should be reduced to
approximately 20 ml by heating on a hot plate at a temperature just below
boiling. Digest the sample in microwave vessels or Parr* Bombs by quantita-
tively transferring the sample to the vessel or bomb, by carefully adding the
6 ml of concentrated nitric acid and 4 ml of concentrated hydrofluoric acid
3-32
-------
and then continuing to follow the procedures described in Section 3.1.5.3.1;
then combine the resultant sample directly with the acid digested portions of
the filter prepared previously in Section 3.1.5.3.1. The resultant combined
sample is referred to as Fraction 1 precursor. Filter the combined solution
of the acid digested filter and probe rinse samples using Whatman 541 filter
paper. Dilute to 300 ml (or the appropriate volume for the expected metals
concentration) with water. This dilution is Fraction 1. Measure and record
the volume of the Fraction 1 solution to within 0.1 ml. Quantitatively remove
a 50-ml aliquot and label as Fraction IB. Label the remaining 250-ml portion
as Fraction 1A. Fraction 1A is used for ICAP or AAS analysis. Fraction IB is
used for the determination of front-half mercury.
3.1.5.3.4 Container No. 4 (Impingers 1-3). Measure and record the
total volume of this sample (Fraction 2) to within 0.5 ml. Remove a 75- to
100-ml aliquot for mercury analysis and label as Fraction 2B. Label the
remaining portion of Container No. 4 as aliquot Fraction 2A. Aliquot Fraction
2A defines the volume of 2A prior to digestion. All of the aliquot Fraction
2A is digested to produce concentrated Fraction 2A. Concentrated Fraction 2A
defines the volume of 2A after digestion which is normally 150 ml. Only
concentrated Fraction 2A is analyzed for metals (except that it is not
analyzed for mercury). The Fraction 2B aliquot should be prepared and
analyzed for mercury as described in Section 3.1.5.4.3. Aliquot Fraction 2A
shall be pH 2 or lower. If necessary, use concentrated nitric acid, by
careful addition and stirring, to lower aliquot Fraction 2A to pH 2. The
sample should be rinsed into a beaker with water and the beaker should be
covered with a ribbed watchglass. The sample volume should be reduced to
approximately 20 ml by heating on a hot plate at a temperature just below
boiling. Next follow either the conventional or microwave digestion proce-
dures described in Sections 3.1.5.3.4.1 and 3.1.5.3.4.2, below.
3.1.5.3.4.1 Conventional Digestion Procedure. Add 30 ml of 50
percent nitric acid and heat for 30 minutes on a hot plate to just below
boiling. Add 10 ml of 3 percent hydrogen peroxide and heat for 20 more
minutes. Add 50 ml of hot water and heat the sample for an additional 20
minutes. Cool, filter the sample, and dilute to 150 ml (or the appropriate
3-33
-------
volume for the expected metals concentrations) with water. This dilution is
concentrated Fraction 2A. Measure and record the volume of the Fraction 2A
solution to within 0.1 ml.
3.1.5.3.4.2 Microwave Digestion Procedure. Add 10 ml of 50 percent
nitric acid and heat for 6 minutes in intervals of 1 to 2 minutes at 600
Watts. Allow the sample to cool. Add 10 ml of 3 percent hydrogen peroxide
and heat for 2 more minutes. Add 50 ml of hot water and heat for an addition-
al 5 minutes. Cool, filter the sample, and dilute to 150 ml (or the appropri-
ate volume for the -expected metals concentrations) with water. This dilution
is concentrated Fraction 2A. Measure and record the volume of the Fraction 2A
solution to within 0.1 ml.
Note: All microwave heating times given are approximate
and are dependent upon the number of samples being digest-
ed at a time. Heating times as given above have been
found acceptable for simultaneous digestion of up to 12
individual samples. Sufficient heating is evidenced by
solvent reflux within the vessel.
3.1.5.3.5 Container Nos. 5A, 5B, and 5C (Impingers 4, 5, and 6).
Keep these samples separate from each other and measure and record the volumes
of 5A and 5B separately to within 0.5 ml. Dilute sample 5C to 500 ml with
water. These samples 5A, 5B, and 5C are referred to respectively as Fractions
3A, 3B, and 3C. Follow the analysis procedures described in Section
3.1.5.4.3.
Because the permanganate rinse and water rinse have the capability
to recover a high percentage of the mercury from the permanganate impingers,
the amount of mercury in the HC1 rinse (Fraction 3C) may be very small,
possibly even insignificantly small. However, as instructed in this method,
add the total of any mercury measured in and calculated for the HC1 rinse
(Fraction 3C) to that for Fractions IB, 2B, 3A, and 3B for calculation of the
total sample mercury concentration.
3-34
-------
3.1.5.3.6 Container No. 6 (Silica Gel). Weigh the spent silica gel
(or silica gel plus impinger) to the nearest 0.5 g using a balance. (This
step may be conducted in the field.)
3.1.5.4 Sample Analysis. For each sampling train, seven individual
samples are generated for analysis. A schematic identifying each sample and
the prescribed sample preparation and analysis scheme is shown in Figure
3.1-3. The first two samples, labeled Fractions 1A and IB, consist of the
digested, samples from the front half of the train. Fraction 1A is for ICAP or
AAS analysis as described in Sections 3.1.5.4.1 and/or 3.1.5.4.2. Fraction IB
is for determination of front-half mercury as described in Section 3.1.5.4.3.
The back half of the train was used to prepare the third through
seventh samples. The third and fourth samples, labeled Fractions 2A and 2B,
contain the digested samples from the moisture knockout, if used, and
HN03/H202 Impingers 1 through 3. Fraction 2A is for ICAP or AAS analysis.
Fraction 2B will be analyzed for mercury.
The fifth through seventh samples, labeled Fractions 3A, 3B, and 3C,
consist of the impinger contents and rinses from the empty and permanganate
implngers 4, 5, and 6. These samples are analyzed for mercury as described in
Section 3.1.5.4.3. The total back-half mercury catch is determined from the
sum of Fraction 2B and Fractions 3A, 3B, and 3C.
3.1.5.4.1 ICAP Analysis. Fraction 1A and Fraction 2A are analyzed
by ICAP using EPA SW-846 Method 6010 or Method 200.7 (40 CFR 136, Appendix C).
Calibrate the ICAP, and set up an analysis program as described in Method 6010
or Method 200.7. The quality control procedures described in Section
3.1.7.3.1 of this method shall be followed. Recommended wavelengths for use
in the analysis are listed below:
3-35
-------
Element Wavelength (rmO
Aluminum 308.215
Antimony 206.833
Arsenic 193.696
Barium 455.403
Beryllium 313.042
Cadmium 226.502
Chromium 267.716
Copper 324.754
Iron 259.940
Lead 220.353
Manganese 257.610
Nickel 231.604
Phosphorus 214.914
Selenium 196.026
Silver 328.068
Thallium 190.864
Zinc 213.856
The 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.
Initially, analyze all samples for the desired target metals (except
mercury) plus iron and aluminum. If iron and aluminum are present in the
sample, the sample may have to be diluted so that each of these elements is at
a concentration of less than 50 ppm to reduce their spectral interferences on
arsenic, cadmium, chromium, and lead.
Note: When analyzing samples in a hydrofluoric acid
matrix, an alumina torch should be used; since all front-
half samples will contain hydrofluoric acid, use an alumi-
na torch.
3.1.5.4.2 AAS by Direct Aspiration and/or Graphite Furnace. If
analysis of metals in Fraction 1A and Fraction 2A using graphite furnace or
direct aspiration AAS is desired, Table 3.1-2 should be used to determine
3-36
-------
Table 3.1-2
APPLICABLE TECHNIQUES, METHODS, AND MINIMIZATION OF INTERFERENCE FOR AAS ANALYSIS
Metal
Sb
Sb
As
Ba
Be
Be
Cd
Cd
Cr
Cr
Cu
Technique
Aspiration
Furnace
Furnace
Aspiration
Aspiration
Furnace
Aspiration
Furnace
Aspiration
•
Furnace
Aspiration
SW-846
Method No.
7040
7041
7060
7080
7090
7091
7130
7131
7190
7191
7210
Wavelength
(nm)
217.6
217.6
193.7
553.6
234.9
234.9
228.8
228.8
357.9
357.9
324.7
Interferences
Cause Minimization
1000 mg/mL Pb
Ni, Cu, or acid
High Pb
Arsenic volatization
Aluminum
Calcium
•-i
Barium ionization
500 ppm Al
High Mg and Si
Be in optical path
Absorption and light
scattering
As above
Excess chloride
Pipet tips
Alkali metal
Absorption and
scatter
200 mg/L Ca
and P
Absorption and
scatter
Use secondary wavelength of 231.1 nm;
match sample & standards' acid concentra-
tion or use nitrous oxide/acetylene flame
Secondary wavelength or Zeeman correction
Spiked samples and add nickel nitrate so-
lution to
digestates prior to analysis
Use Zeeman background correction
High hollow cathode current and narrow
band set
2 mL of KC1 per 100 mL of sample
Add 0.1% fluoride
Use method of standard additions
Optimize parameters to minimize effects
Background correction is required
As above
Ammonium phosphate used as a matrix
modifier
Use cadmium- free tips
KC1 ionization suppressant in samples
and standards
Consult manufacturer's literature
All calcium nitrate for a known
constant effect and to eliminate
effect of phosphate
Consult manufacturer's manual
U)
I
(continued)
-------
Table 3.1-2
APPLICABLE TECHNIQUES, METHODS, AND MINIMIZATION OF INTERFERENCE FOR AAS ANALYSIS
u>
1
U)
oo
Metal
Fe
Pb
Pb
Mn
Ni
Se
Ag
Tl
Tl
Zn
Technique
Aspiration
Aspiration
Furnace
Aspiration
Aspiration
Furnace
Aspiration
Aspiration
Furnace
Aspiration
SU-846
Method No.
7380
7420
7421
7460
7520
7740
7760
7840
7841
7950
Wavelength
(nm)
248.3
283.3
283.3
279.5
232.0
196.0
328.1
276.8
276.8
213.9
Interferences
Cause Minimization
Contamination
217.0 nm alternate
Poor recoveries
403.1 nm alternate
352.4 nm alternate
Fe, Co, and Cr
Nonlinear response
Volatility
Adsorption & scatter
Adsorption & scatter
AgCl insolube
Viscosity
Hydrochloric acid
or chloride
High Si, Cu, & P
Contamination
Great care taken to avoid contamination
Background correction required
Matrix modifier, add 10 uL of phosphorus
acid to 1 mL of prepared sample in
sampler cup
Background correction required
Background correction required
Matrix matching or nitrous -oxide/
acetylene flame
Sample dilution or use 352.3 nm line
Spike samples and reference materials and
add nickel nitrate to minimize
volatilization
Background correction is required and
Zeeman background correction can be useful
Background correction is required
Avoid hydrochloric acid unless silver is
in solution as a chloride complex
Sample and standards monitored for
aspiration rate
Background correction is required
Hydro
-------
which techniques and methods should be applied for each target metal. Table
3.1-2 should also be consulted to determine possible interferences and tech-
niques to be followed for their minimization. Calibrate the instrument
according to Section 3.1.6.3 and follow the quality control procedures
specified in Section 3.1.7.3.2.
3.1.5.4.3 Cold Vapor AAS Mercury Analysis. Fraction IB, Fraction
2B, and Fractions 3A, 3B, and 3C should be analyzed separately for mercury
using cold vapor atomic absorption spectroscopy following the method outlined
in EPA SW-846 Method 7470 or in Standard Methods for Water and Wastewater
Analysis. 15th Edition, Method 303F. Set up the calibration curve (zero to
1000 ng) as described in Si?-846 Method 7470 or similar to Method 303F, using
300-ml BOD bottles instead of Erlenmeyers. Dilute separately, as described
below, a 1 ml to 10 ml aliquot of each original sample to 100 ml with water.
Record the amount of the aliquot used for dilution to 100 ml. If no prior
knowledge exists of the expected amount of mercury in the sample, a 5-ml
aliquot is suggested for the first dilution to 100 ml and analysis. To
determine the stack emission value for mercury, the amount of the aliquot of
the sample used for dilution and analysis is dependent on the amount of
mercury in the aliquot: the total amount of mercury in the aliquot used for
analysis shall be less than 1 /jg, and within the range (zero to 1000 ng) of
the calibration curve. Place each sample aliquot into a separate 300-ml BOD
bottle and add enough Type II water to make a total volume of 100 ml. Then
analyze the 100 ml for mercury by adding to it sequentially the sample
preparation solutions and performing the sample preparation and analysis as
described in the procedures of SW-846 Method 7470 or Method 303F. If, during
the described analysis, the reading maximum(s) are off-scale (because the
aliquot of the original sample analyzed contained more mercury than the
maximum of the calibration range) including the analysis of the 100-ml
dilution of the 1-ml aliquot of the original sample causing a reading maximum
which is off-scale, then perform the following: dilute the original sample
(or a portion of it) with 0.15% HN03 in water (1.5 ml concentrated HN03 per
liter aqueous solution) so that when a 1-ml to 10-ml aliquot of the dilution
of the original sample is then further diluted to 100 ml in the BOD bottle,
3-39
-------
and analyzed by the procedures described above, it will yield an analysis
within the range of the calibration curve.
3.1.6 Calibration
Maintain a laboratory log of all calibrations.
3.1.6.1 Sampling Train Calibration. Calibrate the sampling train
components according to the indicated sections of Method 5: Probe Nozzle
(Section 5.1); Pitot Tube (Section. 5.,2); Metering System (Section 5.3); Probe
Heater (Section 5.4); Temperature Gauges (Section 5.5); Leak-Check of the
Metering System (Section 5.6); and Barometer (Section 5.7).
3.1.6.2 Inductively Coupled Argon Plasma Spectrometer Calibration.
Prepare standards as outlined in Section 3.1.4.4. Profile and calibrate the
instrument according to the instrument manufacturer's recommended procedures
using the above standards. The instrument calibration should be checked once
per hour. If the instrument does not reproduce the concentrations of the
standard within 10 percent, the complete calibration procedures should be
performed.
3.1.6.3 Atomic Absorption Spectrometer - Direct Aspiration,
Graphite Furnace and Cold Vapor Mercury Analyses. Prepare the standards as
outlined in Section 3.1.4.4. Calibrate the spectrometer using these prepared
standards. Calibration procedures are also outlined in the EPA methods
referred to in Table 3.1-2 and in SW-846 Method 7470 or Standard Methods for
Water and Wastewater. 15th Edition, Method 303F (for mercury). Each standard
curve should be run in duplicate and the mean values used to calculate the
calibration line. The instrument should be recalibrated approximately once
every 10 to 12 samples.
3.1.7 Quality Control
3.1.7.1 Sampling. Field Reagent Blanks. When analyzed, the blank
samples in Container Numbers 7 through 12 produced previously in Sections
3-40
-------
3.1.5.2.7 through 3.1.5.2.12, respectively, shall be processed, digested, and
analyzed as follows: Digest and process one of the filters from Container No.
12 per Section 3.1.5.3.1, 100 ml from Container No. 7 per Section 3.1.5.3.2,
and 100 ml from Container No. 8A per Section 3.1.5.3.3. This produces
Fraction Blank 1A and Fraction Blank IB from Fraction Blank 1. [If desired,
the other two filters may be digested separately according to Section
3.1.5.3.1, diluted separately to 300 ml each, and analyzed separately to
produce a blank value for each of the two additional filters. If these
analyses are performed, they will produce two additional values for each of
Fraction Blank, 1A and Fraction. Blank. IB, The three Fraction Blank 1A values
will be calculated as three values of MJU, in Equation 3 of Section 3.1.8.4.3,
and then the three values shall be totalled and divided by 3 to become the
value Mfjjjj to be used in the computation of Mt by Equation 3. Similarly, the
three Fraction Blank IB values will be calculated separately as three values,
totalled, averaged, and used as the value for Rg^ in Equation 8 of Section
3.1.8.5.3. The analyses of the two extra filters are optional and are not a
requirement of this method, but if the analyses are performed, the results
must be considered as described above.] Combine 100 ml of Container No. 8A
with 200 ml of the contents of Container No. 9 and digest and process the
resultant volume per Section 3.1.5.3.4. This produces concentrated Fraction
Blank 2A and Fraction Blank 2B from Fraction Blank 2. A 100-ml portion of
Container No. 8A is Fraction Blank 3A. Combine 100 ml of the contents of
Container No. 10 with 33 ml of the contents of Container No. 8B. This
produces Fraction Blank 3B (use 400 ml as the volume of Fraction Blank 3B when
calculating the blank value. Use the actual volumes when calculating all the
other blank values). Dilute 225 ml of the contents of Container No. 11 to 500
ml with water. This produces Fraction Blank 3C. Analyze Fraction Blank 1A
and Fraction Blank 2A per Section 3.1.5.4.1 and/or 3.1.5.4.2. Analyze
Fraction Blank IB, Fraction Blank 2B, and Fraction Blanks 3A, 3B, and 3C per
Section 3.1.5.4.3. The analysis of Fraction Blank 1A produces the front-half
reagent blank correction values for the metals except mercury; the analysis of
Fraction Blank IB produces the front-half reagent blank correction value for
mercury. The analysis of concentrated Fraction Blank 2A produces the back-
half reagent blank correction values for the metals except mercury, while
3-41
-------
separate analysis of Fraction Blanks 2B, 3A, 3B, and 3C produce the back-half
*
reagent blank correction value for mercury.
3.1.7.2 An attempt may be made to determine if the laboratory
reagents used in Section 3.1.5.3 caused contamination. They should be
analyzed by the procedures in Section 3.1.5.4. The Administrator will
determine whether the laboratory blank reagent values can be used in the
calculation of the stationary source test results.
3.1.7.3 Quality Control. Samples. The following quality control
samples should be analyzed.
3.1.7.3.1 ICAP Analysis. Follow the quality control shown in
Section 8 of Method 6010. For the purposes of a three-run test series, these
requirements have been modified to include the following: two instrument
check standard runs, two calibration blank runs, one interference check sample
at the beginning of the analysis (must be within 25% or analyze by the method
of standard additions), one quality control sample to check the accuracy of
the calibration standards (must be within 25% of calibration), and one
duplicate analysis (must be within 10% of average or repeat all analyses).
3.1.7.3.2 Direct Aspiration and/or Graphite Furnace AAS Analysis
for antimony, arsenic, barium, beryllium, cadmium, copper, chromium, lead,
nickel, manganese, mercury, phosphorus, selenium, silver, thallium, and zinc.
All samples should be analyzed in duplicate. Perform a matrix spike on at
least one front-half sample and one back-half sample or one combined sample.
If recoveries of less than 75 percent or greater than 125 percent are obtained
for the matrix spike, analyze each sample by the method of standard additions.
A quality control sample should be analyzed to check the accuracy of the
calibration standards. The results must be within 10% or the calibration
repeated.
3.1.7.3.3 Cold Vapor AAS Analysis for Mercury. All samples should
be analyzed in duplicate. A quality control sample should be analyzed to
check the accuracy of the calibration standards (within 15% or repeat
3-42
-------
calibration) . Perform a matrix spike on one sample from the nitric impinger
portion (must be within 25% or samples must be analyzed by the method of
standard additions). Additional information on quality control can be
obtained from EPA SW-846 Method 7470 or in Standard Methods for the Examina-
tion of Water and Wastewater. 15th Edition, Method 303F.
3.1.8 Calculations
3.1.8.1 Dry Gas Volume. Using the data from this test, calculate
Vm(stdj, the dry gas sample volume at standard conditions as outlined in
Section 6.3 of Method_5.
3.1.8.2 Volume of Water Vapor and Moisture Content. Using the data
obtained from this test, calculate the volume of water vapor Vw(std) and the
moisture content Bws of the stack gas. Use Equations 5-2 and 5-3 of Method 5.
3.1.8.3 Stack Gas Velocity. Using the data from this test and
Equation 2-9 of Method 2, calculate the average stack gas velocity.
3.1.8.4 Metals (Except Mercury) in Source Sample.
3.1.8.4.1 Fraction 1A, Front Half, Metals (except Hg) . Calculate
separately the amount of each metal collected in Fraction 1 of the sampling
train using the following equation:
Cal Fd V8olntl Eq. 1*
where :
ttflj - total mass of each metal (except Hg) collected in the
front half of the sampling train (Fraction 1) , pg.
Cal - concentration of metal in sample Fraction 1A as read from
the standard curve (pg/ml) .
*If Fractions 1A and 2A are combined, proportional aliquots must be used.
Appropriate changes must be made in Equations 1-3 to reflect this approach.
3-43
-------
Fd - dilution factor (Fd - the inverse of the fractional
portion of the concentrated sample in the solution
actually used in the instrument to produce the reading
Cal. For example, when 2 ml of Fraction 1A are diluted
to 10 ml, Fd - 5).
V80ln ! - total volume of digested sample solution (Fraction 1),
ml.
3.1.8.4.2 Fraction 2A, Back Half, Metals (except Hg) . Calculate
separately the amount of each metal collected in Fraction 2 of the sampling
train using the following equation:
. Eq. 2*
where :
Mbh - total mass of each metal (except Hg) collected in the
back half of the sampling train (Fraction 2) , pg.
Ca2 - concentration of metal in sample concentrated Fraction
2A, as read from the standard curve (/ig/ml) .
Fa - aliquot factor, volume of Fraction 2 divided by volume
of aliquot Fraction 2A (dee Section 3.1.5.3.4).
Va - total volume of digested sample solution (concentrated
Fraction 2A) , ml (see Section 3.1.5.3.4.1 or 3.1.5.3.4.2,
as applicable) .
3.1.8.4.3 Total Train, Metals (except Hg) . Calculate the total
amount of each of the quantified metals collected in the sampling train as
follows :
Eq. 3*
where :
Mt - total mass of each metal (separately stated for each
metal) collected in the sampling train, /*g.
MJUJ - blank correction value for mass of metal detected in
front -half field reagent blank, pg.
M^ - blank correction value for mass of metal detected in
back-half field reagent blank, i*g.
Note: If the measured blank value for the front half
(nifijj.,) is in the range 0.0 to A Mg [where A /*g equals the
value determined by multiplying 1.4 pg per square inch
(1.4 jig/in2) times the actual area in square inches (in2)
3-44
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of the filter used in the emission sample], m^ may be
used to correct the emission sample value (m^) ; if nif^,
exceeds A /jg, the greater of the two following values
(either I. or II.) may be used:
I. A Mg, °r
II. the lesser of (a) m^, or (b) 5 percent of nig,.
If the measured blank value for the back half (m^) is in
the range of 0.0 to 1 ng, 0^ may be used to correct the
emission sample value (mj,h) ; if m,^ exceeds 1 /ig, the
greater of the two following values may be used: 1 ng or
5 percent of mbh.
3.1.8.5 Mercury in Source Sample.
3.1.8.5.1 Fraction IB, Front Half, Hg. Calculate the amount of
mercury collected in the front half, Fraction 1, of the sampling train using
the following equation:
where :
Hgft - - X Vsoln<1 Eq. 4
- total mass of mercury collected in the front half of
the sampling train (Fraction 1), /ig.
- quantity of mercury in analyzed sample, ^g.
Vsoln x - total volume of digested sample solution (Fraction 1) ,
ml.
VflB - volume of Fraction IB analyzed, ml. See the following
notice.
Note: VflB is the actual amount of Fraction IB analyzed.
For example, if 1 ml of Fraction IB were diluted to 100 ml
to bring it into the proper analytical range, and 1 ml of
the 100 -ml dilution were analyzed, V£1B would be 0.01 ml.
3-45
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3.1.8.5.2 Fraction 2B and Fractions 3A, 3B, and 3C, Back Half, Hg.
Calculate the amount of mercury collected in Fractions 2 using Equation 5 and
in Fractions 3A, 3B, and 3C using Equation 6. Calculate the total amount of
mercury collected in the back half of the sampling train using Equation 7.
Qbh2
Hgbh2 - - * Vsoln_2 Eq. 5
where :
Hgbh2 - total mass of mercury collected in Fraction 2, ng.
Qbh2 " quantity of mercury in analyzed sample, pg.
vsoin,2 ~ total volume of Fraction 2, ml.
Vf2B - volume of Fraction 2B analyzed, ml (see the following
note) .
Note: Vf2B is the actual amount of Fraction 2B analyzed.
For example, if 1 ml of Fraction 2B were diluted to 10 ml
to bring it into the proper analytical range, and 5 ml of
the 10 -ml dilution was analyzed, Vf2B would be 0.5.
Use Equation 6 to calculate separately the back-half mercury for
Fractions 3A, then 3B, then 3C.
Qbh3(A,B.C>
Hgbh3(A,B.C> ~ - x Vsoln,3(A,B,C) Eq • 6
V£3(A,B.C)
where :
HSbh3(A,B.C) ~ total mass of mercury collected separately in
Fraction 3A, 3B, or 3C, pg.
Qbh3(A,B.o ~ quantity of mercury in separately analyzed
samples, /*g.
vf3(A,B,o ~ volume of Fraction 3A, 3B, or 3C analyzed, ml
(see Note in Sections 3.1.8.5.1 and 3.1.8.5.2,
and calculate similarly) .
Vsoin,3(A,B,o - total volume of Fraction 3A, 3B, or 3C, ml.
- Hgbh2 + Hgbh3A + Hgbh3B + Hgbh3c Eq. 7
3-46
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where :
Hgbh - total mass of mercury collected in the back half of
the sampling train, AȤ.
3.1.8.5.3 Total Train Mercury Catch. Calculate the total amount of
mercury collected in the sampling train using Equation 8.
Hgt - (Hgfh - Hgfhb) + (Hgbh - Hgbhb) Eq. 8
where :
Hgt - total mass .of .mercury collected in the sampling train,
~ blank correction value for mass of mercury detected in
front-half field reagent blank, jig.
Hgbhb " blank correction value for mass of mercury detected in
back-half field reagent blanks, /*g.
Note: If the total of the measured blank values
Hgbhb) is in c^e range of 0 to 6 /*g, then the total may be
used to correct the emission sample value (Hg^, + Hgbh) ; if
it exceeds 6 pg, the greater of the following two values
may be used; 6 /;g or 5 percent of the emission sample
value (Hgfh + Hgbh) .
3.1.8.6 Metal Concentration of Stack Gas. Calculate each metal
separately for the cadmium, total chromium, arsenic, nickel, manganese,
beryllium, copper, lead, phosphorus, thallium, silver, barium, zinc, selenium,
antimony, and mercury concentrations in the stack gas (dry basis, adjusted to
standard conditions) as follows:
C. - MMt/Vm(ltd)) Eq. 9
where :
C, - concentration of each metal in the stack gas, mg/dscm.
K4 - 1
-------
3.1.8.7 Isokinetic Variation and Acceptable Results. Same as
Method 5, Sections 6.11 and 6.12, respectively.
3.1.9 Bibliography
3.1.9.1 Method 303F in Standard Methods for the Examination of
Water and Wastewater. 15th Edition, 1980. Available from the American Public
Health Association, 1015 18th Street, N.W., Washington, D.C. 20036.
3.1.9.2 . EPA .Methods.. 6010,..7000., 7041., 7060, 7131, 7421, 7470, 7740,
and 7841, Test Methods for Evaluating Solid Waste: Physical/Chemical Methods.
SW-846, Third Edition. September 1988. Office of Solid Waste and Emergency
Response, U.S. Environmental Protection Agency, Washington, D.C. 20460.
3.1.9.3 EPA Method 200.7, Code of Federal Regulations. Title 40,
Part 136, Appendix C. July 1, 1987.
3.1.9.4 EPA Methods 1 through 5, and 12 Code of Federal Regula-
tions. Title 40, Part 60, Appendix A, July 1, 1987.
3-48
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3.2 Determination of Hexavalent Chromium Emissions from Stationary
Sources (Method Cr*6)
3.2.1 Applicability and Principle
3.2.1.1 Applicability. This method applies to the determination of
hexavalent chromium (Cr+6) emissions from hazardous waste incinerators,
municipal waste combustors, sewage sludge incinerators, and boilers and
industrial furances. With the approval of the Administrator, this method may
also be used to measure total..chromium.. The. sampling train, constructed of
Teflon components, has only been evaluated at temperatures less than 300°F.
Trains constructed of other materials, for testing at higher temperatures, are
currently being evaluated.
3.2.1.2 Principle. For incinerators and combustors, the Cr*6
emissions are collected isokinetically from the source. To eliminate the
possibility of Cr*6 reduction between the nozzle and impinger, the emission
samples are collected with a recirculatory train where the impinger reagent is
continuously recirculated to the nozzle. Recovery procedures include a post-
sampling purge and filtration. The impinger train samples are analyzed for
Cr+s by an ion chromatograph equipped with a post-column reactor and a visible
wavelength detector. The IC/PCR separates the Cr+6 as chromate (Cr04") from
other components in the sample matrices that may interfere with the Cr"1"6-
specific diphenylcarbazide reaction that occurs in the post-column reactor.
To increase sensitivity for trace levels of chromium, a preconcentration
system is also used in conjunction with the IC/PCR.
3.2.2 Range. Sensitivity. Precision, and Interference
3.2.2.1 Range. Employing a preconcentration procedure, the lower
limit of the detection range can be extended to 16 nanograms per dry standard
cubic meter (ng/dscm) with a 3 dscm gas sample (0.1 ppb in solution). With
sample dilution, there is no upper limit.
3-49
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3.2.2.2 Sensitivity. A minimum detection limit of 8 ng/dscm with a
3 dscm gas sample can be achieved by preconcentration (0.05 ppb in solution).
3.2.2.3 Precision. The precision of the IC/PCR with sample
preconcentration is 5 to 10 percent. The overall precision for sewage sludge
incinerators emitting 120 ng/dscm of Cr+6 and 3.5 pg/dscm of total chromium is
25% and 9% for Cr+6 and total chromium, respectively; for hazardous waste
incinerators emitting 300 ng/dscm of Cr*6 it is 20 percent.
3.2.2.4 Interference. Components in the sample matrix may cause
Cr"1"6 to convert to trivalent chromium (Cr*3) or cause Cr*3 to convert to Cr+6.
A post-sampling nitrogen purge and sample filtration are included to eliminate
many of these interferences. The chromatographic separation of Cr+6 using ion
chromatography reduces the potential for other metals to interfere with the
post-column reaction. For the IC/PCR analysis, only compounds that coelute
with Cr*6 and affect the diphenylcarbazide reaction will cause interference.
Periodic analysis of deionized (DI) water blanks is used to demonstrate that
the analytical system is essentially free from contamination. Sample cross-
contamination that can occur when high-level and low-level samples or stan-
dards are analyzed alternately is eliminated by thorough purging of the sample
loop. Purging can easily be achieved by increasing the injection volume of
the samples to ten times the size of the sample loop.
3.2.3 Apparatus
3.2.3.1 Sampling Train. Schematics of the recirculating sampling
trains employed in this method are shown in Figures 3.2-1 and 3.2-2. The
recirculatory train is readily assembled from commercially available compo-
nents. All portions of the train in contact with the sample are either glass,
quartz, Tygon, or Teflon, and are to be cleaned as per subsection 3.2.5.1.1.
The metering system is identical to that specified by Method 5 (see
Section 3.8.1); the sampling train consists of the following components:
3-50
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GLASS
IMPINGER
u>
I
Ul
TO
METHOD 5 TYPE
METERBOX
RECIRCULATING
UQLHD
150ml
0.1NKOH
75ml
0.1 N KOH
75ml
0.1 N KOH
WATER AND ICE BATH
EMPTY
SILICA
GEL
Figure 3.2-1
Schematic of recirculalory impinger train with aspirator assembly.
/1O1C, 7/Of!
-------
TEFLON
T-UNION
NOZZLE
I
to
I
TEFLON.
LINES
REdROJLATlNG
LIQUID
PERISTALTIC
PUMP
GLASS
IMPWGER
TEFLON IMPINGERS
WATER AND ICE BATH
TO
METHOD 5-TYPE
METERBOX
Figure 3.2-2
Schematic ol recirculatr impinger Iram with pump/sprayer assembly
-------
3.2.3.1.1 Probe Nozzle.. Glass or Teflon with a sharp, tapered
leading edge. The angle of taper shall be <30° and the taper shall be on the
outside to preserve a constant internal diameter. The probe nozzle shall be
of the button-hook or elbow design, unless otherwise specified by the Adminis-
trator.
A range of nozzle sizes suitable for isokinetic sampling should be
available, e.g., 0.32 to 1.27 cm (1/8 to 1/2 in) (or larger if higher volume
sample trains are used) inside diameter (ID) nozzles in increments of 0.16 cm
(1/16 in). Each nozzle shall be calibrated according to the procedures
outlined in Section 3.2.6.
3.2.3.1.2 Teflon Aspirator or Pump/Sprayer Assembly. Teflon
aspirator capable of recirculating absorbing reagent at 50 ml/min while
operating at 0.75 cfm. Alternatively, a pump/sprayer assembly may be used
instead of the Teflon aspirator. A Teflon union-T is connected behind the
nozzle to provide the absorbing reagent/sample gas mix; a peristaltic pump is
used to recirculate the absorbing reagent at a flow rate of at least 50
ml/min. Teflon fittings, Teflon ferrules, and Teflon nuts are used to connect
a glass or Teflon nozzle, recirculating line, and sample line to the Teflon
aspirator or union-T. Tygon, C-flex** or other suitable inert tubing for use
with peristaltic pump.
3.2.3.1.3 Teflon Sample Line. Teflon, 3/8" outside diameter (OD)
and 1/4" inside diameter (ID), or 1/2" OD x 3/8" ID, of suitable length to
connect aspirator (or T-union) to first Teflon impinger.
3.2.3.1.4 Teflon Recirculation Line. Teflon, 1/4" O.D. and 1/8"
I.D., of suitable length to connect first impinger to aspirator (or T-union).
3.2.3.1.5 Teflon Impingers. Four Teflon Impingers; Teflon tubes
and fittings, such as made by Savillex**, can be used to construct impingers
**..
NOTE: Mention of trade names or specific product does* not constitute
endorsement by the Environmental Protection Agency.
3-53
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2" diameter by 12" long, with vacuum-tight 3/8" O.D. Teflon compression fit-
tings. Alternatively, standard glass impingers that have been Teflon-lined,
with Teflon stems and U-tubes, may be used. Inlet fittings on impinger top to
be bored through to accept 3/8" O.D. tubing as impinger stem. The second and
third 3/8" OD Teflon stem has a 1/4" OD Teflon tube, 2" long, inserted at its
end to duplicate the effects of the Greenburg-Smith impinger stem. The first
impinger stem should extend 2" from impinger bottom, high enough in the
impinger reagent to prevent air from entering recirculating line; the second
and third impinger stems should extent to 1/2" from impinger bottom. The
first impinger should include.a 1/4" O.D, Teflon compression fitting for
recirculation line. The fourth impinger serves as a knockout impinger.
3.2.3.1.6 Glass Impinger. Silica gel impinger. Vacuum-tight
impingers, capable of containing 400 g of silica gel, with compatible fit-
tings. The silica gel impinger will have a modified stem (1/2" ID at tip of
stem).
3.2.3.1.7 Thermometer, (identical to that specified by Method 5) at
the outlet of the silica gel impinger, to monitor the exit temperature of the
gas,
3.2.3.1.8 Metering System, Barometer, and Gas Density Determina-
tions Equipment. Same as Method 5, Sections 2.1.8 through 2.1.10, respec-
tively.
3.2.3.2 Sample Recovery. Clean all items for sample handling or
storage with 10% nitric acid solution by soaking, where possible, and rinse
thoroughly with DI water before use.
3.2.3.2.1 Nitrogen Purge Line. Inert tubing and fittings capable
of delivering 0 to 1 scf/min (continuously adjustable) o_f nitrogen gas to the
impinger train from a standard gas cylinder (see Figure Cr -3). Standard
3/8-inch Teflon tubing and compression fittings in conjunction with an
adjustable pressure regulator and needle valve may be used.
3-54
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I
en
Cn
WATER AND ICE BATH
N2GAS
OUTLET
NITROGEN
CYLINDER
GAS
RECIRCULATING
UNE
4215 7/90
Figure 3.2-3
Schematic ol post test nitrogen purge system
-------
.2.3.2.2 Wash Bottles. Two polyethylene wash bottles, for DI
water ar.c. .itric rinse solution.
3.2.3.2.3 Sample Storage Containers. Polyethylene, with leak-free
screw cap, 500-ml or 1000-ml.
3.2.3.2.4 1000-ml Graduated Cylinder.
3.2.3.2.5 Plastic Storage Containers. Air tight containers to
store silica .gel..
3.2.3.2.6 Funnel and Rubber Policeman. To aid in transfer of
silica gel from impinger to storage container; not necessary if silica gel is
weighed directly in the impinger.
3.2.3.2.7 Balance
3.2.3.3 Sample Preparation for Analysis. Sample preparation prior
to analysis includes purging the sample train immediately following the sample
run, and filtering the recovered sample to remove particulate matter immedi-
ately following recovery.
3.2.3.3.1 Beakers, Funnels, Volumetric Flasks, Volumetric Pipets,
and Graduated Cylinders. Assorted sizes, Teflon or glass, for preparation of
samples, sample dilution, and preparation of calibration standards. Prepare
initially following procedure described in Section 3.2.5.1.3 and rinse between
use with 0.1 N HN03 and DI water.
3.2.3.3.2 Filtration Apparatus. Teflon, or equivalent, for
filtering samples, and Teflon filter holder. Teflon impinger components have
been found to be satisfactory as a sample reservoir for pressure filtration
using nitrogen.
3-56
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3.2.3.4 Analysis.
3.2.3.4.1 IC/PCR System. High performance liquid chromatograph
pump, sample injection valve, post-column reagent delivery and mixing system,
and a visible detector, capable of operating at 520 nm, all with a non-
metallic (or inert) flow path. An electronic recording integrator operating
in the peak area mode is recommended, but other recording devices and integra-
tion techniques are acceptable provided the repeatability criteria and the
linearity criteria for the calibration curve described in Section 3.2.5.5 can
be satisfied. A sample loading system will be required if preconcentration is
employed.
3.2.3.4.2 Analytical Column. A high performance ion chromatograph
(HPIC) non-metallic column with anion separation characteristics and a high
loading capacity designed for separation of metal chelating compounds to
prevent metal interference. Resolution described in Section 3.2.5.4 must be
obtained. A non-metallic guard column with the same ion-exchange material is
recommended.
3.2.3.4.3 Preconcentration Column. An HPIC non-metallic column
with acceptable anion retention characteristics and sample loading rates as
described in Section 3.2.5.5.
3.2.3.4.4 0.45 um filter cartridge. For the removal of insoluble
material. To be used just prior to sample injection/analysis.
3.2.4 Reagents
All reagents should, at a minimum, conform to the specifications
established by the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. All prepared reagents
should be checked by IC/PCR analysis for Cr+6 to ensure that contamination is
below the analytical detection limit for direct injection or, if selected,
preconcentration. If total chromium is also to be determined, the reagents
3-57
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should also be checked by the analytical technique selected to ensure that
contamination is below the analytical detection limit.
3.2.4.1 Sampling.
3.2.4.1.1 Water. Deionized water. It is recommended that water
blanks be checked prior to preparing sampling reagents to ensure that the Cr+6
content is less than the analytical detection limit.
3.2.4M.2 Potassium Hydroxide, 0.1 N. Add 5.6 gm of KOH(s) to
approximately 900 ml of DI water and let dissolve. Dilute to 1000 ml with DI
water. NOTE: At sources with high concentrations of acids and/or S02, the
concentration of KOH should be increased to 0.5 N to ensure that the pH of the
solution is above 8.5 after sampling.
3.2.4.1.3 Silica Gel and Crushed Ice. Same as Method 5, Sections
3.1.2 and 3.1.4, respectively.
3.2.4.2 Sample Recovery. The reagents used in sample recovery are
as follows:
3.2.4.2.1 Water. Same as Subsection 3.2.4.1.1.
3.2.4.2.2 Nitric Acid, 0.1 N. Add 6.3 ml of concentrated HN03 (70
percent) to a graduated cylinder containing approximately 900 ml of DI water.
Dilute to 1000 ml with DI water, and mix well.
3.2.4.2.3 pH Indicator Strip. pH indicator capable of determining
pH of solution between the pH range of 7 and 12, at 0.5 pH intervals.
3.2.4.3 Sample Preparation
3.2.4.3.1 Water. Same as Subsection 3.2.4.1.1.
3.2.4.3.2 Nitric Acid, 0.1 N. Same as Subsection 3.2.4.2.2.
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3.2.4.3.3 Filters. Acetate membrane, or equivalent, filters with
0.45 micrometer or smaller pore size to remove insoluble material.
3.2.4.4 Analysis.
3.2.4.4.1 Chromatographic Eluent. The eluent used in the analyti-
cal system is ammonium sulfate based. It is prepared by adding 6.5 ml of 29
percent ammonium hydroxide (NH4OH) and 33 grams of ammonium sulfate [(NHA)2SO;,]
to 500 ml of DI water. The mixture should then be diluted to 1 liter with DI
water and mixed well. Other combinations of eluents and/or columns may be
employed provided peak resolution, as described in Section 3.2.5.4, repeat-
ability and linearity, as described in Section 3.2.6.2, and analytical
sensitivity are acceptable.
3.2.4.4.2 Post-Column Reagent. An effective post-column reagent
for use with the chromatographic eluent described in Section 3.2.4.4.1 is a
diphenylcarbazide (DPC) based system. Dissolve 0.5 g of 1,5-diphenylcarbazide
(DPC) in 100 ml of ACS grade methanol. Add to 500 ml of degassed DI water
containing 50 ml of 96 percent spectrophotometric grade sulfuric acid. Dilute
to 1 liter with degassed DI water.
3.2.4.4.3 Cr+6 Calibration Standard. Prepare Cr*6 standards from
potassium dichromate (K2Cr207> FW 294.19). To prepare a 1000 ng/ml Cr+6 stock
solution, dissolve 2.829 g of dry K2Cr207 in 1 liter of DI water. To prepare
working standards, dilute the stock solution to the chosen standard concentra-
tions for instrument calibration with 0.05 N KOH to achieve a matrix similar
to the actual field samples.
3.2.4.4.4 Performance Audit Sample. A performance audit sample
shall be obtained from the Quality Assurance Division of EPA and analyzed with
the field samples. The mailing address to request audit samples is:
3-59
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U.S. Environmental Protection Agency
Atmospheric Research and Exposure Assessment Laboratory
Quality Assurance Division
Source Branch, Mail Drop 77-A
Research Triangle Park, North Carolina 27711
The audit sample should be prepared in a suitable sample matrix at a
concentration similar to the actual field samples.
3.2.5 Procedure
SAFETY FIRST - WEAR SAFETY GLASSES AT ALL TIMES DURING THIS TEST
METHOD.
3.2.5.1 Sampling. The complexity of this method is such that to
obtain reliable results, testers should be trained and experienced with test
procedures.
3.2.5.1.1 Pretest Preparation. All components shall be maintained
and calibrated according to the procedures described in APTD-0576, unless
otherwise specified herein.
Rinse all sample train components from the glass nozzle up to the
silica gel impinger and sample containers with hot tap water followed by
washing with hot soapy water. Next, rinse the train components and sample
containers three times with tap water followed by three rinses with DI water.
All the components and containers should then be soaked overnight, or a
minimum of 4 hours, in a 10 percent (v/v) nitric acid solution, then rinsed
three times with DI water. Allow the components to air dry prior to covering
all openings with Parafilm, or equivalent.
3.2.5.1.2 Preliminary Determinations. Same as Method 5, Section
4.1.2.
3.2.5.1.3 Preparation of Sampling Train. Measure 300 ml of 0.1 N
KOH into a graduated cylinder (or tare-weighed precleaned polyethylene
3-60
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container). Place approximately 150 ml of the 0.1 N KOH reagent in the first
Teflon impinger. Split the rest of the 0.1 N KOH between the second and third
Teflon impingers. The next Teflon impinger is left dry. Place a preweighed
200- to 400-g portion of indicating silica gel in the final glass impinger.
(For sampling periods in excess of two hours, or for high moisture sites, 400-
g of silica gel is recommended.)
Retain reagent blanks of the 0.1 N KOH equal to the volumes used
with the field samples.
3.2.5.1.4 Leak-Check Procedures. Follow the leak-check procedures
given in Method 5, Section 4.1.4.1 (Pretest Leak-Check), Section 4.1.4.2
(Leak-Checks During the Sample Run), and Section 4.1.4.3 (Post-Test Leak-
Checks) .
3.2.5.1.5 Sampling Train Operation. Follow the procedures given in
Method 5, Section 4.1.5. The sampling train should be iced down with water
and ice to ensure heat transfer with the Teflon impingers.
NOTE: If the gas to be sampled is above 200°F, it may be necessary
to wrap three or four feet of the Teflon sample and recirculating lines inside
the ice bath to keep the recirculated reagent cool enough so it does not turn
to steam.
For each run, record the data required on a data sheet such as the
one shown in Figure 5-2 of Method 5.
At the end of the sampling run, determine the pH of the reagent in
the first impinger using a pH indicator strip. The pH of the solution shall
be greater than 8.5.
3.2.5.1.6 Calculation of Percent Isokinetic. Same as Method 5,
Section 4.1.6.
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3.2.5.2 Post-Test Nitrogen Purge. The nitrogen purge is used as a
safeguard against the conversion of hexavalent chromium to the trivalent
oxidation state. The purge is effective in the removal of S02 from the
impinger contents.
Attach the nitrogen purge line to the input of the impinger train.
Check to ensure the output of the impinger train is open, and that the
recirculating line is capped off. Open the nitrogen gas flow slowly and
adjust the delivery rate to 10 L/min. Check the recirculating line to ensure
that the pressure. is. not .forcing.-the. impinger reagent out through this line.
Continue the purge under these conditions for one-half hour, periodically
checking the flow rate.
3.2.5.3 Sample Recovery. Begin cleanup procedures as soon as the
train assembly has been purged at the end of the sampling run. The probe
assembly may be disconnected from the sample train prior to sample purging.
The probe assembly should be allowed to cool prior to sample
recovery. Disconnect the umbilical cord from the sample train. When the
probe assembly can be safely handled, wipe off all external particulate matter
near the tip of the nozzle, and cap the nozzle prior to transporting the
sample train to a cleanup area that is clean and protected from the wind and
other potential causes of contamination or loss of sample. Inspect the train
before and during disassembly and note any abnormal conditions.
3.2.5.3.1 Container No. 1 (Impingers 1 through 3). Disconnect the
first impinger from the second impinger and disconnect the recirculation line
from the aspirator or peristaltic pump. Drain the Teflon impingers into a
precleaned graduated cylinder or tare-weighed precleaned polyethylene sample
container and measure the volume of the liquid to within 1 ml or 1 g. Record
the volume of liquid present as this information is required to calculate the
moisture content of the flue gas sample. If necessary, transfer the sample
from the graduated cylinder to a precleaned polyethylene sample container.
With DI water, rinse four times the insides of the glass nozzle, the aspira-
tor, the sample and recirculation lines, the irapingers, and the connecting
3-62
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tubing, and combine the rinses with the impinger solution in the sample
container.
3.2.5.3.2 Container No. 2 (HN03 rinse optional for total chromium).
With 0.1 N HN03, rinse three times the entire train assembly, from the nozzle
to the fourth impinger and combine the rinses into a separate precleaned
polyethylene sample container for possible total chromium analysis. Repeat
the rinse procedure a final time with DI water, and discard the water rinses.
Mark the height of the fluid level on the container or, alternatively if a
balance is available-, weigh the container and record the weight to permit
determination of any leakage during transport. Label the container clearly to
identify its contents.
3.2.5.3.3 Container No. 3 (Silica Gel). Note the color of the
indicating silica gel to determine if it has been completely spent. Quantita-
tively transfer the silica gel from its impinger to the original container,
and seal the container. A funnel and a rubber policeman may be used to aid in
the transfer. The small amount of particulate that may adhere to the impinger
wall need not be removed. Do not use water or other liquids to transfer the
silica gel. Alternatively, if a balance is available in the field, record the
weight of the spent silica gel (or the silica gel plus impinger) to the
nearest 0.5 g.
3.2.5.3.4 Container No. 4 (0.1 N KOH Blank). Once during each
field test, place a volume of reagent equal to the volume placed in the sample
train into a precleaned polyethylene sample container, and seal the container.
Mark the height of the fluid level on the container or, alternatively if a
balance is available, weigh the container and record the weight to permit
determination of any leakage during transport. Label the container clearly to
identify its contents.
3.2.5.3.5 Container No. 5 (DI Water Blank). Once during each field
test, place a volume of DI water equal to the volume employed to rinse the
sample train into a precleaned polyethylene sample container, and seal the
container. Mark the height of the fluid level on the container or, alterna-
3-63
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tively if a balance is available, weigh the container and record the weight to
permit determination of any leakage during transport. Label the container
clearly to identify its contents.
3.2.5.3.6 Container No. 6 (0.1 N HN03 Blank). Once during each
field test if total chromium is to be determined, place a volume of 0.1 N HN03
reagent equal to the volume employed to rinse the sample train into a pre-
cleaned polyethylene sample container, and seal the container. Mark the
height of the fluid level on the container or, alternatively if a balance is
available, weigh the container.and,record.-the weight to permit determination
of any leakage during transport. Label the container clearly to identify its
contents.
3.2.5.4 Sample Preparation. For determination of Cr"1"6, the sample
should be filtered Immediately following recovery to remove any insoluble
matter. Nitrogen gas may be used as a pressure assist to the filtration
process (see Figure Cr+6-4).
Filter the entire impinger sample through a 0.45-micrometer acetate
filter (or equivalent), and collect the filtrate in a 1000-ml graduated
cylinder. Rinse the sample container with DI water three separate times, pass
these rinses through the filter, and add the rinses to the sample filtrate.
Rinse the Teflon reservoir with DI water three separate times, pass these
rinses through the filter, and add the rinses to the sample. Determine the
final volume of the filtrate and rinses and return them to the rinsed polyeth-
ylene sample container. Label the container clearly to identify its contents.
Rinse the Teflon reservoir once with 0.1 N HN03 and once with DI water and
discard these rinses.
If total chromium is to be determined, quantitatively recover the
filter and residue and place them in a vial. (The acetate filter may be
digested with 5 ml of 70 percent nitric acid; this digestion solution may then
be diluted with DI water for total chromium analysis.)
3-64
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VALVE
TEFLON
RESERVOIR
REGULATOR
TEFLON FILTER HOLDER
WITH .45 MICRON FILTER
1000ml
GRADUATED CYLINDER
N2TANK
F i gur e 3.2-4 Schematic of sample filter system.
3-65
4196 Z'90
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NOTE: If the source has a large amount of particulate in the
effluent stream, testing teams may wish to filter the sample twice, once
through a 2 to 5-micrometer filter, and then through the 0.45-micrometer
filter.
3.2.5.4.1 Container 2 (HN03 rinse, optional for total chromium).
This sample shall be analyzed in accordance with the selected procedure for
total chromium analysis. At a minimum, the sample should be subjected to a
digestion procedure sufficient to solubilize all chromium present.
3.2.5.4.2 Container 3 (Silica Gel). Weigh the spent silica gel to
the nearest 0.5 g using a balance. (This step may be conducted in the field.)
3.2.5.5 Sample analysis. The Cr*6 content of the sample filtrate
is determined by ion chromatography coupled with a post-column reactor
(IC/PCR). To increase sensitivity for trace levels of chromium, a preconcen-
tration system is also used in conjunction with the IC/PCR.
Prior to preconcentration and/or analysis, all field samples will be
filtered through a 0.45-/i filter. This filtration should be conducted just
prior to sample injection/analysis.
The preconcentration is accomplished by selectively retaining the
analyte on a solid absorbent (as described in 3.2.3.4.3), followed by removal
of the analyte from the absorbent. The sample is injected into a sample loop
of the desired size (repeated loadings or larger size loop for greater
sensitivity) and the Cr*6 is collected on the resin bed of the column. When
the injection valve is switched, the eluent displaces the concentrated Cr*6
sample moving it off the preconcentration column and onto the 1C anion
separation column. After separation from other sample components, Cr*6 forms
a specific complex in the post-column reactor with a diphenylcarbazide
reaction solution, and the complex is then detected by visible absorbance at a
wavelength of 520 nm. The amount of absorbance measured is proportional to
the concentration of the Cr+6 complex formed. The 1C retention time and
absorbance of the Cr*6 complex is compared with known Cr*6 standards analyzed
3-66
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under identical conditions to provide both qualitative and quantitative
analyses.
Prior to sample analysis, establish a stable baseline with the
detector set at the required attenuation by setting the eluent flowrate at
approximately 1 ml/min and post-column reagent flowrate at approximately 0.5
ml/min. (Note: As long as the ratio of eluent flowrate to PCR flowrate
remains constant, the standard curve should remain linear.) Inject a sample
of DI water to ensure that no Cr*6 appears in the water blank.
First, inject the calibration standards prepared, as described in
Section 3.2.4.4.4, to cover the appropriate concentration range, starting with
the lowest standard first. Next, inject, in duplicate, the performance audit
sample, followed by the 0.1 N KOH field blank and the field samples. Finally,
repeat the injection of the calibration standards to allow for compensation of
instrument drift. Measure areas or heights of the Cr+6/DPC complex chromato-
gram peak. The response for replicate, consecutive injections of samples must
be within 5 percent of the average response, or the injection should be
repeated until the 5 percent criterion can be met. Use the average response
(peak areas or heights) from the duplicate injections of calibration standards
to generate a linear calibration curve. From the calibration curve, determine
the concentration of the field samples employing the average response from the
duplicate injections.
The results for the analysis of the performance audit sample must be
within 10 percent of the reference value for the field sample analysis to be
valid.
3.2.6 Calibration. Maintain a written log of all calibration activities.
3.2.6.1 Sample Train Calibration. Calibrate the sample train
components according to the indicated sections of Method 5: Probe Nozzle
(Section 5.1); Pitot Tube (Section 5.2); Metering System (Section 5.3);
Temperature Gauges (Section 5.5); Leak-Check of the Metering System (Section
5.6); and Barometer (Section 5.7).
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3.2.6.2 Calibration Curve for the IC/PCR. Prepare working stan-
dards from the stock solution described in Section 3.2.4.4.4 by dilution with
a DI water solution to approximate the field sample matrix. Prepare at least
four standards to cover one order of magnitude that bracket the field sample
concentrations. Run the standards with the field samples as described in
Section 3.2.5.5. For each standard, determine the peak areas (recommended) or
the peak heights, calculate the average response from the duplicate injec-
tions, and plot the average response against the Cr"1"6 concentration in ng/L.
The individual responses for each calibration standard determined before and
after field sample analysis must-be-within 5 percent of the average response
for the analysis to be valid. If the 5 percent criteria is exceeded, exces-
sive drift and/or instrument degradation may have occurred, and must be
corrected before further analyses are performed.
Employing linear regression, calculate a predicted value for each
calibration standard with the average response for the duplicate injections.
Each predicted value must be within 7 percent of the actual value for the
calibration curve to be considered acceptable. If not acceptable, remake
and/or rerun the calibration standards. If the calibration curve is still
unacceptable, reduce the range of the curve.
3.2.7 Calculations
3.2.7.1 Dry Gas Volume. Using the data from the test, calculate
^m(std)' t^ie °-ry 8as sample volume at standard conditions as outlined in
Section 6.3 of Method 5.
3.2.7.2 Volume of Water Vapor and Moisture Content. Using the data
from the test, calculate Vw(Btd) and BW8, the volume of water vapor and the
moisture content of the stack gas, respectively, using Equations 5-2 and 5-3
of Method 5.
3.2.7.3 Stack Gas Velocity. Using the data from the test and
Equation 2-9 of Method 2, calculate the average stack gas velocity.
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3.2.7.4 Total ng Cr"1"6 per Sample. Calculate as described below:
m - (S-B) x Vls x d
where:
m - Mass of Cr*6 in the sample, pg.
S - Concentration of sample, ng Cr*6/ml..
B - Concentration of blank, pg Cr*6/ml.
Vls - Volume of sample after filtration, ml.
d - Dilution factor (1 if not diluted).
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3.3 Measurement of HC1 and C13
3.3.1 Isokinetic HC1/C1; Emission Sampling Train (Method QOSO)
3.3.1.1 Scope and Application
3.3.1.1.1 This method describes the collection of hydrogen chloride
(HC1, CAS Registry Number 7647-01-0) and chlorine (C12, CAS Registry Number
7782-50-5) in stack gas emission samples from hazardous waste incinerators,
municipal waste combustors, and boilers and industrial furnaces. The collect-
ed samples are analyzed using Method 9057. This method collects the emission
sample isokinetically and is therefore particularly suited for sampling at
sources, such as those controlled by wet scrubbers, emitting acid particulate
matter (e.g., HC1 dissolved in water droplets). A midget impinger train
sampling method designed for sampling sources of HC1/C12 emissions not in
particulate form is presented in Method 0051.
3.3.1.1.2 This method is not acceptable for demonstrating compli-
ance with HC1 emission standards less than 20 ppra.
3.3.1.1.3 This method may also be used to collect samples for
subsequent determination of particulate emissions (by EPA Method 5, Reference
1) following the additional sampling procedures described.
3.3.1.2 Summary of Method
3.3.1.2.1 Gaseous and particulate pollutants are withdrawn from an
emission source and are collected in an optional cyclone, on a filter, and in
absorbing solutions. The cyclone collects any liquid droplets and is not
necessary if the source emissions do not contain liquid droplets. The Teflon
mat or quartz-fiber filter collects other particulate matter including
chloride salts. Acidic and alkaline absorbing solutions collect gaseous HC1
and C12, respectively. Following sampling of emissions containing liquid
droplets, any HC1/C12 dissolved in the liquid in the cyclone and/or on the
filter is vaporized and ultimately collected in the impingers by pulling
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Ascarite IIR conditioned ambient air through the sampling train. In the
acidified water absorbing solution, the HC1 gas is solubilized and forms
chloride (Cl~) ions. The C12 gas present in the emissions has a very low
solubility in acidified water and passes through to the alkaline absorbing
solution where it undergoes hydrolysis to form a. proton (H+) , Cl- , and
hypochlorous acid (HC10). The Cl" ions in the separate solutions are measured
by ion chromatography (Method 9057). If desired, the particulate matter
recovered from the filter and the probe is analyzed following the procedures
in EPA Method 5 (Reference 1).
3.3.1.3 Interferences
3.3.1.3.1 Volatile materials which produce chloride ions upon
dissolution during sampling are obvious interferences in the measurement of
HC1. One interferant for HC1 is diatomic chlorine (C12) gas which dispropor-
tionates to HC1 and hypochlorous acid (HC10) upon dissolution in water. C12
gas exhibits a low solubility in water, however, and the use of acidic rather
than neutral or basic solutions for collection of hydrogen chloride gas
greatly reduces the dissolution of any chlorine present.
3.3.1.4 Apparatus and Materials
3.3.1.4.1 Sampling Train
3.3.1.4.1.1 A schematic of the sampling train used in this method
is shown in Figure 3.3-1. This sampling train configuration is adapted from
EPA Method 5 procedures, and, as such, the majority of the required equipment
is identical to that used in EPA Method 5 determinations. The new components
required are a glass nozzle and probe, a Teflon union, a quartz-fiber or
Teflon mat filter (see Section 3.3.1.5.5), a Teflon frit, and acidic and
alkaline absorbing solutions.
3.3.1.4.1.2 Construction details for the basic train components are
provided in Section 3.4 of EPA's Quality Assurance Handbook, Volume III
(Reference 2); commercial models of this equipment are also available.
3-71
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I
-J
NJ
Thwmoooiipto —*
Glass
Al glass sampta aiposad aurtaoa to harar
Ihstmonwiar
Optional Knochoul
WSOrrtOIN H,S(
4189
Figure 3.3-1 Isokinetic HC1/C10 Sampling Train
-------
Additionally, the following subsections identify allowable train configuration
modifications.
3.3.1.4.1.3 Basic operating and maintenance procedures for the
sampling train are also described in Reference 2. As correct usage is
important in obtaining valid results, all users should refer to Reference 2
and adopt the operating and maintenance procedures outlined therein unless
otherwise specified. The sampling train consists of the components detailed
below.
3.3.1.4.1.3.1 Probe nozzle. Glass with sharp, tapered (30° angle)
leading edge. The taper shall be on the outside to preserve a constant I.D.
The nozzle shall be buttonhook or elbow design. The nozzle should be coupled
to the probe liner using a Teflon union. It is recommended that a stainless
steel nut be used on this union. In cases where the stack temperature exceeds
210°C (410°F), a one-piece glass nozzle/liner assembly must be used. A range
of nozzle sizes suitable for isokinetic sampling should be available. Each
nozzle shall be calibrated according to the procedures outlined in EPA Method
5 (see References 1 and 2).
3.3.1.4.1.3.2 Probe liner. Borosilicate or quartz-glass tubing
with a heated system capable of maintaining a gas temperature of 120 + 14°C
(248 + 25°F) at the exit end during sampling. Because the actual temperature
at the outlet of the probe is not usually monitored during sampling, probes
constructed and calibrated according to the procedure in Reference 2 are
considered acceptable. Either borosilicate or quartz-glass probe liners may
be used for stack temperatures up to about 480°C (900°F) . Quartz liners shall
be used for temperatures between 480 and 900°C (900 and 1650°F) . (The
softening temperature for borosilicate is 820°C (1508°F), and for quartz is
1500°C (2732°F).) Water-cooling of the stainless steel sheath will be
necessary at temperatures approaching and exceeding 500°C.
3.3.1.4.1.3.3 Pitot tube. Type S, as described in Section 2.1 of
EPA Method 2 (Reference 1). The pitot tube shall be attached to the probe to
allow constant monitoring of the stack-gas velocity. The impact
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(high-pressure) opening plane of the pitot tube shall be even with or above
the nozzle entry plane (see Section 3.1.1 of Reference 2) during sampling.
The Type S pitot tube assembly shall have a known coefficient, determined as
outlined in Section 3.1.1 of Reference 2.
3.3.1.4.1.3.4 Differential pressure gauge. Inclined manometer or
equivalent device as described in Section 2.2 of EPA Method 2 (Reference 1).
One manometer shall be used for velocity-head (delta P) readings and the other
for orifice differential pressure (delta H) readings.
3.3.1.4.1.3.5 Cyclone (optional). Glass.
3.3.1.4.1.3.6 Filter holder. Borosilicate glass, with a Teflon
frit filter support and a sealing gasket. The sealing gasket shall be
constructed of Teflon or equivalent materials. The holder design shall
provide a positive seal against leakage at any point along the filter circum-
ference. The holder shall be attached immediately to the outlet of the
cyclone.
3.3.1.4.1.3.7 Filter heating system. Any heating system capable of
maintaining a temperature of 120 + 14°C (248 ± 25°F) around the filter and
cyclone during sampling. A temperature gauge capable of measuring temperature
to within 3°C (5.4°F) shall be installed so that the temperature around the
filter holder can be regulated and monitored during sampling.
3.3.1.4.1.3.8 Impinger train. The following system shall be used
to determine the stack gas moisture content and to collect HC1 and C12: five
or six impingers connected in series with leak-free ground glass fittings or
any similar leak-free non-contaminating fittings. The first impinger shown in
Figure 1 (knockout or condensate impinger) is optional and is recommended as a
water knockout trap for use under test conditions which require such a trap.
If used, this impinger should be constructed as described below for the
alkaline impingers, but with a shortened stem, and should contain 50 ml of 0.1
N H2S04. The following two impingers (acid impingers which each contain 100
ml of 0.1 N H2S04) shall be of the Greenburg-Smith design with the standard
3-74
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tip (see Method 5, Paragraph 2.1.7). The next two impingers (alkaline
impingers which each contain 100 ml of 0.1 N NaOH) and the last impinger
(containing silica gel) shall be of the Greenburg-Smith design modified by
replacing the tip with a 1.3-cm (1/2-in) I.D. glass tube extending about 1.3
cm (1/2 in) from the bottom of the impinger (see Method 5, Paragraph 2.1.7).
The condensate, acid, and alkaline impingers shall contain known quantities of
the appropriate absorbing reagents. The last impinger shall contain a known
weight of silica gel or equivalent desiccant.
3.3.1.4.1.3.9 Metering system. The necessary components are a
vacuum gauge, leak-free pump, thermometers capable of measuring temperature to
within 3°C (5.4°F), dry-gas meter capable of measuring volume to within 1
percent, an orifice meter (rate meter), and related equipment, as shown in
Figure 1. At a minimum, the pump should be capable of 4 cfm free flow, and
the dry-gas meter should have a recording capacity of 0-999.9 cu ft with a
resolution of 0.005 cu ft. Other metering systems capable of maintaining
sampling rates within 10 percent of isokineticity and of determining sample
volumes to within 2 percent may be used. The metering system should be used
in conjunction with a pitot tube to enable checks of isokinetic sampling
rates.
3.3.1.4.1.3.10 Barometer. Mercury, aneroid, or other barometer
capable of measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg).
In many cases, the barometric reading may be obtained from a nearby National
Weather Service station, in which case the station value (which is the
absolute barometric pressure) is requested and an adjustment for elevation
differences between the weather station and sampling point is applied at a
rate of minus 2.5 mm Hg (0.1 in. Hg) per 300-m (100 ft) elevation increase
(vice versa for elevation decrease).
3.3.1.4.1.3.11 Gas density determination equipment. Temperature
sensor and pressure gauge (as described in Sections 2.3 and 2.4 of EPA Method
2), and gas analyzer, if necessary (as described in EPA Method 3, Reference
1). The temperature sensor ideally should be permanently attached to the
pitot tube or sampling probe in a fixed configuration such that the tip of the
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sensor extends beyond the leading edge of the probe sheath and does not touch
any metal. Alternatively, the sensor may be attached just prior to use in the
field. Note, however, that if the temperature sensor is attached in the
field, the sensor must be placed in an interference-free arrangement with
respect to the Type S pitot tube openings (see EPA Method 2, Figure 2-7). As
a second alternative, if the stack gas is saturated, the stack temperature may
be measured at a single point near the center of the stack.
3.3.1.4.1.3.12 Ascarite tube for conditioning ambient air. Tube
tightly packed with approximately 150.-g of. fresh. 8 to 20 mesh Ascarite IIR
sodium hydroxide coated silica, or equivalent, to dry and remove acid gases
from the ambient air used to remove moisture from the filter and optional
cyclone. The inlet and outlet ends of the tube should be packed with at least
1 cm thickness of glass wood or filter material suitable to prevent escape of
Ascarite II fines. Fit one end with flexible tubing, etc. to allow connection
to probe nozzle.
3.3.1.4.2 Sample Recovery.
3.3.1.4.2.1 Probe liner. Probe and nozzle brushes; nylon bristle
brushes with stainless, steel wire handles are required. The probe brush shall
have extensions of stainless steel, Teflon, or inert material at least as long
as the probe. The brushes shall be properly sized and shaped to brush out the
probe liner and the probe nozzle.
3.3.1.4.2.2 Wash bottles. Two. Polyethylene or glass, 500 ml or
larger.
3.3.1.4.2.3 Glass sample storage containers. Glass, 500- or 1000-
ml. Screw-cap liners shall be Teflon and constructed so as to be leak-free.
Narrow-mouth glass bottles have been found to exhibit less tendency toward
leakage.
3.3.1.4.2.4 Petri dishes. Glass or plastic, sealed around the
circumference with Teflon tape, for storage and transport of filter samples.
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3.3.1.4.2.5 Graduated cylinder and/or balances. To measure
condensed water to the nearest 1 ml or 1 g. Graduated cylinders shall have
subdivisions not >2 ml. Laboratory triple-beam balances capable of weighing
to + 0.5 g or better are required.
3.3.1.4.2.6 Plastic storage containers. Screw-cap polypropylene or
polyethylene containers to store silica gel.
3.3.1.4.2.7 Funnel and rubber policeman. To aid in transfer of
silica gel to container (not necessary if silica gel is weighed in field).
3.3.1.4.2.8 Funnels. Glass, to aid in sample recovery.
3.3.1.5 Reagents
3.3.1.5.1 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
higher purity to permit its use without lessening the accuracy of the determi-
nation.
3.3.1.5.2 ASTM Type II water (ASTM D1193-77 (1983)). All referenc-
es to water in the method refer to ASTM Type II unless otherwise specified.
It is advisable to analyze a blank sample of this reagent prior to sampling,
since the reagent blank values obtained during the field sample analysis must
be less than 10 percent of the sample values (see Method 9057).
3.3.1.5.3 Sulfuric acid (0.1 N) , H2S04. Used as the HC1 absorbing
reagent in the impinger train. To prepare 1 L, slowly add 2.80 ml of concen-
trated H2SOA to about 900 ml of water while stirring, and adjust the final
volume to 1 L using additional water. Shake well to mix the solution. It is
advisable to analyze a blank sample of this reagent prior to sampling, since
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the reagent blank values obtained during the field sample analysis must be
less than 10 percent of the sample values (see Method 9057).
3.3.1.5.4 Sodium hydroxide (0.1 N), NaOH. Used as the C12 absorb-
ing reagent in the impinger train. To prepare 1 L, dissolve 4.00 g of solid
NaOH in about 900 ml of water and adjust the final volume of 1 L using
additional water. Shake well to mix the solution. It is advisable to analyze
a blank sample of this reagent prior to sampling, since the reagent blank
values obtained during the field sample analysis must be less than 10 percent
of the•sample- values (see Method-9057).
3.3.1.5.5 Filter. Quartz-fiber or Teflon mat (e.g., PallflexR
TX40HI45) filter.
3.3.1.5.6 Silica gel. Indicating type, 6-16 mesh. If previously
used, dry at 175°C (350°F) for 2 hours before using. New silica gel may be
used as received. Alternatively, other types of desiccants (equivalent or
better) may be used, subject to the approval of the Administrator.
3.3.1.5.7 Acetone. When using this train for determination of
particulate emissions, reagent grade acetone, <0.001 percent residue, in glass
bottles is required. Acetone from metal containers generally has a high
residue blank and should not be used. Sometimes suppliers transfer acetone to
glass bottles from metal containers; thus, acetone blanks shall be run prior
to field use and only acetone with low blank values (<0.001 percent) shall be
used. In no case shall a blank value greater than 0.001 percent of the weight
of acetone used be subtracted from the sample weight.
3.3.1.5.8 Crushed ice. Quantities ranging from 10-50 Ibs may be
necessary during a sampling run, depending on ambient air temperature.
3.3.1.5.9 Stopcock grease. Acetone-insoluble, heat-stable silicone
grease may be used, if needed. Silicone grease usage is not necessary if
screw-on connectors or Teflon sleeves on ground-glass joints are used.
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3.3.1.6 Sample Collection, Preservation, and Handling
3.3.1.6.1 Sample collection is described in this method. The
analytical procedures for HC1 and C12 are described in Method 9057 and for
particulate matter in EPA Method 5 (Reference 1).
3.3.1.6.2 Samples should be stored in clearly labeled, tightly
sealed containers between sample recovery and analysis. They may be analyzed
up to four weeks after collection.
3.3.1.7 Procedure
3.3.1.7.1 Preparation for Field Test.
3.3.1.7.1.1 All sampling equipment shall be maintained and cali-
brated according to the procedures described in Section 3.4.2 of EPA's Quality
Assurance Handbook, Volume III (Reference 2).
3.3.1.7.1.2 Weigh several 200- to 300-g portions of silica gel in
airtight containers to the nearest 0.5 g. Record on each container the total
weight of the silica gel plus containers. As an alternative to preweighing
the silica gel, it may instead be weighed directly in the impinger just prior
to train assembly.
3.3.1.7.1.3 Check filters visually against light for irregularities
and flaws or pinhole leaks. Label the shipping containers (glass or plastic
Petri dishes) and keep the filters in these containers at all times except
during sampling (and weighing for particulate analysis).
3.3.1.7.1.4 If a particulate determination will be conducted,
desiccate the filters at 20 + 5.6°C (68 + 10°F) and ambient pressure for at
least 24 hours, and weigh at intervals of at least 6 hours to a constant
weight (i.e., <0.5-mg change from previous weighing), recording results to the
nearest 0.1 mg. During each weighing, the filter must not be exposed for more
than a 2-min period to the laboratory atmosphere and relative humidity above
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50 percent. Alternatively (unless otherwise specified by the Administrator),
the filters may be oven-dried at 105°C (220°F) for 2-3 hours, desiccated for 2
hours, and weighed.
3.3.1.7.2 Preliminary Field Determinations.
3.3.1.7.2.1 Select the sampling site and the minimum number of
sampling points according to EPA Method 1 or as specified by the Administra-
tor. Determine the stack pressure, temperature, and range of velocity heads
using EPA Method 2. It is recommended that a leak-check of the pitot lines
(see EPA Method 2, Section 3.1) be performed. Determine the stack-gas
moisture content using EPA Method 4 or its alternatives to establish estimates
of isokinetic sampling rate settings. Determine the stack gas dry molecular
weight, as described in EPA Method 2, Section 3.6. if integrated EPA Method 3
(Reference 1) sampling is used for molecular weight determination, the
integrated bag sample shall be taken simultaneously with, and for the same
total length of time as the sample run.
3.3.1.7.2.2 Select a nozzle size based on the range of velocity
heads so that it is not necessary to change the nozzle size to maintain
isokinetic sampling rates. During the run, do not change the nozzle. Ensure
that the proper differential pressure gauge is chosen for the range of
velocity heads encountered (see Section 2.2 of EPA Method 2).
3.3.1.7.2.3 Select a suitable probe liner and probe length so that
all traverse points can be sampled. For large stacks, to reduce the length of
the probe, consider sampling from opposite sides of the stack.
3.3.1.7.2.4 The total sampling time should be two hours. Allocate
the same time to all traverse points defined by EPA Method 1. To avoid
timekeeping errors, the length of time sampled at each traverse point should
be an integer or an integer plus one-half min. Size the condensate impinger
for the expected moisture catch or be prepared to empty it during the run.
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3.3.1.7.3 Preparation of Sampling Train
3.3.1.7.3.1 Add 50 ml of 0.1 N H2SO<, to the condensate impinger, if
used. Place 100 ml of 0.1 N H2S04 in each of the next two impingers. Place
100 ml of 0.1 N NaOH in each of the following two impingers. Finally,
transfer approximately 200-300 g of preweighed silica gel from its container
to the last impinger. More silica gel may be used, but care should be taken
to ensure that it is not entrained and carried out from the impinger during
sampling. Place the silica gel container in a clean place for later use in
the sample recovery. Alternatively, the weight of the silica gel plus
impinger may be determined to the nearest 0.5 g and recorded.
3.3.1.7.3.2 Using a tweezer or clean disposable surgical gloves,
place a labeled (identified) filter (weighed, if particulate matter to be
determined) in the filter holder. Be sure that the filter is properly
centered and the gasket properly placed to prevent the sample gas stream from
circumventing the filter. Check the filter for tears after assembly is
completed.
3.3.1.7.3.3 To use glass liners, install the selected nozzle using
a Viton-A 0-ring when stack temperatures are <260°C (500°F) and a woven glass-
fiber gasket when temperatures are higher. Other connecting systems utilizing
either 316 stainless steel or Teflon ferrules may be used. Mark the probe
with heat-resistant tape or by some other method to denote the proper distance
into the stack or duct for each sampling point.
3.3.1.7.3.4 Set up the train as in Figure 3.3-1. A minimal amount
of silicone grease may be used on ground glass joints. Connect temperature
sensors to the appropriate potentiometer/display unit. Check all temperature
sensors at ambient temperature.
3.3.1.7.3.5 Place crushed ice around the impingers.
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3.3.1.7.3.6 Turn on and set the filter and probe heating systems at
the desired operating temperatures. Allow time for the temperatures to
stabilize.
3.3.1.7.4 Leak-Check Procedures.
3.3.1.7.4.1 Pretest leak-check. A pretest leak-check is recommend-
ed, but not required. If the tester opts to conduct the pretest leak-check,
the following procedure shall be used.
3.3.1.7.4.1.1 If a Viton-A 0-ring or other leak-free connection is
used in assembling the probe nozzle to the probe liner, leak-check the train
at the sampling site by plugging the nozzle and pulling a 380-mm Hg (15-in.
Hg) vacuum.
NOTE: A lower vacuum may be used, provided that it is not
exceeded during the test.
3.3.1.7.4.1.2 If a woven glass-fiber gasket is used, do not connect
the probe to the train during the leak-check. Instead, leak-check the train
by first plugging the inlet to the cyclone, if used, or the filter holder and
pulling a 380-mm Hg (15-in. Hg) vacuum (see NOTE above). Then, connect the
probe to the train and leak-check at about 25-mm Hg (1-in. Hg) vacuum;
alternatively, leak-check the probe with the rest of the sampling train in one
step at 380-mm Hg (15-in. Hg) vacuum. Leakage rates in excess of 4 percent of
the average sampling rate or 0.00057 m3/min (0.02 cfm), whichever is less, are
unacceptable.
3.3.1.7.4.1.3 The following leak-check instructions for the
sampling train may be helpful. Start the pump with bypass valve fully open
and coarse adjust valve completely closed. Partially open the coarse adjust
valve and slowly close the bypass valve until the desired vacuum is reached.
Do not reverse direction of the bypass valve; this will cause water to back up
into the filter holder. If the desired volume is exceeded, either leak-check
at this higher vacuum or end the leak-check, as shown below, and start over.
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3.3.1.7.4.1.4 When the leak-check is completed, first slowly remove
the plug from the inlet to the probe, cyclone, or filter holder and immediate-
ly turn off the vacuum pump. This prevents the liquid in the impingers from
being forced backward into the filter holder and silica gel from being
entrained backward into the fifth impinger.
3.3.1.7.4.2 Leak-checks during sample run. If during the sampling
run, a component (e.g., filter assembly or impinger) change becomes necessary
or a port change is conducted, a leak-check shall be conducted immediately
after the interruption of sampling and before the change is made. The leak-
check shall be conducted according to the procedure outlined in Section
3.3.1.7.4.1, except that it shall be conducted at a vacuum greater than or
equal to the maximum value recorded up to that point in the test. If the
leakage rate is found to be no greater than 0.00057 m3/min (0.02 cfm) or 4
percent of the average sampling rate (whichever is less), the results are
acceptable. If a higher leakage rate is obtained, the tester shall void the
sampling run. Immediately after a component change or port change, and before
sampling is reinitiated, another leak-check similar to a. pre-test leak-check
is recommended.
3.3.1.7.4.3 Post-test leak-check. A leak-check is mandatory at the
conclusion of each sampling run. The leak-check shall be done using the same
procedures as those with the pre-test leak-check, except that it shall be
conducted at a vacuum greater than or equal to the maximum value reached
during the sampling run. If the leakage rate is found to be no greater than
0.00057 m3/min (0.02 cfm) or 4 percent of the average sampling rate (whichever
is less), the results are acceptable. If a higher leakage rate is obtained,
the tester shall void the sampling run.
3.3.1.7.5 Train Operation.
3.3.1.7.5.1 During the sampling run, maintain an isokinetic
sampling rate to within 10 percent of true isokinetic, unless otherwise
specified by the Administrator. Maintain a temperature around the filter and
(cyclone, if used) of 120 + 14°C (248 + 25°F) .
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3.3.1.7.5.2 For each run, record the data required on a data sheet
such as the one shown in Figure 3.3-2. Be sure to record the initial dry gas
meter reading. Record the dry gas meter readings at the beginning and end of
each sampling time increment, when changes in flow rates are made before and
after each leak-check, and when sampling is halted. Take other readings
required by Figure 3.3-2 at least once at each sample point during each time
increment and additional readings when significant changes (20 percent
variation in velocity head readings) necessitate additional adjustments in
flow rate. Level and zero the manometer. Because the manometer level and
zero may drif.t due, to vibrations,,and.temperature changes, make periodic checks
during the traverse.
3.3.1.7.5.3 Clean the stack access ports prior to the test run to
eliminate the chance of sampling deposited material. To begin sampling,
remove the nozzle cap, verify that the filter and probe heating systems are at
the specified temperature, and verify that the pitot tube and probe are
positioned properly. Position the nozzle at the first traverse point, with
the tip pointing directly into the gas stream. Immediately start the pump and
adjust the flow to isokinetic conditions using a calculator or a nomograph.
Nomographs are designed for use when the Type S pitot tube coefficient is 0.84
±0.02 and the stack gas equivalent density (dry molecular weight) is equal to
29+4. If the stack gas molecular weight and the pitot tube coefficient are
outside the above ranges, do not use the nomographs unless appropriate steps
are taken to compensate for the deviations (see Reference 3).
3.3.1.7.5.4 When the stack is under significant negative pressure
(equivalent to the height of the impinger stem), take care to close the coarse
adjust valve before inserting the probe into the stack, to prevent water from
backing into the filter holder. If necessary, the pump may be turned on with
the coarse adjust valve closed.
3.3.1.7.5.5 When the probe is in position, block off the openings
around the probe and stack access port to prevent unrepresentative dilution of
the gas stream.
3-84
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Plant
Location ___
Operator _^___
Dace
Run No. _^^__
Sample Box No.
Meter Box No.
Meter H*
C
Factor
Pltot Tube Coefficient
Ambient Termperature
Barometric Pressure
Assumed Moisture X
Probe Length, m (ft)
Nozzle Identification No. ______________
Average Calibrated Nozzle Diameter, cm (In)
Probe Heater Setting __________________
Leak Rate, i»3/mln. (cfm)
Probe Liner Material
Schematic of Stack Cross Section
Static Pressure, mm Hg (In Hg)
Filter No.
Traverse Point
Number
Total
Average
Samp line
Line
(0) mln
Vacuum
n Hg
(In. Hg)
Stack
Temperature
(Ts)
°C(f)
Velocity
Head
-------
3.3.1.7.5.6 Traverse the stack cross section, as required by EPA
Method 1 or as specified by the Administrator, being careful not to bump the
probe nozzle into the stack walls when sampling near the walls or when
removing or inserting the probe through the access port, in order to minimize
the chance of extracting deposited material.
3.3.1.7.5.7 During the test run, make periodic adjustments to keep
the temperature around the filter holder (and cyclone, if used) at the proper
level. Add more ice, and, if necessary, salt to maintain a temperature of
<20°C (68°F) at the condenser/silica gel outlet. Also, periodically check the
level and zero of the manometer.
3.3.1.7.5.8 If the pressure drop across the filter becomes too
high, making isokinetic sampling difficult to maintain, it may be replaced in
the midst of a sample run. Using another complete filter holder assembly is
recommended, rather than attempting to change the filter itself. After a new
filter assembly is installed, conduct a leak-check. If determined, the total
particulate weight shall include the summation of all filter assembly catches.
3.3.1.7.5.9 If the condensate impinger becomes too full, it may be
emptied, recharged with 50 ml of 0.1 N H2S04, and replaced during the sample
run. The condensate emptied must be saved and included in the measurement of
the volume of moisture collected and included in the sample for analysis. The
additional 50 ml of absorbing reagent must also be considered in calculating
the moisture. After the impinger is reinstalled in the train, conduct a leak-
check.
3.3.1.7.5.10 A single train shall be used for the entire sample
run, except in cases where simultaneous sampling is required in two or more
separate ducts or at two or more different locations within the same duct, or
in cases where equipment failure necessitates a change of trains. In all
other situations, the use of two or more trains will be subject to the
approval of the Administrator.
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3.3.1.7.5.11 Note that when two or more trains are used, separate
analyses of the particulate catch (if applicable) and the HC1 and C12 impinger
catches from each train shall be performed, unless identical nozzle sizes were
used on all trains. In that case, the particulate catch and the HC1 and C12
impinger catches from the individual trains may be combined, and a single
particulate analysis and single HC1 and C12 analyses of the impinger contents
may be performed.
3.3.1.7.5.12 At the end of the sample run, turn off the coarse
adjust valve, remove the probe and nozzle from the stack, turn off the pump,
and record the final dry gas meter reading.
3.3.1.7.5.13 If there is any possibility that liquid has collected
in the glass cyclone and/or on the filter, connect the Ascarite tube at the
probe inlet and operate the train with the filter heating system at 120 + 14°C
(248 + 25°F) at a low flow rate (e.g., AH - 1) sufficient to vaporize the
liquid and any HC1 in the cyclone or on the filter and pull it through the
train into the impingers. After 30 minutes, turn off the flow, remove the
Ascarite tube, and examine the cyclone and filter for any visible moisture.
If moisture is visible, repeat this step for 15 minutes.
3.3.1.7.5.14 Conduct a post-test leak check. Also, leak-check the
pitot lines as described in EPA Method 2. The lines must pass this leak-check
in order to validate the velocity-head data.
3.3.1.7.5.15 If the moisture value is available, calculate percent
isokineticity (see Section 3.3.1.7.7.10) to determine whether the run was
valid or another test run should be conducted.
3.3.1.7.6 Sample Recovery.
3.3.1.7.6.1 Allow the probe to cool. When the probe can be handled
safely, wipe off all the external surfaces of the tip of the probe nozzle and
place a cap over the tip. Do not cap the probe tip tightly while the sampling
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train is cooling down because this will create a vacuum in the filter holder,
drawing water from the impingers into the holder.
3.3.1.7.6.2 Before moving the sampling train to the cleanup site,
remove the probe, wipe off any silicone grease, and cap the open outlet, being
careful not to lose any condensate that might be present. Wipe off any
silicone grease and cap the filter or cyclone inlet. Remove the umbilical
cord from the last impinger and cap the impinger. If a flexible line is used
between the first impinger and the filter holder, disconnect it at the filter
holder and let any condensed water drain into the first impinger. Wipe off
any silicone grease and cap the filter holder outlet and the impinger inlet.
Ground glass stoppers, plastic caps, serum caps, Teflon tape, ParafilmR, or
aluminum foil may be used to close these openings.
3.3.1.7.6.3 Transfer the probe and filter/impinger assembly to the
cleanup area. This area should be clean and protected from the weather to
minimize sample contamination or loss.
3.3.1.7.6.4 Save portions of all washing solutions used for cleanup
(acetone and Type II water) and the absorbing reagents (0.1 N H2SOA and 0.1 N
NaOH) as blanks. Transfer 200 ml of each solution directly from the wash
bottle being used (rinse solutions) or the supply container (absorbing
reagents) and place each in a separate, prelabeled glass sample container.
3.3.1.7.6.5 Inspect the train prior to and during disassembly and
note any abnormal conditions.
3.3.1.7.6.6 Container No. 1 (filter catch for particulate determi-
nation) . Carefully remove the filter from the filter holder and place it in
its identified Petri dish container. Use one or more pair of tweezers to
handle the filter. If it is necessary to fold the filter, ensure that the
particulate cake is inside the fold. Carefully transfer to the Petri dish any
particulate matter or filter fibers that adhere to the filter holder gasket,
using a dry nylon bristle brush or sharp-edged blade, or both. Label the
container and seal with Teflon tape around the circumference of the lid.
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3.3.1.7.6.7 Container No. 2 (front-half rinse for particulate
determination). Taking care that dust on the outside of the probe or other
exterior surfaces does not get into the sample, quantitatively recover
particulate matter or any condensate from the probe nozzle, probe fitting,
probe liner, and front half of the filter holder by washing these components
with acetone into a glass container. Retain an acetone blank and analyze with
the samples.
3.3.1.7.6.8 Perform rinses as follows: carefully remove the probe
nozzle and clean the inside surface by rinsing with acetone from a wash bottle
and brushing with a nylon bristle brush. Brush until the rinse shows no
visible particles; then make a final rinse of the inside surface with the
acetone. Brush and rinse the inside parts of the Swagelok fitting with the
acetone in a similar way until no visible particles remain.
3.3.1.7.6.9 Have two people rinse the probe liner with acetone by
tilting and rotating the probe while squirting acetone into its upper end so
that all inside surfaces will be wetted with solvent. Let the acetone drain
from the lower end into the sample container. A glass funnel may be used to
aid in transferring liquid washed to the container.
3.3.1.7.6.10 Follow the acetone rinse with a probe brush. Hold the
probe in an inclined position and squirt acetone into the upper end while
pushing the probe brush through the probe with a twisting action; place a
sample container underneath the lower end of the probe and catch any acetone
and particulate matter that is brushed from the probe. Run the brush through
the probe three or more times until no visible particulate matter is carried
out with the acetone or until none remains in the probe liner on visual
inspection. Rinse the brush with acetone and quantitatively collect these
washings in the sample container. After the brushing, make a final acetone
rinse of the probe as described above. Between sampling runs, keep brushes
clean and protected from contamination.
3.3.1.7.6.11 Clean the inside of the front half of the filter
holder and cyclone by rubbing the surfaces with a nylon bristle brush and
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rinsing with acetone. Rinse each surface three times, or more if needed, to
remove visible particulate. Make a final rinse of the brush and filter
holder. Carefully rinse out the glass cyclone and cyclone flask (if applica-
ble) . Brush and rinse any particulate material adhering to the inner surfaces
of these components into the front-half rinse sample. After all rinses and
particulate matter have been collected in the sample container, tighten the
lid on the sample container so that acetone will not leak out when it is
shipped to the laboratory. Mark the height of the fluid level to determine
whether leakage occurs during transport. Label the container to identify its
contents.
3.3.1.7.6.12 Container No. 3 (knockout and acid impinger catch for
moisture and HC1 determination). Disconnect the impingers. Measure the
liquid in the acid and knockout impingers to within +1 ml by using a graduated
cylinder or by weighing it to within ±0.5 g by using a balance (if one is
available). Record the volume or weight of liquid present. This information
is required to calculate the moisture content of the effluent gas. Quantita-
tively transfer this liquid to a leak-free sample storage container. Rinse
these impingers, connecting glassware (and tubing, if used), and the back half
of the filter holder with water and add these rinses to the storage container.
Seal the container, shake to mix, and label. The fluid level should be marked
so that if any sample is lost during transport, a correction proportional to
the lost volume can be applied. Retain rinse water and acidic absorbing
solution blanks and analyze with the samples.
3.3.1.7.6.13 Container No. 4 (alkaline impinger catch for C12 and
moisture determination). Measure and record the liquid in the alkaline
impingers as described in Section 3.3.1.7.6.12. Quantitatively transfer this
liquid to a leak-free sample storage container. Rinse these two impingers and
connecting glassware with water and add these rinses to the container. Seal
the container, shake to mix, and label; mark the fluid level. Retain alkaline
absorbing solution blank and analyze with the samples.
3.3.1.7.6.14 Container No. 5 (silica gel for moisture determina-
tion) . Note the color of the indicating silica gel to determine if it has
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been completely spent and make a notation of its condition. Transfer the
silica gel from the last impinger to its original container and seal. A
funnel may make it easier to pour the silica gel without spilling. A rubber
policeman may be used as an aid in removing the silica gel from the impinger.
It is not necessary to remove the small amount of dust particles that may
adhere strongly to the impinger wall. Because the gain in weight is to be
used for moisture calculations, do not use any water or other liquids to
transfer the silica gel. If a balance is available in the field, weigh the
container and its contents to 0.5 g or better.
3.3.1.7.6.15 Prior to shipment, recheck all sample containers to
ensure that the caps are well secured. Seal the lids of all containers around
the circumference with Teflon tape. Ship all liquid samples upright and all
particulate filters with the particulate catch facing upward.
3.3.1.7.7 Calculations. Retain at least one extra decimal figure
beyond those contained in the available data in intermediate calculations, and
round off only the final answer appropriately.
3.3.1.7.7.1 Nomenclature.
^ - Cross-sectional area of nozzle, m2 (ft2).
Bws - Water vapor in the gas stream, proportion by volume.
Ca - Acetone blank residue concentration, mg/mg.
cd ~ TyPe s Pitot tube coefficient (nominally 0.84 + 0.02),
dimensionless.
ca - Concentration of particulate matter in stack gas, dry
basis, corrected to standard conditions, g/dscm (g/dscf).
I - Percent of isokinetic sampling.
ma - Mass of residue of acetone after evaporation, mg.
M,, - Total amount of particulate matter collected, mg.
Md - Stack-gas dry molecular weight, g/g-mole (Ib/lb-mole).
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^ - Molecular weight of water, 18.0 g/g-mole (18.0 Ib/lb-
mole).
Pbar - Barometric pressure at the sampling site, mm Hg (in. Hg).
Ps - Absolute stack-gas pressure, mm Hg (in. Hg).
Pstd - Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
I - Ideal gas constant, 0.06236 mm Hg-m3 (K-g-mole (21.85 in.
Hg-ft3/°R-lb-mole).
rm - Absolute average dry-gas meter temperature (see Figure 2),
Orr / On \
fi. \ K.J *
Cs - Absolute average stack-gas temperature (see Figure 2), °K
Lstd
V
1C
V,
m(std)
V,
w(std)
Y
AH
Pa
Standard absolute temperature, 293°K (528°R).
Total volume of liquid collected in the impingers and
silica gel, ml.
Volume of gas sample is measured by dry-gas meter, dscm
(dscf).
Volume of gas sample measured by the dry-gas meter, cor-
rected to standard conditions, dscm (dscf).
Volume of water vapor in the gas sample, corrected to
standard conditions, scm (scf).
Stack-gas velocity, calculated by Method 2, Equation 2-9,
using data obtained from Method 5, m/sec (ft/sec).
Weight of residue in acetone wash, mg.
Volume of acetone blank, ml.
Volume of acetone used in wash; ml.
Dry-gas-meter calibration factor, dimensionless.
Average pressure differential across the orifice meter, mm
H20 (in H20).
Density of acetone, mg//il (see label on bottle).
Density of water, 0.9982 g/ml (0.002201 Ib/ml).
Total sampling time, min.
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13.6 - Specific gravity of mercury.
60 - Sec/min.
100 - Conversion to percent.
3.3.1.7.7.2 Average dry gas meter temperature and average orifice
pressure drop. See data sheet (Figure 3.3-2).
3.3.1.7.7.3 Dry gas volume. Correct the sample measured by the dry
gas meter to standard conditions (20°C, 760 mm Hg [68°F, 29.92 in. Hg]) by
using Equation 1:
Tstd Pbar + AH/13.6 Pbar + AH/13.6
VmY - KiVn,Y (1)
where:
K: - 0.3858 K/mm Hg for metric units, or
K! = 17.64°R/in. Hg for English units.
3.3.1.7.7.4 Volume of water vapor.
Pw RTstd
- vio _ - K2 Vlc (2)
where:
K2 - 0.001333 m3/ml for metric units, or
K2 - 0.04707 m3/ml for English units.
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3.3.1.7.7.5 Moisture content.
(3)
Vw(std)
Vm(std) + Vw(std)
NOTE: In saturated or water-droplet-laden gas streams, two
calculations of the moisture content of the stack gas
shall be made, one from the impinger analysis (Equation 3)
and a second from the assumption of saturated conditions .
The lower of the two values of Bw shall be considered
correct. The procedure for determining the moisture
content based upon assumption of saturated conditions is
given in the Note to Section 1.2 of Method 4. For the
purposes of this method, the average stack gas temperature
from Figure 2 may be used to make this determination,
provided that the accuracy of the in- stack temperature
sensor is ± 1°C (2°F) .
3.3.1.7.7.6 Acetone blank concentration. For particulate determi-
nation.
Ca - (4)
3.3.1.7.7.7 Acetone wash blank. For particulate determination.
W. - Ca Vaw A, (5)
3.3.1.7.7.8 Total particulate weight. Determine the total particu-
late catch from the sum of the weights obtained from Container Nos. 1 and 2
less the acetone blank (Wa) .
3.3.1.7.7.9 Particulate concentration.
c, - (0.001 g/mgXniB/V.j.i,,,) (6)
3.3.1.7.7.10 Isokinetic variation.
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3.3.1.7.7.4.10.1 Calculation from raw data.
100 TS[K3F1C + (Vm/Tm) (Pbar + H/13.6)]
I - (7)
60 9 VsPsAn
where:
K3 - 0.003454 mm Hg-m3/ml-K for metric units, or
K3 - 0.002669 in. Hg-ft3/ml °R for English units.
3.3.1.7.4.10.2 Calculation for intermediate values.
TsVm(std)P5td100
(8)
(8)
P.V.A., 0U-BWS)
where:
K4 - 4.320 for metric units, or
K4 - 0.09450 for English units.
3.3.1.7.4.10.3 Acceptable units. If 90 percent < I < 110 percent,
the results are acceptable. If the results are low in comparison with the
standard and I is beyond the acceptable range, or if I is less than 90
percent, the Administrator may opt to accept the results.
3.3.1.8 Quality Control
3.3.1.8.1 Sampling. See EPA Manual 600/4-77-027b for Method 5
quality control.
3.3.1.8.2 Analysis. At the present time, a validated audit
material does not exist for this method. Analytical quality control proce-
dures are detailed in Method 9057.
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3.3.1.9 Method Performance
3.3.1.9.1 The in-stack detection limit for the method is approxi-
mately 0.02 /ig of HC1 per liter of stack gas. The method has a negative bias
below 20 ppm HC1 (Reference 6).
3.3.1.9.2 It is preferable to include the cyclone in the sampling
train to protect the filter from any moisture present. There is research in
progress regarding the necessity of the cyclone at low moisture sources and
the use of Ascarite II in .the .drying .procedure- (Section 3.3.1.7.5.12).
REFERENCES
1. U.S. Environmental Protection Agency, 40 CFR Part 60, Appendix A, Methods
1-5.
2. U.S. Environmental Protection Agency, "Quality Assurance Handbook for Air
Pollution Measurement Systems, Volume III, Stationary Source Specific
Methods," Publication No. EPA-600/4-77-027b, August 1977.
3. Shigehara, R.T., Adjustments in the EPA Nomography for Different Pitot
Tube Coefficients and Dry Molecular Weights, Stack Sampling News, 2:4-11
(October 1974).
4. Steinsberger, S.C. and J.H. Margeson, "Laboratory and Field Evaluation of
a Methodology for Determination of Hydrogen Chloride Emissions from
Municipal and Hazardous Waste Incinerators," U.S. Environmental Protec-
tion Agency, Office of Research and Development, Report No. EPA 600/3-
89/064, NTIS PB89 220586-AS.
5. State of California, Air Resources Board, Method 421, "Determination of
Hydrochloric Acid emissions from Stationary Sources," March 18, 1987.
6. Entropy Environmentalists, Inc., "Laboratory Evaluation of a Sampling and
Analysis Method for Hydrogen Chloride Emissions from Stationary Sources:
Interim Report," EPA Contract No. 68-02-4442, Research Triangle Park,
North Carolina, January 22, 1988.
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3.3.2 Mideet Impinger HCl/Cl, Emission Sampling Train (Method 0051')
3.3.2.1 Scope and Application
3.3.2.1.1 This method describes the collection of hydrogen chloride
(HC1, CAS Registry Number 7647-01-0) and chlorine (C12, CAS Registry Number
7782-50-5) in stack gas emission samples from hazardous waste incinerators,
municipal waste combustors, and boilers and industrial furnaces. The collect-
ed samples are analyzed using Method 9057. This method is designed to collect
HC1/C12 in their gaseous forms. Sources, such as those controlled by wet
scrubbers, that emit acid particulate matter (e.g., HC1 dissolved in water
droplets) must be sampled using an isokinetic HC1/C12 sampling train (see
Method 0050).
3.3.2.2 Summary of Method
3.3.2.2.1 An integrated gas sample is extracted from the stack and
passes through a particulate filter, acidified water, and finally through an
alkaline solution. The filter serves to remove particulate matter such as
chloride salts which could potentially react and form analyte in the absorbing
solutions. In the acidified water absorbing solution, the HC1 gas is solubi-
lized and forms chloride ions (Cl~) as follows:
HC1 + H20 - H30+ + Cl"
The C12 gas present in the emissions has a very low solubility in acidified
water and passes through to the alkaline absorbing solution where it undergoes
hydrolysis to form a proton (H+), Cl", and hypochlorous acid (HC10) as
follows:
H20 + C12 - H+ + Cl" + HC10
The Cl" ions in the separate solutions are measured by ion chromatography
(Method 9057).
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3.3.2.3 Interferences
3.3.2.3.1 Volatile materials which produce chloride ions upon
dissolution during sampling are obvious interferences in the measurement of
HC1. One interferant for HC1 is diatomic chlorine (C12) gas which dispropor-
tionates to HC1 and hypochlorous acid (HC10) upon dissolution in water. C12
gas exhibits a low solubility in water, however, and the use of acidic rather
than neutral or basic solutions for collection of hydrogen chloride gas
greatly reduces the dissolution of any chlorine present. Sampling a 400 ppm
HC1 gas stream containing 50 ppm C12 with this method does not cause a
significant bias. Sampling a 220 ppm HC1 gas stream containing 180 ppm C12
results in a positive bias of 3.4 percent in the HC1 measurement.
3.3.2.3.2 Reducing agents such as S02 may cause a positive bias in
the C12 measurement by the following reaction:
HC10 + HS03" - H2S04 + Cl"
3.3.2.4 Apparatus and Materials
3.3.2.4.1 Sampling Train. The sampling train is shown in Figure 1
and component parts are discussed below.
3.3.2.4.1.1 Probe. Borosilicate glass, approximately 3/8-in (9-mm)
inside diameter, with a heating system to prevent condensation. When the
concentration of alkaline particulate matter in the emissions is high, a 3/8-
in (9-mm) inside diameter Teflon elbow should be attached to the inlet of the
probe; a 1-in (25-mm) length of Teflon tubing with a 3/8-in (9-mm) inside
diameter should be attached at the open end of the elbow to permit the opening
of the probe to be burned away from the gas stream, thus reducing the amount
of particulate entering the train. When high concentrations of particulate
matter are not present, the Teflon elbow is not necessary, and the probe inlet
can be perpendicular to the gas stream. When sampling at locations where gas
temperatures are greater than approximately 400°F, such as wet scrubber
inlets, glass or quartz elbows must be used. In no case should a glass wool
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plug be used to remove particulate.matter; use of such a filtering device
could result in a bias in the data.1 Instead, a Teflon filter should be used
as specified in Section 3.3.2.5.5.
3.3.2.4.1.2 Three-way stopcock. A borosilicate, three-way glass
stopcock with a heating system to prevent condensation. The heated stopcock
should connect directly to the outlet of the probe and filter assembly and the
inlet of the first impinger. The heating system should be capable of prevent-
ing condensation up to the inlet of the first impinger. Silicone grease may
be used, if necessary," to-prevent leakage.
3.3.2.4.1.3 Impingers. Five 30-ml midget impingers with leak-free
glass connectors. Silicone grease may be used, if necessary, to prevent
leakage. For sampling at high moisture sources or for extended sampling times
greater than one hour, a midget impinger with a shortened stem (such that the
gas sample does not bubble through the collected condensate) should be used in
front of the first impinger.
3.3.2.4.1.4 Mae West impinger or drying tube. Mae West design
impinger (or drying tube, if a moisture determination is not to be conducted)
filled with silica gel, or equivalent, to dry the gas sample and to protect
the dry gas meter and pump.
3.3.2.4.1.5 Sample Line. Leak-free, with compatible fittings to
connect the last impinger to the needle valve.
3.3.2.4.1.6 Barometer. Mercury, aneroid, or other barometer
capable of measuring atmospheric pressure within 2.5 mm Hg (0.1 in. Hg). In
many cases, the barometric reading may be obtained from a nearby National
Weather Service station, in which case the station value (which is the
absolute barometric pressure) shall be requested and an adjustment for the
elevation differences between the weather station and sampling point shall be
applied at a rate of minus 2.5 mm Hg (0.1 in. Hg) per 30 m (100 ft) elevation
increase or vice versa for elevation decrease.
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3.3.2.4.1.7 Purge pump, purge line, drying tube, needle valve, and
rate meter. Pump capable of purging sample probe at 2 liters/min, with drying
tube, filled with silica gel or equivalent, to protect pump, and a rate meter,
0 to 5 liters/min.
3.3.2.4.1.8 Metering system. The following items comprise the
metering system which is identical to that used for EPA Method 6 (see Refer-
ence 5) .
3.3.2.4.1.8.1 Valve. Needle valve, to regulate sample gas flow
rate.
3.3.2.4.1.8.2 Pump. Leak-free diaphragm pump, or equivalent, to
pull gas through train. Install a small surge tank between the pump and the
rate meter to eliminate the pulsation effect of the diaphragm pump on the
rotameter.
3.3.2.4.1.8.3 Rate meter. Rotameter, or equivalent, capable of
measuring flow rate to within 2 percent of selected flow rate of 2 liters/min.
3.3.2.4.1.8.4 Volume meter. Dry gas meter, sufficiently accurate
to measure the sample volume within 2 percent, calibrated at the selected flow
rate and conditions encountered during sampling, and equipped with a tempera-
ture gauge (dial thermometer or equivalent) capable of measuring temperature
to within 3°C (5.4°F).
3.3.2.4.1.8.5 Vacuum gauge. At least 760 mm Hg (30 in. Hg) gauge
to be used for leak check of the sampling train.
3.3.2.4.2 Sample Recovery.
3.3.2.4.2.1 Wash bottles. Polyethylene or glass, 500 ml or larger,
two.
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3.3.2.4.2.2 Storage bottles. Glass, with Teflon-lined lids, 100
ml, to store impinger samples (two per sampling run).
3.3.2.5 Reagents
3.3.2.5.1 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 determina-
tion.
3.3.2.5.2 ASTM Type II Water (ASTM D1193-77 (1983)). All referenc-
es to water in the method refer to ASTM Type II unless otherwise specified.
It is advisable to analyze a blank sample of this reagent prior to sampling,
since the reagent blank value obtained during the field sample analysis must
be less than 10 percent of the sample values (see Method 9057).
3.3.2.5.3 Sulfuric acid (0.1 N) , H2SO^. Used as the HC1 absorbing
reagent. To prepare 100 ml, slowly add 0.28 ml of concentrated H2SOA to about
90 ml of water while stirring, and adjust the final volume to 100 ml using
additional water. Shake well to 'mix the solution. It is advisable to analyze
a blank sample of this reagent prior to sampling, since the reagent blank
value obtained during the field sample analysis must be less than 10 percent
of the sample values (see Method 9057).
3.3.2.5.4 Sodium hydroxide (0.1 N), NaOH. Used as the C12 absorb-
ing reagent. To prepare 100 ml, dissolve 0.40 g of solid NaOH in about 90 ml
of water and adjust the final volume to 100 ml using additional water. Shake
well to mix the solution. It is advisable to analyze a blank sample of this
reagent prior to sampling, since the reagent blank value obtained during the
field sample analysis must be less than 10 percent of the sample values (see
Method 9057).
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3.3.2.5.5 Filter. Teflon mat PallflexR TXAOHI75 or equivalent.
Locate in a glass, quartz, or Teflon filter holder with a Teflon filter
support in a filter box heated to 250°F.
3.3.2.5.6 Stopcock grease. Acetone- insoluble, heat-stable silicone
grease may be used, if necessary.
3.3.2.5.7 Silica gel. Indicating type, 6- to 16-mesh. If the
silica gel has been used previously, dry at 175°C (350°F) for 2 hours. New
silica gel may be used as received. Alternatively, other types of desiccants
(equivalent or better) may be used.
3.3.2.6 Sample Collection, Preservation, and Handling
3.3.2.6.1 Sample collection is described in this method. The
analytical procedures are described in Method 9057.
3.3.2.6.2 Samples should be stored in clearly labeled, tightly
sealed containers between sample recovery and analysis. They may be analyzed
up to four weeks after collection.
3.3.2.7 Procedure
3.3.2.7.1 Calibration. Section 3.5.2 of EPA's Quality Assurance
Handbook, Volume III (Reference 4) may be used as a guide for these opera-
tions .
3.3.2.7.1.1 Dry Gas Metering System.
3.3.2.7.1.1.1 Initial calibration. Before its initial use in the
field, first leak check the metering system (sample line, drying tube, if
used, vacuum gauge, needle valve, pump, rate meter, and dry gas meter) as
follows: plug the inlet end of the sampling line, pull a vacuum of 250 mm (10
in) Hg, plug off the outlet of the dry gas meter, and turn off the pump. The
vacuum should remain stable for 30 seconds. Carefully release the vacuum from
3-102
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the system by slowly removing the plug from the sample line inlet. Remove the
sampling line (and drying tube, if applicable), and connect the dry gas
metering system to an appropriately sized wet test meter (e.g., 1 liter per
revolution). Make three independent calibration runs, using at least five
revolutions of the dry gas meter per run. Calculate the calibration factor, Y
(wet test meter calibration volume divided by the dry gas meter volume, with
both volumes adjusted to the same reference temperature and pressure), for
each run, and average the results. If any Y value deviates by more than 2
percent from the average, the metering system is unacceptable for use.
Otherwise, use the average'as'the calibration factor for subsequent test runs.
3.3.2.7.1.1.2 Post-test calibration check. After each field test
series, conduct a calibration check as in Section 3.3.2.7.1.1.1 above, except
for the following variations: (a) the leak check is not to be conducted, (b)
three or more revolutions of the dry gas meter may be used, (c) only two
independent runs need to be made. If the calibration factor does not deviate
by more than 5 percent from the initial calibration factor (determined in
Section 3.3.2.7.1.1.1), the dry gas meter volumes obtained during the test
series are acceptable. If the calibration factor deviates by more than 5
percent, recalibrate the metering system as Section 3.3.2.7.1.1.1, and for the
calculations, use the calibration factor (initial or recalibration) that
yields the lower gas volume for each test run.
3.3.2.7.1.2 Thermometer(s). Prior to each field test, calibrate
against mercury-in-glass thermometers at ambient temperature. If the thermom-
eter being calibrated reads within 2°C (2.6°F) of the mercury-in-glass
thermometer, it is acceptable. If not, adjust the thermometer or use an
appropriate correction factor.
3.3.2.7.1.3 Rate meter. The rate meter need not be calibrated, but
should be cleaned and maintained according to the manufacturer's instructions.
3.3.2.7.1.4 Barometer. Prior to each field test, calibrate against
a mercury barometer. The field barometer should agree within 0.1 in. Hg with
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the mercury barometer. If it does,not, the field barometer should be
adjusted.
3.3.2.7.2 Sampling.
3.3.2.7.2.1 Preparation of collection train. Prepare the sampling
train as follows: The first or knockout impinger should have a shortened stem
and be left empty to condense moisture in the gas stream. The next two midget
impingers should each be filled with 15 ml of 0.1 N H2S04, and the fourth and
fifth impingers should each be filled with-15 ml of 0.1 N NaOH. Place a fresh
charge of silica gel, or equivalent, in the Mae West impinger (or the drying
tube). Connect the impingers in series with the knockout impinger first,
followed by the two impingers containing the acidified reagent, the two
impingers containing the alkaline reagent, and the Mae West impinger contain-
ing the silica gel. If the moisture will be determined, weigh the impinger
assembly to the nearest ± 0.5 g and record the weight.
3.3.2.7.2.2 Leak check procedures. Leak check the probe and three-
way stopcock prior to inserting the probe into the stack. Connect the
stopcock to the outlet of the probe, and connect the sample line to the needle
valve. Plug the probe inlet, turn on the sample pump, and pull a vacuum of at
least 250 mm Hg (10 in. Hg). Turn off the needle valve, and note the vacuum
gauge reading. The vacuum should remain stable for at least 30 seconds.
Place the probe in the stack at the sampling location, and adjust the filter
heating system to 250°F and the probe and stopcock heating systems to a
temperature sufficient to prevent water condensation. Connect the first
impinger to the stopcock, and connect the sample line to the last impinger and
the needle valve. Upon completion of a sampling run, remove the probe from
the stack and leak check as described above. If a leak has occurred, the
sampling run must be voided. Alternatively, the portion of the train behind
the probe may be leak checked between multiple runs at the same site as
follows: Close the stopcock to the first impinger (see Figure 3.3-3A), and
turn on the sample pump. Pull a vacuum of at least 250 mm Hg (10 in. Hg),
turn off the needle valve, and note the vacuum gauge reading. The vacuum
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o
Ln
Mr if RON it wt
Mr it r i ON IUK
t»*SS IMEM WRMTCO
WIM IK AT WE
THHCiMMV
a ASS
SIOPCOCM
SIMNtESS
SIEFl
FIHMO
KIPIIONMI
NEEOIE
VAiVC
Figure 3.3-3 Midget Impinger HC1/C12 Sampling Train
411
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should remain stable for at least 30 seconds. Release the vacuum on the
impinger train by turning the stopcock to the vent position to permit ambient
air to enter (see Figure 3.3-3B). If this procedure is used, the full train
leak check described above must be conducted following the final run and all
preceding sampling runs voided if a leak has occurred.
3.3.2.7.2.3 Purge procedure. Immediately prior to sampling,
connect the purge line to the stopcock and turn the stopcock to permit the
purge pump to purge the probe (see Figure 3.3-3A). Turn on the purge pump,
and adjust the purge rate to 2 liters/min. Purge for at least 5 minutes prior
to sampling.
3.3.2.7.2.4 Sample collection. Turn on sample pump, pull a slight
vacuum of approximately 25 mm Hg (1 in. Hg) on the impinger train, and turn
the stopcock to permit stack gas to be pulled through the impinger train (see
Figure 3.3-3C). Adjust the sampling rate to 2 liters/min, as indicated by the
rate meter, and maintain this rate within 10 percent during the entire
sampling run. Take readings of the dry gas meter, the dry gas meter tempera-
ture, rate meter, and vacuum gauge at least once every five minutes during the
run. A sampling time of one hour is recommended. However, if the expected
condensate catch for this sampling run duration will exceed the capacity of
the sampling train, (1) a larger knockout impinger may be used or (2) two
sequential half-hour runs may be conducted. At the conclusion of the sampling
run, remove the train from the stack, cool, and perform a leak check as
described in Section 3.3.2.7.2.2.
3.3.2.7.3 Sample recovery. Following sampling, disconnect the
impinger train from the remaining sampling equipment at the inlet to the
knockout impinger and the outlet to the last impinger. If performing a
moisture determination, wipe off any moisture on the outside of the train and
any excess silicone grease at the inlet and outlet openings; weigh the train
to the nearest 0.5 g and record this weight. Then disconnect the impingers
from each other. Quantitatively transfer the contents of the first three
impingers (the knockout impinger and the two 0.1 N H2SOA impingers) to a leak-
free storage bottle. Add the water rinses of each of these impingers and
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connecting glassware from the second set of impingers (containing the 0.1 N
NaOH) should be recovered in a similar manner if a C12 analysis is desired.
The sample bottle should be marked so that if any sample is lost during
transport, a correction proportional to the lost volume can be applied. Save
portions of the 0.1 N H2SOA and 0.1 N NaOH used as impinger reagents as
reagent blanks. Take 50 ml of each and place in separate leak-free storage
bottles. Label and mark the fluid levels as previously described.
3.3.2.7.4 Calculations. Retain at least one extra decimal figure
beyond those contained in the available data in intermediate calculations, and
round off only the final answer appropriately.
3.3.2.7.4.1 Nomenclature.
Pstd
R
Lstd
V
Ic
"m(std)
V,
w(std)
Water vapor in the gas stream, proportion by volume.
Molecular weight of water, 18.0 g/g-mole (18.0 Ib/lb-
mole).
Barometric pressure at the exit orifice of the dry
gas meter, mm Hg (in. Hg).
Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Ideal gas constant, 0.06236 mm Hg-m3/°K-g-mole (21.85
in. Hg-ft3/°R-lb-mole).
Average dry gas meter absolute temperature, °K (°R) .
Standard absolute temperature, 293°K (528°R).
Total volume of liquid collected in impingers and
silica gel, ml (equivalent to the difference in
weight of the impinger train before and after sam-
pling, 1 mg - 1 ml).
Dry gas volume as measured by the dry gas meter, dcm
(dcf).
Dry gas volume measured by the dry gas meter, cor-
rected to standard conditions, dscm (dscf).
Volume of water vapor in the gas sample, corrected to
standard conditions, scm (scf).
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Y - Dry gas meter calibration factor.
pw - Density of water, 0.9982 g/ral (0.002201 Ib/ml)
3.3.2.7.4.2 Sample volume, dry basis, corrected to standard
conditions. Calculate as described below:
L.td
:bar
std
where:
- 0.3858°K/mm Hg for metric units.
- 17.64°R/in. Hg for English units.
3.3.2.7.4.3 Volume of water vapor.
(1)
- K2Vlc
(2)
where:
K2 - 0.0013333 m3/ml for metric units.
- 0.04707 ft3/ml for English units.
3.3.2.7.4.4 Moisture content.
'w(.td)
(3)
3.3.2.8 Quality Control
3.3.2.8.1 At the present time, a validated audit material does not
exist for this method. Analytical quality control procedures are detailed in
Method 9057.
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3.3.2.9 Method Performance
3.3.2.9.1 The in-stack detection limit for the method is approxi-
mately 0.08 ng of HC1 per liter of stack gas for a 1-hour sample.
3.3.2.9.2 The precision and bias for measurement of HC1 using this
sampling protocol combined with the analytical protocol of Method 9057 have
been determined. The within laboratory relative standard deviation is 6.2
percent and 3.2 percent at HC1 concentrations of 3.9 and 15.3 ppm, respective-
ly. The method does not exhibit any bias for HC1 when sampling at C12
concentrations less than 50 ppm. '
REFERENCES
1. Steinsberger, S.C. and J.H. Margeson, "Laboratory and Field Evaluation of
a Methodology for Determination of Hydrogen Chloride Emissions from
Municipal and Hazardous Waste Incinerators," U.S. Environmental Protec-
tion Agency, Office of Research and Development, Report No. EPA 600/3-
89/064, NTIS PB 89 220586-AS.
2. State of California, Air Resources Board, Method 421, "Determination of
Hydrochloric Acid Emissions from Stationary Sources," March 18, 1987.
3. Entropy Environmentalists, Inc., "Laboratory Evaluation of a Sampling and
Analysis Method for Hydrogen Chloride Emissions from Stationary Sources:
Interim Report," EPA Contract No. 68-02-4442, Research Triangle Park,
North Carolina, January 22, 1988.
4. U.S. Environmental Protection Agency, "Quality Assurance Handbook for Air
Pollution Measurement Systems, Volume III, Stationary Source Specific
Methods," Publication No. EPA-600/4-77-027b, August 1977.
5. U.S. Environmental Protection Agency, 40 CFR Part 60, Appendix A,
Method 6.
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3.3.3 Protocol for Analysis of Samples from HC1/C1, Emission Sampling
Train fMethod 9057)
3.3.3.1 Scope and Application
3.3.3.1.1 This method describes the analytical protocol for
determination of hydrogen chloride (HC1, CAS Registry Number 7647-01-0) and
chloride (C12, CAS Registry Number 7782-50-5) in stack gas emission samples
collected from hazardous waste and municipal waste incinerators using the
midget impinger HC1/C12 sampling train (Method 0051) or the isokinetic HC1/C12
sampling train (Method 0050).
3.3.3.1.2 The lower detection limit is 0.1 ng of chloride (Cl~) per
ml of sample solution. Samples with concentrations which exceed the linear
range of the analytical instrumentation may be diluted.
3.3.3.1.3 This method is recommended for use only by analysts
experienced in the use of ion chromatography and in the interpretation of ion
chromatograms.
3.3.3.2 Summary of Method
3.3.3.2.1 The stoichiometry of HC1 and C12 collection in the
sampling train (see Methods 0050 and 0051) is as follows: In the acidified
water absorbing solution, the HC1 gas is solubilized and forms chloride ions
(Cl~) according to the following formula:
HC1 + H20 - Had* + Cl'
The C12 gas present in the emissions has a very low solubility in acidified
water and passes through to the alkaline absorbing solution where it undergoes
hydrolysis to form a proton (H+), Cl", and hypochlorous acid (HC10) as shown:
H,0 + Cl, - H+ + Cl' + HC10
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Non-suppressed or suppressed ion chromatography (1C) is used for analysis of
the Cl'.
3.3.3.3 Interferences
3.3.3.3.1 Volatile materials which produce chloride ions upon
dissolution during sampling are obvious interferences in the measurement of
HC1. One likely interferant is diatomic chlorine (C12) gas which dispropor-
tionates to HC1 and hypochlorous acid (HOC1) upon dissolution in water. C12
gas exhibits a low solubility in water, however, and the use of acidic rather
than neutral or basic solutions for collection of hydrogen chloride gas
greatly reduces the dissolution of any chlorine present. Sampling a 400 ppm
HC1 gas stream containing 50 ppm C12 with this method does not cause a
significant bias. Sampling a 220 ppm HC1 gas stream containing 180 ppm C12
results in a positive bias of 3.4 percent in the HC1 measurement. Other
interferants have not been encountered.
3.3.3.3.2 Reducing agents such as S02 may cause a positive bias in
the C12 measurement by the following reaction:
HC10 + HS03' - H2S04 + Cl"
3.3.3.4 Apparatus and Materials
3.3.3.4.1 Volumetric Flasks. Class A, various sizes.
3.3.3.4.2 Volumetric Pipettes. Class A, assortment, to dilute
samples to calibration range of the 1C.
3.3.3.4.3 Ion Chromatograph. Suppressed or non-suppressed, with a
conductivity detector and electronic integrator operating in the peak area
mode. Other detectors, a strip chart recorder, and peak heights may be used
provided the 5 percent repeatability criteria for sample analysis and the
linearity criteria for the calibration curve can be met.
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3.3.3.5 Reagents
3.3.3.5.1 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 determina-
tion.
3.3.3.5.2 ASTM Type II Water (ASTM D1193-77 (1983)). All referenc-
es to water in the method refer to ASTM Type II unless otherwise specified.
3.3.3.5.3 Sulfuric acid (0.1 N) , H2S04. To prepare 100 ml, slowly
add 0.28 ml of concentrated H2S04 to about 90 ml of water while stirring, and
adjust the final volume to 100 ml using additional water. Shake well to mix
the solution.
3.3.3.5.4 Sodium hydroxide (0.1 N), NaOH. To prepare 100 ml,
dissolve 0.40 g of solid NaOH in about 90 ml of water and adjust the final
volume to 100 ml using additional water. Shake well to mix the solution.
3.3.3.5.5 Reagent blank solutions. A separate blank solution of
each sampling train reagent used and collected in the field (0.1 N H2SOA and
0.1 N NaOH) should be prepared for analysis with the field samples. For
midget impinger train sample analysis, dilute 30 ml of each reagent with rinse
water collected in the field as a blank to the final volume of the samples;
for isokinetic train sample analysis, dilute 200 ml to the same final volume
as the field samples also using the blank sample of rinse water.
3.3.3.5.6 Sodium chloride, NaCl, stock standard solution. Solu-
tions containing a nominal certified concentration of 1000 mg/L NaCl are
commercially available as convenient stock solutions from which working
standards can be made by appropriate volumetric dilution. Alternately,
concentrated stock solutions may be produced from reagent grade NaCl that has
3-112
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been dried at 110°C for two or more hours and then cooled to room temperature
in a desiccator immediately before weighing. Accurately weigh 1.6 to 1.7 g of
the dried NaCl to within 0.1 mg, dissolve in water, and dilute to 1 liter.
The exact Cl" concentration can be calculated using the equation:
Mg ClYml - g of NaCl x 103 x 35.453/58.44
Refrigerate the stock standard solutions and store no longer than one month.
3.3.3.5.7 Chromatographic eluent. Effective eluents for non-
suppressed ion chromatography using a resin- or silica-based weak ion exchange
column are a 4 mM potassium hydrogen phthalate solution, adjusted to a pH of
4.0 using a saturated sodium borate solution, and a mM 4-hydroxy benzoate
solution, adjusted to a pH of 8.6 using 1 N sodium hydroxide. An effective
eluent for suppressed ion chromatography is a solution containing 3 mM sodium
bicarbonate and 2.4 mM sodium carbonate. Other dilute solutions buffered to a
similar pH that contain no ions interfering with the chromatographic analysis
may be used. If, using suppressed ion chromatography, the "water dip"
resulting from sample injection is interfering with the chlorine peak, use a 2
mM sodium hydroxide/2.4 mM sodium bicarbonate eluent.
3.3.3.6 Sample Collection, Preservation, and Handling
3.3.3.6.1 Sample collection using the midget impinger HC1/C12 train
or the isokinetic HC1/C12 train is described in Method 0051 or 0050, respec-
tively.
3.3.3.6.2 Samples should be stored in clearly labeled, tightly
sealed containers between sample recovery and analysis. They may be analyzed
up to four weeks after collection.
3.3.3.7 Procedure
3.3.3.7.1 Sample preparation for analysis. Check the liquid level
in each sample, and determine if any sample was lost during shipment. If a
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noticeable amount of leakage has occurred, the volume can be determined from
the difference between the initial and final solution levels, and this value
can be used to correct the analytical results. For midget impinger train
samples, quantitatively transfer each sample solution to a 100 ml volumetric
flask and dilute to 100 ml with water. For isokinetic sampling train samples,
quantitatively transfer each sample to a volumetric flask or graduated
cylinder and dilute with water to a final volume appropriate for all samples.
3.3.3.7.2 Calibration of Ion Chromatograph.
3.3.3.7.2.1 The ion chromatographic conditions will depend on the
type of analytical column used and whether suppressed or non-suppressed ion
chromatography is used. Prior to calibration and sample analysis, establish a
stable baseline. Next, inject a sample of water, and determine if any Cl"
appears in the chromatogram. If Cl" is present, repeat the load/injection
procedure until no Cl" is present.
3.3.3.7.2.2 To prepare the calibration standards, dilute given
amounts (1.0 ml or greater) of the stock standard solution to convenient
volumes, using 0.1 H2S04 or 0.1 NaOH as appropriate. Prepare at least four
standards that are within the linear range of the field samples. Inject the
calibration standards, starting with the lowest concentration standard first,
both before and after injection of the quality control check sample, reagent
blank, and field samples. This allows compensation for any instrument drift
occurring during sample analysis.
3.3.3.7.2.3 Determine the peak areas, or heights, of the standards
and plot individual values versus Cl" concentrations in /ig/ml. Draw a smooth
curve through the points. Use linear regression to calculate a formula
describing the resulting linear curve.
3.3.3.7.3 Sample analysis. Between injections of the series of
calibration standards, inject in duplicate the reagent blanks and the field
samples, including a matrix spike sample. Measure the areas or heights (same
as done for the calibration standards) of the Cl" peaks. Use the average
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response to determine the concentrations of the field samples, matrix spike,
and reagent blanks using the linear calibration curve. The results for a
reagent blank should not exceed 10 percent of the corresponding value for a
field sample.
3.3.3.7.4 Calculations. Retain at least one extra decimal figure
beyond those contained in the available data in intermediate calculations, and
round off only the final answer appropriately.
3.3.3.7.4.1 Total ng HCl per sample. Calculate as described below:
"HC1 - (S-B) x Vs x 36.46/35.453 (1)
where: "HCl - Mass of HCl in sample, ^g,
S - Analysis of sample, fig Cl"/ml,
B - Analysis of reagent blank, pg Cl'/ml,
Vs - Volume of filtered and diluted sample, ml,
36.46 - Molecular weight of HCl, ^g//ig-mole, and
35.45 - Atomic weight of Cl", jjg//ig-mole.
3.3.3.7.4.2 Total ng C12 per sample. Calculate as described below:
MC12 - (S-B) x V2 x 70.91/35.45 (2)
where: MC12 - Mass of C12 in sample, ng,
70.91 - Molecular weight of C12, /ig/Mg-mole, and
35.45 - Atomic weight of Cl", ^g//ig-mole.
3.3.3.7.4.3 Concentration of HCl in the flue gas. Calculate as
described below:
C - K x m/Vn(std) (3)
where: C - Concentration of HCl or C12, dry basis, mg/dscm,
K - 10"3 mg//*g,
m - Mass of HCl or C12 in sample, pg, and
Vm(std) - Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm (from Method
0050 or Method 0051).
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3.3.3.8 Quality Control
3.3.3.8.1 At the present time, a validated audit material does not
exist for this method. However, it is strongly recommended that a quality
control check sample and a matrix spike sample be used.
3.3.3.8.1.1 Quality control check sample. Chloride solutions of
reliably known concentrations are available for purchase from the National
Bureau of Standards (SRM 3182). The QC check sample should be prepared in the
appropriate absorbing reagent at a concentration approximately equal to the
mid range calibration standard. The quality control check sample should be
injected in duplicate immediately after the calibration standards have been
injected for the first time. The Cl" value obtained for the check sample
using the final calibration curve should be within 10 percent of the known
value for the check sample.
3.3.3.8.1.2 Matrix spike sample. A portion of at least one field
sample should be used to prepare a matrix spike sample. Spike the sample
aliquot in the range of the expected concentration. Analyze the matrix spike
sample in duplicate along with the field samples. Based on the matrix spike
results, determine the recovery for the spiked material. This should be
within 10 percent of the known spike value.
3.3.3.9 Method Performance
3.3.3.9.1 The lower detection limit of the analytical method is 0.1
Mg of Cl* per ml of sample solution. Samples with concentrations which exceed
the linear range of the 1C may be diluted.
3.3.3.9.2 The precision and bias for analysis of HC1 using this
analytical protocol have been measured in combination with the midget impinger
HC1/C12 train (Method 0051) for sample collection. The within-laboratory
relative standard deviation is 6.2 percent and 3.2 percent at HC1 concentra-
tions of 3.9 and 15.3 ppm, respectively. The method does not exhibit any bias
for HC1 when sampling at C12 concentrations less than 50 ppm.
3-116
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REFERENCES
1. Steinsberger, S.C. and J.H. Margeson, "Laboratory and Field Evaluation of
a Methodology for Determination of Hydrogen Chloride Emissions from
Municipal and Hazardous Waste Incinerators," U.S. Environmental Protec-
tion Agency, Office of Research and Development, Report No. EPA 600/3-
89/064, NTIS PB89 220586-AS.
2. State of California, Air Resources Board, Method 421, "Determination of
Hydrochloric Acid Emissions from Stationary Sources," March 18, 1987.
3. Entropy Environmentalists, Inc., "Laboratory Evaluation of a Sampling and
Analysis Method for Hydrogen Chloride emissions from Stationary Sources:
Interim Report," EPA-Contract No. 68-02-4442, Research Triangle Park,
North Carolina, January 22, 1988.
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3.4 Determination of Polvchlorinated Dibenzo-p-Dioxlns (PCDDs) and
Polvchlorinated Dibenzofurans (PCDFs) from Stationary Sources
(Method 23)
3.4.1 Applicability and Principle
3.4.1.1 Applicability. This method is applicable to the determina-
tion of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-
furans (PCDFs) from stationary sources.
3.4.1.2 Principle. A sample is withdrawn from the gas stream
isokinetically and collected in the sample probe, on a glass fiber filter, and
on a packed column of adsorbent material. The sample cannot be separated into
a particle vapor fraction. The PCDDs and PCDFs are extracted from the sample,
separated by high resolution gas chromatography, and measured by high resolu-
tion mass spectrometry.
3.4.2 Apparatus
3.4.2.1 Sampling. A schematic of the sampling train used in this
method is shown in Figure 3.4-1. Sealing greases may not be used in assem-
bling the train. The train is identical to that described in Section 2.1 of
Method 5 (40 CFR Part 60, Appendix A) with the following additions:
3.4.2.1.1 Reagents. 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.
3.4.2.1.2 Nozzle. The nozzle shall be made of nickel, nickel-
plated stainless steel, quartz, or borosilicate glass.
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. I III 01 I loli 101
Gooseneck
8Typ«PttolTub«
. |oiii|MiinUiioSoii!;u«
XA»-2 Imp
(I) loiiipeinltneSouioi
Vnci't'iii
Una
riv-xi-i
Figure 3.4-1 Sampling Train
-------
3.4.2.1.3 Sample Transfer Lines. The sample transfer lines, if
needed, shall be heat-traced, heavy walled TFE (1/2 in. OD with 1/8 in. wall)
with connecting fittings that are capable of forming leak-free, vacuum-tight
connections without using sealing greases. The line shall be as short as
possible and must be maintained at 120°C.
3.4.2.1.4 Filter Support. Teflon or Teflon-coated wire.
3.4.2.1.5 Condenser. Glass, coil type with compatible fittings. A
schematic diagram is shown in Figure 3.4-2.
3.4.2.1.6 Water Bath. Thermostatically controlled to maintain the
gas temperature exiting the condenser at <20°C (68°F).
3.4.2.1.7 Adsorbent Module. Glass container to hold the solid
adsorbent. A schematic diagram is shown in Figure 3.4-2. Other physical
configurations of the resin trap/condenser assembly are acceptable. The
connecting fittings shall form leak-free, vacuum tight seals. No sealant
greases shall be used in the sampling train. A coarse glass frit is included
to retain the adsorbent.
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Condenser
Sotbenl Trap
Flue Gas Flow
$20/15
I
t~>
N)
37cm-
8 mm Glass Cooliofj Coil
To Suit
$20/16
Water Jacket Cooling Coil Glass Wool ring Wuler Jacket XAU - 2 Glass Sintered Disk
Figure 3.4-2 Condenser and adsorbent trap
-------
3.4.2.2 Sample Recovery.
3.4.2.2.1 Fitting Caps. Ground glass, Teflon tape, or aluminum
foil (Section 3.4.2.2.6) to cap off the sample-exposed sections of the train.
3.4.2.2.2 Wash Bottles. Teflon, 500-ml.
3.4.2.2.3 Probe-Liner Probe-Nozzle, and Filter-Holder Brushes.
Inert bristle brushes with precleaned stainless steel or Teflon handles. The
probe brush shall have extensions of stainless steel or Teflon, at least as
long as the probe. The brushes shall be properly sized and shaped to brush
out the nozzle, probe liner, and transfer line, if used.
3.4.2.2.4 Filter Storage Container. Sealed filter holder, wide-
mouth amber glass jar with Teflon-lined cap, or glass petri dish.
3.4.2.2.5 Balance. Triple beam.
3.4.2.2.6 Aluminum Foil. Heavy duty, hexane-rinsed.
3.4.2.2.7 Metal Storage Container. Air-tight container to store
silica gel.
3.4.2.2.8 Graduated Cylinder. Glass, 250-ml with 2-ml graduation.
3.4.2.2.9 Glass sample Storage container. Amber glass bottle for
sample glassware washes, 500- or 1000-ml, with leak-free Teflon-lined caps.
3.4.2.3 Analysis.
3.4.2.3.1 Sample Container. 125- and 250-ml flint glass bottles
with Teflon-lined caps.
3.4.2.3.2 Test Tube. Glass.
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3.4.2.3.3 Soxhlet Extraction Apparatus. Capable of holding 43 x
123 mm extraction thimbles.
3.4.2.3.4 Extraction Thimble. Glass, precleaned cellulosic, or
glass fiber.
3.4.2.3.5 Pasteur Pipettes. For preparing liquid chromatographic
columns.
3.4.2.3.6 Reacti-vials. Amber glass, 2-ml, silanized prior to use.
3.4.2.3.7 Rotary Evaporator. Buchi/Brinkman RF-121 or equivalent.
3.4.2.3.8 Nitrogen Evaporator Concentrator. N-Evap Analytical
Evaporator Model III or equivalent.
3.4.2.3.9 Separatory Funnels. Glass, 2-liter.
3.4.2.3.10 Gas Chromatograph. Consisting of the following compo-
nents :
3.4.2.3.10.1 Oven. Capable of maintaining the separation column at
the proper operating temperature +1°C and performing programmed increases in
temperature at rates of at least 3°C/min.
3.4.2.3.10.2 Temperature Gauge. To monitor column, oven, detector,
and exhaust temperatures +1°C.
3.4.2.3.10.3 Flow System. Gas metering system to measure sample,
fuel, combustion gas, and carrier gas flows.
3.4.2.3.10.4 Capillary Columns. A fused silica column, 60 x 0.25
mm inside diameter (ID), coated with DB-5 and a fused silica column, 30 m x
0.25 mm ID coated with DB-225. Other column systems may be used provided that
the user is able to demonstrate, using calibration and performance checks,
3-123
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that the column system is able to meet the specifications of Section
3.4.6.1.2.2.
3.4.2.3.11 Mass Spectrometer. Capable of routine operation at a
resolution of 1:10000 with a stability of ±5 ppm.
3.4.2.3.12 Data System. Compatible with the mass spectrometer and
capable of monitoring at least five groups of 25 ions.
3.4.2.3.13 Analytical Balance. To measure within 0.1 mg.
3.4.3 Reagents
3.4.3.1 Sampling.
3.4.3.1.1 Filters. Glass fiber filters, without organic binder,
exhibiting at least 99.95 percent efficiency (<0.05 percent penetration) on
0.3-micron dioctyl phthalate smoke particles. The filter efficiency test
shall be conducted in accordance with ASTM Standard Method D 2986-71
(Reapproved 1978) (incorporated by reference - see §60.17).
3.4.3.1.1.1 Precleaning. All filters shall be cleaned before their
initial use. Place a glass extraction thimble, 1 g of silica gel, and a plug
of glass wool into a Soxhlet apparatus, charge the apparatus with toluene, and
reflux for a minimum of 3 hours. Remove the toluene and discard it, but
retain the silica gel. Place no more than 50 filters in the thimble onto the
silica gel bed and top with the cleaned glass wool. Charge the Soxhlet with
toluene and reflux for 16 hours. After extraction, allow the Soxhlet to cool,
remove the toluene extract, and retain it for analysis. Remove the filters
and dry them under a clean N2 stream. Store the filters in a glass petri dish
sealed with Teflon tape.
3.4.3.1.2 Adsorbent Resin. Amberlite XAD-2 resin, thoroughly
cleaned before initial use.
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3.4.3.1.2.1 Cleaning Procedure. This procedure.may be carried out
in a giant Soxhlet extractor. An all-glass filter thimble containing an
extra-coarse frit is used for extraction of XAD-2. The frit is recessed 10-15
mm above a crenelated ring at the bottom of the thimble to facilitate drain-
age. The resin must be carefully retained in the extractor cup with a glass
wool plug and a stainless steel ring because it floats on methylene chloride.
This process involves sequential extraction in the following order:
Solvent Procedure
Water Initial rinse: Place resin in a beaker,
rinse once with water, and discard. Fill
with water a second time, let stand over-
night, and discard.
Water Extract with water for 8 hours.
Methanol Extract for 22 hours.
Methylene Chloride Extract for 22 hours.
Methylene Chloride Extract for 22 hours.
(fresh)
3.4.3.1.2.2 Drying.
3.4.3.1.2.2.1 Drying Column. Pyrex pipe, 10.2 cm ID by 0.6 m long,
with suitable retainers.
3.4.3.1.2.2.2 Procedure. The adsorbent must be dried with clean
inert gas. Liquid nitrogen from a standard commercial liquid nitrogen
cylinder has proven to be a reliable source of large volumes of gas free from
organic contaminants. Connect the liquid nitrogen cylinder to the column by a
length of cleaned copper tubing, 0.95 cm ID, coiled to pass through a heat
source. A convenient heat source is a water-bath heated from a. steam line.
The final nitrogen temperature should only be warm to the touch and not over
40°C. Continue flowing nitrogen through the adsorbent until all the residual
solvent is removed. The flow rate should be sufficient to gently agitate the
particles but not so excessive as to cause the particles to fracture.
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3.4.3/1.2.3 Quality Control Check, the adsorbent oust be checked
for residual methylene chloride as well as PCDDs and PCDFs.
3.4.3.1.2.3.1 Extraction. Weigh a 1.0 g sample of dried resin into
a small vial, add 3 ml of toluene, cap the vial, and shake it well.
3.4.3.1.2.3.2 Analysis. Inject a 2-nl sample of the extract into a
gas chromatograph operated under the following conditions:
Column: 6 ft x 1/8 in. stainless steel containing 10 percent OV-1.01
on 100/120 Supelcoport.
Carrier Gas: Helium at a rate of 30 ml/min.
Detector: Flame ionization detector operated at a sensitivity of 4
x 10'11 A/mV.
Injection Fort Temperature: 250°C.
Detector Temperature: 305°C.
Oven Temperature: 30°C for 4 min; programmed to rise at 40°C/min
until it reaches 250°C; return to 30°C after 17 minutes.
Compare the results of the analysis to the results from the refer-
ence solution. Prepare the reference solution by injecting 2.5 j*l of methy-
lene chloride into 100 ml of toluene. This corresponds to 100 pg of methylene
chloride per g of Adsorbent. The maximum acceptable concentration is 1000
pg/g of adsorbent. If the adsorbent exceeds this level, drying must be
continued until Che excess methylene chloride is removed.
3.4.3.1.2.3.3 Storage. The adsorbent must be used within 4 weeks
of cleaning. After cleaning, it may be stored in a wide mouth amber glass
container with a Teflon-lined cap or placed in one of the glass adsorbent
modules tightly sealed with glass stoppers. If precleaned adsorbent is
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purchased in sealed containers, it must be used within 4 weeks after the seal
is broken.
3.4.3.1.3 Glass Wool. Cleaned by sequential immersion in three
aliquots of methylene chloride, dried in a 110°C oven, and stored in a
methylene chloride-washed glass jar with a Teflon-lined screw cap.
3.4.3.1.4 Water. Deionized distilled and stored in a methylene
chloride-rinsed glass container with a Teflon-lined screw cap.
3.4.3.1.5 Silica Gel. Indicating type, 6 to 16 mesh. If previous-
ly used, dry at 175°C (350°F) for two hours. New silica gel may be used as
received. Alternatively, other types of desiccants (equivalent or better) may
be used, subject to the approval of the Administrator.
3.4.3.1.6 Chromic Acid Cleaning Solution. Dissolve 20 g of sodium
dichromate in 15 ml of water, and then carefully add 400 ml of concentrated
sulfuric acid.
3.4.3.2 Sample Recovery.
3.4.3.2.1 Acetone. Pesticide quality.
3.4.3.2.2 Methylene Chloride. Pesticide quality.
3.4.3.2.3 Toluene. Pesticide quality.
3.4.3.3 Analysis.
3.4.3.3.1 Potassium Hydroxide. ACS grade, 2-percent
(weight/volume) in water.
3.4.3.3.2 Sodium Sulfate. Granulated, reagent grade. Purify prior
to use by rinsing with methylene chloride and oven drying. Store the cleaned
material in a glass container with a Teflon-lined screw cap.
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3.4.3.5.3 Sulfurtc Acid. Reagent^ grade
3.4.3.3.4 Sodium Hydroxide. 1.0 N. Weigh 40 g of sodium hydroxide
into a 1-liter volumetric flask. Dilute to 1 liter with water.
3.4.3.3.5 Hexane. Pesticide grade.
3.4.3.3.6 Methylene Chloride. Pesticide grade.
3.4.3.3.7 Benzene. Pesticide grade.
3.4.3.3.8 Ethyl Acetate.
3.4.3.3.9 Methanol. Pesticide grade.
3.4.3.3.10 Toluene. Pesticide grade.
3.4.3.3.11 Nonane. Pesticide grade.
3.4.3.3.12 Cyclohexane. Pesticide grade.
3.4.3.3.13 Basic Alumina. Activity grade 1, 100-200 mesh. Prior
to use, activate the alumina by heating for 16 hours at 130°C before use.
Store in a desiccator. Pre-activated alumina may be purchased from a supplier
and may be used as received.
3.4.3.3.14 Silica Gel. Blo-Sil A, 100-200 mesh. Prior to use.
activate the silica gel by heating for at least 30 minutes at 180°C. After
cooling, rinse the silica gel sequentially with methanol and methylene
chloride. Heat the rinsed silica gel at 50°C for 10 minutes, and then
increase the temperature gradually to 180°C over 25 minutes and maintain it at
this temperature for 90 minutes. Cool at room temperature and store in a
glass container with a Teflon-lined screw cap.
3.4.3.3.15 Silica Gel Impregnated with Sulfuric Acid. Combine
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100 g of silica gel with 44 g of concentrated sulfuric acid in a screw-capped
• * . *
glass bottle and agitate thoroughly. Dispense the solids with a stirring rod
until a uniform mixture is obtained. Store the mixture in a glass container
with a Teflon-lined screw cap.
3.4.3.3.16 Silica Gel Impregnated with Sodium Hydroxide. Combine
39 g of 1 N sodium hydroxide with 100 g of silica gel in a screw-capped glass
bottle and agitate thoroughly. Disperse solids with a stirring rod until a
uniform mixture is obtained. Store the mixture in glass container with a
Teflon-lined screw cap.
3.4.3.3.17 Carbon/Celite. Combine 10.7 g of AX-21 carbon with
124 g of Celite 545 in a 250-ml glass bottle with a Teflon-lined screw cap.
Agitate the mixture thoroughly until a uniform mixture is obtained. Store in
the glass container.
3.4.3.3.18 Nitrogen. Ultra high purity.
3.4.3.3.19 Hydrogen. Ultra high purity.
3.4.3.3.20 Internal Standard Solution. Prepare a stock standard
solution containing the isotopically labeled PCDDs and PCDFs at the concen-
trations shown in shown in Table 3.4-1 under the heading "Internal Standards"
in 10 ml of nonane.
3.4.3.3.21 Surrogate Standard Solution. Prepare a stock standard
solution containing the isotopically labeled PCDDs and PCDFs at the concen-
trations shown in Table 1 under the heading "Surrogate Standards" in 10 ml of
nonane.
3.4.3.3.22 Recovery Standard Solution. Prepare a stock standard
solution containing the isotopically labeled PCDDs and PCDFs at the concen-
trations shown in Table 1 under the heading "Recovery Standards" in 10 ml of
nonane.
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Table 3.4-1
COMPOSITION OF THE SAMPLE FORTIFICATION AND RECOVERY
STANDARDS SOLUTIONS
Analyte Concentration
(pg/^1)
Internal Standards
13C12-2,3,7,8-TCDD 100
13C12-l,2,3,7,8-PeCCD 100
"cS-l^laXelT.S-HpCDD 100
13C12-2,3,7,8-TCDF 100
13C12-l,2,3,7,8-PeCDF 100
13C12-l,2,3,6,7,8-HxCDF 100
13cJ2-l,2,3,4,6,7,8-HpCDF 100
Surrogate Standards
37Cl4-2,3,7,8-TCDD 100
13C12-l,2,3,4,7,8-HxCDD 100
13C12-2,3,4,7,8-PeCDF 100
13C12-l,2,3,4,7,8-HxCDF 100
13C12-l,2,3,4,7,8,9-HpCDF 100
Recovery Standards
13C12-1,2,3,4-TCDD 500
13C12-l,2,3,7,8,9-HxCDD 500
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3.4.4 procedure
* '
3.4.4.1 Sampling. The complexity of this method is such that, in
order to obtain reliable results, analysts should be trained and experienced
with the analytical procedures.
3.4.4.1.1 Preparation Prior to Analysis.
3.4.4.1.1.1 Cleaning Glassware. All glass components of the train
upstream of and including the adsorbent module, shall be cleaned as described
in Section 3A of the "Manual of Analytical Methods for the Analysis of
Pesticides in Human and Environmental Samples." Special care shall be devoted
to the removal of residual silicone grease sealants on ground glass connec-
tions of used glassware. Any residue shall be removed by soaking the glass-
ware for several hours in a chromic acid cleaning solution prior to cleaning
as described above.
3.4.4.1.1.2 Adsorbent Trap. The traps must be loaded in a clean
area to avoid contamination. They may not be loaded in the field. Fill a
trap with 20 to 40 g of XAD-2. Follow the XAD-2 with glass wool and tightly
cap both ends of the trap. Add 100 /tl of the surrogate standard solution
(Section 3.4.3.3.21) to each trap.
3.4.4.1.1.3 Sample Train. It is suggested that all components be
maintained according to the procedure described in APTD-0576.
3.4.4.1.1.4 Silica Gel. Weigh several 200 to 300 g portions of
silica gel in an air-tight container to the nearest 0.5 g. Record the total
weight of the silica gel plus container, on each container. As an alterna-
tive, the silica gel may be weighed directly in its impinger or sample holder
just prior to sampling.
3.4.4.1.1.5 Filter. Check each filter against light for irregular-
ities and flaws or pinhole leaks. Pack the filters flat in a clean glass
container.
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3.4.4.1.2 Preliminary Determinations. Same as Section 4.. 1.2 of
Method 5. -
* ..-,, "*
3.4.4.1.3 Preparation of Collection Train.
3.4.4.1.3.1 During preparation and assembly of the sampling train,
keep all train openings where contamination can enter, sealed until just prior
to assembly or until sampling is about to begin. NOTE: Do not use sealant
grease in assembling the train.
3.4.4.1.3.2 Place approximately 100 ml of water in the second and
third impingers, leave the first and fourth impingers empty, and transfer
approximately 200 to 300 g of preweighed silica gel from its container to the
fifth impinger.
3.4.4.1.3.3 Place the silica gel container in a clean place for
later use in the sample recovery. Alternatively, the weight of the silica gel
plus impinger may be determined to the nearest 0.5 g and recorded.
3.4.4.1.3.4 Assemble the train as shown in Figure 3.4-1.
3.4.4.1.3.5 Turn on the adsorbent module and condenser coil
recirculating pump and begin monitoring the adsorbent module gas entry
temperature. Ensure proper sorbent temperature gas entry temperature before
proceeding and before sampling is initiated. It is extremely important that
the XAD-2 adsorbent resin temperature never exceed 50°C because thermal
decomposition will occur. During testing, the XAD-2 temperature must not
exceed 20°C for .efficient capture of the PCDDs and PCDFs.
*
3.4.4.1.4 Leak-Check Procedure. Same as Method 5, Section 4.1.4.
3.4.4.1.5 Sample Train Operation. Same as Method 5, Section 4.1.5.
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3.4.4.2 Sample Recovery. Proper .cleanup procedure begins as soon
as Che probe is removed from the stack at the end of the sampling period.
Seal the nozzle end of the sampling probe with Teflon tape or aluminum foil.
When the probe can be safely handled, wipe off all external particu-
late matter near the tip of the probe. Remove the probe from the train and
close off both ends with aluminum foil. Seal off the inlet to the train with
Teflon tape, a ground glass cap, or aluminum foil.
Transfer the probe and impinger assembly to the cleanup area. This
area shall be clean and enclosed so that the chances of losing or contaminat-
ing the sample are minimized. Smoking, which could contaminate the sample,
shall not be allowed in the cleanup area.
Inspect the train prior to and during disassembly and note any
abnormal conditions, e.g., broken filters, coloured impinger liquid, etc.
Treat the samples as follows:
3.4.4.2.1 Container No. 1. Either seal the filter holder or
carefully remove the filter from the filter holder and place it in its
identified container. Use a pair of cleaned tweezers to handle the filter.
If it is necessary to fold the filter, do so such that the particulate cake is
inside the fold. Carefully transfer to the container any particulate matter
and filter fibers which adhere to the filter holder gasket, by using a dry
inert bristle brush and a sharp-edged blade. Seal the container.
3.4.4.2.2 Adsorbent Module. Remove the module from the train,
tightly cap both ends, label it, cover with aluminum foil, and store it on ice
for transport to the laboratory.
3.4.4.2.3 Container No. 2. Quantitatively recover material
deposited in the nozzle, probe transfer lines, the front half of the filter
holder, and the cyclone, if used, first, by brushing while rinsing three times
each with acetone, and then by rinsing the probe three times with methylene
chloride. Collect all the rinses in Container No. 2.
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Rinse the back half of the 'filter.holder three times with acetone.
Rinse the connecting line between the filter and the condenser three times
with acetone. Soak the connecting line with three separate portions of
methylene chloride for 5 minutes each. If using a separate condenser and
adsorbent trap, rinse the condenser in the same manner as the connecting line.
Collect all the rinses in Container No. 2 and mark the level of the liquid on
the container.
3.4.4.2.4 Container No. 3. Repeat the methylene chloride-rinsing
described in Section 3.4.4.2.3 using toluene as the rinse solvent. Collect
the rinses in Container No. 3 and mark the level of the liquid on the con-
tainer.
3.4.4.2.5 Impinger Water. Measure the liquid in the first three
impingers to with ±1 ml by using a graduated cylinder or by weighing it to
within ±0.5 g by using a balance. Record the volume or weight of liquid
present. This information is required to calculate the moisture content of
the effluent gas.
Discard the liquid after measuring and recording the volume or
weight.
3.4.4.2.6 Silica Gel. Note the color of the indicating silica gel
to determine if it has been completely spent and make a mention of its
condition. Transfer the silica gel from the fifth impinger to its original
container and seal.
3.4.5 Analysis
All glassware shall be cleaned as described in Section 3A of the
"Manual of Analytical Methods for the Analysis of Pesticides in Human and
Environmental Samples.* All samples must be extracted within 30 days of
collection and analyzed within 45 days of extraction.
3.4.5.1 Sample Extraction.
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3.4.5.1.1 Extraction System. Plate an extractable thimble (Section
3.4.2.3.4), 1 g of silica gel, and a plug of glass wool into the Soxhlet
apparatus, charge the apparatus with toluene, and reflux for a minimum of 3
hours. Remove the toluene and discard it, but retain the silica gel. Remove
the extraction thimble from the extraction system and place it in a glass
beaker to catch the solvent rinses.
3.4.5.1.2 Container No. 1 (Filter). Transfer the contents of
container number 1 directly to the glass thimble of the extraction system and
extract them simultaneously with the XAD-2 resin.
3.4.5.1.3 Adsorbent Module. Suspend the adsorbent module directly
over the extraction thimble in the beaker (see Section 3.4.5.1.1.). The glass
frit of the module should be in the up position. Using a Teflon squeeze
bottle containing toluene, flush the XAD-2 into the thimble onto the bed of
cleaned silica gel. Thoroughly rinse the glass module catching the rinsings
in the beaker containing the thimble. If the resin is wet, effective extrac-
tion can be accomplished by loosely packing the resin in the thimble. Add the
XAD-2 glass wool plug to the thimble.'
3.4.5.1.4 Container No. 2 (Acetone and Methylene Chloride Rinse).
Concentrate the sample to a volume of about 1-5 ml using the rotary evaporator
apparatus, at a temperature of less than 37°C. Rinse the sample container
three times with small portions of methylene chloride and add these to the
concentrated solution and concentrate further to near dryness. This residue
contains particulate matter removed in the rinse of the train probe and
nozzle. Add the concentrate to the filter and the XAD-2 resin in the Soxhlet
apparatus described in Section 3.4.5.1.1.
3.4.5.1.5 Extraction. Add 100 ^1 of the internal standard solution
(Section 3.4.3.3.20) to the extraction thimble containing the contents of the
adsorbent cartridge, the contents of Container No. 1, and the concentrate from
Section 3.4.5.1.3. Cover the contents of the extraction thimble with the
cleaned glass wool plug to prevent the XAD-2 resin from floating into the
solvent reservoir of the extractor. Place the thimble in the extractor, and
3-135
-------
add the toluene .contained in the beaker to the solvent reservoir. Pour
additional toluene to fill the reservoir approximately 2/3 full. Add Teflon
boiling chips and assemble the apparatus. Adjust the heat source to cause the
extractor to cycle three times per hour. Extract the sample for 16 hours.
After extraction, allow the Soxhlet to cool. Transfer the toluene extract and
three 10-ml rinses to the rotary evaporator. Concentrate the extract to
approximately 10 ml. At this point the analyst may choose to split the sample
in half. If so, split the sample, store one half for future use, and analyze
the other according to the procedures in Sections 3.4.5.2 and 3.4.5.3. In
either case, use a nitrogen evaporative concentrator to reduce the volume of
the sample being analyzed to near dryness. Dissolve the residue in 5 ml of
hexane.
3.4.5.1.6 Container No. 3 (Toluene Rinse). Add 100 pL of the
Internal Standard solution (Section 3.4.3.3.20) to the contents of the
container. Concentrate the sample to a volume of about 1-5 ml using the
rotary evaporator apparatus at a temperature of less than 37°C. Rinse the
sample container three times with small portions of toluene and add these to
the concentrated solution and concentrate further to near dryness. Analyze
the extract separately according to the procedures in Sections 3.4.5.2 and
3.4.5.3, but concentrate the solution in a rotary evaporator apparatus rather
than a nitrogen evaporative concentrator.
3.4.5.2 Sample Cleanup and Fractionation.
3.4.5.2.1 Silica Gel Column. Pack one end of a glass column, 20 mm
x 230 mm, with glass wool. Add in sequence, 1 g silica gel, 2 g of sodium
hydroxide impregnated cilica gel, 1 g silica gel, 4 g of acid-modified silica
gel, and 1 g of silica gel. Wash the column with 30 ml of hexane and discard
it. Add the sample extract, dissolved in 5 ml of hexane to the column with
two additional 5-ml rinses. Elute the column with an additional 90 ml of
hexane and retain the entire eluate. Concentrate this solution to a volume of
about 1 ml using the nitrogen evaporative concentrator (Section 3.4.2.3.8).
3-136
-------
3.4.5.2.2 Basic Alumina Column. Shorten a 25-ml disposable Pasteur
pipette to about 16 ml. Pack the lower section with glass wool and 12 g of
basic alumina. Transfer the concentrated extract from the silica gel column
to the top of the basic alumina column and elute the column sequentially with
120 ml of 0.5 percent methylene chloride in hexane followed by 120 ml of 35
percent methylene chloride in hexane. Discard the first 120 ml of eluate.
Collect the second 120 ml of eluate and concentrate it to about 0.5 ml using
the nitrogen evaporative concentrator.
3.4.5.2.3 AX-21 Carbon/Celite 545 Column. Remove the bottom 0.5
in. from the tip of a 9-ml disposable Pasteur pipette. Insert a glass fiber
filter disk in the top of the pipette 2.5 cm from the constriction. Add
sufficient carbon/celite mixture to form a 2 cm column. Top with a glass, wool
plug. In some cases, AX-21 carbon fines may wash through the glass wool plug
and enter the sample. This may be prevented by adding a celite plug to the
exit end of the column. Rinse the column in sequence with 2 ml of 50 percent
benzene in ethyl acetate, 1 ml of 50 percent methylene chloride in cyclohex-
ane, and 2 ml of hexane. Discard these rinses. Transfer the concentrate in 1
ml of hexane from the basic alumina column to the carbon/celite column along
with 1 ml of hexane rinse. Elute the column sequentially with 2 ml of 50
percent methylene chloride in hexane and 2 ml of 50 percent benzene in ethyl
acetate and discard these eluates. Invert the column and elute in the reverse
direction with 13 ml of toluene. Collect this eluate. Concentrate the eluate
in a rotary evaporator at 50°C to about 1 ml. Transfer the concentrate to a
Reacti-vial using a toluene rinse and concentrate to a volume of 200 /il using
a stream of N2. Store extracts at room temperature, shielded from light,
until the analysis is performed.
3.4.5.3 Analysis. Analyze the sample with a gas chromatograph
coupled to a mass spectrometer (GC/MS) using the instrumental parameters in
Sections 3.4.5.3.1 and 3.4.5.3.2. Immediately prior to analysis, add a 20-jil
aliquot of the Recovery Standard solution from Table 1 to each sample. A 2-pl
aliquot of the extract is injected into the GC. Sample extracts are first
analyzed vising the DB-5 capillary column to determine the concentration of
each isomer of PCDDs and PCDFs (tetra- through octa-). If tetra-chlorinated
3-137
-------
dibenzofurans are detected in this analysis, then analyze another aliquot of
the sample in a.separate run, using the DB-.225 column to measure the 2,3,7,8-
tetrachlorodibenzofuran isomer. Other column systems may be used, provided
that the user is able to demonstrate, using calibration and performance
checks, that the column system is able to meet the specifications of
Section 3.4.6.1.2.2.
3.4.5.3.1 Gas Chromatograph Operating Conditions.
3.4.5.3.1.1 Injector. Configured for capillary column, splitless,
250°C.
3.4.5.3.1.2 Carrier Gas. Helium, 1-2 ml/min.
3.4.5.3.1.3 Oven. Initially at 150°C. Raise by at least 40°C/min
to 190°C and then at 3°C/min up to 300°C.
3.4.5.3.2 High Resolution Mass Spectrometer.
3.4.5.3.2.1 Resolution. 10000 m/e.
3.4.5.3.2.2 lonization Mode. Electron impact.
3.4.5.3.2.3 Source Temperature 250°C.
3.4.5.3.2.4 Monitoring Mode. Selected ion monitoring. A list of
the various ions to be monitored is summarized in Table 3.4-2.
3.4.5.3.2.5 Identification Criteria, The following identification
criteria shall be used for the characterization of polychlorinated dibenzo-
dioxins and dibenzofurans.
3-138
-------
Table 3.4-2
ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH
RESOLUTIONS MASS SPECTROMETRY JOR PCDD's AND'PCDF's
Descriptor Accurate
number mass
2 292.9825
303.9016
305.8987
315.9419
317.9389
319.8965
321.8936
327.8847
330.9792
331.9368
333.9339
339.8597
341.8567
351.9000
353.8970
355.6546
357.8516
367.8949
369.8919
375.8364
409.7974
Ion
type
LOCK
M
M+2
M
M+2
M
M+2
M
QC
M
M+2
M+2
M+4
M+2
M+4
M+2
M+4
M+2
M+4
M+2
M+2
Elemental
composition
C7Fn
C12H435C140
C12H4"C1370
13C12H435C140
13C12H4"C1337C10
C12H435C102
C12H4"C1337C102
C12H437C1402
C7Fi3
13C12H435C1402
13CUH435C137C102
C12H335C14(37C10
C12H43SC1337C120
13C12H333C1437C10
13C12H333C1337C120
C12H335C1337C102
C12H33SC1337C1202
13C12H3"C1437C102
l3cuH33SCl337Cl202'
C12H435C1537C10
CUH335C1637C10
Analyte
PFK
TCDF
TCDF
TCDF (S)
TCDF (S)
TCDD
TCDD
TCDD (S)
PFK
TCDD (S)
TCDD (S)
PECDF
PeCDF
. PeCDF (S)
PeCDF (S)
PeCDD
PeCDD
PeCDD (S)
PeCDD (S)
HxCDPE
HpCPDE
3-139
-------
Table 3.4-2 (Continued)
ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH
RESOLUTION MASS SPECTROMETRY FOR PCDD'S AND PCDF's
Descriptor Accurate
number mass
3 373.8208
375.8178
383.8639
385.8610
389.8157
391.8127
392.9760
401.8559
403.8529
445.7555
430.9729
4 407.7818
409.7789
417.8253
419.8220
423.7766
425.7737
435.8169
Ion
type
M+2
M+4
M
M+2
M+2
M+4
LOCK
M+2
M+4 .
M+4
QC
M+2
M+4
M
M+2
M+2
M+4
M+2
Elemental
composition
C12H23SC1337C10
C12H235C1437C120
13C12H235CleO
13C12H235C1S37C10
C12H235C1537C102
C12H235C1437C1202
C,F13
13C12H235C1S37C102
»C12H23>C143'C120
f* u 33/*i 37/*1 f\
^*12 2 6 2
C9F17
CuH19Clt*7C10
CjfOfOf
uCuHMCl^)
1JCUKMC1,"C10
CUH»C1.«C102
CUH3SC1537C1202
13Cl2H3SCle37C102
Analyte
HxCDF
HxCDF
HxCDF (S)
HxCDF (S)
HxCDD
HxCDD
PFK
HxCDD (S)
HxCDD (S)
OCDPE
PFK
HpCDF
HpCDF
HpCDF (S)
HpCDF (S)
HpCDD
HpCDD
HpCDD (S)
3-140
-------
Table 3.4-2 (Continued)
ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH
RESOLUTION MASS SPECTROMETRY FOR PCDD'S AND PCDF's
Descriptor Accurate
number mass
437.8140
479.7165
430.9729
441.7428
443.7399
457.7377
459.7348
469.7779
471.7750
513.6775
442.9728
Ion
type
M-t-4
M+4
LOCK
M+2
M+4
M+2
M+4
M+2
M+4
M+4
QC
Elemental
composition
13C12H35C1537C1202
C12H35C1737C120
C9F17
C1235C1737C10
C1235C1637C120
C1235C1737C102
C1235C1637C1202
13C12«C1737C102
13C1235C1637C1202
C12"C1,37C1202
ClO^l?
Analyte
HpCDD (S)
NCPDE
PFK
OCDF
OCDF
OCDD
OCDD
OCDD (S)
OCDD (S)
DCDPE
PFK
a) The following nuclidic masses were used:
H - 1.007825 0 - 15.994915
C - 12.000000 "Cl - 34.968853
13C - 13.003355 37C1 - 36.965903
F - 18.9984
S - Labeled Standard
QC - Ion selected for monitoring instrument stability during the GC/MS
analysis
3-141
-------
Table 3.4-3
ACCEPTABLE RANGES FOR ION-ABUNDANCE RATIOS OF PCDD's AND PCDF's
Number of
Chlorine
atoms
4
5
6
6"
7b
7
8
Ion
type
M/M+2
M+2/M+4
M+2/M+4
M/M+2
M/M+2
M+2/M+4
M+2/M+4
Theoretical
ratio
0.77
1.55
1.24
0.51
0.44
1.04
0.89
Control limits
Lower Upper
0.65
1.32
1.05
0.43
0.37
0.88
0.76
0.89
1.78
1.43
0.59
0.51
1.20
1.02
a) Used only for "C-HxCDF
b) Used only for 13C-HpCDF
3-142
-------
1. The integrated ion-abundance ratio (M/M+2 or M+2/M+4) shall be
•' * ' "
within 15 percent of the theoretical value. ""The acceptable ion-abundance
ratio ranges for the identification of chlorine-containing compounds are given
in Table 3.
2. The retention time for the analytes must be within 3 seconds of
the corresponding 13C-labeled internal standard, surrogate or alternate
standard.
3. The monitored ions, shown in Table 3.4-2 for & given analyte,
shall reach their maximum within 2 seconds of each other.
4i The identification of specific isomers that do not have corre-
sponding 13C-labeled standards is done by comparison of the relative retention
time (RRT) of the analyte to the nearest internal standard retention time with
reference (i.e., within 0.005 RRT units) to the comparable RRTs found in the
continuing calibration.
5. The signal to noise ratio for all monitored ions must be greater
than 2.5.
6. The confirmation of 2,3,7,8-TCDD and 2,3,7,8-TCDF shall satisfy
all of the above identification criteria.
7. For the identification of PCDFs, no signal may be found in the
corresponding PCDPE channels.
3.4.5.3.2.6 Quantitation. The peak areas for the two ions moni-
tored for each analyte are summed to yield the total response for each
analyte. Each internal standard is used to quantitate the indigenous PCDDs or
PCDFs in its homologous series. For example, the l3C12-2,3,7,8-tetrachlorodi-
benzodioxin is used to calculate the concentrations of all other tetra-
chlorinated isomers. Recoveries of the tetra- and penta-internal standards
are calculated using the 13CU-1,2,3,4-TCDD. Recoveries of the hexa- through
octa- internal standards are calculated using "Cj^-l.Z.S^.S.
3-143
-------
Recoveries of the surrogate standards are calculated using, the corresponding
homolog from the internal standard.
3.4.6 Calibration
Same as Method 5 with the following additions.
3.4.6.1 GC/MS System.
3.4.6.1.1 Initial Calibration. Calibrate the GC/MS system using
the set of five standards shown in Table 3.4-4. The relative standard
deviation for the mean response factor from each of the unlabeled analytes
(Table 4) and of the internal, surrogate, and alternate standards shall be
less than or equal to the values in Table 3.4-5. The signal to noise ratio
for the GC signal present in every selected ion current profile shall be
greater than or equal to 2.5. The ion abundance ratios shall be within the
control limits in Table 3.
3.4.6.1.2 Daily Performance Check.
3.4.6.1.2.1 Calibration Check. Inject one /il of solution Number 3
from Table 4. Calculate the relative response factor (RRF) for each compound
and compare each RRF to the corresponding mean RRF obtained during the initial
calibration. The analyzer performance is acceptable if the measured RRFs for
the labeled and unlabeled compounds for the daily run are within the limits of
the mean values shown in Table 3.4-5. In addition, the ion-abundance ratios
shall be within the allowable control limits shown in Table 3.4-3.
3.4.6.1.2.2 Column Separation Check. Inject a solution of a
mixture of PCDDs and PCOFs that documents resolution between 2,3,7,8-TCDD and
other TCDD isomers. Resolution is defined as a valley between peaks that is
less than 25 percent of the lower of the two peaks. Identify and record the
retention time windows for each homologous series.
3-144
-------
Table 3.4-4
COMPOSITION OF THE INITIAL CALIBRATION SOLUTIONS
Concentrations
Compound Solution No. 1 2 3
Unlabeled Analvtes
2,3,7,8-TCDD
2,3,7.8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2.3,4,7,8-PeCDF
1.2. 3,4,7. 8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3.7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6.7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4.6,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Internal Standards
13C12-2.3.7,8-TCDD
13C12-1.2.3.7,8-PeCDD
13Cl2-1.2.3,6,7,8-HxCDD
l3C12-l,2,3,4,6,7,8-HpCDD
13C12-OCDD
»Cl2-2,3.7,8-TCDF
13C12_l,2,3,7,8-PeCDF
l3C12-l,2,3,6,7,8-HxCDF
13C12-l,2,3,4,6,7.8-HpCDF
Surrogate Standards
37C V 2,3,7, 8-TCDD '
13Cl2-2,3,4,7,8-PeCDF
13Cl2-l,2,3,4,7,8-HxCDD
l3C12-1.2,3,4,7,8-HxCDF
13C12-l,2,3,4,7,8.9-HpCDF
0.5
0.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5.0
5.0
100
100
100
100
200
100
100
100
100
0.5
2.5
2.5
2.5
2.5
1
1
5
5
5
5
5
5
5
5
5
5
5
5
5
10
10
100
100
100
100
200
100
100
100
100
1
5
5
5
5
5
5
25
25
25
25
25
25
' 25
25
25
25
25
25
25
50
50
100
100
100
100
200
100
100
100
100
5
25
25
25
25
(pg/ML)
4 5
50
50
250
250
250
250
250
250
250
250
250
250
250
250
250
500
500
100
100
100
100
200
100
100
100
100
50
250
250
250
250
100
100
500
500
500
500
500
500
500
500
500
500
500
500
500
1000
1000
100
100
100
100
200
100
100
100
100
100
500
500
500
500
3-145
-------
Table 3.4-4 (Continued)
* * .
— •.
COMPOSITION OF THE INITIAL CALIBRATION SOLUTIONS
Compound
Concentrations (pg/^L)
Solution No. 1 2 3 4 5
Alternative Standard
13C12 -1.2,3,7,8,9-HxCDF
Recovery Standards
13C12-1.2,3,4-TCDD
13C12-l,2,3,7,8,9-HxCDD
2.5
25
250 500
100
100
100
100
100
100
100
100
100
100
3-146
-------
Table 3.4-5
MINIMUM REQUIREMENTS FOR INITIAL AND DAILY CALIBRATION
RESPONSE FACTORS
. • *
Compound
Unlabeled Analvtes
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,4,5,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
OCDD
OCDF
Internal Standards
"C12- 2,3,7,8-TCDD
"C12-l,2,3,7,8-PeCCD
13C12- 1,2,3,6,7 , 8-HxCDD
"C12-l,2,3,4,6,7,8-HpCDD
13C12-OCDD
"Cu-2,3,7,8-TCDF
"C^-l^.S^.S-PeCDF
13C12-l,2,3,6,7,8-HxCDF
Surrogate Standards
37Cl4-2,3,7,8-TCDD
"C12-2,3,4,7,8-PeCDF
"C^-l^.S^^.S-HxCDD
"CU-1,2,3,4,7,8-HXCDF
13C12-l,2,3,4.7,8,9-HpCDF
Alternate Standard
"CU-I^.S^.S^-HXCDF
Relative
Initial Calibratio
RSD
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
30
25
30
25
30
30
30
30
30
30
25
25
25
25
25
25
Response Factors
n Daily Calibration
% Difference
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
30
25
30
25
30
30
30
30
30
30
25
25
25
25
25
25
3-147
-------
Perform a similar resolution check on the confirmation 001111101 to
document the resolution between 2,3,7,8-TCDF and other TCDF isomers.
3.4.6.2 Lock Channels. Set mass spectrometer lock channels as
specified in Table 3.4-3. Monitor the quality control check channels speci-
fied in Table 3.4-3 to verify instrument stability during the analysis.
3.4.7 Quality Control
3.4.7.1 Sampling Train Collection Efficiency Check. Add 100 pi of
the surrogate standards in Table 3.4-1 to the adsorbent cartridge of each
train before collecting the field samples.
*
3.4.7.2 Internal Standard Percent Recoveries. A group of nine
carbon-labeled PCDDs and PCDFs representing, the tetra- through octachlori-
nated homologues, is added to every sample prior to extraction. The role of
the internal standards is to quantitate the native PCDDs and PCDFs present in
the sample as well as to determine the overall method efficiency. Recoveries
of the internal standards must be between 40 to 130 percent for the tetra-
through hexachlorinated compounds while the range is 25 to 130 percent for the
higher hepta- and octachlorinated homologues.
3.4.7.3 Surrogate Recoveries. The five surrogate compounds in
Table 3.4-4 are added to the resin the adsorbent sampling cartridge before the
sample is collected. The surrogate recoveries are measured relative to the
internal standards and are a measure of collection efficiency. They are not
used to measure native PCDDs and PCDFs. All recoveries shall be between 70
and 130 percent'. Poor recoveries for all the surrogates may be an indication
of breakthrough in the sampling train. If the .recovery of all standards is
below 70 percent, the sampling runs must be repeated. As an alternative, the
sampling runs do not have to be repeated if the final results are divided by
the fraction of surrogate recovery. Poor recoveries of isolated surrogate
compounds should not be grounds for rejecting an entire set of samples.
3-148
-------
3.4.7.4 Toluene QA Rinse. Report the results of the toluene QA
rinse separately from the total sample catch. Do not add it to the total
sample.
3.4.8 Quality Assurance
3.4.8.1 Applicability. When the method is used to analyze samples
to demonstrate compliance with a. source emission regulation, an audit sample
must be analyzed, subject to availability.
3.4.8.2 Audit Procedure. Analyze an audit sample with each set of
compliance samples. The audit sample contains tetra through octa isomers of
PCDD and PCDF. Concurrently, analyze the audit sample and a set of compliance
samples in the same manner to evaluate the technique of the analyst and the
standards preparation. The same analyst, analytical reagents, and analytical
system shall be used both for the compliance samples and the EPA audit sample.
3.4.8.3 Audit Sample Availability. Audit samples will be supplied
only to enforcement agencies for compliance tests. The availability of audit
samples may be obtained by writing:
Source Test Audit Coordinator (MD-77B)
Quality Assurance Division
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
or by calling the Source Test Audit Coordinator (STAC) at (919) 541-7834. The
request for the audit sample must be made at least 30 days prior to the
scheduled compliance sample analysis.
3.4.8.4 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit instructions
included with the audit sample. Fill in the audit sample concentration and
the analyst's name on the audit response form included with the audit instruc-
tions. Send one copy to the EPA Regional Office or the appropriate enforce-
ment agency and a second copy to the STAC. The EPA Regional office or the
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appropriate enforcement agency will report t,he results of the audit to the
laboratory being audited. Include this response with the results of the
compliance samples in relevant reports to the EPA Regional Office or the
appropriate enforcement agency.
3.4.9 Calculations
Same as Method 5, Section 6 with the following additions.
3.4.9.1 Nomenclature.
A,t - Integrated ion current of the noise at the retention time
of the analyte.
A*ei - Integrated ion current of the two ions characteristic of
the internal standard i in the calibration standard.
AciJ - Integrated ion current of the two ions characteristic of
compound i in the jth calibration standard.
A*eij - Integrated ion current of the two ions characteristic of
the internal standard i in the jth calibration standard.
AC(i - Integrated ion current of the two ions characteristic of
surrogate compound i in the calibration standard.
At - Integrated ion current of the two ions characteristic of
compound in the sample.
A\ - Integrated ion current of the two ions characteristic of
internal standard i in the sample.
A,, - Integrated ion current of the two ions characteristic of
the recovery standard.
A,t - Integrated ion current of the two ions characteristic of
surrogate compound i in the sample.
C4 - Concentration of PCDD or PCDF i in the sample, pg/M3.
Cj - Total concentration of PCDDs or PCDFs in the sample,
Pg/M».
mel <• Mass of compound i in the calibration standard injected
into the analyzer, pg.
m*el - Mass of labeled compound i in the calibration standard
Injected into the analyzer, pg.
m*t - Mass of internal standard i added to the sample, pg.
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-• Mass of_,.recovery standard in the calibration standard
injected into the analyzer, pg.
- Mass of surrogate compound i in the calibration standard,
Pg-
- Relative response factor.
RRFt, - Recovery standard response factor.
RRF, - Surrogate compound response factor.
3.4.9.2 Average Relative Response Factor.
\ - 1/n _J [AeiXci/(A*eijmci)] Eq. 23-1
3.4.9.3 Concentration of the PCDDs and PCDFs.
Ct - m*tV
-------
3.4.10 Bibliography
•"-•- »,
1. American Society of Mechanical Engineers. Sampling for the Determination
of Chlorinated Organic Compounds in Stack Emissions. Prepared for U.S.
Department of Energy and U.S. Environmental Protection Agency. Washing-
ton, D.C. December 1984. 25 p.
2. American Society of Mechanical Engineers. Analytical Procedures to Assay
Stack Effluent Samples and Residual Combustion Products for Polychlori-
nated Dibenzo-p-Dioxins (PCDD) and Polychlorinated Dibenzofurans (PCDF).
Prepared for the U.S. Department of Energy and U.S. Environmental
Protection Agency. Washington, D.C. December 1984. 23 p.
3. Thompson, J.R. (ed.) Analysis of Pesticide Residues in Human and
Environmental Samples. U.S. Environmental Protection Agency. Research
Triangle Park, NC. 1974.
4. Triangle Laboratories. Case Study: Analysis of Samples for the Presence
of Tetra Through Octachloro-p-Dibenzodioxins and Dibenzofurans. Research
Triangle Park, NC. 1988. 26 p.
5. U.S. Environmental Protection Agency. Draft Method 8290 - The Analysis
of Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofurans by
High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry.
In: Test Methods for Evaluating Solid Waste. Washington, D.C. SW-846.
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3.5 Sampling for Aldehyde and Ke^nfie Effusions from Stationary Sources
(Method 0011)
3.5.1 Scope and Application
This method is applicable to the determination of Destruction and Removal
Efficiency (ORE) of formaldehyde, CAS Registry number 50-00-0, and possibly
other aldehydes and ketones from stationary sources as specified in the
regulations. The methodology has been applied specifically to formaldehyde;
however, many laboratories have extended the application to other aldehydes
and ketones. Compounds derivatized with 2,4-dinitrophenyl-hydrazine can be
detected as low as 6.4 x 10"a Ibs/cu ft (1.8 ppbv) in stack gas over a 1 hr
sampling period, sampling approximately 45 cu ft.
3.5.2 Summary of Method
3.5.2.1 Gaseous and particulate pollutants are withdrawn isokine-
tically from an emission source and are collected in aqueous acidic 2,4-
dinitrophenyl-hydrazine. Formaldehyde present in the emissions reacts with
the 2,4-dinitrophenyl-hydrazine to form the formaldehyde dinitrophenylhydra-
zone derivative. The dinitrophenylhydrazone derivative is extracted, solvent-
exchanged, concentrated, and then analyzed by high performance liquid chroma-
tography. •
3.5.3 Interferences
3.5.3.1 A decomposition product of 2,4-dinitrophenyl-hydrazine,
2,4-dinitroaniline, can be an analytical interferant if concentrations are
high. 2,4-Dinitroaniline can coelute with 2,4-dinitrophenylhydrazone of
formaldehyde under high performance liquid chromatography conditions, which
may be used for the analysis. High concentrations of highly-oxygenated
compounds, especially acetone, that have the same retention time or nearly the
same retention time as the dinitrophenylhydrazone of formaldehyde, and that
also absorb at 360 nm, will interfere with the analysis.
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Formaldehyde, acetone, and 2,4-dinitr.paniline contamination of the aqueous
acidic 2,4-dinitrophenyl-hydrazine (DNPH) reagent is frequently encountered.
The reagent must be prepared vithin five days of use in the field and must be
stored in an uncontaminated environment both before and after sampling in
order to minimize blank problems. Some concentration of acetone contamination
is unavoidable, because acetone is ubiquitous in laboratory and field opera-
tions. However, the acetone contamination must be minimized.
3.5.4 Apparatus and Materials
3.S.4.1 A schematic of the sampling train is shown in Figure
3.5-1. This sampling train configuration is adapted from EPA Method 4
procedures. The sampling train consists of the following components: Probe
Nozzle, Pitot Tube, Differential Pressure Gauge, Metering System, Barometer,
and Gas Density Determination Equipment.
3.5.4.1.1 Probe Nozzle: Quartz or glass with sharp, tapered (30*
angle) leading edge. The taper shall be on the outside to preserve a constant
inner diameter. The nozzle shall be buttonhook or elbow design. A range of
nozzle sizes suitable for isokinetic sampling should be available in incre-
ments of 0.15 cm(l/16 in), e.g., 0.32 to 1.27 cm (1/8 to 1/2 in), of larger if
higher volume sampling trains are used. Each nozzle shall be calibrated
according to the procedures outlined in Section 3.5.8.1
*
3.5.4.1.2 Probe Liner: Borosilicate glass or quartz shall be used
for the probe liner. The tester should not allow the temperature in the probe
to exceed 120 ± 14'C (248 ± 25*F).
3.5.4.1.3 Pitot Tube: The Pitot tube shall be Type S. as described
in Section 2.1 of EPA Method 2, or any other appropriate device. The pitot
tube shall be attached to the probe to allow constant monitoring of the stack
gas velocity. The impact (high pressure) opening plane of the pitot tube
shall be even with or above the nozzle entry plan (see EPA Method 2, Figure 2-
6b) during sampling. The Type S pitot tube assembly shall have a known
coefficient, determined as outlined in Section 4 of EPA Method 2.
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Temperature
Semor
CO
1
Thermometer
S-typePKotTub*
Modified Greenburg-
SmNh bnplngers
OrMc*
MmonMlvr
Formaldehyde Sampling Train
Figure 3.5-1
5
i
-------
3.5.4.1.4 Differential Pressure Gauge: The differential pressure
gauge shall be an inclined manometer or equivalent device as described in
Section 2.2 of EPA Method 2. One manometer shall be used for velocity-head
reading and the other for orifice differential pressure readings.
3.5.4.1.5 Impingers: The sampling train requires a minimum of four
impingers, connected as shown in Figure 3.5-1, with ground glass (or equiva-
lent) vacuum-tight fittings. For the first, third, and fourth impingers, use
the Greenburg-Smith design, modified by replacing the tip with a 1.3 cm inside
diameter (1/2 in) glass tube extending to 1.3 cm (1/2 in) from the bottom of
the flask. For the second impinger, use a Greenburg-Smith impinger with the
standard tip. Place a thermometer capable of measuring temperature to within
1°C (2*F) at the outlet of the fourth impinger for monitoring purposes.
3.5.4.1.6 Metering System: The necessary components are a vacuum
gauge, leak-free pump, thermometers capable of measuring temperature within
3*C (5.4*F), dry-gas meter capable of measuring volume to within 1%, and
related equipment as shown in Figure 3.5-1. At a minimum, the pump should be
capable of 4 cfm free flow, and the dry gas meter should have a recording
capacity of 0-999.9 cu ft with a resolution of 0.005 cu ft. Other metering
systems may be used which are capable of maintaining sample volumes to within
2%. The metering system may be used in conjunction with a pitot tube to
enable checks of isokinetic sampling rates.
3.5.4.1.7 Barometer: The barometer may be mercury, aneroid, or
other barometer capable of measuring atmospheric pressure to within 2.5 mm Hg
(0.1 in Hg). In many cases, the barometric reading may be obtained from a
nearby National Weather Service Station, in which case the station value
(which is the absolute barometric pressure) is requested and an adjustment for
elevation differences between the weather station and sampling point is
applied at a rate of minus 2.5 mm Hg (0.1 in Hg) per 30 a (100 ft) elevation
increases (vice versa for elevation decrease).
3.5.4.1.8 Gas Density Determination Equipment: Temperature sensor
and pressure gauge (as described in Sections 2.3 and 2.3 of EPA Method 2), and
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gas analyzer, if^necessary (as described in EPA Method 3).. The temperature
-' * ' ' • f — *. r
sensor ideally should be permanently attached to the pitot tube or sampling
probe in a fixed configuration such that the tip of the sensor extends beyond
the leading edge of the probe sheath and does not touch any metal. Alterna-
tively, the sensor may be attached just prior to use in the field. Note,
however, that if the temperature sensor is attached in the field, the sensor
must be placed in an interference-free arrangement with respect to the Type S
pitot openings (see EPA Method 2, Figure 2-7). As a second alternative, if a
difference of no more than 1% in the average velocity measurement is to be
introduced, the temperature gauge need not be attached to the probe or pitot
tube.
3.5.4.2 Sample Recovery
3.5.4.2.1 Probe Liner: Probe nozzle and brushes; Teflon bristle
brushes with stainless steel wire handles are required. The probe brush shall
have extensions of stainless steel, Teflon, or inert material at least as long
as the probe. The brushes shall be properly sized and shaped to brush out the
probe liner, the probe nozzle, and the impingers.
3.5.4.2.2 Wash Bottles: Three wash bottles are required. Teflon or
glass wash bottles are recommended; polyethylene wash bottles should not be
used because organic contaminants may be extracted by exposure to organic
solvents used for sample recovery.
3.5.4.2.3 Graduate Cylinder and/or Balance: A graduated cylinder or
balance is required to measure condensed water to the nearest 1 ml or 1 g.
Graduated cylinders shall have division not >2 ml. Laboratory balances
capable of weighing to ±0.5 g are required.
3.5.4.2.4 Amber Glass Storage Containers: One-liter wide-mouth
amber flint glass bottles with Teflon-lined caps are required to store
impinger water samples. The bottles must be sealed with Teflon tape.
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3.5.4..2.5 Rubber Policeman.and Funnel: A rubber policeman and
*""' •» i.
funnel are required to aid in the transfer of material into and out of
containers in the field.
3.5.4.3 Reagent Preparation
3.5.4.3.1 Bottles/Caps: Amber 1- or 4-L bottles with Teflon-lined
caps are required for storing cleaned DNPH solution. Additional 4-L bottles
are required to collect waste organic solvents.
3.5.4.3.2 Large Glass Container: At least one large glass* (8 to
16 L) is required for mixing the aqueous acidic DNPH solution.
3.5.4.3.3 Stir Plate/Large Stir Bars/Stir Bar Retriever: a magnetic
stir plate and large stir bar are required for the mixing of aqueous acidic
DNPH solution. A stir bar retriever is needed for removing the stir bar from
the large container holding the DNPH solution.
3.5.4.3.4 Buchner Filter/Filter Flask/Filter Paper: A large filter
flask (2-4 L) with a buchner filter, appropriate rubber stopper, filter paper,
and connecting tubing are required for filtering the aqueous acidic DNPH
solution prior to cleaning.
3.5.4.3.5 Separatory Funnel: At least one large separatory funnel
(2 L) is required for cleaning the DNPH prior to use.
3.5.4.3.6 Beakers: Beakers (150 ml, 250 ml, and 400 ml) are useful
for holding/measuring organic liquids when cleaning the aqueous acidic DNPH
solution and for weighing DNPH crystals.
3.5.4.3.7 Funnels: At lease one large funnel is needed for pouring
the aqueous acidic DNPH into the separator funnel.
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3.5.4.3.8 Graduated Cylinders: At/least one large graduated
cylinder (1 to 2 L) is required for measuring organic-free reagent water and
acid when preparing the DNPH solution.
3.5.4.3.9 Top-Loading Balance: A one-place top loading balance is
needed for weighing out the DNPH crystals used to prepare the aqueous acidic
DNPH solution.
3.5.4.3.10 Spatulas: Spatulas are needed for weighing out DNPH when
preparing the aqueous DNPH solution.
3.5.4.4 Crushed Ice: Quantities ranging from 10-50 Ib may be
necessary during a sampling run, depending upon ambient temperature. Samples
which have been taken must be stored and shipped cold; sufficient ice for this
purpose must be allowed.
3.5.5 Reagents
3.5.5.1 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 determina-
tion.
3.5.5.2 Organic-free reagent water: All references to water in
this method refer to organic-free reagent water, as defined in Chapter One.
3.5.5.3 Silica Gel: Silica gel shall be indicating type, 6-16
mesh. If the silica gel has been used previously, dry at 175*C (350*F) for 2
hours before using. New silica gel may be used as received. Alternatively,
other types of desiccants (equivalent or better) may be used.
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3.5.5.4 2,4-dinJLtrophenyIhydrazihe (DNPH), [2,-4-(02N)2C6H3]NHNH2 -
The quantity of water may vary from 10 to 30%.
3.5.5.4.1 The 2,4-dinitrophenylhydrazine reagent must be prepared in
the laboratory within five days of sampling use in the field. Preparation of
DNPH can also be done in the field, with consideration of appropriate proce-
dures required for safe handling of solvent in the field. When a container of
prepared DNPH reagent is opened in the field, the contents of the opened
container should be used within 48 hours. All laboratory glassware must be
washed with detergent and water and rinsed with water, methanol, and methylene
chloride prior to use.
NOTE: DNPH crystals or DNPH solution should be handled with plastic gloves
at all times with prompt and extensive use of running water in case
of skin exposure.
3.5.5.4.2 Preparation of Aqueous Acidic DNPH Derivatizing Reagent::
Each batch of DNPH reagent should be prepared and purified within five days of
sampling, according to the procedures described below.
NOTE: Reagent bottles for storage of cleaned DNPH derivatizing solution
must be rinsed with acetonitrile and dried before use. Baked
glassware is not essential for preparation of DNPH reagent. The
glassware must not be rinsed with acetone or an unacceptable concen-
tration of acetone contamination will be introduced. If field
preparation of DNPH is performed, caution must be exercised in
avoiding acetone contamination.
3.5.5.4.2.1 Place an 8 L container under a fume hood on a
magnetic stirrer. Add a large stir bar and fill the container half full of
organic-free reagent water. Save the empty bottle from the organic-free
reagent water. Start the stirring bar and adjust the stir rate to be as fast
as possible. Using a graduated cylinder, measure 1.4 ml of concentrated
hydrochloric acid. Slowly pour the acid into the stirring water. Fumes may
be generated and the water may become warm. Weight the DNPH crystals on a
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one-place balance (see Table 3.5-1 for approximate amounts) and add to the
stirring acid solution. Fill the 8-L container to the 8-L mark with organic-
free reagent water and stir overnight. If all of the DNPH crystals have
dissolved overnight, add additional DNPH and stir for two more hours.
Continue the process of adding DNPH with additional stirring until a saturated
solution has been formed. Filter the DNPH solution using vacuum filtration.
Gravity filtration may be used, but a much longer time is required. Store the
filtered solution in an amber bottle at room temperature.
3.5.5.4.2.2 Within five days of proposed use, place about 1.6 L
of the DNPH reagent in a 2-L separatory funnel. Add approximately 200 ml of
methylene chloride and stopper the funnel. Wrap the stopper of the funnel
with paper towels to absorb any leakage. Invert and vent the funnel. Then
shake vigorously for 3 minutes. Initially, the funnel should be vented
frequently (every 10 -15 sec). After the layers have separated, discard the
lower (organic) layer.
3.5.5.4.2.3 Extract the DNPH a second time with methylene
chloride and finally with cyclohexane. When the cyclohexane layer has
separated from the DNPH reagent,the cyclohexane layer will be the top layer in
the separatory funnel. Drain the lower layer (the cleaned extract DNPH
reagent solution) into an amber bottle that has been rinsed with acetonitrile
and allowed to dry.
3.5.5.4.3 Quality Control: Take two aliquots of the extracted DNPH
reagent. The size of the aliquots is dependent upon the exact sampling
procedure used, but 100 ml is reasonably representative. To ensure that the
background in the reagent is acceptable for field use, analyze one aliquot of
the reagent according to the procedure of Method 8315. Save the other aliquot
of aqueous acidic DNPH for use as a method blank when the analysis is per-
formed.
3.5.5.4.4 Shipment to the Field: Tightly cap the bottle containing
extracted DNPH reagent using a Teflon-lined cap. Seal the bottle with Teflon
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Table 3.5-1
APPROXMIATE AMOUNT OF CRYSTALLINE DNPH USED
TO PREPARE A SATURATED SOLUTION
Amount of Moisture in DNPH
Weight Required per 8 L of Solution
10 weight percent
15 weight percent
30 weight percent
31 g
33 g
40 g
Table 3.5-2
INSTRUMENT DETECTION LIMITS AND REAGENT CAPACITY
FOR FORMALDEHYDE ANALYSIS1
Analyte
Formaldehyde
Acetaldehyde
Acrolein
Ace tone/Prop ionaldehyde
Butyraldehyde
Methyl ethyl ketone
Valeraldehyde
Isovaleraldehyde
Hexaldehyde
Benzaldehyde
o-/m-/p-Tolualdehyde
D ime thy Ibenzaldehyde
Detection Limit, ppbv2
1.8
1.7
1.5
1.5
1.5
1.5
1.5
1.4
1.3
1.4
1.3
1.2
Reagent Capacity, ppmv
66
70
75
75
79
79
84
84
88
84
89
93
^ygenated compounds in addition to formaldehyde are included for
comparison wieh formaldehyde; extension of the methodology to other compounds
is possible.
Detection limits are determined in solvent. These values therefore
represent the optimum capability of the methodology.
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tape. -After the*bottle Is.labeled, the bottle may be placed in a friction-top
can (paint can or equivalent) containing a 1-2 inch layer of granulated
charcoal and stored at ambient temperature until use.
3.5.5.4.4.1 If the DNPH reagent has passed the Quality Control
criteria, the reagent may be packaged to meet necessary shipping requirements
and sent to the sampling area. If the Quality Control criteria are not met,
the reagent solution may be re-extracted or the solution may be re-prepared
and the extraction sequence repeated.
3.5.5.4.4.2 If the DNPH reagent is not used in the field within
five days of extraction, an aliquot may be taken and analyzed as described in
Method 0011A. If the reagent meets the Quality Control requirements, the
reagent may be used. If the reagent does not meet the Quality Control
requirements, the reagent must be discarded and new reagent must be prepared
and tested.
3.5.5.4.5 Calculation of Acceptable Concentrations of Impurities in
DNPH Reagent: The acceptable impurity concentration (AIC, /jg/ml) is calculat-
ed from the expected analyte concentration in the sampled gas (EAC, ppbv), the
volume of air that will be sampled at standard conditions (SVOL, L), the
formula weight of the analyte (FW, g/mol), and the volume of DNPH reagent that
will be used in the impingers (RVOL, ml):
AIC - 0.1 x [EAC x SVOL X FW/22.4 x (FW + 180)/FV](RVOL x 1,000)
where:
0.1 is the acceptable contaminant concentration,
22.4 is a factor relating ppbv to g/L,
180 is a facto relating underivatized to derivatized analyte
1,000 is a unit conversion factor.
3.5.5.4.6 Disposal of Excess DNPH Reagent: Excess DNPH reagent may
be returned to the laboratory and recycled or treated as aqueous waste for
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disposal purposes. 2,4-dinitrophenylhydrazine is a flammable solid when dry,
so water should not be evaporated from the solution of the reagent.
3.5.5.5 Field Spike Standard Preparation: To prepare a formalde-
hyde field spiking standard at 4.01 mg/ml, use a 500 pi syringe to transfer
0.5 ml to 37% by weight of formaldehyde (401 mg/ml) to a 50 ml volumetric
flask containing approximately 50 ml of methanol. Dilute to 50 ml with
methanol.
3.5.5.6 Hydrochloric Acid, HCL: Reagent grade hydrochloric acid
(approximately 12N) is required for acidifying the aqueous DNPH solution.
3.5.5.7 Methylene Chloride, CH2C12: Methylene chloride (suitable
for residue and pesticide analysis, GC/MS, HPLC, GC, Spectrophotometry or
equivalent) is required for cleaning the aqueous acidic DNPH solution, rinsing
glassware, and recovery of sample trains.
3.5.5.8 Cyclohexane, C6H12: Cyclohexane (HPLC grade) is required
for cleaning the aqueous acidic DNPH solution.
NOTE: Do not use spectroanalyzed grades of Cyclohexane if this sampling
methodology is extended to aldehydes and ketones with four or more
carbon atoms.
3.5.5.9 Methanol, CH3OH: Methanol (HPLC grade or equivalent) is
required for rinsing glassware.
3.5.5.10 Acetonitrile, CH3CN: Acetonitrile (HPLC grade or equiva-
lent) is required for rinsing glassware.
3.5.5.11 Formaldehyde, HCHO: Analytical grade or equivalent
formaldehyde is required for preparation of standards. If other aldehydes or
ketones are used, analytical grade or equivalent is required.
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3.5.6 ftpfltple Collection. Preservation, and Handling
3.5.6.1 Because of the complexity of this method, field personnel
should be trained in and experienced with the test procedures in order to
obtain reliable results.
3.5.6.2 Laboratory Preparation:
3.5.6.2.1 All the components shall be maintained and calibrated
according to the procedure described in APTD-0576, unless otherwise specified.
3.5.6.2.2 Weigh several 200 to 300 g portions of silica gel in
airtight containers to the nearest 0.5 g. Record on each container the total
weight of the silica gel plus containers. As an alternative to preweighing
the silica gel, it may instead be weighed directly in the impinger or sampling
holder just prior to train assembly.
3.5.6.3 Preliminary Field Determinations :
»
3.5.6.3.1 Select the sampling site and the minimum number of
sampling point according to EPA Method 1 or other relevant criteria. Deter-
mine the stack pressure, temperature, and range of velocity heads using EPA
Method 2. A leak-check of the pitot lines according to EPA Method 2, Section
3.1, must be performed. Determine the stack gas moisture content using EPA
Approximation Method 4 or its alternatives to establish estimates of isokine-
tic sampling-rate settings. Determine the stack gas dry molecular weight, as
described in EPA Method 2, Section 3.6. If integrated EPA Method 3 sampling
is used for molecular weight determination, the integrated bag sample shall be
taken simultaneously with, and for the same total length of time as, the
sample run.
3.5.6.3.2 Select a nozzle size based on the range of velocity heads
so that is not necessary to change the nozzle size in order to maintain
isokinetic sampling rates below 28 L/min (1.0 cfm) . During the run, do not
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change the nozzle. Ensure that the. proper differential pressure gauge is
chosen for the range of velocity heads encountered (see Section 2.2. of EPA
Method 2).
3.5.6.3.3 Select a suitable probe liner and probe length so that all
traverse points can be sampled. For large stacks, to reduce the length of the
probe, consider sampling from opposite sides of the stack.
3.5.6.3.4 A minimum of 45 ft3 of sample volume is required for the
determination of the Destruction and Removal Efficiency (DRE) of formaldehyde
from incineration systems (45 ft3 is equivalent to one hour of sampling at
0.75 dscf). Additional sample volume shall be collected as necessitated by
the capacity of the DNPH reagent and analytical detection limit constraints.
To determine the minimum sample volume required, refer to sample calculations
in Section 10.
3.5.6.3.5 Determine the total length of sampling time needed to
obtain the identified minimum volume by comparing the anticipated average
sampling rate with the volume requirement. Allocate the same time to all
traverse points defined by EPA Method 1. To avoid timekeeping errors, the
length of time campled at each traverse point should be an integer or an
integer plus 0.5 min.
3.5.6.3.6 In some circumstances (e.g., batch cycles) it may be
necessary to sample for shorter times at the traverse points and to obtain
smaller gas•volume samples. In these cases, careful documentation must be
maintained in order to allow accurate calculation of concentrations.
*
3.5.6.4 Preparation of Collection Train:
3.5.6.4.1 During preparation and assembly of the sampling train,
keep all openings where contamination can occur covered with Teflon film or
aluminum foil until just prior to assembly or until sampling is about to
begin.
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3.5.6.4.2 Place 100 ml of cleaned DNPH.. solution in each of the first
* "
two impingers, and leave the third impinger empty. If additional capacity is
required for high expected concentrations of formaldehyde in the stack gas,
200 ml of DNPH per impinger may be used-or additional impingers may be used
for sampling. Transfer approximately 200 to 300 g of pre-weighed silica gel
from its container to the fourth impinger. Care should be taken to ensure
that the silica gel is not entrained and carried out from the impinger during
sampling. Place the silica gel container in a clean place or later use in the
sample recovery. Alternatively, the weight of the silica gel plus impinger
may be determined to the nearest 0.5 g and recorded.
3.5.6.4.3 With a glass or quartz liner, install the selected nozzle
using a Viton-A 0-ring with stack temperatures are <260°C (500"F) and a woven
glass-fiber gasket when temperatures are higher. See APTD-0576 (Rom, 1972)
for details. Other connection systems utilizing either 316 stainless steel or
Teflon ferrules may be used. Mark the probe with heat-resistant tape or by
some other method to denote the proper distance into the stack or duct for
each sampling point.
3.5.6.4.4 Assemble the train as shown in Figure 3.5-1. During
assembly, do not use any silicone grease on ground-glass joints upstream of
the impingers. Use Teflon tape, if required. A very light coating of
silicone grease may be used on ground-glass joints downstream of the
impingers, but the silicone grease should be limited to the outer portion (see
APTD-0576) of the ground-glass joints to minimize silicone grease contamina-
tion. If necessary, Teflon tape may be used to seal leaks. Connect all
temperature sensors to an appropriate potentiometer/display unit. Check all
temperature sensors at ambient temperatures.
3.5.6.4.5 Place crushed ice all around the impingers.
3.5.6.4.6 Turn on and set the probe heating system at the desired
operating temperature. Allow time for the temperature to stabilize.
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3.5.6.5 Leak-Check Procedures:
--- .»
3.5.6.5.1 Pre-test Leak Check
3.5.6.5.1.1 After Che sampling train has been assembled, turn on
and set the probe heating system at the desired operating temperature. Allow
time for the temperature to stabilize. If a Viton-A 0-ring or other leak-free
connection is used in assembling the probe nozzle to the probe liner, leak
check the train at the sampling site by plugging the nozzle and pulling a 381
mm Hg (15 in Hg) vacuum.
NOTE: A lower vacuum may be used, provided that the lower vacuum is not
exceeded during the test.
3.5.6.5.1.2 If an asbestos string is used, do not connect the
probe to the train during the leak check. Instead, leak-check the train by
first attaching a carbon-filled leak check impinger to the inlet and then
plugging the inlet and pulling a 381 mm Hg (15 in Hg) vacuum. (A lower vacuum
any be used if this lower vacuum is not exceeded during the test.) Next
connect the probe to the train and leak-check at about 25 mm Hg (1 in Hg)
vacuum. Alternatively, leak-check the probe with the rest of the sampling
train in one step at 381 mm Hg (15 in Hg) vacuum. Leakage rates in excess of
(a) 4% of the average sampling rate or (b) X).00057 ms/«in (0.02 cfm), are
unacceptable.
3.5.6.5.1.3 The following leak check instructions for the
sampling train descried in ADPT-0576 and APTD-0581 may be helpful. Start the
pump with the fine-adjust valve fully open and coarse-valve completely closed.
Partially open the coarse-adjust valve and slowly close the fine-adjust valve
until the desired vacuum is reached. Do not reverse direction of the fine-
adjust valve, as liquid will back up into the train. If the desired vacuum is
exceeded, either perform the leak check at this higher vacuum or end the leak
check, as shown below, and start over.
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3.5.6/5.1.4 When the leak check is"completed," first slowly remove
the plug from the inlet to the probe. When the vacuum drops to 127 mm (5 in)
Hg or less, immediately close the coarse-adjust valve. Switch off the pumping
system and reopen the fine-adjust valve. Do not reopen the fine-adjust valve
until the coarse-adjust valve has been closed to prevent the liquid in the
impingers from being forced backward in the sampling line and silica gel from
being entrained backward into the third impinger.
3.5.6.5.2 Leak Checks During Sampling Run:
3.5.6.5.2.1 If, during the sampling run, a component change
(i.e., impinger) becomes necessary, a leak check shall be conducted immediate-
ly after the interruption of sampling and before the change is made. The leak
check shall be done according to the procedure described in Section 3.5.6.5.1,
except that is shall be done at a vacuum greater than or equal to the maximum
value recorded up to that point in the test. If the leakage rate is found to
be no greater than 0.00057 m3/min (0.02 cfm or 4% of the average sampling rate
(whichever is less), the results are acceptable. If a higher leakage rate is
obtained, the tester must void the sampling run.
NOTE: Any correction of the sample volume by calculation reduces the
integrity of the pollutant concentration data generated and must be
avoided.
3.5.6.5.2.2 Immediately after a component change and before
sampling is reinitiated, a leak check similar to a pre-test leak check must
also be conducted.
3.5.6.5.3 Post-test Leak Check:
3.5.6.5.3.1 A leak check is mandatory at the conclusion of each
sampling run. The leak check shall be done with the same procedures as the
pre-test leak check, except that the post-test leak check shall be conducted
at a vacuum greater than or equal to the maximum value reached during the
sampling run. If the leakage rate is found to be no greater than 0.00057
3-169
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m3/min (0.02 cfm) or 4% of the average sampling rate (whichever is less), the
••—. ^,
results are acceptable. If, however, a higher leakage rate is obtained, the
tester shall record the leakage rate and void the sampling run.
3.5.6.6 Sampling Train Operation:
3.5.6.6.1 During the sampling run, maintain an isokinetic sampling
rate to within 10% of true isokinetic, below 20 L/min (1.0 cfm). Maintain a
temperature around the probe of 120'C (248* ± 25'F).
3.5.6.6.2 For each run, record the data on a data sheet such as the
one shown in Figure 3.5-2. Be sure to record the initial dry-gas meter
reading. Record the dry-gas meter readings at the beginning and end of each
sampling time increment, when changes in flow rates are made, before and after
each leak check, and when sampling is halted. Take other readings required by
Figure 2 at least once at each sample point during each time increment and
additional readings when significant adjustments 20% variation in velocity
head readings) necessitate additional adjustments in flow rate. Level and
zero the manometer. Because the manometer level and zero may drift due to
vibrations and temperature changes, make periodic checks during the traverse.
3.5.6.6.3 Clean the stack access ports prior to the test run to
eliminate the change of sampling deposited material. To begin sampling,
remove the nozzle cap, verify that the filter and probe heating systems are at
the specified temperature, and verify that the pitot tube and probe are
properly positioned. Position the nozzle at the first traverse point, with
the tip pointing directly into the gas stream. Immediately start the pump and
adjust the flow to isokinetic conditions. Nomographs, which aid in the rapid
adjustment of the isokinetic sampling rate without excessive computations, are
available. These nomographs are designed for use when the Type S pitot tube
coefficient is 0.84 + 0.02 and the stack gas equivalent density (dry molecular
weight) is equal to 29 i 4. APTD-0576 details the procedure for using the
nomographs. If the stack gas molecular weight and the pitot tube coefficient
are outside the above ranges, do not use the nomographs unless appropriate
steps are taken to compensate for the deviations.
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Plant
Location
Operator
Data
Hun No..
Sample BOK No.
Mater HO
C Factor
Ambient Temperature.
Barometric Pressure .
Assumed Moisture %
Probe Length, m(ft) _
NouleldentMcatlonNo.
Average CaHbratad Nozzle Diameter, cm (In).
Probe Healing Satting
Leak Rate, mVmkv (dm)
Proba Uner Material
Plot Tube Coefficient C,
Schematic of Stack Croae Section
Static Pressure, mm Hg (In. Hq)
FIRer No. .
Traverse Polr*
Number
Total
Average -
Sampang
Time
(0)Mla
Vacuum
mmHg
(In HflJ
Stack
Temperature
•#»
Velocity
Head
ip»)
mm(tn)HtO
Pressure
Differential
Across
Of Wee
Meter
mm(HjO)
(tnH.O)
Volume
m»(ll»)
Gae Sample Temp.
a! Dry Gee Meter
Inlet Outlet
•C(T) •Cff)
Avg. Avg.
FMer Holder
Temperature
•CfF)
Temperature
ofGas
Leaving
Last
bnpinger
•CfF)
• .
I
*—
~-I
Figure 3.5-2 Field Data Sheet
-------
3.5.6.6.4 When Che stack is under significant negative pressure
(equivalent to the height of the impinger stem), take care to close the
coarse-adjust valve before inserting the probe into the stack in order to
prevent liquid from backing up through the train. If necessary, the pump may
be turned on with the coarse-adjust valve closed.
3.5.6.6.5 When the probe is in position, block off the openings
around the probe and stack access port to prevent unrepresentative dilution of
the gas stream.
3.5.6.6.6 Traverse the stack cross section, as required by EPA
Method 1, being careful not to bump the probe nozzle into the stack walls when
sampling near the walls or when removing or inserting the probe through the
access port, in order to minimize the chance of extracting deposited material.
3.5.6.6.7 During the test run, make periodic adjustments to keep the
temperature around the probe at the proper levels. Add more ice and, if
necessary, salt, to maintain a temperature of <20*C (68*F) at the silica gel
outlet. Also, periodically check the level and zero of the manometer.
3.5.6.6.8 A single train shall be used for the entire sampling run,
except in cases where simultaneous sampling is required in two or more
separate ducts or at two or more different locations within the same duct, or
in cases where equipment failure necessitates a change of trains. An addition-
al train or additional trains may also be used for sampling when the capacity
of a single train is exceeded.
3.5.6.6.9 When two or more trains are used, separate analyses of
components from each train shall be performed. If multiple trains have been
used because the capacity of a single train would be exceeded, first impingers
from each train may be combined, and second impingers from each train may be
combined.
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3.5.6.0.10 At the end .of the sampling run, turn off the coarse -
adjust valve, remove the probe and nozzle from the stack, turn off the pump,
record the final dry gas meter reading, and conduct a post-test leak check.
Also, leak check the pitot lines as described in EPA Method 2. The lines must
pass this leak check in order to validate the velocity-head data.
3.5.6.6.11 Calculate percent isokineticity (see Method 2) to
determine whether the run was valid or another test should be made.
3.5.7 Sample Recovery
3.5.7.1 Preparation:
3.5.7.1.1 Proper cleanup procedure begins as soon as the probe is
removed from the stack at the end of the sampling period. Allow the probe to
cool. When the probe can be handled safely, wipe off all external particulate
matter near the tip of the probe nozzle and place a cap over the tip to
prevent losing or gaining particulate matter. Do not cap the probe tip
tightly while the sampling train is cooling because a vacuum will be created,
drawing liquid from the impingers back through the sampling train.
3.5.7.1.2 Before moving the sampling train to the cleanup site,
remove the probe from the sampling train and cap the open outlet, being
careful not to lose any condensate that might be present. Remove the umbili-
cal cord from the last impinger and cap the impinger. If a flexible line is
used, let any condensed water or liquid drain into the impingers. Cap off any
open impinger inlets and outlets. Ground glass stoppers, Teflon caps or caps
of other inert materials may be used to seal all openings.
3.5.7.1.3 Transfer the probe and impinger assembly to an area that
is clean and protected from wind so that the chances of contaminating or
losing the sample are minimized.
>
3.5.7.1.4 Inspect the train before and during disassembly, and note
any abnormal conditions.
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3.5.7.1.5 Save a portion of all washing solution (methylene chlo-
ride, water) used for cleanup as a blank, transfer 200 ml of each solution
directly from the wash bottle being used and place each in a separate,
prelabeled sample container.
3.5.7.2 Sample Containers:
3.5.7.2.1 Container 1: Probe and Impinger Catches. Using a
graduated cylinder, measure to the nearest ml, and record the volume of the
solution in the first three impingers. Alternatively, the solution may be
weighed to the nearest 0.5 g. Include any condensate in the probe in this
determination. Transfer the impinger solution from the graduated cylinder
into the amber flint glass bottle. Taking care that dust on the outside of
the probe or other exterior surfaces does not get into the sample, clean all
surfaces to which the sample is exposed (including the probe nozzle, probe
fitting, probe liner, first impinger, and impinger connector) with methylene
chloride. Use less than 500 ml for the entire wash (250 ml would be better,
if possible). Add the washing to the sample container.
3.5.7.2.1.1 Carefully remove the probe nozzle and rinse the
inside surface with methylene chloride from a wash bottle. Brush with a
Teflon bristle brush, and rinse until the rinse shows no visible particles or
yellow color, after which make a final rinse of the inside surface. Brush and
rinse the inside parts of the Swagelok fitting with methylene chloride in a
similar way.
3.5.7.2.1.2 Rinse the probe liner with methylene chloride. While
squirting the methylene chloride into the upper end of the probe, tilt and
rotate the probe so that all inside surfaces will be wetted with methylene
chloride. Let the methylene chloride drain from the lower end into the sample
container. The tester may use a funnel (glass or polyethylene) to aid in
transferring the liquid washes to the container. Follow the rinse with a
Teflon brush. Hold the probe in an inclined position, and squirt methylene
i
chloride into the upper end as the probe brush ic being pushed with a twisting
action through the probe. Hold the sample container underneath the lower end
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of-the probe, and catch any.jinethylene chloride, water, ancTparticulate matter
that is brushed from the probe. Run the brush through the probe three times
or more. With stainless steel or other metal probes, run the brush through in
the above prescribed manner at least six times since there may be small
crevices in which particulate matter can be entrapped. Rinse the brush with
methylene chloride or water, and quantitatively collect these washing in the
sample container. After the brushing, make a final rinse of the probe as
described above.
NOTE: Two people should clean the probe in order to minimize sample
losses. Between sampling runs, brushes must be kept clean and free
from contamination.
3.5.7.2.1.3 Rinse the inside surface of each of the first three
impingers (and connecting tubing) three separate times. Use a small portion
of methylene chloride for each rinse, and brush each surface to which the
sample is exposed with a Teflon bristle brush to ensure recovery of fine
particulate matter. Water will be required for the recovery of the impingers
in addition to the specified quantity of methylene chloride. There will be at
least two phases in the impingers. This two-phase mixture does not pour well,
and a significant amount of the impinger catch will be left on the walls. The
use of water as a rinse makes the recovery quantitative. Make a final rinse
of each surface and of the brush, using both methylene chloride and water.
3.5.7.2.1.4 After all methylene chloride and water washing and
particulate matter have been collected in the sample container, tighten the
lid so the solvent, water, and DNPH reagent will not leak out when the
container is shipped to the laboratory. Hark the height of the fluid level to
determine whether leakage occurs during transport. Seal the container with
Teflon tape. Label the container clearly to identify its contents.
3.5.7.2.1.5 If the first two impingers are to be analyzed
separately to check for breakthrough, separate the contents and rinses of the
two impingers into individual containers. Care must be taken to avoid
physical carryover from the first impinger to the second. The formaldehyde
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hydrazone is a splid which floats and froths on top of the. impinger solution.
Any physical carryover of collected moisture into the second impinger will
invalidate a breakthrough assessment.
3.5.7.2.2 Container 2: Sample Blank. Prepare a blank by using an
amber flint glass container and adding a volume of DNPH reagent and methylene
chloride equal to the total volume in Container 1. Process the blank in the
same manner as Container 1.
3.5.7.2.3 Container 3: Silica Gel. Note the color of the indicat-
ing silica gel to determine whether it has been completely spent and make a
notation of its condition. The impinger containing the silica gel may be used
as a sample transport container with both ends sealed with tightly fitting
caps or plugs. Ground-glass stoppers or Teflon caps maybe used. The silica
gel impinger should then be labeled, covered with aluminum foil, and packaged
on ice for transport to the laboratory. If the silica gel is removed from the
impinger, the tester may use a funnel to pour the silica gel and a rubber
policeman to remove the silica gel from the impinger. It is not necessary to
remove the small amount of dust particles that may adhere to the impinger wall
and are difficult to remove. Since the gain in weight is to be used for
moisture calculations, do not use water or other liquids to transfer the
silica gel. If a balance is available in the field, the spent silica gel (or
silica gel plus impinger) maybe weighed to the nearest 0.5 g.
3.5.7.2.4 Sample containers should be placed in a cooler, cooled by
(although not in contact with) ice. Sample containers must be placed verti-
cally and, since they are glass, protected from breakage during shipment.
Samples should be cooled during shipment so they will be received cold at the
laboratory.
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3.5.8 Calibration
3.5.8.1 Probe Nozzle: Probe nozzles shall be calibrated before
their initial use in the field. Using a micrometer, measure the inside
diameter of the nozzle to the nearest 0.025 mm (0.001 in). Make measurements
at three separate places across the diameter and obtain the average of the
measurements. The difference between the high and low numbers shall not
exceed 0.1 mm (0.004 in), when the nozzles become nicked or corroded, they
shall be replaced and calibrated before use. Each nozzle must be permanently
and uniquely identified.
3.5.8.2 Pitot Tube: The Type S pitot tube assembly shall be
calibrated according to the procedure outlined in Section 4 of EPA Method 2,
or assigned a nominal coefficient of 0.84 if it is not visibly nicked or
corroded an% if it meets design and intercomponent spacing specifications.
3.5.8.3 Metering System
3.5.8.3.1 Before its initial use in the field, the metering system
shall be calibrated according to the procedure outlined in APTD-0576. Instead
of physically adjusting the dry-gas meter dial readings to correspond to the
wet-test meter readings, calibration factors may be used to correct the gas
meter dial readings mathematically to the proper values. Before calibrating
the metering system, it is suggested that a leak check be conducted. For
metering systems having diaphragm pumps, the normal leak check procedure will
not detect leakages with the pump. For these cases, the following leak check
procedure will apply: make a ten-minute calibration run at 0.00057 m3/min
(0.02 cfm). At the end of the run, take the difference of the measured wet-
test and dry-gas meter volumes and divide the difference by 10 to get the leak
rate. The leak rate should not exceed 0.00057 m3/min (0.02 cfm).
3.5.8.3.2 After each field use, check the calibration of the
metering system by performing three calibration runs at a single intermediate
orifice setting (based on the previous field test). Set the vacuum at the
maximum value reached during the test series. To adjust the vacuum, insert a
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valve between the wet-test meter and -the inlet of the mete-ring system.
Calculate the average value of the calibration factor. If the calibration has
changed by more the 5%, recalibrate the meter over the full range of orifice
settings, as outlined in AFTD-0576.
3.5.8.3.3 Leak check of metering system: The portion of the
sampling train from the pump to the orifice meter (see Figure 1) should be
leak checked prior to initial use and after each shipment. Leakage after the
pump will result in less volume being recorded than is actually sampled. Use
the following procedure: Close the main valve on the meter box. Insert a
one-hole rubber stopper with rubber tubing attached into the orifice exhaust
pipe. Disconnect and vent the low side of the orifice manometer. Close off
the low side orifice tap. Pressurize the system to 13 - 18 cm (5 - 7 in)
water column by blowing into the rubber tubing. Pinch off the tubing and
observe the manometer for 1 min. A loss of pressure on the manometer indi-
cates a leak in the meter box. Leaks must be corrected.
NOTE: If the dry-gas-meter coefficient values obtained before and after a
test series differ by >5%, either the test series must be voided or
calculations for test series must be performed using whichever meter
coefficient value (i.e., before or after) gives the lower value of
total sample volume.
3.5.6.4 Probe Heater: The probe heating system must be calibrated
before its initial use in the field according to the procedure outlined in
APTD-0576. Probes constructed according to APTD-0581 need not be calibrated
if the calibration curves in APTD-0576 are used.
3.5.8.5 Temperature gauges: Each thermocouple must be permanently
and uniquely narked on the casting. All mercury-in-glass reference thermome-
ters must conform to ASTM E-l 63C or 63F specifications. Thermocouples should
be calibrated in the laboratory with and without the use of extension leads.
If extension leads are used in the field, the thermocouple readings at the
ambient air temperatures, with and without the extension lead, must be noted
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and recorded. Correction is necessary if the use of an extension lead
.- * ' *
produces a change >1.5%.
3.5.8.5.1 Impinger and dry-gas meter thermocouples: For the
thermocouples used to measure the temperature of the gas leaving the impinger
train, three-point calibration at ice water, room air, and boiling water
temperatures is necessary. Accept the thermocouples only if the readings at
all three temperatures agree to +2C (3.6*F) with those of the absolute value
of the reference thermometer.
3.5.8.5.2 Probe and stack thermocouple: for the thermocouples used
to indicate the probe and stack temperatures, a three-point calibration at ice
water, boiling water, and hot oil bath temperatures must be performed. Use of
a point at room air temperature is recommended. The thermometer and thermo-
couple must agree to within 1.5% at each of the calibration points. A
calibration curve (equation) may be constructed (calculated) and the data
extrapolated to cover the entire temperature range suggested by the manufac-
turer.
3.5.8.6 Barometer: Adjust the barometer initially and before each
test series to agree to within +2.5 mm Hg (0.1 in Hg) of the mercury barometer
or the correct barometric pressure value reported by a nearby National Weather
Service Station (same altitude above sea level).
3.5.8.7 Triple-beam balance: Calibrate the triple-beam balance
before each test series, using Class S standard weights. The weights must be
within ±0.5% of the standards, or the balance must be adjusted to meet these
limits.
3.5.9 Calculations
Carry out calculations, retaining at least one extra decimal figure beyond
that of the acquired data. Round off figures after final calculations.
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3.5.9.1 Calculation of Total Formaldehyde: To determine the total
formaldehyde in mg, use the following equation:
[g/mole aldehyde]
Total mg formaldehyde - Cd x V x DF x x 103 mg/pg
[g/mole DNPH derivative]
where:
Cd - measured concentration of DNPH - formaldehyde derivative, /*g/ml
V - organic extract volume ml
DF - dilution factor
3.5.9.2 Formaldehyde concentration in stack gas:
Determine the formaldehyde concentration in the stack gas using the
following equation:
Cf»- K [total formaldehyde, mg] V.j.^,
where :
K - 35.31 fc3/m3 if V.(ttd) is expressed in English units
- 1.00 m'/m3 if VM(Btd) is expressed in metric units
VB((td) - volume of gas sample a measured by dry gas meter,
corrected to standard conditions, dscm (dscf)
3.5.9.3 Average Dry Gas Meter Temperature and Average Orifice
Pressure Drop are obtained from the data sheet.
3.5.9.4 Dry Gas Volume: Calculate VB(>td} and adjust for leakage,
if necessary, using the equation in Section 6.3 of EPA Method 5.
3.5.9.5 Volume of Water Vapor and Moisture Content: Calculate the
volume of vater vapor and moisture content from equations 5-2 and 5-3 of EPA
Method 5.
3.5. 10 Determination of VplVTBf t? Pf
To determine the minimum sample volume to be collected, use the following
sequence of equations.
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3.5.10.1 From prior analysis of the waste feed, the concentration
of formaldehyde (FORM) introduced into the combustion system can be calculat-
ed. The degree of destruction and removal efficiency that is required is used
to determine the amount of FORM allowed to be present in the effluent. This
amount may be expressed as:
Max FORM Mass - [ (WF) (FORM cone) (100 - %DRE) ] /100
where :
WF - mass flow rate of waste feed per h, g/h (Ib/h)
FORM - concentration of FORM (wt %) introduced into the
combustion process
DRE - percent Destruction and Removal Efficiency required
Max FORM - mass flow rate (g/h [lb/]) of FORM emitted from the
combustion sources
3.5.10.2 The average discharge concentration of the FORM in the
effluent gas is determined by comparing the Max FORM with the volumetric flow
rate being exhausted from the source. Volumetric flow rate data are available
as a result of preliminary EPA Method 1-4 determinations:
Max FORM cone - [Max FORM Mass] / W.tti*tu
where :
DV.£f(ttd) ~ volumetric flow rate of exhaust gas, dscm (dscf)
FORM cone - anticipated concentration of the FORM in the
exhaust gas stream, g/dscm (Ib/dscf)
N.
3.5.10.3 In making this calculation, it is recommended that a
safety margin of at least ten be included.
x 10 / FORM cone] - V^
where :
detectable amount of FORM in entire sampling train
minimum dry standard volume to be collected at dry-
gas meter
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3.5.10.4 The following analytical detection limits and DNPH Reagent
Capacity (based on a total volume of 200 ml in two impingers) must also be
considered in determining a volume to be sampled.
3.5.11 Quality Control
3.5.11.1 Sampling: See EPA Manual 600/4-77-02b for Method 5
quality control.
3.5.11.2 Analysis: The quality assurance program required for this
method includes the analysis of the field and method blanks, procedure
validations, and analysis of field spikes. The assessment of combustion data
and positive identification and quantitation of formaldehyde are dependent on
the integrity of the samples received and the precision and accuracy of the
analytical methodology. Quality assurance procedures for this method are
designed to monitor the performance of the analytical methodology and to
provide the required information to take corrective action if problems are
observed in laboratory operations or in field sampling activities.
3.5.11.2.1 Field Blanks: Field blanks must be submitted with
the samples collected at each sampling site. The field blanks include the
sample bottles containing aliquots of sample recovery .solvents, methylene
chloride and water, and unused DNPH reagent. At a minimum, one complete
sampling train will be assembled in the field staging area, taken to the
sampling are, and leak-checked at the beginning and end of the testing (or for
the same total number of times as the actual sampling train). The probe of
the blank train must be heated during the sample test. The train will be
recovered as if it were an actual test sample. No gaseous sample will be
passed through the blank sampling train.
3.5.11.2.2 Method Blanks: A method blank must be prepared for
each set of analytical operations, to evaluate contamination and artifacts
that can be derived from glassware, reagents, and sample handling in the
laboratory.
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3.5.11.2.3 Field Spike: A fie.ld spike is performed by introduc-
* ' '
ing 200 ^L of the Field Spike Standard into~'an impinger containing 200 ml of
DNPH solution. Standard impinger recovery procedures are followed and the
spike is used as a check on field handling and recovery procedures. An
aliquot of the field spike standard is retained in the laboratory for deriva-
tization and comparative analysis.
3.5.12 Method Performance
3.5.12.1 Method performance evaluation: The expected method
performance parameters for precision, accuracy, and detection limits are
provided in Table 3.5-3.
Addition of a Filter to the Formaldehyde Sampling Train
As a check on the survival of particulate material through the impinger
system, a filter can be added to the impinger train either after the second
impinger or after the third impinger. Since the impingers are in an ice bath,
there is no reason to heat the filter at this point.
Any suitable medium (e.g., paper, organic membrane) may be used for the filter
if the material conforms to the following specifications:
1) the filter has at least 95% collection efficiency (<5% penetration)
for 3 /m dioctyl phthalate smoke particles. The filter efficiency
test shall be conducted in accordance with ASTM standard method
D2986-71. Test data from the supplier's quality control program are
sufficient for this purpose.
2) the filter has a low aldehyde blank value (<0.015 mg formaldeh-
yde/cm2 of filter area). Before the test series, determine the
average formaldehyde blank value of at least three filters (from the
lot to be used for sampling) using the applicable analytical
procedures.
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Table 3.5-3 -.
EXPECTED METHOD PERFORMANCE FOR FORMALDEHYDE
Parameter Precision1 Accuracy2 Detection Limit3
Matrix: Dual trains ±15% RPD ±20% 1.5 x 10'7 lb/ft3
(1.8 ppbv)
Relative percent difference limit for dual trains.
2Limit for field spike recoveries.
3The lower reporting limit having less than 1% probability of false positive
detection.
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Recover the exposed filter into a separate clean container and return the
container over ice to the laboratory for analysis. If the filter is being
analyzed for formaldehyde, the filter may be recovered into a container or
DNPH reagent for shipment back to the laboratory. If the filter is being
examined for the presence of particulate material, the filter may be recovered
into a clean dry container and returned to the laboratory.
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3.6 ' Analysis for Aldehydes and Ketones..bv Hifth Performance Liquid
Chromatographv fHPLC) (Method OOllA)
3.6.1 Scope and Application
3.6.1.1 Method OOllA covers the determination of free formaldehyde
in the aqueous samples and leachates and derived aldehydes/ketones collected
by Method 0011.
Compound Name CAS No.*
Formaldehyde 50-00-0
Acetaldehyde 75-07-0
* Chemical Abstract Services Registry Number
3.6.1.2 Method OOllA is a high performance liquid chromatographic
(HPLC) method optimized for the determination of formaldehyde and acetaldehyde
in aqueous environmental matrices and leachates of solid samples and stack
samples collected by Method 0011. When this method is used to analyze
unfamiliar sample matrices, compound identification should be supported by at
least one additional qualitative technique. A gas chromatograph/mass spec-
trometer (GC/MS) may be used for the qualitative confirmation of results from
the target analytes, using the extract produced by this method.
3.6.1.3 The method detection limits (MDL) are listed in Tables
3.6-1 and 3.6-2. The MDL for a specific sample may differ from that listed,
depending upon the nature of interferences in the sample matrix and the amount
of sample used in the procedure.
3.6.1.4 The extraction procedure for solid samples is similar to
that specified in Method 1311 (1). Thus, a single sample may be extracted to
measure the analytes included in the scope of other appropriate methods. The
analyst is allowed the flexibility to select chromatographic conditions
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Table 3.6-1 ...
•
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY CONDITIONS
AND METHOD DETECTION LIMITS USING SOLID
SORBENT EXTRACTION
Analyze Retention Time MDL
(minutes)
Formaldehyde 7.1 7.2
HPLC conditions: Reverse phase CIS column, 4.6 x 250 mm; isocratic elution
using methanoI/water (75:25, v/v); flow rate 1.0 mL/min.; detector 360 nm.
* After correction for laboratory blank.
Table 3.6-2
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY CONDITIONS
AND METHOD DETECTION LIMITS USING METHYLENE
CHLORIDE EXTRACTION
Analyte
Formaldehyde
Acetaldehyde
Retention Time
(minutes)
7.1
8.6
MDL
Ug/L)*
7.2
171*
HPLC conditions: Reverse phase CIS column, 4.6 x 250 mm; isocratic elution
using methanol/water (75:25, v/v); flow rate 1.0 mL/min.; detector 360 nm.
* These values include reagent blank concentrations of approximately 13 Mg/L
formaldehyde and 130 Mg/L acetaldehyde.
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appropriate for -the simultaneous measurement of contaminations of these analy-
tes.
3.6.1.5 This method is restricted to use by, or under the supervi-
sion of analysts experienced in the use of chromatography and in the interpre-
tation of chromatograms. Each analyst must demonstrate the ability to
generate acceptable results with this method.
3.6.1.6 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 chemi-
cals specified in this method. A reference file of material safety data
sheets should also be made available to all personnel involved in the chemical
analysis. Additional references to laboratory safety are available.
3.6.1.7 Formaldehyde has been tentatively classified as a known or
suspected, human or mammalian carcinogen.
3.6.2 Summary of Method
3.6.2.1 Environmental Liquids and Solid Leachates
3.6.2.1.1 For wastes comprised of solids or for aqueous wastes
containing significant amounts of solid material, the aqueous phase, if any,
is separated froa the solid phase and stored for later analysis. If neces-
sary, the particle size of the solids in the waste is reduced. The solid
phase is extracted with an amount of extraction fluid equal to 20 times the
weight of the solid phase of the waste. A special extractor vessel is used
when testing for volatiles. Following extraction, the aqueous extract is
separated from the solid phase by filtration employing 0.6 to 0.8 pm glass
fiber filters.
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3.6,2.1.2 If compatible (i.e., multiple phases will not form on
combination), the initial aqueous phase of the waste is added to the aqueous
extract, and these liquids are analyzed together. If incompatible, the
liquids are analyzed separately and the results are mathematically combined to
yield a volume weighted average concentration.
3.6.2.1.3 A measured volume of aqueous sample or an appropriate
amount of solids leachate is buffered to pH 5 and derivatized with 2,4-
dinitrophenylhydrazine (DNPH), using either the solid sorbent or the methylene
derivatization/extraction option. If the solid sorbent option is used, the
derivative is extracted using solid sorbent cartridges, followed by elution
with ethanol. If the methylene chloride option is used, the derivative is
extracted with methylene chloride. The methylene chloride extracts are
concentrated using the Kuderna-Danish (K-D) procedure and solvent exchanged
into methanol prior to HPLC analysis. Liquid chromatographic conditions are
described which permit the separation and measurement of formaldehyde in the
extract by absorbance detection at 360 run.
3.6.2.2 Stack Gas Samples Collected by Method 0011
3.6.2.2.1 The entire sample returned to the laboratory is extracted
with methylene chloride and the methylene chloride extract is brought up to a
known volume. An aliquot of the methylene chloride extract is solvent
exchanged and concentrated or diluted as necessary.
3.6.2.2.2 Liquid chromatographic conditions are described that
permit the separation and measurement of formaldehyde in the extract by
absorbance detection at 360 run.
3.6.3 Interferences
3.6.3.1 Method interferences may be caused by contaminants in
solvents, reagents, glassware, and other sample processing hardware that lead
to discrete artifacts and/or elevated baselines in the chromatograms. All of
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these materials oust be routinely demonstrated to be free from interferences
under the conditions of the analysis by analyzing laboratory reagent blanks.
3.6.3.1.1 Glassware must be scrupulously cleaned. Clean all
glassware as soon as possible after use by rinsing with the last solvent used.
This should be followed by detergent washing with hot water, and rinses with
tap water and distilled water. It should then be drained, dried, and heated
in a laboratory oven at 130*C for several hours before use. Solvent rinses
with methanol may be substituted for the oven heating. After drying and
cooling, glassware should be stored in a clean environment to prevent any
accumulation of dust or other contaminants.
3.6.3.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of solvents by distillation in
all-glass systems may be required.
3.6.3.2 Analysis for formaldehyde is especially complicated by its
ubiquitous occurrence in the environment.
3.6.3.3 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 matrix being sampled. No interferences have been observed in the matrices
studied as a result of using solid sorbent extraction as opposed to liquid
extraction. If interferences occur in subsequent samples, some additional
cleanup may be necessary.
3.6.3.4 The extent of interferences that nay be encountered using
liquid chromatographic techniques has not been fully assessed. Although the
HPLC conditions described allow for a resolution of the specific compounds
covered by this method, other matrix components may interfere.
3.6.4 Apparatus and Materials
3.6.4.1 Reaction vessel - 250 ml Florence flask.
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3.6.4.2 Separatory funnel - 205 ml,.with Teflon stopcock
. • . * ' *
3.6.4.3 Kuderna-Danish (K-D) apparatus.
3.6.4.3.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025
or equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
3.6.4.3.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or equivalent.
3.6.4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
3.6.4.3.4 Snyder column - Two ball macro (Kontes K-569001-0219 or
equivalent).
3.6.4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
3.6.4.4 Vials - 10, 25 ml, glass with Teflon lined screw caps or
crimp tops.
3.6.4.5 Boiling chips - Solvent extracted with methylene chloride,
approximately 10/40 mesh (silicon carbide or equivalent).
3.6.4.6 Balance - Analytical, capable of accurately weighing to
the nearest 0.0001 g.
3.6.4.7 pH meter - Capable of measuring to the nearest 0.01 units.
3.6.4.8 High performance liquid chromatograph (modular)
3.6.4.8.1 Pumping system - Isocratic, with constant flow control
capable of 1.00 ml/min.
3.6.4.8.2 High pressure injection valve with 20 ftL loop.
3.6.4.8.3 Column - 250 mm x 4.6 mm ID, 5 tan particle size, C18 (or
equivalent).
3.6.4.8.4 Absorbance detector - 360 nm.
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3.6.4,8.5 Strip-chart recorder compatible with detector - Use of a
• • . - * ' "
data system for measuring peak areas and retention times is recommended.
3.6.4.9 Glass fiber filter paper.
3.6.4.10 Solid sorbent cartridges - Packed with 500 mg CIS (Baker
or equivalent).
3.6.4.11 Vacuum manifold - Capable of simultaneous extraction of up
to 12 samples (Supelco or equivalent).
3.6.4.12 Sample reservoirs - 60 ml capacity (Supelco or equiva-
lent) .
3.6.4.13 Pipet - Capable of accurately delivering 0.10 ml solution
(Pipetman or equivalent).
3.6.4.14 Water bath - Heated, with concentric ring cover, capable
of temperature control ((+) 2*C), The bath should be used under a hood.
3.6.4.15 Volumetric Flasks - 250 or 500 ml.
3.6,5 Reagents
3.6.5.1 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 determina-
tion.
3.6.5.2 Organic-free water - All references to water in this
method refer to organic-free reagent water, as defined in Chapter 1 SW-846.
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3.6.5..3 Methylene chloride, CH2C12 -HPLC grade or equivalent.
3.6.5.4 Methanol, CH3OH - HPLC grade or equivalent.
3.6.5.5 Ethanol (absolute), CH3CH2OH - HPLC grade or equivalent.
3.6.5.6 2,4-Dinitrophenylhydrazine (DNPH) (70% (W/W)), [2,4-
(02N)2C6H3]NHNH2, in organic-free reagent water.
3.6.5.7 Formalin (37.6 percent (w/w)), formaldehyde in organic -
free reagent water.
3.6.5.8 Acetic acid (glacial), CH3C02H.
3.6.5.9 Sodium hydroxide solutions NaOH, 1.0 N and 5 N.
3.6.5.10 Sodium chloride, NaCl.
3.6.5.11 Sodium sulfite solution, Na2S03, 0.1 M.
3.6.5.12 Hydrochloric Acid, HC1, 0.1 N.
3.6.5.13 Extraction fluid - Dilute 64.3 ml of 1.0 N NaOH and 5.7 ml
glacial acetic acid to 900 ml with organic-free reagent water. Dilute to 1
liter with organic-free reagent water. The pH should be 4.93 + 0.02.
3.6.5.14 Stock standard solutions
3.6.5.14.1 Stock formaldehyde (approximately 1.00 mg/ml) - Prepare
by diluting 265 pi formalin to 100 ml with organic-free reagent water.
3.6.5.14.1.1 Standardization of formaldehyde stock solution -
Transfer a 25 ml aliquot of a 0.1 M Na2S03 solution to a beaker and record the
pH. Add a 25.0 ml aliquot of the formaldehyde stock solution (Section
3.6.5.14.1) and record the pH. Titrate this mixture back to the original pH
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using 0.1 N HC1. The formaldehyde concentration is calculated using the
following equation:
Concentration (mg/ml) - 30.03 x (N HCl) x (ml HC1) 25.0
where :
N HCl - Normality of HCl solution used
ml HCl - ml of standardized HCl solution used
30.03 - MW of formaldehyde
%
3.6.5.14.2 Stock formaldehyde and acetaldehyde - Prepare by adding
265 nL formalin and 0.1 g acetaldehyde to 90 ml of water and dilute to 100 ml.
The concentration of acetaldehyde in this solution is 1.00 mg/ml. Calculate
the concentration of formaldehyde in this solution using the results of the
assay performed in Section 3.6.5.14.1.1.
3.6.5.14.3 Stock standard solutions must be replaced after six
months, or sooner, if comparison with check standards indicates a problem.
3.6.5.15 Reaction Solutions
3.6.5.15.1 DNPH (1.00 /*g/L) - Dissolve 142.9 mg of 70% (w/w) reagent
in 100 ml absolute ethanol. Slight heating or sonication may be necessary to
effect dissolution.
3.6.5.15.2 Acetate buffer (5 N) Prepare by neutralizing glacial
acetic acid to pH 5 with 5 N NaOH solution. Dilute to standard volume with
water .
3.6.5.15.3 Sodium chloride solution (saturated) Prepare by mixing
of the reagent grade solid with water.
3.6.6 SflflTPlC Collection. Preservation, and Handling
3.6.6.1 See the introductory material to this Chapter, Organic
Analytes, Section 4.1 of SV-846.
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3.6.6.2 Environmental liquid and leachate samples must be refrig-
erated at 4°C, and must be derivatized within 5 days of sample collection and
analyzed within 3 days of derivatization.
3.6.6.3 Stack gas samples collected by Method 0011 must be
refrigerated at 4°C. It is recommended that samples be extracted within 30
days of collection and that extracts be analyzed within 30 days extraction.
3.6.7 Procedure
3.6.7.1 Extraction of Solid Samples
3.6.7.1.1 All solid samples should be homogeneous. When the sample
is not dry, determine the dry weight of the sample, using a representative
aliquot.
3.6.7.1.1.1 Determination of dry weight - In certain cases, sample
results are desired based on a dry weight basis. When such data is desired,
or required, a portion of sample for dry weight 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. Signifi-
cant laboratory contamination may result from drying a heavily
contaminated hazardous waste sample.
3.6.7.1.1.2 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 fpiflple x 100
g of sample
3.6.7.1.2 Measure 25 g of solid into a 500 ml bottle with a Teflon
lined screw cap or crimp top, and add 500 ml of extraction fluid (Section
3.6.5.13). Extract the solid by rotating the bottle at approximately 30 rpm
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for 18 hours. Filter the extract through glass fiber paper and store in
sealed bottles at 4*C. Each ml of extract .represents 0.050 g solid.
3.6.7.2 Cleanup and Separation
3.6.7.2.1 Cleanup procedures may not be necessary for a relatively
clean sample matrix. The cleanup procedures recommended in this method have
been used for the analysis of various sample types. If particular circum-
stances demand the use of an alternative cleanup procedure, the analyst must
determine the elution profile and demonstrate that the recovery of formalde-
hyde is no less then 85% of recoveries specified in Table 3.6-3. Recovery may
be lower for samples which form emulsions.
*
3.6.7.2.2 If the sample is not clean, or the complexity is unknown,
the entire sample should be centrifuged at 2500 rpm for 10 minutes. Decant
the supernatant liquid from the centrifuge bottle, and filter through glass
fiber filter paper into a container which can be tightly sealed.
3.6.7.3 Derivatization
3.6.7.3.1 For aqueous samples, measure a 50 to 100 ml aliquot of the
sample. Quantitatively transfer the sample aliquot to the reaction vessel
(Section 3.6.4.1).
3.6.7.3.2 For solid samples, 1 to 10 ml of leachate (Section
3.6.7.1) will usually be required. The amount used for a particular sample
must be determined through preliminary experiments.
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Table 3.6-3
SINGLE OPERATOR ACCURACY AND PRECISION
USING SOLID SORBENT EXTRACTION
Analyte
Formaldehyde
Matrix
Type
Reagent
Water
Final
Effluent
Phenol
formaldehyde
Sludge
Average
Percent
Recovery
86
90
93
Standard
Deviation
Percent
9.4
11. 0
12.0
Spike
Range
(*
-------
Note: For all reactions, the total volume of the aqueous layer should be
adjusted to 100 ml with water. ~
3.6.7.3.3 Derivatization and extraction of the derivative can be
accomplished using the solid sorbent (Section 3.6.7.3;4) or methylene chloride
option (Section 3.6.7.3.5).
3.6.7.3.4 Solid Sorbent Option
3.6.7.3.4.1 Add 4 ml of acetate buffer and adjust the pH to 5.0 ±
0.1 with glacial acetic acid or 5 N NaOH. Add 6 ml of DNFH reagent, seal the
container, and place on a wrist-action shaker for 30 minutes.
•
3.6.7.3.4.2 Assemble the vacuum manifold and connect to a water
aspirator or vacuum pump. Assemble solid sorbent cartridges containing a
minimum of 1.5 g of C18 sorbent, using connectors supplied by the manufactur-
er, and attach the sorbent train to the vacuum manifold. Condition each
cartridge by passing 10 ml dilute acetate buffer (10 ml 5 N acetate buffer
dissolved in 250 ml water) through the sorbent cartridge train.
3.6.7.3.4.3 Remove the reaction vessel from the shaker and add 10
ml saturated NaCl solution to the vessel.
3.6.7.3.4.4 Add the reaction solution to the sorbent train and
apply a vacuum so that the solution is drawn through the cartridges at a rate
of 3 to 5 ml/min. Release the vacuum after the solution has passed through
the sorbent.
3.6.7.3.4.5 Elute each cartridge train with approximately 9 ml of
absolute ethanol, directly into a 10 ml volumetric flask. Dilute the solution
to volume with absolute ethanol. mixed thoroughly, and place in a tightly
sealed vial until analyzed.
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3.6.7.3.5 Methylene Chloride Option
3.6.7.3.5.1 Add 5 m of acetate buffer and adjust the pH to 5.0 ±
0.5 with glacial acetic acid or 5 N NaOH. Add 10 ml of DNPH reagent, seal the
container, and place on a wrist-action shaker for 1 hour.
3.6.7.3.5.2 Extract the solution with three 20 ml portions of
methylene chloride, using a 250 ml separatory funnel, and combine the methy-
lene chloride layers. If an emulsion forms upon extraction, remove the entire
emulsion and centrifuge at 2000 rpm for 10 minutes. Separate the layers and
proceed with the next extraction.
•
3.6.7.3.5.3 Assemble a Kuderna-Danish (K-D) concentrator by
attaching a 10 ml concentrator tube to a 500 ml evaporator flask. Wash the K-
D apparatus with 25 ml of extraction solvent to complete the quantitative
transfer.
3.6.7.3.5.4 Add one to two clean boiling chips to the evaporative
flask and attach a three ball Snyder column. Preset 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 10 ml, remove the K-D apparatus and allow it to drain and
cool for a least 10 min.
3.6.7.3.5.5 Prior to liquid chromatographic analysis, the solvent
must be exchanged to methanol. The analyst must ensure quantitative transfer
of the extract concentrate. The exchange is performed as follows:
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3.6.7.3.5.5.1 Following K-D concentration of the methylene chloride
extract to < 10 ml using the macro Snyder column, allow the apparatus to cool
and drain for at least 10 minutes.
3.6.7.3.5.5.2 Momentarily remove the Snyder column, add 5 ml of the
methanol, a new glass bed, or boiling chip, and attach the micro 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 concentra-
tion. 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 < 5 ml, remove the K-D apparatus and allow it to drain"and
cool for at least 10 minutes.
3.6.7.3.5.5.3 Remove the Snyder column and rinse the flask and its
lower joint with 1-2 ml of methanol and add to concentrator tube. A 5-ml
syringe is recommended for this operation. Adjust the extract volume to 10
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 or crimp top. Proceed with liquid chromatographic analysis if
further cleanup is not required.
3.6.7.4 Extraction of Stack Gas Samples Collected by Method 0011
3.6.7.4.1 Measure the aqueous volume of the sample prior to extrac-
tion (for moisture determination in case the volume was not measured in the
field). Pour the sample into a separatory funnel and drain the methylene
chloride into a volumetric flask.
3.6.7.4.2 Extract the aqueous solution with two or three aliquots of
methylene chloride. Add the methylene chloride extracts to the volumetric
flask.
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"3.6.7.4.3 Fill the volumetric flask to the line with methylene
chloride. Mix well and remove an aliquot. ..
3.6.7.4.4 If high levels of formaldehyde are present, the extract
can be diluted with mobile phase, otherwise the extract must be solvent
exchanged as described in Section 3.6.7.5.3.3. If low levels of formaldehyde
are present, the sample should be concentrated during the solvent exchange
procedure.
3.6.7.5 Chromatographic Conditions
Column: CIS, 250 mm x 4.6 mm ID, 5 pm particle size
Mobile Phase: methanoI/water, 75:25 (v/v), isocratic
Flow Rate: 1.0 ml/min
UV Detector: 360 run
Injection Volume: 20/^1
3.6.7.6 Calibration
3.6.7.6.1 Establish liquid chromatographic operating parameters to
produce a retention time equivalent to that indicated in Table 3.6-1 for the
solid sorbent options, or in Table 3.6-2 for methylene chloride option.
Suggested chromatographic conditions are provided in Section 3.6.7.5. Prepare
derivatized calibration standards according to the procedure in Section
3.6.7.6.1.1. Calibrate the chromatographic system using the external standard
technique (Section 3.6.7.6.1.2).
3.6.7.6.1.1 Preparation of calibration standards
•
3.6.7.6.1.1.1 Prepare calibration standard solutions of formalde-
hyde and acetaldehyde in water from the stock standard (Section 3.6.5.14.2).
Prepare these solutions at the following concentrations (in /jg/ml) by serial
dilution of the stock standard solution: 50, 20, 10. Prepare additional
calibration standard solutions at the following concentrations, by dilution of
the appropriate 50, 20, or 10 /ig/ml standard: 5. 0.5, 2, 0.2, 1, 0.1.
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3.6.7.6.1.1.2 Process each calibration standard solution through
the'derivatizatio'n option used for sample processing (Section 3.6.7.3.4 or
3.6.7.3.5).
3.6.7.6.1.2 External standard calibration procedure
3.6.7.6.1.2.1 Analyze each derivatized calibration standard using
the chromatographic conditions listed in Tables 3.6-1 and 3.6-2, and tabulate
peak area against concentration injected. The results may be used to prepare
calibration curves for formaldehyde and acetaldehyde.
3.6.7.6.1.2.2 The working calibration curve must be verified on
each working day by the measurement of one or more calibration standards. If
the response for any analyte varies from the previously established responses
by more the 10%, the test must be repeated using a fresh calibration standard
after it is verified that the analytical system is in control. Alternatively,
a new calibration curve may be prepared for that compound. If an autosampler
is available, it is convenient to prepare a calibration curve daily by
analyzing standards along with test samples.
3.6.7.7 Analysis
3.6.7.7.1 Analyze samples by HPLC, using conditions established in
Section 3.6.7.6.1. Tables 3.6-1 and 3.6-2 list the retention times and MDLs
that were obtained under these conditions. Other HPLC columns, chromatograph-
ic conditions, or detectors may be used if the requirements for Section
3.6.8.1 are met, or if the data are within the limits described in Tables
3.6-1 and 3.6-2.
3.6.7.7.2 The width of the retention time window used to make
identifications should be based upon measurements of actual retention time
variations of standards over the course of a day. Three times the standard
deviation of a retention time for a compound can be used to calculate a
suggested window size; however, the experience of the analyst should weigh
heavily in the interpretation of the chromatograms.
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3.6.7.7.3 If the peak area exceeds the linear range of the calibra-
tion curve, a smaller sample volume should be used. Alternatively, the final
solution may be diluted with ethanol and reanalyzed.
3.6.7.7.4 If the peak area measurement is prevented by the presence
of observed interferences, further cleanup is required. However, none of the
3600 method series have been evaluated for this procedure.
3.6.7.8 Calculations
3.6.7.8.1 Calculate each response factor as follows (mean value
based on 5 points):
concentration of standard
RF - area of the signal
5
(I RFA)
_ i
mean - RF - RF -
3.6.7.8.2 Calculate the concentration of formaldehyde and acetalde-
hyde as follows:
Mg/ml - (RF) (area of signal) (concentration factor)
where:
Final volume of extract
concentration factor -
Initial sample (or leachate) volume
NOTE: For solid samples, a dilution factor must be included in the equa-
tion to account for the weight of the sample used.
3.6.7.8.3 Calculate the total weight of formaldehyde in the stack
gas sample as follows:
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total jjg/ml - (RF) (area of signal) (concentration £actor>
where:
Final Volume of Extract
concentration factor -
Initial Extract Volume
3.6.8 Quality Control
3.6.8.1 Refer to Chapter One of SW-846 for guidance on quality
control procedures.
3.6.9 Method Performance
3.6.9.1 The MDL concentrations listed in Table 3.6-1 were obtained
using organic-free water and solid sorbent extraction. Similar results were
achieved using a final effluent and sludge leachate. The MDL concentrations
listed in Table 3.6-2 were obtained using organic-free water and methylene
chloride extraction. Similar results were achieved using representative
matrices.
3.6.9.2 This method has been tested for linearity of recovery from
spiked organic-free water and has been demonstrated to be applicable over the
range from 2 x MDL to 200 x MDL.
3.6.9.3 In a single laboratory evaluation vising several spiked
matrices, the average recoveries presented in Tables 3.6-3 and 3.6-4 were
obtained using solid sorbent and methylene chloride extraction, respectively.
The standard deviations of the percent recovery are also included in Tables
3.6-3 and 3.6-4.
«
3.6.9.4 A representative chromatogram is presented in
Figure 3.6-1.
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3.6.10 References
1. Federal Register; 1986, 51, 40643-40652; November 7.
2. EPA Methods 6010, 7000, 7041, 7060, 7131, 7421, 7470, 7740, and
7841 Test Methods for Evaluating Solid Waste: Physical/Chemical
Methods. SV-846, Third Edition. September 1988. Office of Solid
Waste and Emergency Response, U.S. Environmental Protection Agency,
Washington, D.C. 20460.
3-205
-------
Table 3.6-4
SINGLE OPERATOR ACCURACY AND PRECISION
USING METHYLENE CHLORIDE EXTRACTION
Analyte
Formaldehyde
A«**r*1 riahwrt*
nnm w T_ m J_ J ~m 1 1 J ^^
Matrix
Type
Reagent
VAt«r
Ground-
water
Liquids
Reagent
Water
Ground-
water
Liquids
(2 types)
Solids
Average
Percent
Recovery
X
91
92.5
69.6
60.1
63.6
44.0
58.4
Standard
Deviation
Percent
P
2.5
8.2
16.3
3.2
10.9
20.2
2.7
Spike
Range
(Mg/L)
50-1000
50
250
50-1000
50
250
0.10-1.0'
Number
of
Analyses
9
6
12
•
9
12
12
12
x - Average recovery expected for this aethod
p • Average standard deviation expected for this Method.
3-206
-------
Figure 3.6-1
REPRESENTATIVE CMMNATOGJUM OF A SO »g/L SOLUTION OF FORMALDEHYDE
fOk-Q • Foraaldthydt dtrlvitlvt
ACCT-0 • AettildtHydt
3-207
-------
METHOD 0011A
fsTARf)
1
1
7 * ' *8u^0 SCff 010
*0 Wfjfl^flfci'Y*
:erfem 7 solid
seterminction. if
1
1
7 i 2 weign sompio
into Bottle: odd
•itraction fluid:
mtroct (8 hours:
ftlter
{
1
7.2.1 Perform
cleanup, if
necessary
i
r
7.2.2 Centrifuge
sample, if
necessary
r
7.3 3erwatirotion:
measure aliquot for
liquid sampto or
liquid eitraet of solid
sample: dilute to
»otoi »oiume of 100
-
solid ^r 7.3.3 ^v methyient
sorBont S Eitraetiom NV eniona*
i
>. methylene S
>^hloride?/^
7.3.4.1 Aad acetate
suffer and adjust
pH with acetic acid
or sodium
hydroiido: add ONM
reagent: seal
container shake 30
1
f
7.3.4.2 AssemBle
vacuum manifold ond
connect to pump;
auombto
cartridges: attach
sorbont train to
manifold: condition
cartridge
1
i
7.3.4.3 Remove
from shaker, odd
sodium cMorldo
eM»f •
Mo* n
[
74.4.4 Add the
T
74.44 Oute train
wtth ethane)
tflUVete AA osAkidJiel
vnwv 19 »wmf"w
v/fHlODOtl ffril
1
NX' 74.5.1 AGO ;:efs-i
•
JI4 *tm ;;
or so;
riag«n
C3nfQir«r;
i
-*3 ^sP*
• «
V*
7.3.5.2 iirrsr
sol'n with 3. 2C-T-I
aorfioni of
^^etnyi^ftj cff.or'cei
co^^otne n^efnyi^nf
cn
-------
METHOD OOLIA
continued
7 A [jfconjn .C
7.5.1.1.1 Proooro
calibration standards
7.5.1.1.2 Oorivotixo
stondflrd solutions
7.5.1.2.1 AnclylO
standards on* tabulate
poak orta against
coneontrotion injoctod
7.5.1.2.2 VorHy
•orkine cotibwon
eurvo daHy *Hh 1
or *toro standards
7.6.1 AnolyM Oy
*?LC using
sooeifiod
conditions: otHor
condition^ or
hordwon may bo
usad if QC
rtduiromoflts oro
7.8.2 UM rotation
timts to intorprot
ehromatograms
7.6.3 if poak area
•icMds linoar
workiitf rang a. UM
a sm«H«r samp*o
»oiumo or too final
soiuHon may bo
dituttd *im
othanol and
roonatytoa
T.MIf poak dfw
furthar tioanuf is
noodod
7.7 1 Ca
^ftoons* 'sc
'or
of
7.7
Qtotnydot in
noting Oilution
for solid senr0ios
3-209
-------
Section 4.0
•--• *.,
PROCEDURE FOR ESTIMATING THE TOXICITY EQUIVALENCY OF
CHLORINATED DIBENZO-P-DIOXIN AND DIBENZOFURAN CONGENERS
PCDDs and PCDFs must be determined using the method given in Section
3.4 of this document. In this method, individual congeners or homologues1
are measured and then summed to yield a total PCDD/PCDF value. No toxicity
factors are specified in the method to compute risks from such emissions.
For the purpose of estimating risks posed by emissions from boilers
and industrial furnaces, however, specific congeners and homologues must be
measured using the specified method and then multiplied by the assigned
toxicity equivalence factors (TEFs), using procedures described in "Interim
Procedures for Estimating Risks Associated with Exposures to Mixtures of
Chlorinated Dibenzo-p-Dioxins and Dibenzofurans (CDDs and CDFs) and 1989
Update," EPA/625/3-89/016, March 1989. The resulting 2,3,7,8-TCDD equivalents
value is used in the subsequent risk calculations and modeling efforts as
discussed in the BIF final rule.
The procedure for calculating the 2,3,7,8-TCDD equivalent is as
follows:
1. Using Method 23, determine the concentrations of 2,7,3,8-conge-
ners of various PCDDs and PCDFs in the sample.
2. Multiply the congener concentrations in the sample by the TEF
listed in Table 4.0-1 to express the congener concentrations in
terms of 2,3,7,8-TCDD equivalent. Note that congeners not
1The term "congener" refers to any one particular member of the same
chemical family; e.g., there are 75 congeners of chlorinated dibenzo-p-
dioxins. The term "homologue" refers to a group of structurally related
chemicals that have the same degree of chlorination. For example, there are
eight homologues of CDs, monochlorinated through octachlorinated. Dibenzo-p-
dioxins and dibenzofurans that are chlorinated at the 2,3,7, and 8 positions
are denoted as "2378" congeners, except when 2,3,7,8-TCDD is uniquely referred
to: e.g., 1,2,3,7,8-PeCDF and 2,3,4,7,8-PeCDF are both referred to as "2378-
PeCDFs."
4-1
-------
Table 4.0-1 ..
"*"•• «.
2,3,7,8-TCDD TOXICITY EQUIVALENCE FACTORS (TEFs)1
Compound
I-TEFs, 89
Mono-, Di-, and TriCDDs
2,3,7,8-TCDD
Other TCDDS
2,3,7,8-PeCDD
Other PeCDDs
2,3,7,8-HxCDD
Other HxCDDs
2,3,7,8-HpCDD
Other HpCDDs
OCDD
Mono-, Di-, and TriCDFs
2,3,7,8-TCDF
Other TCDFs
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDFs
2378-HxCDFs
Other HxCDFs
2378-HpCDFs
Other HpCDFs
OCDF
1
0
0.5
0
0.1
0
0.01
0
0.001
0
0.1
0
0.05
0.5
0
0.1
0
0.01
0
0.001
Reference: Adapted froa NATO/CCHS, 1988a.
Interim Procedures for Estimating Risks Associated with Exposures to Mixtures
of Chlorinated Dibenzo-p-Dioxins and Dibenzofurans (CDDs and CDFs) 1989
Update EPA/625/3-89/016, March 1989
4-2
-------
chlorinated at 2,3,7 and 8 positions have a zero toxicity
factor in this table.
3. Add the products obtained in step 2, to obtain the total
2,3,7,8-TCDD equivalent in the sample.
Sample calculations are provided in EPA document No. EPA/625/3-
89/016, March 1989, which can be obtained from the EPA, ORD Publications
Office, Cincinnati, Ohio (Phone no. 513-569-7562).
4-3
-------
Section 5.0.
* ' *
HAZARDOUS WASTE COMBUSTION AIR QUALITY SCREENING PROCEDURE
The HWCAQSP is a combined calculation/reference table approach for
conservatively estimating short-term and annual average facility impacts for
stack emissions. The procedure is based on extensive short-term modeling of
11 generic source types and on a set of adjustment factors for estimating
annual average concentrations from short-term concentrations. Facility
impacts may be determined based on the selected worst-case stack or on
multiple stacks, in which the impacts from each stack are estimated separately
and then added to produce the total facility impact.
This procedure is most useful for facilities with multiple stacks,
large source-to-property boundary distances, and complex terrain between 1 and
5 km from the facility. To ensure a sufficient degree of conservatism, the
HWCAQSP may not be used if any of the five screening procedure limitations
listed below are true:
• The facility is located in a narrow valley less than 1 km wide;
• The facility has a stack taller than 20 m and is located such
that the terrain rises to the stack height within 1 km of the
facility;
• The facility has a stack taller then 20 m and is located within
5 km of the shoreline of a large body of water;
• The facility property line is within 200 m of the stack and the
physical stack height is less than 10 m; or
• On-site receptors are of concern, and stack height is less than
10 m.
If any of these criteria are met or the Director determines that
this procedure is not appropriate, then detailed site-specific modeling or
modeling using the "Screening Procedures for Estimating the Air Quality Impact
of Stationary Sources.* EPA -450/4-88-010, Office of Air Quality Planning and
5-1
-------
Standards, August 1988, is required. Detailed site-specific dispersion
modeling must conform to the EPA "Guidance on Air Quality Models (Revised)",
EPA 450/2-78-027R, Office of Air Quality Planning and Standards, Research
Triangle Park, North Carolina, July 1986. This document provides guidance on
both the proper selection and regulatory application of air quality models.
Introduction
The Hazardous Waste Combustion Air Quality Screening Procedure
(HUCAQSP) (also referred to hereafter as "the screening procedure" or "the
procedure") provides a quick, easy method for estimating maximum (hourly) and
annual average ambient air impacts associated with the combustion of hazardous
waste. The methodology is conservative in nature and estimates dispersion
coefficients1 based on facility-specific information.
The screening procedure can be used to determine emissions limits at
sites where the nearest meteorological (STAR) station is not representative of
the meteorology at the site. If the screen shows that emissions from the site
are adequately protective, then the need to collect site-specific meteorologi-
cal data can be eliminated.
The screening procedure is generally most helpful for facilities
meeting one or more of the following conditions:
Multiple stacks with substantially different release specifica-
tions (e.g., stack heights differ by >50 percent, exit tempera-
tures differ by >50'K, or the exit follow races differ by more
than a factor of 2),
Terrain located between 1 km and 5 km from the site increases
in elevation by more than the physical height of the shortest
stack (i.e., the facility is located in complex terrain), or
lThe term dispersion coefficient refers to the change in ambient air
concentration (jig/m3) resulting from a source with an emission rate of 1
g/sec.
5-2
-------
Significant distance between the .facility's stacks and the site
b'oundary [guidance on determining whether a distance is "sig-
nificant" is provided in Step 6(B) of the procedure].
Steps 1 through 9 of the screening procedure present a simplified
method for determining emissions based on the use of the "worst-case" stack.
If the simplified method shows that desired feed rates result in emissions
that exceed allowable limits for one or more pollutants, a refined analysis to
examine the emissions from each stack can be conducted. This multiple-stack
method is presented in Step 10.
The steps involved in screening methodology are as follows:
Step 1. Define Source Characteristics
Step 2. Determine the Applicability of the Screening Procedure
Step 3. Select the Worst-Case Stack
Step 4. Verify Good Engineering Practice (GEP) Criteria
Step 5. Determine the Effective Stack Height and Terrain-Adjusted
Effective Stack Height
Step 6. Classify the Site as Urban or Rural
Step 7. Determine Maximum Dispersion Coefficients
Step 8. Estimate Maximum Ambient Air Concentrations
Step 9. Determine Compliance with Regulatory Limits
Step 10. Multiple Stack Method
Step 1: Define Source Characteristics
Provide the following source data:2
Worksheet space is provided for three stacks. If the facility has
additional stacks, copy the form and revise stack identification numbers for
4, 5, etc.
5-3
-------
Stack Data: ' •- Stack No. 1 .. Stack $o. 2 Stack No. 3
Physical stack height (m)
Exhaust temperature (*K)
Flow rate (m3/sec)
Nearby Building Dimensions:
Consider all buildings within five building heights or five maximum projected
widths of the stack(s). For the building with the greatest height, fill in
the spaces below.
Building Height (m)
Maximum projected building width (m)
Nearby Terrain Data:
Determine maximum terrain rise for the following three distance ranges from
the facility (not required if the highest stack is less than 10 m in height)
(m) (») (m)
0 - 0.5 km 0 - 2.5 km 0 - 5 km
Distance from facility to nearest shoreline (km)
Valley width (km)
Step 2: Determine the Applicability of the Screening Procedure
Fill in the following data:
Xej. go.
Is the facility in a valley < km in width?
Is the terrain rise within 1 km of the facility
greater than the physical stack height of the
tallest stack? (Only applies to stacks £20 meters
in height)
5-4
-------
Is the- distance £P the nearest shoreline <5 km? •
(Only applies to facilities with stacks >20
meters in height)
For the building listed in Step 1, is the closest
property boundary <5 times the building height or
<5 times the maximum projected building width?
(Only applies to facilities with a stack height
<2.5 times the building height)
If the answer is "no" to all the preceding questions, then the HWCAQSP is
acceptable. If the answer to any question is "yes", the procedure is not
acceptable.
Step 3: Select the Worst-Case Stack
If the facility has several stacks, a worst-case stack must be
chosen to conservatively represent release conditions at the facility. Follow
the steps below to identify the worst-case stack.
Apply the following equation to each stack:
K - HVT
where: K - an arbitrary parameter accounting for the relative influ-
ence of the stack height and plume rise.
H - Physical stack height (m)
V - Flow rate (m'/sec)
T - Exhaust temperature (*K)
5-5
-------
Complete the following table to compute the *K" value for each stack:
Stack No. Stack height x Flow rate x Exit temp - K
1
2
3
tack height
(m)
x
x
X
X
Flow rate
(m3/sec)
x
X
X
X
Exit temp
CK)
Select the stack with the lowest "K" value. This is the worst-case stack that
will be used for Steps 4 through 9.
Worst-Case Stack is identified as Stack No.
Step 4: Verify Good Engineering Practice (GEP) Criteria
Confirm that the selected worst-case stack meets Good Engineering
Practice (GEP) criteria. The stack height to be used in the subsequent steps
of this procedure must not be greater than the maximum GEP. Maximum and
minimum GEP stack heights are defined as follows:
GEP (minimum) - H * (1.5 x L)
GEP (maximum) - greater of 65 m or H + (1.5 x L)
where: H - height of the building selected in Step 1 measured from ground
level elevation at the base of the stack
L - the lesser dimension of the height or projected width of the
building selected in Step 1
Record the following data for the worst-case stack:
Stack height (n) -
H(m) -
L(m) -
Then compute the following:
GEP (minimum) (m) -
GEP (maximum) (m) -
5-6
-------
• If che physical height of the.worst-case stack exceeds the
maximum GEP, then use the maximum GEP stack height for the
subsequent steps of this analysis;
• If the physical height of the worst-case stack is less than the
minimum GEP, then use generic source number 11 as the selected
source for further analysis and proceed directly to Step 6;
• If the physical height of the worst-case stack is between the
minimum and maximum GEP, then use the actual physical stack
height for the subsequent steps of this analysis.
Step 5: Determine the Effective Stack Height and the Terrain-Adjusted
Effective Stack Height (TAESH)
The effective stack height is an important factor in dispersion
modeling. The effective stack height is the physical height of the stack plus
plume rise. As specified in Step 4, the stack height used to estimate the
effective stack height must not exceed GEP requirements. Plume rise is a
function of the stack exit gas temperature and flow rate.
In this analysis, the effective stack height is used to select the
generic source that represents the dispersion characteristics of the facility.
For facilities located in flat terrain and for all facilities with worst-case
stacks less than or equal to 10 meters in height, generic source numbers are
selected strictly on the basis of effective stack height. In all other cases,
the effective stack height is further adjusted to take into account the
terrain rise near the facility. This "terrain-adjusted effective stack
height" (TAESH) is then used to select the generic source number that repre-
sents the dispersion characteristics of the facility. Follow the steps below
to identify the effective stack height, the TAESH (where applicable), and the
corresponding generic source number.
5-7
-------
(A) Gb to Table. 5. 0-1 and find the plume rise value corresponding
to the stack temperature and exit flow rate for the worst-case stack deter-
mined in Step 3.
Plume rise - _ (m)
(B) Add the plume rise to the GEP stack height of the worst-case
stack determined in Steps 3 and 4.
GEP Stack Height(m) + Plume Rise(m) - Effective Stack Height (m)
(C) Go to the first column of Table 5.0-2 and identify the range of
effective stack heights that includes the effective stack height estimated in
Step 5(B). Record the generic source number that corresponds to this range.
Generic source number -
(D) If the source is located in flat terrain3, or if the generic
source number identified in Step 5(C) above is 1 or 11 (regardless of terrain
classification), use the generic source number determined in Step 5(C) and
proceed directly to Step 6. Otherwise, continue to Step 5(E).
(E) For those situations where the conditions in Step 5(D) do not
apply, the effective stack height must be adjusted for terrain. The TAESH for
each distance range is computed by subtracting the terrain rise within the
distance range from the effective stack height.4
3The terrain is considered flat and terrain adjustment factors are not
used if the maximum terrain rise within 5 km of the facility (see Step 1) is
less than 10 percent of the physical stack height of the worst-case stack.
*Refer to Step 1 for terrain adjustment data. Note that the distance
from the source to the outer radii of each range is used. For example, for
the range >0.5 - 2.5 km, the maximum terrain rise in the range 0.0 • 2.5 km is
used.
5-8
-------
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5-9
-------
Table 5.0-2
SELECTION OF GENERIC SOURCE NUMBER
Effective Stack Height (m)
<10.0
10.0 - 14.9
15.0 - 19.9
20.0 - 24.9
25.0 - 30.9
31.0 - 41.9
42.0 - 52.9
53.0 - 64.9
65.0 - 122.9
113.0+
Dovnwash
Generic Source No.
1
2
3
4
5
6
7
8
9
10
11
Table 5.0-3
CLASSIFICATION OF LAND USE TYPES
Type1
11
12
Cl
Rl
R2
R3
R4
Al
A2
A3
A4
A5
Description
Heavy Industrial
Light/Moderate Industrial
Commercial
Common Residential
(Normal Easements)
Compact Residential
(Single Family)
Compact Residential
(Mulct -Family)
Estate Residential
(Multi-Acre Plots)
Metropolitan Natural
Agricultural
Undeveloped
(Grasses/Weeds)
Undeveloped
(Heavily Wooded)
Water Surfaces
Urban or rural designation2
Urban
Urban
Urban
Rural
Urban
Rural
Rural
Rural
Rural
Rural
Rural
Rural
EPA, Guideline on Air Quality Models (Revised), EPA-450/2-78-027,
Office of Air Quality Planning and Standards, Research Triangle
Park, North Carolina, July, 1986.
Auer, August H. Jr., "Correlation of Land Use and Cover with Meteo-
rological Anomalies," Journal of Applied Meteorology, pp. 636-643
1978.
5-10
-------
Distance Effective Stark - Maxiaum Terrain - TAESH(m)
Range Height (m) Rise (m)
(km) [see Step 5(B)] (see Step 1)
0.0 - 0.5
>0.5 - 2.5
>2.5 - 5.0
If the terrain rise for any of the distance ranges is greater than the
effective stack height, set the TAESH equal to zero and use generic source
number 1 for that distance range.
Record the generic source numbers from Table 5.0-2 based on each of
the TAESH values.
Distance Range Generic Source No.
(km) (after terrain adiustment)
0.0 - 0.5
>0.5 - 2.5
>2.5 - 5.0
Step 6: Classify the Site as Urban or Rural
(A) Classify the land use near the facility as either urban or
rural by determining the percentage of urban land use types (as defined in
5-11
-------
Table 3; for further guidance see the footnoted references) that fall within 3
km of the facility.5
Method Used to Estimate Visual Planimeter
Percent Urban Land Use:
Estimated Percentages Urban Rural
If the urban land use percentage is less than or equal to 30 percent based on
a visual estimate, or 50 percent based on a planimeter, the local land use is
considered rural. Otherwise, the local land use is considered urban.
Classification Urban Rural
(check applicable space)
(B) Based on the TAESH and the urban/rural classification of
surrounding land use, use the following table to determine the threshold
distance between any stack and the nearest facility boundary.
*The delineation of urban and rural areas, can be difficult for the
residential-type areas listed in Table 5.0-3. The degree of resolution in
Table 5.0-3 for residential areas often cannot be identified without conduct-
ing site area inspections. This process can require extensive analysis,
which, for many applications, can be greatly streamlined without sacrificing
confidence in selecting the appropriate urban or rural classification. The
fundamental simplifying assumption is based on the premise that many applica-
tions will have clear-cut urban/rural designations, i.e., most will be in
rural settings that can be definitively characterized through a review of
aerial photographs, zoning naps, or U.S. Geological Survey topographical maps.
5-12
-------
Terrain adjusted effective stack
height range (m)
1 - 9.9
10 - 14.9
15 - 19.9
20 - 24.9
25 - 30.9
31 - 41.9
42 - 52.9
53 - 64.9
65 - 112.9
113+
Distance
-------
generic source numbers 1 or 11, use Step 7(A)(1)... For rolling or complex
terrain (excluding generic sources number 1 and 11), use Step 7(A)(2).
(1) Search down the appropriate generic source number column [based
on Step 5(C>], beginning at the minimum fenceline distance
listed in Step 6(B).7 Record the maximum average hourly dis-
persion coefficient encountered.
Maximum Average Hourly Dispersion Coefficient - (A»g/m3/g/sec)
(2) For each of the three distance-based generic source numbers
listed in Step 5(E), search down the appropriate generic source
number columns, beginning at the minimum fenceline distance
listed in Step 6(B).5 Note that different columns may be used
for each of the three distance ranges if there is a need for
terrain adjustment. Record the maximum dispersion coefficient
for each generic source number.
Distance Range Generic Source No. Maximum Dispersion Coefficient
(km) [from Step 5(E)] Ug/m3/»/sec)
0.0 - 0.5
>0.5 - 2.5
>2.5 - 5.0
>5.0 - 20.0
7Exclude all distances that are closer to the facility than the property
boundary. For example, if the actual distance to Che nearest property
boundary is 265 meters, begin at the 300 meter distance in Tables 5.0-4 and
5.0-5.
5-14
-------
Table 3.0-4
ISCT PREDICATED MAXIMUM CONCENTRATIONS (UG/N>)* fOR HAZARDOUS WASTE COHBUSTORS USING URBAN CONDITIONS
Distance
(KM)
0.20
0.25
0.50
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
.00
.10
.20
.30
.40
.50
.60
.70
.80
.90
2.00
2.25
2.50
2.75
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
Based on » 1
Generic
Source
01
(<10M)
680.1
521.9
407.7
326.2
268.5
240.8
218.5
200.3
185.1
172.2
161.2
151.6
143.2
135.8
129.2
123.3
118.0
108.8
101.1
94.6
89.0
84.1
79.8
76.0
72.7
69.6
66.9
61.1
56 4
52.6
49.3
40.2
54.5
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Cram/Second
Generic
Source
(10 M)
517.5
418.2
351.7
304.2
268.5
240.7
218.5
200.3
185.1
172.2
161.2
151.6
143.2
135.8
129.2
123.3
118.0
108.0
101.1
94.6
89.0
84.1
79.8
76.0
72.7
69.6
66.9
61.1
56.4
52.6
49.3
40.2
14.5
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Generic
Source
(15 N)
368.7
303.7
256.2
221.6
195.6
175.4
159.2
145.9
134.9
125.5
117.4
110.5
104.4
99.0
94.2
89.9
86.0
79.3
73.7
68.9
64.8
61.3
58.2
55.4
53.0
50.7
48.8
44.5
41.1
38.3
35.9
29.3
25.2
30.7
27.8
2S.5
23.8
22.3
17.6
15.0
Generic
Source
(20 N)
268.7
232.6
199.0
172.7
152.5
136.7
124.1
113.8
105.1
97.8
91.6
86.1
81.4
77.2
73.4
70.1
67.0
61.8
57.4
53.7
50.6
47.8
45.4
43.2
41.3
39.6
38.0
34.7
32.1
29.9
28.0
22.8
106
30.7
37.8
25.5
23.8
22.3
17.6
15.0
Generic
Source
(25 M)
168.5
163.0
147.0
130.2
115.7
103.9
94.4
86.5
80.0
74.4
69.6
65.5
61.9
58.7
55.8
53.3
51.0
47.0
43.7
40.
38.
36.
34.
32.
31.4
30.1
28.9
26.4
24.4
22.7
21.3
17.4
U.9
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Generic
Source
(316M)
129.8
124.2
118.3
107.9
97.1
87.6
79.7
73.1
67.
62.
58.
55.
52.
49.
47.2
45.0
43.1
39.7
36.9
34.5
32.5
30.7
29.2
27.8
26.5
25.4
24.4
22.3
20.6
19.2
18.0
14.7
12.6
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Generic
Source
«7
(42 N)
63.4
67.6
63.5
60.0
59.6
56.6
52.9
49.2
45.8
42.7
40.1
37.7
35.6
33.8
32.1
30.7
29.4
27.1
25.2
23.5
22.1
20.9
19.9
18.9
18.1
17.3
16.7
15.2
14.0
10.0
9.4
7.6
6.6
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Generic
Source
(53°H)
30.1
38.5
41 .5
40.5
37.8
37.2
36.7
35.4
33.8
32.0
30.2
28.6
27.1
25.7
24.5
23.4
22.4
20.6
19.2
18.0
16.9
16.0
15.2
14.4
13.8
13.2
12.7
11.6
10.7
10.0
9.4
7.6
6.6
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Generic
Source
(65 M)
18.4
19.8
25.0
27.3
27.4
26.3
24.7
24.5
24.3
23.7
22.9
22.0
21.1
20.2
19.3
18.5
17.7
16.4
15.2
14.2
13.4
12.7
12.0
11.4
10.9
10.5
10.1
9.2
8.5
7.9
7.4
6.1
5.?
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Generic
Source
HMO
(113 N)
1.6
3.2
4.2
5.4
5.8
5.8
5.8
6.6
7.1
7.4
7.5
7.5
7.4
7.2
7.0
6.8
6.5
.5
.4
.3
.1
.9
5.6
5.4
5.2
5.0
4.8
4.4
4.1
3.8
3.6
2.9
2.5
30.7
27.8
25.5
23.8
22.3
17.6
15.01
Generic
Source
#11 -.
(Downwash)
662.3.
500.0
389.3
311.9
268.5
240.8
218.5*
200.3
185.1
172.2
161.2
151.6
143.2
135.8
129.2
123.3
118.0
108.8
101.1
94.6
89.0
84.^
79.8
76.0
72.7
69.6
66.9
61.1
56.4
52.6
49.3
40.2
54.5.
30.7
27.8
25.5
23.8
22.3
17.6
15.0
Emission Rate
Ln
r-
Cn
-------
Table 5*0-5
ISCT PREDICATED MAXIMUM CONCENTRATIONS (UG/N'>* FOR HAZARDOUS WASTE COMBUSTORS USING RURAL CONDITIONS
Distance
(KM)
0.20
0.2S
0.30
0.35
0.40
0.45
0 SO
0.55
0.40
0.65
0.70
0.75
0.80
0.85
0.90
0.95
.00
.10
.20
.30
.40
.50
.60
.70
.80
.90
2.00
2.25
2.50
2.75
3.00
4.00
5. no
6.00
7.00
8.00
9.00
10.00
15.00
20 00
Based on a
Generic
Source
•1
«10M)
1771.1
1310.6
1002.3
798.4
656.9
621.5
AM. 5
630.1
616.6
596.7
573.2
546.
520.
495.
471.
448.
426.
387.
353.
323.
296.
273.
252.
234.
218.
203.7
190.7
164.4
141. T
127.0
113.4
78.8
59.1
56.7
40.4
35.8
32.2
9,4
20.5
15 9
1 Gram/Second
Generic
Source
»2
(10 M)
670.3
678.4
629.2
569.6
516.5
471.1
412.4
399.2
370.4
345.4
323.4
304.0
286.8
271.5
257.8
245.4
234.2
214.7
198.4
189.6
182.2
174.6
167.0
159.6
152.4
145.6
139.1
124.5
112.1
101.5
92.4
67.3
*4_A
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Emission Ra!
Generic
Source
«3
(15 M)
308.6
316.9
303.4
262.3
278.7
277.6
272.0
263.8
254.0
243.6
232.9
222.3
212.1
202.4
193.3
184.7
176.8
162.5
150.3
139.9
130.8
122.9
115.9
109.7
104.1
99.1
94.6
85.1
77.3
70.9
65.6
50.6
41.4
46.7
40.4
35.8
32.2
29.4
20.5
15.9
e
Generic
Source
ft
(20 M)
176.8
183.6
199.1
200.7
194.4
184.3
172.7
168.0
169.1
168.1
165.6
162.0
157.7
153.0
148.1
143.1
138.1
128.2
119.3
111.5
104.5
98.3
92.8
87.9
83.5
79.5
75.9
68.3
A2.1
56.9
52.6
40.6
» ?
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Generic
Source
•5
(25 M)
102.8
104.6
100.4
117.0
125.2
127.5
125.7
121.6
116.2
110.3
104.5
98.8
98.8
99.0
98.6
97.6
96.3
91.9
87.4
82.9
78.7
74.7
71.0
67.6
64.4
61.5
58.8
53.0
48.2
38.1
35.2
27.2
222
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Generic
Source
#6
(31 M>
76.5
71.8
75.0
71.1
82.7
89,7
92.9
93.3
91.8
89.2
85.8
82.2
78.5
74.9
71.4
72.3
72.6
71.1
69.1
66.7
64.2
61.6
59.1
56.7
54.3
52.1
50.0
45.4
41.4
38.1
35.2
27.2
?2.2
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Generic
Source
m
(42 M)
28.0
38.0
39.7
36.3
25.3
35.6
34.4
38.6
42.6
45.3
47.0
47.7
47.8
47.4
46.6
45.6
44.4
41.8
39.1
36.6
34.3
32.3
31.8
31.6
31.3
30.9
30.4
28.9
27.2
25.6
24.0
29.0
15.A
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Generic
Source
«8
(53 M)
10.1
17.6
24.0
25.9
24.6
21.7
21.6
22.1
21.7
20.9
23.3
25.5
27.1
28.3
29.1
29.6
29.8
29.5
28.6
27.5
26.2
24.9
23.6
22.5
21.4
20.4
19.5
18.1
17.9
17.5
17.0
14.3
12.0
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Generic
Source
09
(65 M)
3.5
7.9
12.6
16.8
18.1
17.6
15.9
13.6
14.3
14.7
14.6
14.3
13.8
15.0
16.3
17.3
18.2
19.3
19.8
19.8
19.5
19.0
18.4
17.7
17.0
16.3
15.7
14.2
12.?
11.8
11.2
10.4
9.1
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Generic
Source
*10
(113 M)
0.0
0.2
0.8
1.9
3.1
4.3
5.5
6.5
6.7
6.4
5.9
5.5
5.1
4.7
4.5
4.2
4.0
3.9
4.1
4.2
4.2
4.2
4.2
4.3
4.5
4.8
5.1
5.4
5.5
5.4
5.2
4.3
2.5
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Generic
Source
#11
(Dounwash)
1350.8 -
1227.3
1119.3
1023.8
938.9
851.8
787.8
730.6
676.4
633.4
592.0
554.6 •
522.1
491.8
464.2
438.9
415.8
375.0
340.3
310.4
284.6,
262.0
242.2
224.7
211.9
198.4
186.3
160.8
140.7
124.5
112.5
78.3
5B.«
46.7
40.4
35.8
32.2
29.4
20.5
15.9
Cn
-------
(B) Determine annual/hourly ratio for rural analysis. The maximum
• • * '
average annual dispersion coefficient is approximated by multiplying the
maximum hourly dispersion coefficient (identified in Step 7(A) by the appropr-
iate ratio selection from Table 6. The generic source number(s) [from Steps
5(C) or 5(E)], urban/rural designation (from Step 6), and the terrain type are
used to select the appropriate scaling factor. Use the noncomplex terrain
designation for all sources located in flat terrain, for all sources where the
physical stack height of the worst-case stack is less than or equal to 10 m,
for all sources where the worst-case stack is less than the minimum GEP, and
for those sources where all of the TAESH values in Step 5(E) are greater than
zero. Use the complex terrain designation in all other situations.
(C) Determine maximum average annual dispersion coefficient. The
maximum average annual dispersion coefficient is determined by multiplying the
maximum hourly dispersion coefficient [Step 7(A)] by its corresponding
annual/hourly ratio [Step 7(B)].
Terrain
Flat
Rolling
or
Complex
Distance
from
Stack (m)
0 - 20.0
0 - 0.5
>0.5 -2.5
>2.5 -5.0
>5.0 - 20.0
Generic
Source
Number
Maximum Hourly
Dispersion
Coefficient
(Mg/m3/g/sec)
Annual/
Hourly
Ratio
Maximum Annual
Dispersion
Coefficient
(MgV/g/sec)1
'•Maximum hourly dispersion coefficient times annual/hourly ratio.
Step 8: Estimate Maximum Ambient Air Concentrations - see procedures pre-
scribed in subpart H of 40 CFR Part 266.
Step 9: Determine Compliance with Regulatory Limits - see procedures pre-
scribed in subpart H of 40 CFR Pare 266.
5-17
-------
Step 10: Multiple Stack Method (Optional) .
This option is a special case procedure that may be helpful when (1)
the facility exceeded the regulatory limits for one or more pollutants, as
detailed in Step 9, and (2) the facility has multiple stacks with substantial-
ly different emission rates and effective release heights. Only those
pollutants that fail the Step 9 screening limits need to be addressed in this
exercise.
This procedure assesses the environmental impacts from each stack
and then sums the results to estimate total impacts. This option is conceptu-
ally the same as the basic approach (Steps 1 through 9) and does not involve
complex calculations. However, it is more time-consuming and is recommended
only if the basic approach fails to meet the risk criteria. The procedure is
outlined below.
(A) Compute effective stack heights for each stack.8
Stack GEP Stack Flow rate
No. height (m;
(m)
1
2
3
Exit temp
CK)
Plume
rise
(m)
Effective
stack
height
(m)
Add an additional page if more than three stacks are involved. Circle the
maximum and minimum effective stack heights.
'Follow the procedure outlined in Step 4 of the basic screening procedure
to determine the GEP for each stack. If a stack's physical height exceeds the
maximum GEP, use the maximum GEP values. If a stack's physical height is less
than the minimum GEP, use generic source number 11 in the subsequent steps of
this analysis. Follow the procedure in Steps 5(A) and 5(B) to determine the
effective height of each stack.
5-18
-------
(B) Determine if this multiple-stack.screening procedure will
• • . . * ' ' *
likely produce less conservative results than the procedure in Steps 1 through
9. To do this, compute the ratio of maximum-to-minimum effective stack
height:
Maximum Effective Stack Height -
Minimum Effective Stack Height
If the above ratio is greater than 1.25, proceed with the remaining steps.
Otherwise, this option is less likely to significantly reduce the degree of
conservatism in the screening method.
(C) Determine if terrain adjustment is needed and select generic
source numbers. Select the shortest stack height and maximum terrain rise out
to 5 km from Step 1 and determine if the facility is in flat terrain.
Shortest stack height (m) -
Maximum terrain rise in meters out to 5 km -
Terrain Rise (m) x 100 -
Shortest Stack Height (m)
If the value above is greater than 10 percent, the terrain is considered
nonflat; proceed to Step 10(D). If the ratio is less than or equal to 10
percent, the terrain is considered flat. Identify the generic source numbers
based on effective stack heights computed in Step 10(A). Refer to Table 5.0-2
provided earlier to identify generic source numbers. Record the generic
source numbers identified and proceed to Step 10(F).
Stack No.
123
Generic Source Numbers
5-19
-------
(D) Cqmpute the TAESH and.select generic source numbers (four
sources located in nonflat terrain).
1. Compute the TAESH for all remaining stacks using the following
equation:
HE - TR - TAESH
where: HE - effective stack height (m)
TR - maximum terrain rise for each distance range (m)
TAESH - terrain-adjusted effective stack height (m)
Use the table below to calculate the TAESH for each stack.9
Stack
No.
1
2
3
Distance Range (km)
HE
0 - 0.5
TR - TAESH
X).5 - 2.5
HE
TR - TAESH
HE
>2.5 - 5.0
TR - TAESH
For those stacks where the terrain rise within a distance range is
greater than the effective stack height (i.e., HE - TR is less than zero), the
TAESH for that distance range is set equal to zero, and generic source number
1 should be used for that distance range for all subsequent distance ranges.
Additionally, for all stacks with a physical stack height of less than or
"Refer to Step 1 for terrain adjustment data. Note that the distance
from the source to the outer radii of each range is used. For example, for
the range >0.5 - 2.5 km, the maximum terrain rise in the range 0.0 • 2.5 km is
used.
5-20
-------
equal to 10 meters, use generic source number. 1 .for all distance ranges.10
For the remaining stacks, proceed to Step 1(5'(D)(2).
2. For the remaining stacks, refer to Table 5.0-2 and, for each
distance range, identify the generic source number that includes the TAESH.
Use the values obtained from Steps 10(D)(1) and 10 (D)(2) to complete the
following summary worksheet;
Generic Source Number After Terrain Adjusted (if needed)
Stack No.
1
2
3
0 - 0.5 km
>0.5 - 2.5 km
>2.5 - 5.0 km
(E) Identify maximum average hourly dispersion coefficients. Based
on the land use classification of the site (e.g., urban or rural), use either
Table 5.0-4 or Table 5.0-5 to determine the appropriate dispersion coefficient
for each distance range for each stack. Begin at the minimum fenceline
distance indicated in Step 7(B) and record on Worksheet 5.0-1 the dispersion
coefficient for each stack/distance range. For stacks located in facilities
in flat terrain, the generic source numbers were computed in Step 10(C). For
stacks located in facilities in rolling and complex terrain, the generic
source numbers were computed in Step 10(D). For flat terrain applications and
for stacks with a physical height of less than or equal to 10 meters, only one
generic source number is used per stack for all distance ranges. For other
situations up to three generic source numbers may be needed per stack (i.e., a
unique generic source number per distance range). In Tables 5.0-4 and 5.0-5,
the dispersion coefficients for distances of 6 km to 20 km are the same for
"This applies to all stacks less than or equal to 10 meters regardless
of the terrain classification.
5-21
-------
Worksheet 5.0-1 Dispersion Coefficient by Downwind Distance1
'" D Is cane*
0.20
0.25
0.30
0.3S
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
O.M
o.as
0.90
0.95
1.00
1.10
1.20
1.30
1.40
1.50
1.60
1.70
l.M
1.90
2.00
2.25
2.50
2.75
3.00
4.00
5.00
«.oo
7.00
• .00
9.00
10.00
15.00
20.00
Stack -1
auek 2
Stack 3
lBote: Thla procedure places til stacks at tho seae potat. but allow* for ceaiid«r«.tteo of different
•ffaetlv* stack h«tght*. Th« dUcaoe* to tha elo»a*t boundary (oxtraetod fcoa Stop 1) ahould bo th« closest
distance to toy stack.
5-22
-------
all generic source numbers in order to conservatively represent terrain beyond
5 Van (past the limits of the terrain analysi-s).
(F) Estimate maximum hourly ambient air concentrations. In this
step, pollutant-specific emission rates are multiplied by appropriate disper-
sion coefficients to estimate ambient air concentrations. For each stack,
emissions are multiplied by the dispersion coefficient selected in Step 10(E)
and summed across all stacks to estimate ambient air concentrations at various
distances from the facility. From these summed concentrations, the maximum
hourly ambient air concentration is selected. First, select the maximum
emission rate of the pollutant.11 Record these data in the spaces provided
below.12
Maximum Annual Emission Rates (g/sec)
Pollutant Stack 1 Stack 2 Stack 3
Complete a separate copy of Worksheet 5.0-2 for each pollutant and
select the highest hourly concentration from the summation column at the far
right of the worksheet. Record the maximum hourly air concentration for each
pollutant analyzed (add additional lines if needed):
Pollutant Maximum Hourly Air Concentration
"Recall that it is recommended that this analysis be performed for only
one or two pollutants. The pollutants chosen for this analysis should be
those that show the most significant exceedances of the risk threshold.
"Refer to Step 8 of the basic screening procedure. At this point in the
screening procedure, annual emissions are used to represent hourly average
emission rates. These values will be adjusted by the annual/hourly ratio to
estimate annual average concentrations.
5-23
-------
Worksheet 5.0-2 Maximum Hourly Ambient Air Concentration
Pollutant
Total
DUtanca
(ta>
.10
• »5
.»
.$»
,40
•• :«i .
'•:;" ,$0
;'' ' .s$
•• ,*o ' .
.45
.70
.•0
.§5
.to
.99
.00
.10
i.io
I.JO
1.40
l.SO
• . . track 1
. ;':---" w « DC - c
• •
• •
* -
• •
• -
. * -
• • '
„
M
• " ,
« •
* •
• •
• »
• •
* •
• «
• •
• •
K »
* •
Stack 2
ER x DC - C
• -
* •
• •
• •
x «•
• •
• -
• •
B •
« -
* ' •
a -
• •
* -
* •
• •
• -
• -
• •
* •
* •
Stack 3
ER K DC - C
x -
X •>
X •
X -
X •
X •
X •
X -
X "
X •
X "
X •
X -
X •
X ••
X •
• •
X •
X -
X «
X -
Sunned
Concentration
from all
Stack*
in
N)
*•
ER- Annual Average Emission Rate
DC*1 Hourly Dispersion Coeffiecient (from Worksheet 5.0-1)
C= Estimated Maximum Hourly Ambient Air Concentration
-------
VJorksheet 5.0-2 Maximum Hourly Ambient Air Concentration
Pollutant
Total
Pittance
(I*)
l.<0
i.™
•; i »o
•:• t.« •
••• 2. oo
i:' 2.25
:• 2. 50
2.75
3.00
*.oo
5.00
6.00
7.00
• .00
9.00
10.00
15.00
20.00
H«ck I
.'. : '.'-'.'• Ot « W • C
• -
X •
X -
• •
• •
• •
• •
X •
X « i
X •
X •
X "
X •
X •
X »
X •
X •
X •
Stack 2
ER x DC - C
x •
X «
X -
X •
X "
• —
X "
X •
X "
X -
x •
X "
x •
x -
X -
X -
X •
X »
Stack 3
ER x DC - C
x «
X -
X -
X -
X »
X —
X —
X -
X —
X -
* "
X -
X -
X -
X -
X •*
X •
X •
Sunned
Concent rat Ion
from all
Stack*
in
I
N)
Ul
ER=Annual Average Emission Rate
DC= Hourly Dispersion Coefficient (from Worksheet 5.0-1)
C= Estimated Maximum Hourly Ambient Air Concentration
-------
Worksheet 5.0-2 Maximum Ambient Air Concentration
Pol L
Total
Distance
ER " Annual average ••lesion rat*
DC - Boorly 41*pac*lon coefficient (froai Worksheet 1)
C • E*tl*at«d •iicla>» hourly aaiblent air concentration
-------
(G) Determine the complex/noncomplex designation for each stack.
For each stack, subtract the maximum terrain rise within 5 km of the site from
the physical stack height and designate the stack as either complex or
noncomplex. If the stack height minus the maximum terrain rise (within 5 km)
is greater than zero or if the stack is less than 10 meters in physical
height, then assign the stack a noncomplex designation. If the stack height
minus the maximum terrain rise (within 5 km) is less than or equal to zero,
then assign the stack a complex designation.
Perform the following computation for each stack and record the
information in the spaces provided. Check in the spaces provided whether the
stack designation is complex or noncomplex.
Stack Stack Maximum Complex Noncomplex
No. Height (m) Terrain Rise (m)
1 - - (m)
2 - ; - (m)
(H) Identify annual/hourly ratios. Extract the annual/hourly
ratios for each stack by referring to Table 5.0-6. Generic source numbers
(from Steps 10(C) or 10(D), urban/rural designation (from Step 6), and complex
or noncomplex terrain designations (from Step 10(G)) are used to select the
appropriate scaling factor needed to convert hourly maximum concentrations to
estimates of annual average concentrations.
5-27
-------
Complete the following table;13 ^
Stack No. Generic Source No. Annual/hourly racio
Steps 10 (C or D) (from Table 5.0-6)
Distance ranges (km) Distance ranges (km)
0-0.5 >0.5-2.5 >2. 5-5.0 0-0.5 >0.5-2.5 >2. 5-5.0
1 _ _ _ _ _ _
2 _ _ _ _ _ _
3 _ _ _ _ _ _
(I) Select the highest annual/hourly ratio among all of the
stacks,14 and then estimate the maximum annual average ambient air concentra-
tions for each pollutant by completing the following table, where:
C - Maximum total hourly ambient air concentration (Mg/m3) for
pollutant "N" from Step 10(F),
C. - Maximum annual average air concentration for pollutant "N"
(Mg/m3) ,
R - Annual/hourly ratio.
13If any stack (excluding generic stack number 1 and 11) in Step 10(D)
shows a negative terrain adjusted stack height, use the complex terrain
annual/hourly ratios.
14As an option, the user can identify the stack with the highest ratio
for each distance range (rather than the absolute highest). In this case,
extra sheets would be needed to show estimated annual average concentrations
from each stack by multiplying emission rate times maximum hourly dispersion
coefficient times maximum annual/hourly ratio for applicable distance range.
Then sum across all stacks for each downwind distance.
5-28
-------
Table 5.0-6
95TH FERCENTILE OF ANNUAL/HOURLY RATIOS
Source
1
2
3
4
5
6
7
8
9
10
11
Noncomplex Terrain
Urban Rural
0.019
0.033
0.031
0.029
0.028
0.028
0.031
0.030
0.029
0.029
0.018
0.014
0.019
0.018
0.017
0.017
0.017 -
0.015
0.013
0.011
0.008
0.015
Source
1
2
3
4
5
6
7
8
9
10
11
Complex Terrain
Urban Rural
0.020
0.020
0.030
0.051
0.067
0.05$
0.036
0.026
0.026
0.017
0.020
0.053
0.053
0.057
0.047
0.039
0.034
0.031
0.024
0.024
0.013
0.053
5-29
-------
Pollutant
X
X
(J) Use the maximum annual average concentrations from Step 10(1)
to determine compliance with regulatory requirements.
5-30
-------
Section 6.0
SIMPLIFIED LAND USE CLASSIFICATION-PROCEDURE FOR "COMPLIANCE
WITH TIER I AND TIER II LIMITS
6.1 Introduction
This section provides a simplified procedure to classify areas in
the vicinity of boilers and industrial furnance sites as urban or rural in
order to set risk-based emission limits under subpart H of 40 CFR Part 266.
Urban/rural classification is needed because dispersion rates differ between
urban and rural areas and thus, the risk per unit emission rate differs
accordingly. The combination of greater surface roughness (more
buildings/structures to generate turbulent mixing) and the greater amount of
heat released from the surface in an urban area (generates buoyancy-induced
mixing) produces greater rates of dispersion. The emission limit tables in
the regulation, therefore, distinguish between urban and rural areas.
EPA guidance (EPA 1986) provides two alternative procedures to
determine whether the character of an area is predominantly urban or rural.
One procedure is based on land use typing and the other is based on population
density. Both procedures require consideration of characteristics within a 3-
km radius from a source, in this case the facility stack(s). The land use
typing method is preferred because it more directly relates to the surface
characteristics that affect dispersion rates. The remainder of this discus-
sion is, therefore, focused on the land use method.
While the land use method is more direct, it can also be labor-
intensive to apply. For this discussion, the land use method has been
simplified so that it is consistent with EPA guidance (EPA 1986; Auer 1978),
while streamlining the process for the majority of applications so that a
clear-cut decision can be made without the need for detailed analysis. Table
6.0-1 summarizes the simplified approach for classifying areas as urban or
rural. As shown, the applicant always has the option of applying standard
(i.e.. more detailed) analyses to more accurately distinguish between urban
and rural areas. However, the procedure presented here allows for simplified
determinations, where appropriate, to expedite the permitting process.
6-1
-------
Table 6.0-1 .
CLASSIFICATION OF LAND USE TYPES
Type1
11
12
Cl
Rl
R2
R3
R4
Al
A2
A3
A4
A5
Description
Heavy Industrial
Light/Moderate Industrial
Commercial
Common Residential
(Normal Easements)
Compact Residential
(Single Family)
Compact Residential
(Multi- Family)
Estate Residential
(Multi-Acre Plots)
Metropolitan Natural
Agricultural
Undeveloped
(Grasses/Weeds)
Undeveloped
(Heavily Wooded)
Water Surfaces
Urban or rural designation2
Urban
Urban
Urban
Rural
Urban
Urban
Rural
Rural
Rural
Rural
Rural
Rural
EPA, Guideline on Air Quality Models (Revised), EPA-450/2-78-027,
Office of Air Quality Planning and Standards, Research Triangle
Park, North Carolina, July. 1986.
Auer, August H. Jr.,. "Correlation of Land Use and Cover with Meteo-
rological Anomalies," Journal of Applied Meteorology, pp. 636-6^3,
1978.
6-2
-------
6.2 Simplified Land Use Process
... • -
The land use approach considers four primary land use types:
industrial (I), commercial (C), residential (R), and agricultural (A). Within
these primary classes, subclasses are identified, as shown in Table 6.0-1.
The goal is to estimate the percentage of the area within a 3-km radius that
is urban type and the percentage that is rural type. Industrial and commer-
cial areas are classified as urban; agricultural areas are classified as
rural.
The delineation of urban and rural areas, however, can be more
difficult for the residential type areas shown in Table 6.0-1. The degree of
resolution shown in Table 6.0-1 for residential areas often cannot be identi-
fied without conducting site area inspections and/or referring to zoning maps.
This process can require extensive analysis, which, for many applications, can
be greatly streamlined without sacrificing confidence in selecting the
appropriate urban or rural classification.
The fundamental simplifying assumption is based on the premise that
many applications will have clear-cut urban/rural designations, i.e., most
will be in rural settings that can be definitively characterized through a
brief review of topographical maps. The color coding on USGS topographical
maps provides the most effective means of simplifying the typing scheme. The
suggested typing designations for the color codes found on topographical maps
are as follows:
Green Wooded areas (rural).
White White areas generally will be treated as rural. This code
applies to areas that are unwooded and do not have densely
packed structures which would require the pink code (house
omission tint). Parks, industrial areas, and unforested
rural land will appear as white on the topographical maps.
Of these categories, only the industrial areas could
potentially be classified as urban based on EPA 1986 or
Auer 1978. Industrial areas can be easily identified in
most cases by the characteristics shown in Figure 6.0-1.
For this simplified procedure, white areas that have an
industrial classification will be treated as urban areas.
6-3
-------
Figure 6.0-1
Suppftmtmary Publication Symbols
117 Singlt track ... .......
aw
118 Singtt track abandontd
« •**«• me* •*» IMW
119 Singlt track undtr construction—
•*» tMW Of. «•* JT
120 Muitiolt main lint track
oar
JV* ewitr n «•**»? '^
121 Muitiolt track abandontd .-iZ?K!—
m «m(Mf trm* •
IA«4«OOMC0
122 Muitiolt track undtr construction _ _*.'££!*_
' •*• WOT ar.MM* jr
123 Juxtaposition
*r
124 Railroad in strttt
125 Yards
176 Urfa buiidinfs : s £S £ £3
178 Stwap disoosa) or filtration olant. ^=~*Z
196 Tanks: oil. fas. watsr. ttc . • • • • c«
197 Tanks: oil. gas. watar. ttc—
•TlMW^MV ^* ••'WW CkMK^ jg MI j0|
- - j,-.
6-4
-------
Section 7.0
*•--• •„
STATISTICAL METHODOLOGY FOR BEVILL RESIDUE DETERMINATIONS
This section describes the statistical comparison of waste-derived
residue to normal residue for use in determining eligibility for the Bevill
exemption under 40 CFR 266.112.
7.1 Comparison of Waste-derived Residue with Normal Residue
To meet the special criteria under part 266.112(b)(1), waste-derived
residue must not contain Appendix VIII, Part 261, constituents (toxic constit-
uents) at concentrations significantly higher than in residue generated
without burning or processing hazardous waste. Concentrations of toxic
constituents in normal residue are determined based on analysis of a minimum
of 10 composite samples. (Note that "normal" residue refers to residue
generated by a facility when operating without burning hazardous waste.) The
95th percent confidence interval about the mean of the normal residue concen-
trations must be used in the comparison of waste-derived residue with normal
residue; the confidence interval is determined as described in Section 7.2
below. The concentration of a toxic constituent in the waste-derived residue
is not considered to be significantly higher than in the normal residue if the
concentration in the waste-derived residue does not exceed the upper 95th
percent confidence interval about the mean that was established for the normal
residue. Concentrations of toxic constituents in waste-derived residue are
determined based on analysis of samples taken over a compositing period of not
more than 24 hours.
7.2 Calculation of the 95th Percent Confidence Interval About the Mean
for Toxic Constituents in Normal Residue
The 95th percent confidence interval about the mean is calculated
for a set of values using a "t" distribution. In use of the "c" distribution,
it is assumed that the values are normally distributed; the "t" distribution
is applicable for use with small sample sets (i.e. approximately 10-30
7-1
-------
samples). The 95Ch percent confidence interval about the mean is determined
• * . • * ' " •
using the following equation:
95th percent confidence interval - 1 X ± t«/2 (s//n)
n
- I Xt
where X - mean of the normal residue concentrations, X - i-1
n
« - the level of significance - 0.05,
s - standard deviation of the normal residue concentrations,
s - I (Xt - X)2 /(n-1) 1/2 , and
i-1
n - sample size.
The values of the "t" distribution at the «/2 level of significance and n-1
degrees of freedom are given in Table 7.0-1.
For example, a normal residue test results in 10 samples with the
following analysis results for toxic compound A:
Sample Concentration of
Number Compound A (ppm)
1 10
2 10
3 15
4 10
5 7
6 12
7 10
8 16
9 15
10 10
The mean and standard deviation of these measurements, calculated using
equations above, are 11.5 and 2.9 respectively. . Assuming that the values are
normally distributed, the upper 95th percent confidence interval value about
the mean is given by:
7-2
-------
Table 7.0-1
c DISTRIBUTION VALUES
degrees Percentage
of Point of
freedom t Distribution
«*/2 - 0.025
1 12.706
2 4.303
3 3.182
4 2.776
5 2.571
6 2.447
7 2.365
8 2.306
9 2.262
10 2.228
11 2.201
12 2.179
13 2.160
14 2 . 145
15 2.131
16 2.120
17 2.110
18 2.101
19 2.093
20 2.086
21 2.080
22 2.074
23 , 2.069
24 2.064
25 2.060
26 2.056
27 2.052
28 2.048
29 2.045
7-3
-------
95th percent confidence interval value - 11.5 +-2.262 x (2.9//10) - 13.6
ppm
Thus, if the concentration of compound A in the waste-derived residue is below
13.6 ppm, then the waste-derived residue is eligible for the Bevill exemption
for toxic compound A.
7.3 Normal Distribution Assumption
As noted in Section 7.2 above, this statistical approach (use of the
95th percent confidence interval about the mean) for calculation of the
concentration in normal residue is based on the assumption that the concentra-
tion data are distributed normally. The Agency is aware that concentration
data of this type may not be distributed normally, particularly when concen-
trations are near the detection limits. There are a number of procedures that
can be used to test the distribution of a data set. For example, the Shapiro-
Vilk test, examination of a histogram or plot of the data on normal probabili-
ty paper, and examination of the coefficient of skewness are methods that may
be applicable, depending on the nature of the data (Reference 1 and 2).
If the concentration data are not adequately represented by a normal
distribution, the data may be transformed to attain a near normal distribu-
tion. The Agency has found that concentration data, especially when near
detection levels, often exhibit a lognormal distribution. The assumption of a
lognormal distribution has been used in various programs at EPA, such as in
the Office of Solid Waste Land Disposal Restrictions program for determination
of BOAT treatment standards. The transformed data may be tested for normality
using the procedures identified above. If the transformed data are better
represented by a normal distribution than the untransformed data, the trans-
formed data should be used in determining the 95th percent confidence interval
using the procedures in Section 7.2 above.
In all cases where the applicant for the Bevill exemption wishes to
use other than an assumption of normally distributed data, or believes that
use of an alternate statistical approach is appropriate to the specific data
7-4
-------
set, the applicant must provide supporting rationale and demonstrate to the
Director or permitting authority that the data treatment is based upon sound
statistical practice.
7.4 Nondetect Values
The Agency is developing guidance regarding the treatment of
nondetect values (data where the concentration of the constituent being
measured is below the lowest concentration for which the analytical method is
valid) in carrying out the statistical determinations described above. Until
the guidance information is available, facilities may present their own
approach to the handling of nondetect data points, but must provide supporting
rationale in the operating record for consideration by the Director or
permitting authority.
7.5 References
1. Shapiro, S,S. and Wilk, M.B. (1965), "An Analysis of Variance Test
for Normality (complete samples), " Biometrika, 52, 591-611.
2. Bhattacharyya, G.K. and R.A. Johnson (1977), Statistical Concepts
and Methods, John Wiley and Sons, New York.
7-5
-------
Section 8.0.
.• *
PROCEDURES FOR DETERMINING DEFAULT VALUES FOR AIR POLLUTION
CONTROL SYSTEM REMOVAL EFFICIENCIES
During interim status, owners or operators of boilers and industrial
furnaces burning hazardous waste must submit documentation to EPA that certi-
fies that emissions of HC1, C12, metals, and particulate matter (PM) are not
likely to exceed allowable emission rates. See certification of precompliance
under 40 CFR 266.103(b). This documentation also establishes interim status
feed rate and operating limits for the facility. For the initial certifica-
tion, estimates of emissions and system removal efficiencies (SREs) can be
made to establish the operating limits. Subsequently, owners or operators
must use emissions testing to demonstrate that emissions do not exceed
allowable levels, and to establish operating limits. See 40 CFR 266.103(c).
However, initial estimates of emissions for certification of precompliance can
be based on estimated or established SREs.
The SRE combines the effect of partitioning of the chorine, metals,
or PM and the air pollution control system removal efficiency (APCS RE) for
these pollutants. The SRE is defined as:
SRE - (species input - species emitted) / species input
The SRE can be calculated from the partitioning factor (PF) and APCS
RE by the following formula:
SRE - 1 - [(PF/100) X (1 - APCS RE/100)]
where: PF - percentage of the pollutant partitioned to the combustion gas
Estimates of the PF and/or the APCS RE can be based on either EPA's
default values or engineering judgement. EPA's default values for the APCS RE
for metals, HC1, C12, and PM are described in this section. EPA's default
values for partitioning of these pollutants are described in Section 9.0.
8-1
-------
Guidelines for the use of engineering judgement to estimate'APCS REs or PFs
are described in Section 9.4.
i
8.1 APCS RE Default Values for Metals
EPA's default assumptions for APCS RE for metals are shown in
Table 8.1-1. The default values in the table are conservative estimates of
the removal efficiencies for metals in BIFs, depending on the volatility of
the metal and the type of APCS.
The volatility of a metal depends on the temperature, the thermal
input, the chlorine content of the waste, and the identity and concentration
of the metal. Metals that do not vaporize at combustion zone temperatures are
classified as "nonvolatile". Such metals typically enter the APCS in the form
of large particles that are removed relatively easily. Metals that vaporize
in the combustion zone and condense before entering the APCS are classified as
"volatile". Such metals typically enter the APCS in the form of very fine,
submicron particles that are rather inefficiently removed in many APCSs.
Metals that vaporize in the combustion zone and do not condense before
entering the APCS are classified as "very volatile". Such metals enter the
APCS in the form of a vapor that is very inefficiently removed in many APCSs.
Typically, BIFs have combustion zone temperatures high enough to
vaporize any hazardous metal at concentrations sufficient to exceed risk-based
emission limits. For this reason, the default assumption is that there are no
nonvolatile metals. Tables 8.1-2 and 8.1-3 are used to determine whether
metals are classified as "volatile" or "very volatile" depending on the
temperature entering the APCS, the thermal input, and whether the waste is
chlorinated or nonchlorinated.
A waste is considered chlorinated if chlorine is present in concen-
trations greater than 0.1 percent by weight. In the EPA guidance document
"Guidance for Metals and Hydrogen Chloride Controls for Hazardous Waste
Incinerators, Volume IV of the Hazardous Waste Incineration Guidance Series,"1
8-2
-------
Table 8.1-1
*
AIR POLLUTION CONTROL SYSTEMS (APCS) AND THEIR CONSERVATIVELY
ESTIMATED EFFICIENCIES FOR CONTROLLING TOXIC METALS (%)
Metal Volatility
US
VS-20
VS-60
ESP-1
ESP -2
ESP-4
VESP
FF
SD/FF
DS/FF
IVS
APCS Nonvolatile
40
80
87
90
92
95
90
90
97
95
90
Volatile
30
75
75
75
80
80
85
80
90
90
87
Very
Volatile
20
20
40
0
0
0
40
0
0
0
75
VS - Vet Scrubber including: Sieve Tray Tower
Packed Tower
Bubble Cap Tower
VS-20 - Venturi Scrubber, ca. 20-30 in V.G. «p
VS-60 - Venturi Scrubber, ca. >60 in W.C. »p
ESP-1 - Electrostatic Precipitacor; 1 stage
ESP-2 - Electrostatic Precipitator; 2 stage
ESP-4 - Electrostatic Precipitator; 4 stage
IVS - Ionizing Vec Scrubber
DS - Dry Scrubber
FT - Fabric Filter (Baghouse)
SO - Spray Dryer (Vet/Dry Scrubber)
VESP • Vet Electrostatic Precipitator
8-3
-------
Table 8.1-2
TEMPERATURE (F) ENTERING APCS ABOVE WHICH METALS ARE CLASSIFIED AS
VERY VOLATILE IN COMBUSTION OF NONCHLORINATED WASTES
Metal
Name
Arsenic
Cadmiua
Chromium
Beryllium
Antimony
Barium
Lead
Mercury
Silver
Thallium
Symbol
As
Cd
Cr
Be
Sb
Ba
Pb
Hg
*g
Tl
Thermal Input (MMBtu/hr):
1
320
1040
2000
1680
680
2240
1280
340
1820
900
10
280
940
1760
1440
600
1820
1180
300
1640
800
100
240
860
1580
1240
540
1540
.1080
260
1480
700
1000
200
780
1420
1080
480
1360
1000
220
1340
620
10000
160 i
720 i
1350
980
, ^ -s
1240
920
180
1220,
5uO
Example:
Interpolation of thermal input is not allowed. If a BIF fires
between two ranges, the APCS temperature under the higher ther--
input must be used.
For a BIF firing 10 • 100 MMBtu/hr, Mercury is considered very
volatile at APCS temperatures above 260 F and volatile at APCS
temperatures of 260 F and below.
-------
Table 8.1-3
TEMPERATURE (F) ENTERING APCS ABOVE WHICH METALS ARE CLASSIFIED AS
VERY VOLATILE IN COMBUSTION OF CHLORINATED WASTES
Metal
Name
Arsenic
Cadmium
Chromium
Beryllium
Antimony
Barium
Lead
Mercury
Silver
Thallium
Symbol
As
Cd
Cr
Be
Sb
Ba
Pb
Hg
Ag
Tl
Thermal Input (MMBtu/hr)1
1
320
1040
>140
1680
680
2060
>140
340
1080
900
10
280
940
>140
1440
600
1840
>140
300
940
800
100
240
860
>140
1240
540
1680
>140
260
840
700
1000
200
780
>140
1080
480
1540
>140
220
740
620
10000
160
720
>140
980
420
142TD
>140
180
660
540
Example:
Interpolation of thermal input is not allowed. If a BIF fires
between two ranges, the APCS temperature under the higher thermal
input must be used.
For a BIF firing 10 - 100 MMBtu/hr, Mercury is considered very
volatile at APCS temperatures above 260 F and volatile at APCS
temperatures of 260 F and below.
8-5
-------
one percent is used for the chlorinated/nonchlorinated cutoff. However, best
engineering Judgement, based on examination--of pilot-scale data reported by
Carroll et al.2 on the effects of waste chlorine content on metals emissions,
suggests that the 1 percent cutoff may not be sufficiently conservative.
Tables 8.1-2 and 8.1-3 were compiled based on equilibrium calcula-
tions. Metals are classified as very volatile at all temperatures above the
temperature at which the vapor pressure of the metal is greater than 10
percent of the vapor pressure that results in emissions exceeding the most
conservative risk-based emissions limits.
8.2 APCS RE Default Values for HC1 and Cl;
»
Default assumptions for APCS RE for HC1 in BIFs are shown in
Table 8.2-1. This table is identical to the column for other BIFs except that
cement kilns have a minimum HC1 removal efficiency of 83 percent. Because of
the alkaline nature of the raw materials, in cement kilns, most of the chlorine
is converted to chloride salts. Thus, the minimum APCS RE for HC1 for cement
kilns is independent of the APCS train.
Removal efficiency of C12 for most types of APCS is generally
minimal. Therefore, the default assumption for APCS RE for C12 for all APCSs
is 0 percent. This is applicable to all BIFs, including cement kilns.
8.3 APCS RE Default Values for Ash
Default assumptions for APCS RE for PM are also shown in Table
8.1-4. These figures are conservative estimates of PM removal efficiencies
for different types of APCSs. They are identical to the figures in the
Nonvolatile APCS RE column for hazardous metals presented in Table 8.1-1
because the same collection mechanisms and collection efficiencies that apply
to nonvolatile metals also apply to PM.
8-6
-------
Table 8.2-1
AIR POLLUTION CONTROL SYSTEMS (APCS-) AND THEIR CONSERVATIVELY
ESTIMATED EFFICIENCIES FOR REMOVING HYDROGEN CHLORIDE (HC1) AND
PARTICULATE MATTER (PM) (%)
HC1
APCD
US
VS- 20
VS-60
ESP-1
ESP- 2
ESP -4
VESP
FF
SD/FF
DS/FF
VS/IVS
IVS
Cement Kilns
97
97
98
83
83
83
83
83
98
98
99
99
Other BIF*
97
97
98
0
0
0
70
0
98
98
99
99
PM
40
80
87
90
92
95
90
90
97
95
95
90
WS - Wet Scrubber including: Sieve Tr*y Tower
Pecked Tover
Bubble Cap Tover
PS - Proprietary Wet Scrubber Design
(A number of proprietary vet scrubbers have come on the market in
recent years- that are highly efficient on both partculctes and
corrosive gases. Two such units are offered by Calvert Environmen-
tal Equipment Co. aad by Hydra-Sonic Systems, Inc.).
VS-20 - Venturi Scrubber, ca. 20*30 in V.G. »p
VS-60 - Venturi Scrubber, ca,. >60 in V.C. »p
ESP-1 - Electrostatic Precipitator; 1 stage
ESP-2 - Electrostatic Precipitator; 2 stage
ESP-4 - Electrostatic Precipitator; 4 stage -
IVS - Ionizing Vet Scrubber
DS - Dry Scrubber
FF - Fabric Filter (BaghouaaX
SD * Spray Dryer (Vet/Dry Scrubber)
8-7
-------
8.4 References """ "*
1. U.S. Environmental Protection Agency. "Guidance on Metals and
Hydrogen Chloride Controls for Hazardous Waste Incinerators,"
Office of Solid Waste, Washington, D.C., August 1989.
2. Carroll, G.J., R.C. Thurnau, R.E. Maumighan, L.R. Waterland, J.W.
Lee, and D.J. Fournier. The Partitioning of Metals in Rotary Kiln
Incineration. Proceedings of the Third International Conference on
New Frontiers for Hazardous Waste Management. NTIS Document No.
EPA/600/9-89/072, p. 555 (1989).
8-8
-------
Section 9.0.. ...
•! * . '
PROCEDURES FOR DETERMINING DEFAULT VALUES FOR PARTITIONING
OF METALS, ASH, AND TOTAL CHLORIDE/CHLORINE
Pollutant partitioning factor estimates can come from two sources:
default assumptions or engineering judgement. EPA's default assumptions are
discussed below for metals, HC1, C12, and PM. The default assumptions are
used to conservatively predict the partitioning factor for several types of
BIFs. Engineering judgement-based partitioning factor estimates are discussed
in Section 9.4.
9.1 Partitioning Default Value for Metals
To be conservative, the Agency is assuming that 100 percent of each
metal in each feed stream is partitioned to the combustion gas. Owners/
operators may use this default value or a supportable, site-specific value
developed following the general guidelines provided in Section 9.4.
9.2 Special Procedures for Chlorine. HC1. and C12
The Agency has established the special procedures presented below
for chlorine because the emission limits are based on the pollutants HC1 and
C12 formed from chlorine fed to the combustor. Therefore, the owner/operator
must estimate the controlled emission rate of both HC1 and C12 and show that
they do not exceed allowable levels. '
1. The default partitioning value for the fraction of chlorine in
the total feed streams that is partitioned to combustion gas is
100 percent. Owners/operators nay use this default value or a
supportable, site-specific value developed following the
general guidelines provided in Section 9.4.
2. To determine the partitioning of chlorine in the combustion gas
to HC1 versus C12, either use the default values below or use
supportable site-specific values developed following the
general guidelines provided in Section 9.4.
9-1
-------
•t For BIFs excluding halogen acid furnaces (HAFs), with a
total feed stream chlorine/hydrogen ratio < 0.95, the
default partitioning factor is 20 percent C12, 80 percent
HC1.
• For HAFs and for BIFs with a total feed stream
chlorine/hydrogen ratio > 0.95, the default partitioning
factor is 100 percent C12.
To determine the uncontrolled (i.e., prior to acid gas APCS)
emission rate of HC1 and C12, multiply the feed rate of chlo-
rine times the partitioning factor for each pollutant. Then,
for HC1, convert the chorine emission rate to HC1 by multiply-
ing it by the ratio of the molecular weight of Cl to the
molecular weight of HC1 (i.e., 35.5/36.5). No conversion is
needed for C12.
9.3 Special Procedures for Ash
This section: (1) explains why ash feed rate limits are not
applicable to cement and light-weight aggregate kilns; (2) presents the
default partitioning values for ash; and (3) explains how to convert the
0.08 gr/dscf, corrected to 7% 02, PM emission limit to a PH emission rate.
Waiver for Cement and Light-Weight Aggregate Kilns. For cement
kilns and light-weight aggregate kilns, raw material feed streams contain the
vast majority of the ash input, and a significant amount of the ash in the
feed stream is entrained into the kiln exhaust gas. For these devices, the
ash content of the hazardous waste stream is expected to have a negligible
effect on total ash emissions. For this reason, there is no ash feed rate
compliance limit for cement kilns or light-weight aggregate kilns. Nonethe-
less, cement kilns and light-weight aggregate kilns are required to initially
certify that PM emissions are not likely to exceed the PM limit, and subse-
quently, certify through compliance testing that the PM limit is not exceeded.
Default Partitioning Value for Ash. The default assumption for
partitioning of ash depends on the feed stream firing system. There are two
methods by which materials may be fired into BIFs: suspension-firing and bed-
firing.
9-2
-------
The suspension category includes atomized and lanced pumpable
liquids and suspension-fired pulverized solids. The default partitioning
assumption for materials fired by these systems is that 100 percent of the ash
partitions to the combustion gas.
The bed-fired category consists principally of stoker boilers and
raw materials (and in some cases containerized hazardous waste) fed into
cement and light-weight aggregate kilns. The default partitioning assumption
for materials fired on a bed is that 5 percent of the ash partitions to the
combustion gas.
Converting the PM Concentration-Based Standard to a PM Mass Emission
Rate. The emission limit for BIFs is 0.08 gr/dscf, corrected to 7% 02, unless
a more stringent standard applies [e.g., a New Source Performance Standard
(NSPS) or a State standard implemented under the State Implementation Plan
(SIP)]. To convert the 0.08 gr/dscf standard to a PM mass emission rate:
1. Determine the flue gas 02 concentration (percent by volume,
dry) and flue gas flow rate (dry standard cubic feet per
minute); and
2. Calculate the allowable PM mass emission rate by multiplying
the concentration-based PM emission standard times the flue gas
flow rate times a dilution correction factor equal to [(21 - 02
concentration from step 1)/(21 -7)].
9.4 Use of Engineering Judgement to Estimate Partitioning and APCS RE
Values
Engineering judgement may be used in place of EPA's conservative
default assumptions to estimate partitioning and APCS RE values provided that
the engineering judgement is defensible and properly documented. To properly
document engineering judgement, the owner/operator must keep a written record
of all assumptions and calculations necessary to justify the APCS RE used.
The owner/operator must provide this record to the Director upon request and
must be prepared to defend the assumptions and calculations used.
9-3
-------
If the. engineering judgement is based .on. emissions testing, the
* *"" *•
testing will often document the emission rate of a pollutant relative to the
feed rate of that pollutant rather than the partitioning factor or APCS RE.
Examples of situations where the use of engineering judgement may be
supportable to estimate a partitioning factor, APCS RE, or SRE include:
Using emissions testing data from the facility to support an
SRE, even though the testing may not meet full QA/QC procedures
(e.g., triplicate test runs). The closer the test results
conform with full QA/QC procedures and the closer the operating
conditions during the test conform with the established operat-
ing conditions for the facility, the more supportable the
engineering Judgement will be.
Applying emissions testing data documenting an SRE for one
metal, including nonhazardous surrogate metals to another less
volatile metal.
Applying emissions testing data documenting an SRE from one
facility to a similar facility.
Using APCS vendor guarantees of removal efficiency.
9.5 Restrictions on Use of Test Data
The measurement of an SRE or an APCS RE may be limited by the
detection limits of the measurement technique. If the emission of a pollutant
is undetectable, then the calculation of SRE or APCS RE should be based on the
lower limit of detectability. An SRE or APCS RE of 100 percent is not
acceptable.
Further, mas* balance data of facility inputs, emissions, and
products/residues may not be used to support a partitioning factor, given the
v
inherent uncertainties of such procedures. Partitioning factors other than
the default values may be supported based on engineering judgement, consider-
ing, for example, process chemistry. Emissions test data may be used to
support an engineering judgement-based SRE, which includes both partitioning
and APCS RE.
9-4
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Section 10 .-0
• • . • *
ALTERNATIVE METHODOLOGY FOR IMPLEMENTING METALS CONTROLS
10.1 Applicability
This method for controlling metals emissions applies to cement kilns and
other industrial furnaces operating under interim status that recycle emission
control residue back into the furnace.
10.2 Introduction
Under this method, cement kilns and other industrial furnaces that
recycle emission control residue back into the furnace must comply with a kiln
dust concentration limit (i.e., a collected particulate matter (PM) limit) for
each metal, as well as limits on the maximum feedrates of each of the metals
in: (1) pumpable hazardous waste; and (2) all hazardous waste.
The following subsections describe how this method for controlling
metals emissions is to be implemented:
• Subsection 10.3 discusses the basis of the method and the
assumptions upon which it is founded;
• Subsection 10.4 provides an overview of the implementation of the
method;
• Subsection 10.5 is a step-by-step procedure for implementation of
the method;
• Subsection 10.6 describes the compliance procedures for this
method; and
• Appendix A describes the statistical calculations and tests to be
used in the method.
10-1
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10.3 Basis , .....
v.
The viability of this method depends on three fundamental assumptions:
(1) Variations in the ratio of the metal concentration in the emitted
particulate to the metal concentration in the collected kiln dust
(referred to as the enrichment factor or EF) for any given metal
at any given facility will fall within a normal distribution that:
can be experimentally determined.
(2) The metal concentrations in the collected kiln dust can be
accurately and representatively measured (using procedures
specified in "Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods" (SW-846), incorporated by reference in
40 CFR 260.11).
(3) The facility will remain in compliance with the applicable
particulate matter (PM) emission standard.
Given these assumptions, metal emissions can be related to the measured
concentrations in the collected kiln dust by the following equation:
ut, (Ib Emi teed Metal \
fyfLt I —™™—»™————.^—^^^••^^•i* I V
\ *U I
I Ib Ptf\ _.._ / Ib Dust Metal \ EF (Ib Emi tted Metal/Ib PM\ (i s
\ bz ] \ Ib Dusc } \ Ib Dust Mec&l/lb Dust )
Where:
ME is the metal emitted;
PME is the particulate matter emitted;
DMC is the metal concentration in the collected kiln dust; and
EF is the enrichment factor, which is the ratio of the metal
concentration in the emitted particulate matter to the metal
concentration in the collected kiln dust.
10-2
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This equation can be rearranged to calculate a maximum allowable dust metal
. . *
concentration limit (DMCL) by assuming worst'-case conditions that: metal
emissions are at the Tier III (or Tier II) limit (see 40 CFR 266.106), and
that particulate emissions are at the particulate matter limit (PML):
7K n „ . Tier III Limit (1* Bitted Metals
lb DUSt Metal - _ 1 _ — _ L _ (2)
lb Dust n^T / lb PM\ „ I lb Emitted Metal/ lb PM\
\ hi I { lb Dust Metal/ lb Dust )
The enrichment factor used in the above equation must be determined
experimentally from a minimum of 10 tests in which metal concentrations are
measured in kiln dust and stack samples taken simultaneously. This approach
provides a range of enrichment factors that can be inserted into a statistical
distribution (t-distribution) to determine EF95Z and EF99I. EF95X is the value
at which there is a 95% confidence level that the enrichment factor is below
this value at any given time. Similarly, EF99X is the value at which there is
a 99% confidence level that the enrichment factor is below this value at any
given time. EF9JX is used to calculate the "violation" dust metal
concentration limit
,„.«..., 7, Tie, III Limit (lbEmitledMet&1\
DMC,r / lb Dust Metal \ m J hr /
v \ lb Dust ) OUT I lb PM\ -- / lb Emitted Metal/lb PM
™* \ hr »" \ lb Dust Metal/lb Dust
If the kiln dust metal concentration is just above this "violation" limit, and
the PM emissions are at the PH emissions limit, there is a 5% chance that the
metal emissions are above the Tier III limit. In such a case, the facility
would be in violation of the metals standard.
To provide a margin of safety, a second, more conservative kiln dust
metal concentration limit is also used. This "conservative" dust metal
concentration limit (DMCLe) is calculated using a -"safe" enrichment factor
10-3
-------
(SEF). .If EF99X is greater than two ttaes the value of EF95», the "safe1
"""" •„ -,
enrichment factor can be calculated using Equation 4a:
SEF * 2 £FM% (4a)
If EF98Z is not greater than two times the value of EF95I, the "safe"
enrichment factor can be calculated using Equation 4b:
SEF * EFM (4b)
In cases where the enrichment factor cannot be determined because the kiln
dust metal concentration is nondetectable, the "safe" enrichment factor is as
follows:
SEF -100
For all cases, the "conservative" dust metal concentration limit is calculated
using the following equation:
Tier III Limit I lb Baiitt9d Metal \
I Ib Dust Metal \ m \ hr / (5)
\ lb Dust ) na/r [lb PM\ SEp I lb Emitted Metal/lb PM\
\ hr ) \ lb Dust Metal/lb Dust I
If the kiln dust metal concentration at a facility is just above the
"conservative" limit based on the "safe" enrichment factor provided in
Equation 4a, and the PM emissions are at the PM emissions limit, there is a 5%
chance that the metal emissions are above one-half the Tier III limit. If the
kiln dust metal concentration at the facility is just above the "conservative"
limit based on the "safe* enrichment factor provided in Equation 4b, and the
PM emissions are at the PM emissions limit, there is a 1% chance that the
metal emissions are above the Tier III limit. In either case, the facility
10-4
-------
would be unacceptably close to a violation. If this situation occurs more
- • * -
than 5% of the time, the facility would be re'quired to rerun the series of 10
tests to determine the enrichment factor. To avoid this expense, the facility
would be advised to reduce its metals feedrates or to take other appropriate
measures to maintain its kiln dust metal concentrations in compliance with the
"conservative" dust metal concentration limits.
In cases where the enrichment factor cannot be determined because the
kiln dust metal concentration is nondetectable, and thus no EF95X exists, the
"violation" dust metal concentration limit is set at ten times the
"conservative" limit:
DMCLV = 10 x DMCL- (6)
y C
10.4 Overview
The flowchart for implementing the method is shown in Figure 10.4-1.
The general procedure is as follows:
• Follow the certification of precompliance procedures described in
Subsection 10.6 (to comply with 40 CFR 266.103(b)).
• For each metal of concern, perform a series of tests to establish
the relationship (enrichment factor) between the concentration of
emitted aetal and the metal concentration in the collected kiln
dust.
• Use the demonstrated enrichment factor, in combination with the
Tier III (or Tier II) metal emission limit and the most stringent
applicable particulate emission limit, to calculate the
"violation" and "conservative" dust metal concentration limits.
Include this information with the certification of compliance
under 40 CFR 266.103(c).
10-5
-------
CompI!ance ImpIementat i on FIow Chart
Tier 111
Emission Limit
Waste Analysis Plan
Precompllance
- See Figure 2
TIM Available
(Before Certification of
I Compliance Is Due?
Fall
'Emissions
-No
.1
Yea
1 Obtain Tine
MayRetest Extension or
Stop Burning
Notify tlrootor.
•urnlnv Hour*
AllowdtoSuMt
eortlf loatlon
Fort Mto Urtto
by 901 fa-
in Violation
Violation of
IS Standards
Yes
I
Yes
More Than 3
Failures In Lost
€0 Tests?
Exceed Violation Kiln
Dust Concentration
Limit?
Now Pass
T
Still Exceed
Optional Analysis of Spore
Sonnies to Statistically
Ify Limit Exceeded
Tests to Determine
Enrichment Factor
-3 out of ttt 5 tort* at
oavllanoo (Mto
I
Pass Emissions
Certification
-Sot •ConNrvatlvo" and
•Violation' Kiln Dwt
Conoontratlon Llrtt*
Dally and/or Weekly Klin
Dust Monitoring for
Continued ConpMance
1
Exceed Conservative
Kiln Dust Concentration?
Test Plan
Statistical Test to
Determine If Enrichment
Factor Has Increased
Increased
Not
Increased
Quarterly
Enrichment
Factor
Verification
Tests
Quarterly Test
Due?
•No-
•Yes
-------
• Perform daily and/or weekly monitoring of the cement kiln dust
«
metal concentration to ensure (wi'th appropriate QA/QC) that the
metal concentration does not exceed either limit.
If the cement kiln dust metal concentration exceeds the
"conservative" limit more than 5% of the time (i.e., more
than three failures in last 60 tests), the series of tests
to determine the enrichment factor must be repeated.
If the cement kiln dust metal concentration exceeds the
"violation" limit, a violation has occurred.
• Perform quarterly tests to verify that the enrichment factor has
not increased significantly. If the enrichment factor has
increased, the series of tests to determine the enrichment factor
must be repeated.
10.5 Implementation Procedures
A step-by-step description for implementing the method is provided
below:
(1) Prepare initial limits and test plans.
• Determine the Tier III metal emission limit. The Tier II metal
emission limit may also be used (see 40 CFR 266.106).
• Determine the applicable PH emission standard. This standard is
the most stringent particulate emission standard that applies to
the facility. A facility may elect to restrict itself to an even
more stringent self-imposed PM emission standard, particularly if
the facility finds that it is easier to control particulate
emissions than to reduce the kiln dust concentration of a certain
metal (i.e., lead).
10-7
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• Determine which metals need to he monitored (i.e., all hazardous
metals for which Tier III emission limits are lower than PM
emission limits -• assuming PM is pure metal).
• Follow the compliance procedures described in Subsection 10.6.
• Follow the guidelines described in Stf-846 for preparing test plans
and waste analysis plans for the following tests:
Compliance tests to determine limits on metal feedrates in
pumpable hazardous wastes and in all hazardous wastes (as
well as to determine other compliance parameters);
Initial tests to determine enrichment factors;
Quarterly tests to verify enrichment factors;
Analysis of hazardous waste feedstreams; and
Daily and/or weekly monitoring of kiln dust for continuing
compliance.
(2) Conduct tests to determine the enrichment factor.
• These tests must be conducted within a 14-day period. No more
than two tests may be conducted in any single day. If the tests
are not completed within a 14-day period, they must be repeated.
• Simultaneous stack samples and kiln dust samples must be taken.
Stack sampling must be conducted with the multiple metals
train according to procedures provided in Section 10.3 of
this Methods Manual.
Kiln dust sampling must be conducted as follows:
Follow the sampling and analytical procedures
described in SV-846 and the waste analysis plan as
they pertain to the condition and accessibility of the
dust.
Samples should be representative of the last ESP or
Fabric Filter in the APCS series.
10-8
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The feedrates of hazardous metals in all pumpable hazardous waste
« • •
streams and in all hazardous waste streams must be monitored
during these tests. It is recommended (but not required) that the
feedrates of hazardous metals in all feedscreams also be
monitored.
At least ten single (noncomposited) runs are required during the
tests.
The facility must follow a normal schedule of kiln dust
recharging for all of the tests.
Three of the first five tests must be compliance tests in
conformance with 40 CFR 266.103(c); i.e., they must be used
to determine maximum allowable feedrates of metals in
pumpable hazardous wastes, and in all hazardous wastes, as
well as to determine other compliance limits (see 40 CFR
266.103(c)(l)).
The remainder of the tests need not be conducted under full
compliance test conditions; however, the facility must
operate at its compliance test production rate, and it must
burn hazardous waste during these tests such that the
feedrate of each metal for pumpable and total hazardous
wastes is at least 25% of the feedrate during compliance
testing. If these criteria, and those discussed below, are
not met for any parameter during a test, then either the
test is not valid for determining enrichment factors under
this method, or the compliance limits for that parameter
must be established based on these test conditions rather
than on the compliance test conditions.
Verify that compliance emission limits are not exceeded.
Metal emissions must not exceed Tier III (or Tier II)
limits.
PM emissions must not exceed the most stringent of
applicable PM standards (or an optional self- imposed
particulate standard).
10-9
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• The facility must generate normal, marketable product using normal
raw materials and fuels under normal operating conditions (for
parameters other than those specified under this method) when
these tests are conducted.
• Chromium must be treated as a special case:
The enrichment factor for total chromium is calculated in
the same way as the enrichment factor for other metals
(i.e., the enrichment factor is the ratio of the
concentration of total chromium in the emitted particulate
matter to the concentration of total chromium in the
collected kiln dust).
The enrichment factor for hexavalent chromium (if measured)
is defined as the ratio of the concentration of hexavalent
chromium in the emitted particulate matter to the
concentration of total chromium in the collected kiln dust.
(3) Use the enrichment factors measured in Step 2 to determine EF95I, EF991,
and SEF.
• Calculate EF95I and EF99I according to the t-distribution as
described in Appendix A.
• Calculate SEF by
Equation Aa if EF951 is determinable and if EF98, is greater
than two times EF95I>
Equation 4b if EF95X is determinable and if EFMX is not
greater than two times EF95l.
Equation 4c if EF9SS is not determinable.
The facility may choose to set an even more conservative SEF to
give itself a larger margin of safety between the point where
corrective action is necessary and the point where a violation
occurs.
10-10
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(4) Prepare certification of compliance
. • * '
• Calculate the "conservative" dust metal concentration limit
(DMCLe) using Equation 5.
Chromium is treated as a special case. The "conservative"
kiln dust chromium concentration limit is set for total
chromium, not for hexavalent chromium. The limit for total
chromium must be calculated using the Tier III (or Tier II)
metal limit for hexavalent chromium.
If the stack samples described in Step 2 were analyzed
for hexavalent chromium, the SEF based on the
hexavalent chromium enrichment factors (as defined in
Step 2) must be used in this calculation.
If the stack samples were not analyzed for hexavalent
chromium, then the SEF based on the total chromium
enrichment factor must be used in this calculation.
Calculate the "violation" dust metal concentration limit
using Equation 3 if EF95X is determinable, or using Equation 6 if
EF951 is not determinable.
Chromium is treated as a special case. The "violation" kiln
dust chromium concentration limit is set for total chromium,
not for hexavalent chromium. The limit for total chromium
must be calculated using the Tier III (or Tier II) metal
limit for hexavalent chromium.
If the stack samples taken in Step 2 were analyzed for
hexavalent chromium, the EF85J based on the hexavalent
chromium enrichment factor (as defined in Step 2)
should be used in this calculation.
If the stack samples were not analyzed for hexavalent
chromium, the EF85I based on the total chromium
enrichment factor must be used in this calculation.
Submit certification of compliance.
10-11
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• Steps 2-4 must be repeated for recertification, which is required
once every 3 years (see §266.103(d)).
(5) Monitor metal concentrations in kiln dust for continuing compliance, and
maintain compliance with all compliance limits for the duration of
interim status.
• Metals to be monitored during compliance testing are classified as
either "critical" or "noncritical" metals.
All metals must initially be classified as "critical" metals
and be monitored on a daily basis.
A "critical" metal may be reclassified as a "noncritical"
metal if its concentration in the kiln dust remains below
10% of its "conservative" kiln dust metal concentration
limit for 30 consecutive daily samples. "Noncritical"
metals must be monitored on a weekly basis.
A "noncritical" metal must be reclassified as a "critical"
metal if its concentration in the kiln dust is above 10% of
its "conservative" kiln dust metal concentration limit for
any single daily or weekly sample.
• Noncompliance with the sampling and analysis schedule prescribed
by this method is a violation of the metals controls under
§266.103.
• Follow the sampling, compositing, and analytical procedures
described in this method and in SW-846 as they pertain to the
condition and accessibility of the kiln dust.
• Follow the same procedures and sample at the same locations as
were used for kiln dust samples collected to determine the
enrichment factors (as discussed in Step 2).
• Samples oust be collected at least once every 8 hours, and a daily
composite must be prepared according to Stf-846 procedures.
10-12
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At least one composite sample is required. This sample is
* -
referred to as the "required" sample.
For QA/QC purposes, a facility may elect to collect two or
more additional samples. These samples are referred to as
the "spare" samples. These additional samples must be
collected over the same time period and according to the
same procedures as those used for the "required" sample.
Samples for "critical" metals must be daily composites.
Samples for "noncritical" metals must be weekly composites.
These samples can be composites of the original 8-hour
samples, or they can be composites of daily composite
samples.
• Analyze the "required" sample to determine the concentration of
each metal.
This analysis must be completed within 48 hours of the close
of the sampling period. Failure to meet this schedule is a
violation of the metals standards of §266.103.
• If the "conservative" kiln dust metal concentration limit is
exceeded for any metal, refer to Step 8.
• If the "conservative" kiln dust metal concentration limit is not
exceeded, continue with the daily or weekly monitoring (Step 5)
for the duration of interim status.
• Conduct quarterly enrichment factor verification tests, as
described in Step 6.
(6) Conduct quarterly enrichment factor verification tests.
• After certification of compliance with the metals standards, a
facility must conduct quarterly enrichment factor verification
tests every three months for the duration of interim status. The
first quarterly test must be completed within three months of
10-13
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certification (or recertification).. Each subsequent quarterly
test must be completed within three months of the preceding
quarterly test. Failure to meet this schedule is a violation.
• Simultaneous stack samples and kiln dust samples must be
collected.
• Follow the same procedures and sample at the same locations as
were used for kiln dust samples and stack samples collected to
determine the enrichment factors (as discussed in Step 2).
• At least three single (noncomposited) runs are required. These
tests need not be conducted under the operating conditions of the
initial compliance test; however, the facility must operate under
the following conditions:
It must operate at compliance test production rate.
It must burn hazardous waste during the test, and for the
2-day period immediately preceding the test, such that the
feedrate of each metal for pumpable and total hazardous
wastes consist of at least 25% of the operating limits
established during the compliance test.
It must remain in compliance with all compliance parameters
(see §266.103(c)(l)).
It must follow a normal schedule of kiln dust recharging.
It must generate normal marketable product from normal raw
materials during the tests.
(7) Conduct a statistical test to determine if the enrichment factors
measured in the quarterly verification tests have increased
significantly from the enrichment factors determined in the tests
conducted in Step 2. The enrichment factors have increased
significantly if all three of the following criteria are met:
• By applying the t-test described in Appendix A, it is determined
that the enrichment factors measured in the quarterly tests are
10-14
-------
not taken from the same population as the enrichment factors
measured in the Step 2 tests;
• The EF95X calculated for the combined data sets (i.e., the
quarterly test data and the original Step 2 test data) according
to the t-distribution (described in Appendix A) is more than 10%
higher than the EF95I based on the enrichment factors previously
measured in Step 2; and
• The highest measured kiln dust metal concentration recorded in the
previous quarter is more than 10% of the "violation" kiln dust
concentration limit that would be calculated from the combined
EF95Z.
If the enrichment factors have increased significantly, the tests to
determine the enrichment factors must be repeated (refer to Step 11).
If the enrichment factors have not increased significantly, continue to
use the kiln dust metal concentration limits based on the enrichment
factors previously measured in Step 2, and continue with the daily
and/or weekly monitoring described in Step 5.
(8) If the "conservative" kiln dust metal concentration limit was exceeded
for any metal in any single analysis of the "required" kiln dust sample,
the "spare" samples corresponding to the same period may be analyzed to
determine if the exceedance was due to a sampling or analysis error.
• If no "spare" samples were taken, refer to Step 9.
• If the average of all the samples for a given day (or week, as
applicable) (including the "required" sample and the "spare"
samples) does not exceed the "conservative" kiln dust metal
concentration limit, no corrective measures are necessary;
continue with the daily and/or weekly monitoring as described in
Step 5.
10-15
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• If the average of all the. samples for a given day (or week, as
applicable) exceeds Che "conservative" kiln dust metal
concentration limit, but the average of the "spare" samples is
below the "conservative" kiln dust metal concentration limit,
apply the Q-test, described in Appendix A, to determine whether
the "required" sample concentration can be judged as an outlier.
If the "required" sample concentration is judged an outlier,
no corrective measures are necessary; continue with the
daily and/or weekly monitoring described in Step 5.
If the "required" sample concentration is not Judged an
outlier, refer to Step 9.
(9) Determine if the "violation" kiln dust metal concentration has been
exceeded based on either the average of all the samples collected during
the 24-hour period in question, or if discarding an outlier can be
statistically justified by the Q-test described in Appendix A, on the
average of the remaining samples.
• If the "violation" kiln dust metal concentration limit has been
exceeded, a violation of the metals controls under §266.103(c) has
occurred. Notify the Director that a violation has occurred.
Hazardous waste may be burned for testing purposes for up to 720
operating hours to support a revised certification of compliance.
Note that the Director may grant an extension of the hours of
hazardous waste burning under §266.103(c)(7) if additional burning
time is needed to support a revised certification for reasons
beyond the control of the owner or operator. Until a revised
certification of compliance is submitted to the Director, the
feedrate of the metals in violation in total and pumpable
hazardous waste feeds is limited to 50% of the previous compliance
test limits.
10-16
-------
• If the "violation" kiln dust metal concentration has not been
«
exceeded:
- - If the exceedance occurred in a daily composite sample,
refer to Step 10.
If the exceedance occurred in a weekly composite sample,
refer to Step 11.
(10) Determine if the "conservative" kiln dust metal concentration limit has
been exceeded more than three times in the last 60 days.
• If not, log this exceedance and continue with the daily and/or
weekly monitoring (Step 5).
• If so, the tests to determine the enrichment factors must be
repeated (refer to Step 11).
• This determination is made separately for each metal; For
example,
Three exceedances for each of the ten hazardous metals are
allowed within any 60-day period.
Four exceedances of any single metal in any 60-day period is
not allowed.
• This determination should be made daily, beginning on the first
day of daily monitoring. For example, if four exceedances of any
single metal occur in the first four days of daily monitoring, do
not wait until the end of the 60-day period; refer immediately to
Step 11.
(11) The tests to determine the enrichment factor must be repeated if: (1)
more than three exceedances of the "conservative" kiln dust metal
concentration limit occur within any 60 consecutive daily samples; (2)
an excursion of the "conservative" kiln dust metal concentration limit
occurs in any weekly sample; or (3) a quarterly test indicates that the
enrichment factors have increased significantly.
10-17
-------
• The facility must notify the Director if these tests must be
repeated.
• The facility has up to 720 hazardous-waste-burning hours to
redetermine the enrichment factors for the metal or metals in
question and to recertify (beginning with a return to Step 2).
During this period, the facility must reduce the feed rate of the
metal in violation by 50%. If the facility has not completed the
recertification process within this period, it must stop burning
or obtain an extension. Hazardous waste burning may resume only
when the recertification process (ending with Step 4) has been
completed.
• Meanwhile, the facility must continue with daily kiln dust metals
monitoring (Step 5} and must remain in compliance with the
"violation" kiln dust metal concentration limits (Step 9).
10.6 Precomplianee Procedures
Cement kilns and other industrial furnaces that recycle emission control
residue back into the furnace must comply with the same certification
schedules and procedures (with the few exceptions described below) that apply
to other boilers and industrial furnaces. These schedules and procedures, as
set forth in §266.103, require no later than the effective date of the rule,
each facility submit a certification which establishes precompliance limits
for a number of compliance parameters (see §266.103(b)(3)), and that each
facility immediately begin to operate under these limits.
These precompliance limits must ensure that interim status emissions
limits for hazardous metals, particulate matter, HC1, and C12 are not likely
to be exceeded. Determination of the values of the precompliance limits must
be made based on either (1) conservative default assumptions provided in this
Methods Manual, or (2) engineering judgement.
10-18
-------
The flowchart for implementing the precompliance procedures is shown in
. •> * ' ' *
Figure 10.6-1. The step-by-step precompliance implementation procedure is
described below. The precompliance implementation procedures and numbering
scheme are similar to those used for the compliance procedures described in
Subsection 10.5.
(1) Prepare initial limits and test plans.
• Determine the Tier III metal emission limit. The Tier II metal
emission limit may also be used (see 40 CFR 266.106).
• Determine the applicable PM emission standard. This standard is
the most stringent particulate emission standard that applies to
the facility. A facility may elect to restrict itself to an even
more stringent self-imposed PM emission standard, particularly if
the facility finds that it is easier to control particulate
emissions than to reduce the kiln dust concentration of a certain
metal (i.e. , lead).
• Determine which metals need to be monitored (i.e., all hazardous
metals for which Tier III emission limits are lower than PM
emission limits -- assuming PM is pure metal).
• Follow the procedures described in SU-846 for preparing waste
analysis plans for the following tasks:
Analysis of hazardous waste feedstreams.
Daily and/or weekly monitoring of kiln dust concentrations
for continuing compliance.
(2) Determine the "safe" enrichment factor for precompliance. In this
context, the "safe" enrichment factor is a conservatively high estimate
of the enrichment factor (the ratio of the emitted metal concentration
to the metal concentration in the collected kiln dust). The "safe"
enrichment factor must be calculated from either conservative default
values, or engineering judgement.
10-19
-------
Figure 10.6-1
PrecompIi ance I np Iementat i on FIow Chart
Tier HI or Tier II
Emission Limit
Waste Analysis Plan
Notify Director.
Up to 720 Waste-turning
Hars Allowed to Sutalt
Revised Certification
of Precaol lance
Estimate Enrichment Foctor
-Otfdult ValuM cr
Yes
More Than 3
Fallures In Last
€0 Tests
Precomp Nance
-Mt "dr-flfloatlon of
ftr*oa»l!am' II In
Out* Camnfratlcn LMtt
-NO-
St II
Exceed
Now Pass
Doily and/or Weekly Kiln
Dust Monitoring for
Continued Compliance
Optional Analysis of Spare
'-iples to Statistically
i
-------
• Conservative default values for the .."safe" enrichment factor are
, • . * ' *
as follows:
SEF - 10 for all hazardous metals except mercury. SEF - 10
for antimony, arsenic, barium, beryllium, cadmium,
chromium, lead, silver, and thallium.
SEF - 100 for mercury.
• Engineering judgement may be used in place of conservative default
assumptions provided that the engineering judgement is defensible
and properly documented. The facility must keep a written record
of all assumptions and calculations necessary to justify the SEF.
The facility must provide this record to EPA upon request and must
be prepared to defend these assumptions and calculations.
Examples of situations where the use of engineering judgement is
appropriate include:
Use of data from precompliance tests;
Use of data from previous compliance tests; and
Use of data from similar facilities.
(3) This step does not apply to precompliance procedures.
(4) Prepare certification of precompliance.
• Calculate the "conservative* dust metal concentration limit
(DMCLg) using Equation 5.
• Submit certification of precompliance. This certification must
include precompliance limits for all compliance parameters that
apply to other boilers and industrial furnaces (i.e., those that
do not recycle emission control residue back into the furnace) as
listed in §266.103(b)(3). except that it is not necessary to set
precompliance limits on maximum feedrate of each hazardous metal
in all combined feedstreams.
10-21
-------
• Furnaces that recycle collected PM hack into the furnace (and that
elect to comply with this method (see §266.103(c)(3)(ii)) are
subject to a special precompliance parameter, however. They must
establish precompliance limits on the maximum concentration of
each hazardous metal in collected kiln dust, (which must be set
according to the procedures described above).
(5) Monitor metal concentration in kiln dust for continuing compliance, and
maintain compliance with all precompliance limits until certification of
compliance has been submitted.
• Metals to be monitored during precompliance testing are classified
as either "critical" or "noncritical" metals.
All metals must initially be classified as "critical" metals
and be monitored on a daily basis.
A "critical" metal may be reclassified as a "noncritical"
metal if its concentration in the kiln dust remains below
10% of its "conservative" kiln dust metal concentration
limit for 30 consecutive daily samples. "Noncritical"
metals must be monitored on a weekly basis, at a minimum.
A "noncritical" metal must be reclassified as a "critical"
metal if its concentration in the kiln dust is above 10% of
its "conservative" kiln dust metal concentration limit for
any single daily or weekly sample.
• It is a violation if the facility fails to analyze the kiln dust
for any "critical" metal on any single day or for any
•noncritical" metal during any single week, when hazardous waste
is burned.
• Follow the sampling, compositing, and analytical procedures
described in this method and in SW-846 as they pertain to the
condition and accessibility of the kiln dust.
10-22
-------
• Samples must be collected at least once every 8 hours, and a daily
composite prepared according to'SW-846 procedures.
At least one composite sample is required. This sample is
referred to as the "required" sample.
For QA/QC purposes, a facility may elect to collect two or
more additional samples. These samples are referred to as
the "spare" samples. These additional samples must be
collected over the same time period and according to the
same procedures as those used for the "required" sample.
Samples for "critical" metals must be daily composites.
Samples for "noncritical" metals must be weekly composites,
at a minimum. These samples can be composites of the
original 8-hour samples, or they can be composites of daily
composite samples.
• Analyze the "required" sample to determine the concentration of
each metal.
This analysis must be completed within 48 hours of the close
of the sampling period. Failure to meet this schedule is a
violation.
• If the "conservative" kiln dust metal concentration limit is
exceeded for any metal, refer to Step 8.
• If the "conservative" kiln dust metal concentration limit is not
exceeded, continue with the daily and/or weekly monitoring
(Step 5) for the duration of interim status.
(6) This step does not apply to precompliance procedures.
(7) This step does not apply to precompliance procedures.
(8) If the "conservative* kiln dust metal concentration limit was exceeded
for any metal in any single analysis of the "required" kiln dust sample,
10-23
-------
the "spare" samples corresponding to the same period may be analyzed to
determine if the exceedance is due to "A sampling or analysis error.
• If no "spare" samples were taken, refer to Step 9.
• If the average of all the samples for a given day (or week, as
applicable) (including the "required* sample and the "spare"
samples) does not exceed the "conservative" kiln dust metal
concentration limit, no corrective measures are necessary;
continue with the daily and/or weekly monitoring as described in
Step 5.
• If the average of all the samples for a given day (or week, as
applicable) exceeds the "conservative" kiln dust metal
concentration limit, but the average of the "spare" samples is
below the "conservative" kiln dust metal concentration limit, -
apply the Q-test, described in Appendix A, to determine whether
the "required" sample concentration can be judged as an outlier.
If the "required" sample concentration is judged an outlier,
no corrective measures are necessary; continue with the
daily and/or weekly monitoring described in Step 5,
If the "required" sample concentration is not judged an
outlier, refer to Step 10.
(9) This step does not apply to precompliance procedures.
(10) Determine if the "conservative" kiln dust metal concentration limit has
been exceeded more than three times in the last 60 days.
• If not, log this exceedance and continue with the daily and/or
weekly monitoring (Step 5).
• If so, the tests to determine the enrichment factors must be
repeated (refer to Step 11).
10-24
-------
• This determination is made separately for each metal; for example
Three exceedances for each of the ten hazardous metals are
allowed within any 60-day period.
Four exceedances of any single metal in any 60-day period is
not allowed.
• This determination should be made daily, beginning on the first
day of daily monitoring. For example, if four exceedances of any
single metal occur in the first four days of daily monitoring, do
not wait until the end of the 60-day period; refer immediately to
Step 11.
(11) A revised certification of precompliance must be submitted to the
Director (or certification of compliance must be submitted) if: (1)
more than three exceedances of the "conservative" kiln dust metal
concentration limit occur within any 60 consecutive daily samples; or
(2) an exceedance of the "conservative" kiln dust metal concentration
limit occurs in any weekly sample.
• The facility must notify the Director if a revised certification
of precompliance must be submitted.
• The facility has up to 720 waste-burning hours to submit a
certification of compliance or a revised certification of
precompliance. During this period, the feed rate of the metal in
violation must be reduced by 50%. In the case of a revised
certification of precompliance, engineering judgement must be used
to ensure that the "conservative" kiln dust metal concentration
will not be exceeded. Examples of how this goal might be
accomplished include:
Changing equipment or operating procedures to reduce the
kiln dust metal concentration;
Changing equipment or operating procedures, or using more
detailed engineering Judgement, to decrease the estimated
10-25
-------
SEF and thus increase the "conservative" kiln dust metal
* ' •
concentration limit;
Increasing the "conservative" kiln dust metal concentration
limit by imposing a stricter PM emissions standard; or
Increasing the "conservative" kiln dust metal concentration
limit by performing a more detailed risk assessment to
increase the metal emission limits.
Meanwhile, the facility must continue with daily kiln dust metals
monitoring (Step 5).
10-26
-------
Appendix A.
STATISTICS"
A.1 Determination of Enrichment Factor
After at least 10 initial emissions tests are performed, an enrichment
factor for each metal must be determined. At the 95% confidence level, the
enrichment factor, EF95X, is based on the test results and is statistically
determined so there is only a 5% chance that the enrichment factor at any given
time will be larger than EF95I. Similarly, at the 99% confidence level, the
enrichment factor, EF99X, is statistically determined so there is only a 1%
chance that the enrichment factor at any given time will be larger than EF99Z.
For a large number of samples (n > 30), EF95: is based on a normal
distribution, and is equal to:
HP * ze o
(1)
where:
(2)
(3)
For a 95 % confidence level, zc is equal to 1.645.
10-27
-------
For a small number of samples (n. < .30), EF85X is based on the
t-distribution and is equal to:
£F,5% - 2F «• tc S (4)
where the standard deviation, S, is defined as:
i
(5)
n-1
te is a function of the number of samples and the confidence level that is
desired. It increases in value as the sample size decreases and the confidence
level increases. The 95% confidence level is used in this method to calculate
the "violation" kiln dust metal concentration limit; and the 99% confidence level
is sometimes used to calculate the "conservative" kiln dust metal concentration
limit. Values of tc are shown in Table A-l for various degrees of freedom
(degrees of freedom - sample size - 1) at the 95% and 99% confidence levels. As
the sample size approaches infinity, the normal distribution is approached.
A.2 Comparison of Enrichment Factor Groups
To determine if the enrichment factors measured in the quarterly tests are
significantly different from the enrichment factors determined in the initial
Step 2 tests, the t-test if used. In this test, the value t,*,,:
(6)
10-28
-------
Table A-l t-Distribution
n-1
or
n1+n2-2
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
25
30
40
60
120
•
t.95
6.31
2.92
2.35
2.13
2.02
1.94
1.90
1.86
1.83
1.81
1.80
1.78
1.77
1.76
1.75
1.75
1.74
1.73
1.73
1.72
1.71
1.70
1.68
1.67
1.66
1.645
t.99
31.82
6.96
4.54
3.75
3.36
3.14
3.00
2.90
2.82
2.76
2.72
2.68
2.65
2.62
2.60
2.58
2.57
2.55
2.54
2.53
2.48
2.46
2.42
2.39
2.36
2.33
10-29
-------
WH
J
(7)
is compared to terit at the desired confidence level. The 95% confidence level
is used in this method. Values of tertt are shown in Table A-l for various
degrees of freedom (degrees of freedom - nt + n2 - 2) at the 95% and 99%
confidence levels. If t,^., is greater then tcrlt, it can be concluded with 95%
confidence that the two groups are not from the same population.
A. 3 Relection of Data
If the concentration of any hazardous metal in the "required" kiln dust
sample exceeds the kiln dust metal concentration limit, the "spare" samples are
analyzed. If the average of the combined "required" and "spare" values is still
above the limit, a statistical test is used to decide if the upper value can be
rejected.
The "Q-test" is used to determine if a data point can be rejected. The
difference between the questionable result and its neighbor is divided by the
spread of the entire data set. The resulting ratio, <^,M, is then compared with
rejection values that are critical for a particular degree of confidence, where
Q.... is:
The 90% confidence level for data rejection is used in this method. Table A-2
provides the values of Qecit *c che 90% confidence level. If Q.,.. is larger than
Qcrif tne data point can be discarded. Only one data point from a sample group
can be rejected using this method.
10-30
-------
Table A-2 Cricical Values for Use in the Q-Test
n
3
4
5
6
7
8
9
10
Qent
0.94
0.76
0.64
0.56
0.51
0.47
0.44
0.41
10-31
-------
ENVIRONMENTAL PROTECTION AGENCY
40 CFR Parts 260, 261,264, 265, 266,. 270, and 271
«l|-o/a-
[EPA/OSW-FR-9£ ;SWH-FRLr ]
BtHBaogof HaooBdoos Waste in Boilers and Industrial Furnaces
AGENCY: EnvironmentalProtection Agency (EPA).
ACTION: Final Rule.
SUMMARY: Under this final rule, the Environmental Protection Agency (EPA) is
expanding controls on hazardous waste combustion to regulate air emissions from the
burning of hazardous waste in boilers and industrial furnaces. Currently, such burning is
exempt from regulation. EPA is promulgating this final rule after considering public
comment on rules proposed on May 6,1987, plus the comments on EPA's supplemental
notices of October 26,1989 and April 27,1990.
These rules control emissions of toxic organic compounds, toxic metals, hydrogen
chloride, chlorine gas, and particulate matter from boilers and industrial furnaces burning
hazardous waste. In addition the rules subject owners and operators of these devices to the
general facility standards applicable to hazardous waste treatment, storage, and disposal
facilities. Further, today's final rule subjects hazardous waste storage units at regulated
burner facilities to Part 264 permit standards. Burner storage operations at existing
facilities are generally now subject only to interim status standards under Part 265.
Finally, today's rule takes final action on two pending petitions for rulemaldng: (1)
based on a petition by Dow Chemical Company, EPA is designating halogen acid furnaces
as industrial furnaces under §260.10; and (2) based on a petition by the American Iron and
Steel Institute, EPA is classifying coke and coal tar fuels produced by recycling coal tar
decanter sludge, EPA Hazardous Waste No. KO87, as products rather than solid waste.
The rule also makes several technical corrections to regulations dealing with loss of interim
status for facilities that achieved interim status as of November 7,1984.
-------
EFFECTIVE DATE: This final rule is effective on [date six months from promulgation].
Technical correc&oos to section 270,73 are effective immediately.
ADDRESSES: The official record for this rulemaking is identified as Docket Numbers F-
87-BBFP-FFFFF and F-89-BBSP-FFFFF, and is located in the EPA RCRA Docket,
Room 2427* 401M Street SW., Washington, DC 20460. The docket is available for
inspection from 9 ajn. to 4 pm., Monday tlirough Fiiday, except on Federal holidays. The
public most make an appoimment to review docket materials by calling (202) 475-9327.
The public may copy up to 100 pages from the docket at no charge. Additional copies cost
$.15 per page.
FOR FURTHER INFORMATION CONTACT: For general information contact
the RCRA Hotline at: (800) 424-9346 (toll-free) or (202) 382-3000 locally. For
information on specific aspects of this final rule, contact Dwight Hlustick, Office of Solid
Waste (OS-322W), U.S. Environmental Protection Agency, 401 M Street SW.,
Washington, DC 20460, (703) 308-8460.
SUPPLEMENTARY INFORMATION:
Preamble Outline
PART ONE: BACKGROUND
I. Legal Authority
II. Overview of the Final Rule
A. Controls for Emissions of Organic Compounds
B. Controls for Emissions of Toxic Metals
C. Controls for Emissions of Hydrogen Chloride and Chlorine Gas
D. Emission Standard for Paniculate Matter
E. Permitting Procedures
F. Controls During Interim Status
G. Units Exempt from Air Emissions Standards
H. Pollution Prevention Impacts
m. Relationship to Other Rules
A. Regulations to be Promulgated Under the New Clean Air Act
B. April 27,1990 Proposed Incinerator Amendments
C. July 28,1990 Proposed Amendment to Definition of Wastewater Treatment Unit to
Exempt Sludge Dryers
D. Land Disposal Restriction Standards
PART TWO: DEVICES SUBJECT TO REGULATION
I. Boilers
n. Industrial Furnaces
A. Cement Kilns
B. Light-Weight Aggregate Kilns
C. Halogen Acid Furnaces
1. Current Practices
-------
2. Designation of HAFs as Industrial Furnaces
D, Smeteng, Melting, and Refining Furnaces Burning Hazardous Waste to Recover
Metals
PART1HREE: STANDARDS FOR BOILERS AND INDUSTRIAL FURNACES
BURNING HAZARDOUS WASTE
I. Emission Standard for Paniculate Matter
A. Basis for Final Rule
1. Alternatives Considered
2. Basis for Standard
B. late ••im Status Compliance Procedures
C. Implementation
D. Controls for Emissions of Toxic Organic Compounds
A. ORE Standard
1. Selection of POHCs for DRE Testing
2. Use of POHC Surrogates
3. Waiver of DRE Trial Burn for Boilers Operating Under the Special Operating
Requirements
B. PIC Controls
1. Use of a CO Limit to Control PICs
2. Tier I PIC Controls: 100 ppmv CO limit
3. Tier n PIC Controls: Limits on CO and HC
4. Special Requirements for Furnaces
5. Special Considerations for Cement Kilns
C. Automatic Waste Feed Cutoff Requirements
D. CEM Requirements for PIC Controls
E. Control of Dioxin and Furan Emissions
ffl. Risk Assessment Procedures
A. Health Effects Data
1. Carcinogens
2. Noncarcinogens
B. Air Dispersion Modeling
1. Option for Site-Specific Modeling
2. Terrain-Adjusted Effective Stack Height
3. Conservatism in Screening Limits
4. GEP Stack Height
5. Plume Rise Table
6. Compliance by Manipulating Effective Stack Height
7. Effect of HC1 Emissions on Acid Rain
8. Building Wake Effects
C. Consideration of Indirect Exposure and Environmental Impacts
1. Indirect Exposure
2.Non-human Health Related Environmental Impacts
D. Acceptable Risk Level for Carcinogens
E. Use of MEI and Consideration of Aggregate Risk
F. Risk Assessment Assumptions
IV. Controls for Emissions of Toxic Metals
A. Background Information
1. Metals Standards under Other Statutes
2.1987 Proposed Rule
3.1989 Supplement to Proposed Rule
B. How the Standards Work
1. Tier HI Standards
2. Tier n Standards
3. Tier I Standards
-------
C Implementation
1. Tier I Implementation
2. Tier U Implementation
3. Tier HI Implementation
4. Special Requirements for Furnaces that Recycle Collected Paniculate Matter
5 Trial Burns
6. Monitoring and Analysis Requirements
D. Interim Status Compliance Requirements
V. Controls for Emissions of Hydrogen Chloride and Chlorine Gas
A. Background Information
B. Response to Comments
LShort-TennHCIRAC
2. Need for Cl2 Controls
3. HC1 Emission Test Procedures
4. Technology-Based HC1 Controls
C. Implementation
1. Emissions Testing
2. Waste Analysis
3. Interim Status Compliance Requirements
VI. Nontechnical Requirements
VII. Interim Status Standards
A.Certification Schedule
1. Certification of Precompliance
2. Certification of Compliance
3. Recertification
4. Failure to Comply with the Certification Schedule
5. Development of the Certification Schedule
B. Limits on Operating Parameters
C. Automatic Waste Feed Cutoff
D. Sham Recycling Policy
E. Submittal of Part B Applications
F. DRE Testing
G. Chlorinated Dioxins and Furans
H. Special Requirements for Furnaces
I. Special Metals Controls for Furnaces that Recycle Collected Paniculate Matter
J. Recordkeeping
Vffl. Implementation of Today's Rule
A. Newly Regulated Facilities
1. Definition of "In Existence"
2. Section 3010 Notification
3. Part A Permit Application
B. Interim Status Facilities
C. Permitted facilities
1. Amendment to §270.42(g)
2. Procedures to Modify Permits
D. Addition of Storage Units at Direct Transfer Facilities That Obtain Interim Status
1. Unauthorized States
2. Authorized States
E. Compliance with BIF versus Incinerator Rules
DC. Permit Procedures
A. Part B Information
B. Special Forms of Permits
1. Permits for New Boilers and Industrial Furnaces
-------
2. Permit Procedures for Interim Status Facilities
X. Exemption of Small Quantity Burners
A. Response to Comments
B. Basis for Today's Rule
1. Composition of Hazardous Waste Stream
2. Toxicity of Hazardous Constituents
3. Destruction Efficiency
4. Assumptions Regarding Metals and Chlorine in Waste Fuels
C, How the Exemption is Implemented
1. Use of Terrain-Adjusted Effective Stack Height
2. Multiple Stacks
D. Wasics Ineligible for Exemption
E. Exemption of Associated Storage
F. Notification and Recordkeeping Requirements
XI. Exemption of Low Risk Waste from DRE Standard and Particulate Matter Emissions
Standard
A. Exemption from Compliance with the DRE Standard
B. Exemption from Compliance with the Particulate Standard
C. Eligibility Requirements
D. How the Low-Risk Waste Exemption Works
1. Constituents of Concern
2. Estimation of Worst-Case Emissions
3. Dispersion Modeling
4. Acceptable Ambient Levels
5. Constituents with Inadequate Health Effects Data
XH. Storage Standards
A. Permit Standards for Storage
B. Consideration of Requirement for Liquid Waste Fuel Blending Tanks
C. Standards for Direct Transfer Operations
1. General Operating Requirements
2. Inspections and Recordkeeping
3. Equipment Integrity
4. Containment and Detection of Releases
5. Response to Leaks or Spills
6. Design and Installation of New Equipment
7. Closure
Xin. Applicability of the Bevill Exclusion to Combustion Residues When Burning
Hazardous Waste
A. Basis for Applying the Bevill Exclusion to Derived-From Residues
B. Evolution of Interpretations
C. Case-by-Case Determinations
1. Eligible Devices
2. Two-Part Test
D. Recordkeeping
E. Other Considerations
1. Generic Determinations
2. Burning for Destruction
PART FOUR: MISCELLANEOUS PROVISIONS
I. Regulation of Carbon Regeneration Units
A. Basis for Regulating Carbon Regenerating Units as Thermal Treatment Units
B. Definition of Carbon Regeneration Unit and Revised Definition of Incinerator
C. Units in Existence on the Effective Date are Eligible for Interim Status
n. Regulation of Sludge Dryers
A. July 1990 Proposal
-------
B. Summary of Public Comments
HI. Classification of Coke and By-Product Coal Tar
A. AISI Petition
B. Process Description
C. Basis for Approval of the AISI Petition
IV. Regulation of Landfill Gas
V. Definitions of Infrared and Plasma Arc Incinerators
PART FIVE: ADMINISTRATIVE, ECONOMIC, AND ENVIRONMENTAL IMPACTS,
AND LIST OF SUBJECTS
L State Authority
A. Applicability of Rules in Authorized States
B-Effect on State Authorizations
IL Regulatory' Impacts
A. Cost Analysis
1. Background
2. Revised Cost Analysis
B. Regulatory Flexibility Act
C. Paperwork Reduction Act
III. List of Subjects
Appendices
PART ONE: BACKGROUND
I. Legal Authority
These regulations are promulgated under authority of sections 1006,2002,3001
through 3007, 3010, and 7004 of the Solid Waste Disposal Act of 1970, as amended by
the Resource Conservation and Recovery Act of 1976, the Quiet Communities Act of 1978,
the Solid Waste Disposal Act Amendments of 1980, and the Hazardous and Solid Waste
Amendments of 1984, 42 U.S.C. 6905, 6912, 6921 through 6927, 6930, and 6974.
n. Overview of the Final Rule
A. Controls for Emissions of Organic Compounds
Today's rule requires boilers and industrial furnaces to comply with the same
destruction and removal efficiency (DRE) standard currently applicable to hazardous waste
incinerators: 99.9999% DRE for dioxin-listed waste, and 99.99% DRE for all other
hazardous wastes. In addition, the rule controls emissions of products of incomplete
combustion (PICs) by limiting flue gas concentrations of carbon monoxide (CO), and
where applicable, hydrocarbons (HC) to ensure that the device is operated under good
combustion conditions. Finally, emissions testing and health-risk assessment is required
for chlorinated dioxins and furans for facilities meeting specified criteria where the potential
for significant concentrations may exist
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B. Controls for Emissions of Toxic Metals
The rules establish emission limits for 10 toxic metals listed in Appendix Yin of 40
CFR Part 261 based on projected inhalation health risks to a hypothetical maximum
exposed individual (MEI). The standards for the carcinogenic metals (arsenic, beryllium,
cadaoiom, and chromium) limit the increased lifetime cancer risk to the MEI to a maximum
of 1 in 100,000. The risk from the four carcinogens must be summed to ensure that the
combined risk is no greater than 1 in 100,000. The standards for the noncarcinogenic
metals (antimony, barium, lead, mercury, silver, and thallium) are based on Reference
Doses (RfDs) below which adverse health effects have not been observed.
The standards are implemented through a three-tiered approach. Compliance with
any tier is acceptable. The tiers are structured to allow higher emission rates (and feed
rates) as the owner or operator elects to conduct more site-specific testing and analyses
(e.g., emissions testing, dispersion modeling). Thus, the feed rate limits under each of the
tiers are derived based on different levels of site-specific information related to facility
design and surrounding terrain. Under Tier I, the Agency has provided very conservative
waste feed rate limits in "reference" tables as a function of effective stack height and terrain
and land use in the vicinity of the stack and assumed reasonable, worst-case dispersion.
The owner or operator demonstrates compliance by waste analysis, not emissions testing or
dispersion modeling. Consequently, the Tier I feed rate limits are based on an assumed
reasonable, worst-case dispersion scenario, and an assumption that all metals fed to the
device are emitted (i.e., no partitioning to bottom ash or product, and no removal by an air
pollution control system (APCS)).
Under Tier II, the owner or operator conducts emissions testing (but not dispersion
modeling) to get credit for partitioning to bottom ash or product, and APCS removal
efficiency. Thus, the Agency has developed conservative emission rate limits in reference
tables, again as a function of effective stack height and terrain and land use in the vicinity of
the stack. The Agency also assumed reasonable, worst-case dispersion under Tier n.
Under Tier ffl, the owner or operator would conduct emissions testing and site-
specific dispersion modeling to demonstrate that the actual (measured) emissions do not
exceed acceptable levels considering actual (predicted) dispersion.
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The standards are implemented through limits on specified operating parameters,
including hazardous waste feed rate and metals composition, feed rate of metals from all
feed streams, combustion chamber temperature, and APCS-specific parameters.
C. Controls for Emissions of Hydrogen Chloride and Chlorine Gas
The rales control emissions of hydrogen chloride (HC1) and free chlorine (Cl2)
under the same general approach as that used for metals. The owner and operator must
comply with and implement the HC1 and Ci2 controls in the same manner as for metals.
D. Emission Standard for Paniculate Matter
The rules limit paniculate matter (PM) emissions to 0.08 gr/dscf, corrected to 7
percent oxygen (C>2). This is the same standard that currently applies to hazardous waste
incinerators and is intended to supplement the risk-based metals controls. (Metals
emissions are generally controlled by limiting feed rates of metals and controlling PM.)
Compliance with the standard is demonstrated by emissions testing, and the standard is
implemented by operating limits in the permit on parameters including: ash content of feed
streams, feed rate of specific feed streams, and air pollution control system operating
parameters. All boilers and industrial furnaces must comply with the standard; however,
cement and aggregate kilns need not monitor the ash feed rate of all feed streams to
demonstrate compliance with the standard given that paniculate matter from these devices is
generated primarily from raw materials. Instead, the rule provides that these devices must
comply with the operating limits on the paniculate matter control system to ensure
continued operation at levels achieved during the compliance test (under interim status) or
trial burn (under the Pan B permit application).
E. Permitting Procedures
The final rule requires similar permitting procedures for regulated BIFs that apply to
hazardous waste incinerators. For example, owners and operators are required to submit a
Pan B permit application for evaluation in order to be eligible for an operating permit.
Permit applications will be called on a schedule considering the relative hazard to human
health and environment the facility poses compared to other storage, treatment, and
disposal facilities within the Director's purview.
F. Controls During Interim Status
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Today's final role requires boilers and industrial furnaces that have interim status to
comply with substantive emissions controls for metals, HCi, C12, particulates, and CO
(and, where applicable, HC and dioxins and furans). Owners and operators must certify
compliance with the emissions controls under a prescribed schedule, establish limits on
prescribed operating parameters, and operate within those limits throughout interim status.
G. Uwis Exempt from Air Emissions Standards
The rule conditionally exempts from regulation the following devices: (1) boilers
and industrial furnaces that bum small quantities of hazardous waste fuel (i.e., the small
quantity burner exemption) and that operate the device under prescribed conditions; (2)
smelting, melting, and refining furnaces that process hazardous waste solely for the
purpose of metal reclamation and not partially for destruction or energy recovery; and (3)
coke ovens if the only hazardous waste they process is K087.
The small quantity burner exemption — as provided in section 3004(q)(2)(B) — is a
risk-based exemption specifically alluded to in the statute. The exemption is provided only
to hazardous waste fuels generated on-site, and is conditioned on a number of
requirements, including a one-time notification and recordkeeping.
The Agency is also providing a temporary exemption for metal reclamation furnaces
from today's burner standards until we determine how best to apply rules designed for
combustion processes to noncombustion metal reclamation operations. (It should be noted
that section 3004(q) requires EPA to issue rules controlling air emissions from devices
burning hazardous waste for energy recovery by a specified date. Section 3004(q) does
not apply to devices burning hazardous waste for the sole purpose of material recovery.
Although EPA has authority to issue such regulations, the section 3004(q) deadline does
not apply.) To distinguish between wastes that are processed solely for metal reclamation
rather than (partial) destruction, the final rule considers a hazardous waste processed by a
smelting, melting, or refining furnace with a total concentration of Appendix VIE, Part 261
toxic organic constituents exceeding 500 ppm to be burned at least partially for treatment or
destruction. To distinguish between processing for material recovery and burning for
energy recovery, the final rule considers a hazardous waste processed by a metal
reclamation furnace with a hearing value exceeding 5,000 Btu/lb to be burned at least
partially for energy recovery. Metals reclamation furnaces claiming the exemption must
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notify the Agency, sample and analyze their hazardous wastes to document compliance
with the conditions of die exemption, and keep records of such documentation.
Coke ovens are exempt from today's rule if the only hazardous waste they process
is K087 as an ingredient to produce coke. Given that K087 is for practical purposes just
like other materials used to produce coke and comes from the same process as these other
materials, h would be anomalous to assert RCRA control over the coking process.
H. Pollution Prevention Impacts
This rule provides an incentive to reduce the generation of metal and chlorine-
bearing hazardous waste at the source given that the metals and HC1 emissions controls will
be implemented by additional requirements attendant to the disposal of those wastes, i.e.,
feed rate limits for individual metals and total chlorine. These requirements are, in essence,
tied to the economics of disposing of given volumes of waste since feed rates depend, In
part, on the volume of waste the facility operator needs to burn. Thus, the metals and HC1
controls do not simply require a percent reduction in emissions, irrespective of the volume
and rate of incoming waste streams. Rather, the controls are health-based and, thus,
provide limits on emissions rates of metals and HC1 that would be implemented by feed rate
limits.
Waste generators who send their waste to industrial furnaces such as cement kilns
and light-weight aggregate kilns that act as commercial waste management facilities will
have the incentive to reduce the generation of metal and chlorine-bearing wastes because
waste management fees are likely to increase for such waste given that the burner has a
fixed metal and chlorine feed rate allotment (due to prescribed feed rates and facility
operating conditions). Wastes with extremely high metals content may no longer be
acceptable for burning in many cases unless the waste generator reduces the metals content
of the waste. Any alternative for the disposal of such wastes may be unavailable or the
costs of such treatment may be high enough to create the incentive to reduce waste
generation rates at the source. This is a typical scenario for pollution prevention measures
to be undertaken by waste generators.
Similarly, generators who burn their wastes on site also have the incentive to reduce
the generation of metal and chlorine-bearing wastes given that the rule will provide a fixed
feed rate allotment for their boiler or industrial furnace.
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III. Relationship to Other Rules
A. Regulations to be Promulgated Under the New Clean Air Act
Title HI of the recent Clean Air Act Amendments of 1990, amending section 112 of
the Act dealing with hazardous air pollutants, potentially addresses many of the same
sources that would be regulated under today's rule. That section requires the Agency to
develop a list of major and area sources of hazardous air pollutants (a major source is a
stationary source that has the potential to emit up to 10 tons per year of a hazardous air
pollutant, or 25 tons per year of a combination of such pollutants, and area sources are
other stationary sources emitting hazardous air pollutants), and to develop technology-
based controls for such sources over specified time periods. See Clean Air Act, amended
sections 112(c), and (d). Additional controls shall be imposed within eight years after
promulgation of each of these technology-based standards, if such controls are needed to
protect public health with an ample margin of safety, or to prevent adverse environmental
effect. (Cost, energy, and other relevant factors must be considered in determining
whether regulation is appropriate in the case of environmental effects.) In addition, if the
technology-based standards for carcinogens do not reduce the lifetime excess cancer risk
for the most exposed individual to less than one a million (10-6), then EPA must
promulgate health-based standards. See amended section 112(f)(2)(A).
It is premature for the Agency to attempt to provide a definitive opinion on the
relationship of these provisions to today's rule. Sources covered by the present rule may
not ultimately be required to be further regulated under amended section 112. In this
regard, amended section 112(n)(7) provides that if sources' air emissions are regulated
under subtitle C, "the Administrator shall take into account any regulations of such
emissions ... and shall , to the maximum extent practicable and consistent with the
provisions of this section, ensure that the requirements of such subtitle and this section are
consistent" Thus, at a minimum, Congress was concerned about the potential for
duplicative regulation and urged the Agency to guard against it. Since the Agency regards
today's rules as protective (based on present knowledge), it may be possible to avoid
further air emissions regulation. (EPA notes, however, that these sources will likely be
listed as major sources, and the Agency will study whether further emissions controls are
required in the course of implementing amended section 112.)
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B. April 27,1990 Proposed Incinerator Amendments
On April 27, 1990 (55 FR 17862), EPA proposed amendments to the existing
hazardous waste incinerator standards of Subpart O, Part 264 to make the incinerator
standards conform to the emissions standards being promulgated today for boilers and
industrial furnaces burning hazardous waste. The proposed rule would add emission
standards for products of incomplete combustion (i.e., carbon monoxide and hydrocarbon
limits), metals, and hydrogen chloride and chlorine gas.
In the proposed rule for incinerators, EPA also proposed to revise or to add
definitions for a number of thermal treatment devices: industrial furnace, incinerator,
plasma arc and infrared incinerators. Those definitions are being promulgated in today's
rule. In addition, EPA proposed in the incinerator rulemaking to clarify the regulatory
status of carbon regeneration units and fluidized bed incinerators. Those clarifications are
also promulgated in today's final rule.
Finally, EPA proposed to revise the definition of principal organic hazardous
constituents (POHCs) used to demonstrate destruction and removal efficiency (DRE). The
revised definition would allow the Director on a case-by-case basis to approve as POHCs
compounds that are neither constituents in the hazardous waste nor organic. That revised
definition of POHC is finalized in today's rule as a part of the DRE standard to control
organic emissions from boilers and industrial furnaces.
C. My 28,1990 Proposed Amendment to Definition of Wastewater Treatment Unit to
Exempt Sludge Dryers
On July 28,1990 (see 55 FR 29280), EPA proposed to clarify the regulatory status
of sludge dryers to make it clear that sludge dryers that meet the definition of a tank and that
were a part of a wastewater treatment unit were exempt from RCRA regulation even if they
heretofore met the definition of an incinerator. Today's final rule promulgates a definition
of sludge dryer and revises the definition of incinerator to explicitly exclude sludge dryers.
See Part Four, section n of today's preamble.
D. Land Disposal Restriction Standards
In the May 6, 1987 proposal, the Agency indicated that once the present rules
became final, the Agency would amend certain of the land disposal restriction standards
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that specified incineration as a treatment standard (at that time, the standard for HOCs under
the California list rule), to also include burning in boilers and industrial furnaces. See 52
FR at 17021. Since that time, the issue has become more involved. In particular,
significant issues regarding the relationship of the Bevill amendment and land disposal
restrictions exist (which the Agency in fact referenced in the rulemaking record to the
California list rule when considering this issue). The Agency believes it inappropriate to
try and resolve these issues in this proceeding, given the tim. onstraints created by the
District Court's order and the fact that this rulemaking does not deal principally with issues
relating to the land disposal restrictions program. The Agency consequently plans to
address these questions in a later proceeding and not to finalize the May 1987 proposal at
this time.
PART TWO: DEVICES SUBJECT TO REGULATION
I. Boilers
EPA defines a boiler in §260.10 as an enclosed device using controlled flame
combustion and having the following characteristics: (1) the combustion chamber and
primary energy recovery section must be of integral design; (2) thermal recovery efficiency
must be at least 60 percent; and (3) at least 75 percent of the recovered energy must be
"exported" (i.e., not used for internal uses such as preheating of combustion air or fuel, or
driving combustion air fans or feed water pumps).
Today's final rule applies to all boilers burning hazardous waste for any purpose ~
energy recovery or destruction. (We note, however, that an existing boiler may not burn
hazardous waste for destruction (i.e., waste that is not a fuel) before certifying compliance
with the interim status emissions standards.) ,
Nonindustrial boilers are currently prohibited from burning hazardous waste unless
they are operated in conformance with the incinerator standards of Subpart O of Parts 264
or 265. On the effective date of today's rule, however, nonindustrial boilers burning
hazardous waste will be subject to these boiler and industrial furnace rules. We note that
nonindustrial boilers generally cannot bum hazardous waste until they receive an operating
permit under today's rule (unless they are already operating under the incinerator
standards). This is because the prohibition is not rescinded until the effective date of the
rule, and a facility would have to be "in existence" with respect to hazardous waste burning
on that date to be eligible for interim status.
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EPA believes that approximately 925 boilers burn hazardous waste fuels.
Approximately 600 of these boilers bum very small quantities of hazardous waste and will
be conditionally exempt under the small quantity burner provision of today's rule. See
§266.109. (We note that these boilers burn less than one percent of the total hazardous
waste currently being burned in boilers and industrial furnaces.) EPA also believes that
approximately 200 boilers will stop burning hazardous waste because they burn quantities
exceeding the small quantity burner tAer.iption but do not burn enough waste to justify the
cost of complying with today's rule. Thus, approximately 125 boilers will continue to
burn hazardous waste and will be subject to the interim status and permit standards
provided by §§266.102 and 266.103 of today's rule.
II. Industrial Furnaces
Under today's revised definition, EPA defines an industrial furnace in §260.10 as
those designated devices that are an integral component of a manufacturing process and that
use thermal treatment to recover materials or energy. With the addition of halogen acid
furnaces by today's rule, the Agency has designated 12 devices as industrial furnaces:
cement kilns; lime kilns; aggregate kilns (including light-weight aggregate kilns and
aggregate drying kilns used in the asphaltic concrete industry); phosphate kilns; coke
ovens; blast furnaces; smelting, melting, and refining furnaces; titanium dioxide chloride
process oxidation reactors; methane reforming furnaces; pulping liquor recovery furnaces;
and combustion devices used in the recovery of sulfur values from spent sulfuric acid. The
definition also includes criteria and procedures for designating additional devices as
industrial furnaces.
Any industrial furnace burning or processing any hazardous waste for any purpose
~ energy recovery, material recovery, or destruction — is subject to today's rule, with
certain exceptions. Furnaces (like boilers) burning small quantities of hazardous waste fuel
are exempt from regulation under §266.108, coke ovens are exempt from regulation if the
only hazardous waste they burn is Hazardous Waste No. K087, and regulation of smelters
processing hazardous waste solely for material recovery is deferred (see discussion in
section IIJD).
The Agency believes that approximately 75 industrial furnaces burn over one
million tons of hazardous waste annually. The regulated universe appears to comprise
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approximately 40 cement kilns, 18 light-weight aggregate kilns, and 15 halogen acid
furnaces. Each of these types of furnaces is described below.
A. Cement Kilns
Cement kilns are horizontal inclined rotating cylinders, refractory lined and
internally fired, to calcine a blend of 80% limestone and 20% shale to produce Portland
ceir.enL There is a wet process and a dry process for producing cement. In the wet
process, the limestone and shale are ground wet and fed into the kiln in a slurry. In the dry
process, raw materials are ground dry. Wet process kilns are longer than dry process kilns
in order to facilitate water evaporation from the wet raw material. Wet kilns can be more
than 450 feet in length. Dry kilns are more thermally efficient and frequently use preheaters
or precalciners to begin the calcining process before the raw material is fed into the kiln.
Combustion gases and raw materials move counterflow in kilns. The kiln is
inclined, and raw materials are fed into the upper end while fuels are normally fed into the
lower end. Combustion gases thus move up the kiln counter to the flow of raw materials.
The raw materials get progressively hotter as they travel the length of the kiln. The raw
materials eventually begin to soften and fuse at temperatures between 2,250 and 2,700°F to
form the clinker product. Clinker is then cooled, ground, and mixed with other materials
such as gypsum to form Portland cement
Combustion gases leaving the kiln typically contain from 6 to 30% of the feed
solids as dust. Paniculate emissions are typically controlled with electrostatic precipitators
or fabric filters (baghouses), and are often recycled to the kiln feed system.
Dry kilns with a preheater or precalciner often use a by-pass duct to remove from 5
to 30% of the kiln off-gases from the main duct. The by-pass gas is passed through a
separate air pollution control system to remove particulate matter. By-pass dust is not
reintroduced into the kiln system to avoid a build-up of metal salts that can affect product
quality.
Some cement kilns burn hazardous waste fuels to replace from 25 to 75% of normal
fossil fuels. Most kilns burn liquid waste fuels but several burn small (e.g., six gallon)
containers of viscous or solid hazardous waste fuels. Containers have been fired into the
upper, raw material end of the kiln and at the midpoint of the kiln.
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Several cement companies have also expressed an interest in using solid hazardous
waste sach as contaminated soils as an ingredient to produce cement. Cement kilns that
bum hazardous waste as an ingredient are regulated by today's rule.1 Under today's rule,
a facility may burn (or process) hazardous waste solely as a bona fide ingredient during
interim status beginning with the effective date of the rule. If a waste is burned partially for
detraction or energy recovery, however, it is not burned solely as an ingredient and
special restrictions apply during interim status (see discussion below). EPA considers a
wane to be burned at least partially for destruction if it contains a total of 500 ppm or more
by weight of nonmetal hazardous constituents listed in Appendix Vffl, Pan 261. Further,
EPA considers a waste to be burned at least partially for energy recovery if it has a heating
value of 5,000 Btu/lb or more.
Today's rule does not allow burning of a waste for the purpose of destruction
during interim status prior to certification of compliance (see §266.103(c)) with all
applicable emission standards. Further, the rule applies special requirements during interim
status on owners/operators who feed hazardous waste into a kiln system at any location
other than the "hot" end where product is discharged. Hazardous waste burned
(processed) solely as an ingredient, however, is not subject to the special requirements
because emissions from such burning would not pose an adverse effect on human health
and the environment.2
B. Ugfa-Weight Aggregate Kilns
Light-weight aggregate (LWA) describes a special use aggregate with a specific
gravity much less than sand and gravel which is used to produce insulation and
nonstructural and light-weight concrete. LWA is produced much like cement, but the
feedstocks are special clays, pumice, scoria, shale, or slate.
The LWA kiln is configured much like a cement kiln. The raw material is crushed
and introduced at the upper end of a rotary kiln. In passing through the kiln, the materials
reach temperatures of 1,900 to 2,100°F. Heat is provided by a burner at the lower end of
the kiln where clinker is discharged.
1 See discussion in section VH.H of Part Three of the text
2 This is because nonmetal toxic constituents will not be present in the waste at
significant levels (i.e., less than 500 ppm) and metal emissions will be adequately
controlled under today's rule by the air pollution control system irrespective of where the
waste is fed into the loin system.
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LWA kilns are also major sources of paniculate emissions and are equipped with
wet scrubbers, fabric filters, or electrostatic precipitators. Wet scrubbers dominated the
industry until recently. Many facilities are now converting to dry systems to reduce the
cost of residue management by recycling the collected dust into the kiln.
LWA kilns that burn hazardous waste fuel typically burn 100% liquid hazardous
waste fuels.
C. Halogen Acid Furnaces
The Dow Chemical Company (DOW) filed a rulemaking petition with EPA on
March 31, 1986, in accordance with the provisions of 40 CFR 260.20, requesting that
EPA designate their halogen acid furnaces (HAFs) as industrial furnaces. HAFs are
typically modified firetube boilers that process secondary waste streams containing 20 to 70
percent chlorine or bromine to produce a halogen acid product by scrubbing acid from the
combustion gases. Currently HAFs that produce steam meet the definition of a boiler while
HAFs that do not generate steam meet the definition of an incinerator even though they use
hazardous waste as a fuel and as an ingredient to produce halogen acid product. Today's
rule designates HAFs that do not generate steam as an industrial furnace for the reasons
given below.
DOW petitioned the Agency to designate their HAFs as industrial furnaces after the
Agency changed the definition of incinerator in 1985 from a "purpose of burning test" to a
"design test" and developed new classifications for boilers and industrial furnaces. The
Agency inadvertently did not designate HAFs as industrial furnaces at that time which
potentially left certain HAFs operating not in compliance with the incinerator standards
promulgated in 1981. Although HAFs (prior to today's rule) technically meet the definition
of incinerator, the Agency has indicated its intention since receiving the DOW petition to
correct the problem and to properly designate HAFs as industrial furnaces.
On May 6, 1987 (52 FR 17033), EPA proposed to grant this petition and to add
halogen acid furnaces (HAFs) to the list of devices that are designated as industrial furnaces
under 40 CFR 260.10. On April 27,1990 (55 FR 17917), the Agency proposed changes
to the proposed designation of HAFs as industrial furnaces. With modifications based on
additional information and comments, today's rule adds HAFs to the list of devices that are
included in the definition of an industrial furnace under 260.10.
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fa today'* rule, EPA is defining an "industrial furnace" in 260.10 as an enclosed
device that uses thermal treatment to recover (or produce) materials or energy as an integral
component of a manufacturing process.3 EPA has previously designated 11 devices as
industrial furnaces: (1) cement kilns; (2) lime kilns; (3) aggregate kilns (including light-
weight aggregate kilns and aggregate drying kilns used in the asphaltic concrete industry);
(4)pix>s$£ia&MliH;(5)cokecvens; (6) blast furnaces; (7) smelting, melting, and refining
furnaces; (€) titanium dioxide chloride process oxidation reactors; (9) methane reforming
furnaces; (10) pulping liquor recovery furnaces; and (11) combustion devices used to
recover sulfur values from spent sulfuric acid.
The industrial furnace definition in 260.10 also provides criteria and procedures for
adding devices to the list. A device may be defined as an industrial furnace if it meets one
or more of the following criteria: (1) the device is designed and used primarily to recover
material products; (2) the device is used to burn or reduce raw materials to make material
products; (3) the device is used to burn or reduce secondary materials as effective
substitutes for raw materials in processes that use raw materials as principal feedstocks; or
(4) the device is used to burn or reduce secondary materials as ingredients in industrial
processes to manufacture material products.
As explained below, the basis for designating HAFs as industrial furnaces under
260.10 is that HAFs are integral components of a manufacturing process, they recover
materials and energy, and they meet two of the criteria (1 and 4) described above for
classifying a device as an industrial furnace.
1. Current Practices. Information available to EPA indicates that at least 3
companies in the United States operate at least 30 devices that may be halogen acid
furnaces. These devices typically process chlorinated or brominated secondary materials
with 20 to 70 percent halogen content (by weight) to produce an acid product, either
hydrogen chloride (HC1) or hydrogen bromide (HBr), both of which have a halogen
content that ranges from 3 to greater than 25 percent (by weight). These secondary
3 This definition of industrial furnace is the revised definition as noticed on April 27,
1990 (55 FR 17869). The previous definition read "an enclosed device using controlled
flame combustion to recover materials or energy as an integral component of a
manufacturing process." Public comments on the proposal are discussed in the Comment
Response Document for the BIF Regulations. EPA revised the definition to include
nonflame devices (i.e., by referring to thermal treatment) because controlled-flame devices
and nonflame devices can have the same emissions and pose the same hazard to human
health and the environment
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materials typically have as-fired heating values of approximately 9,000 Btu/lb and are
typically produced on site.
Some of the HAFs currently in use are modified firetube boilers that generate and
export steam. These HAFs meet the definition of a boiler under §260.10, and, thus, will be
regulated as boilers. The remaining HAFs, although modified firetube boilers, do not
generate steam and thus do not meet EPA's definition of a boiler. Today's rule classifies
these nonboiler HAFs as industrial furnaces. For the remainder of this discussion, the term
"HAF" refers to these nonboiler HAFs.
2. Designation of HAFs as Industrial Furnaces.
a. Dow's Petition. On March 31,1986, the Dow Chemical Company (DOW) filed
a rulemaking petition with EPA in accordance with the provisions of 40 CFR 260.20,
requesting that HAFs at Dow Chemical be designated as industrial furnaces. EPA
proposed to grant this petition in the May 6,1987 proposal. Today's rule includes HAFs
in the definition of an industrial furnace under §260.10. Further background discussion on
DOW's petition is contained in the May 6,1987 proposed rule.
b. May 1987 and April 1990 Proposed Rules. EPA proposed to designate HAFs
as industrial furnaces for the reasons discussed in the May 6, 1987 proposed rule. To
ensure that a particular device was an industrial furnace involved in bona fide production of
acid4 as an integral component of a manufacturing process, and was not an incinerator
equipped with halogen emissions removal devices, the 1987 proposed HAF definition
required that: (1) the furnace be located on site at a chemical production facility; (2) the
waste fed to the device be halogenated; and (3) the acid product from the device contain at
least 6 percent halogen acid.
Based on comments received on the 1987 proposal and on further consideration by
the Agency, EPA proposed revisions to the HAF definition in the April 1990 notice. These
revisions were proposed for two reasons: (1) to better clarify the differences between
4 The Agency's concern is that devices capturing some HC1 in scrubber effluent not
automatically be classified as HAFs if they find a way to utilize the scrubber effluent The
HC1 content of the effluent from wet scrubbers used to control HC1 emissions from the
incineration of chlorine-bearing waste is normally on the order of 1 percent or less. EPA
does not consider such low HC1 content scrubber water a bona fide product for purposes of
designation as an industrial furnace even if the scrubber water is beneficially used in a
manner that specifically relates to its HC1 content.
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HAFs and incinerators equipped with wet scrubbers to control halogen acid emissions, and
(2) to better reflect industry practice.
To ensure that a particular device is an integral component of a chemical
manufacturing process, the April 1990 proposal included requirements that at least 50
percent of the acid product be used on site and that any off-site waste fed to the HAF be
generated by a SIC 2S1 (inorganic chemicals) or SIC 286 (organic tf f micals) process. To
ensure mat the waste is burned as a bona fide ingredient to produce the halogen acid
product, die April 1990 proposal also required liiai each waste fed to the HAF have an "as-
generated" halogen content of at least 20 percent In addition, to better reflect industry
practice, the 1990 proposal required that the acid product have a halogen acid content of 3
percent rather than 6 percent, an amount that still clearly distinguished the HAF acid
product from incinerator scrubber water, which has an acid content of well below 1
percent. Finally, EPA proposed in April 1990 to list hazardous waste fed to a HAF as
inherently waste-like to ensure that halogenated waste fed to a HAF (and the HAF itself)
would be subject to regulation. This would preclude a claim that the secondary materials
were used as ingredients to make a product, and, thus, not a solid waste under
c. Summary of Public Comments. Commenters on the 1987 and 1990 proposed
rules objected to the requirements that 50 percent of the acid product be used on site and
that any off-site waste feed be limited to SIC 281 or 286 processes. The commenters
argued that minimum specifications on the halogen content of the feed and/or the acid
content of the HAF product are sufficient to distinguish bona fide HAF operations from
incinerator operations, and that the requirement that a substantial portion of the product be
used on site serves only to limit the legitimate treatment of halogenated wastes and the sale
of bona fide. HAF products without being necessary to protect human health and the
environment
After consideration of these commenters' concerns, the Agency believes that both
the proposed off-site restriction for waste fed to HAFs and the proposed on-site acid
product use restriction are indeed unnecessary to ensure that HAFs are integral components
of manufacturing processes. The Agency agrees with the commenters that the requirements
specifying the minimum halogen content of the waste feed and the minimum halogen acid
concentration of the HAF product are sufficient to ensure that HAFs are integral
components of a manufacturing process (i.e., the process of halogen acid production).
EPA is not adopting these proposed conditions given that air emissions from HAFs will be
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regulated under today's rule, that these proposed conditions were directed at how to
classify these devices rather than how to ensure their safe operation, and that HAF
operations (as properly controlled) are environmentally advantageous in that they utilize
acid values rather than dispose them and therefore should not needlessly be discouraged.
Today's rule, therefore, does not restrict the use of HAF waste feeds generated off site or
require that any percentage of the acid product be used on site.
In today's rule, the Agency considers a bj?ra f&L HAF operation as one in which a
secondary material with a minimum as-generaied halogen content of 20 percent by weight
is processed into an acid product with a minimum halogen content of 3 percent by weight.
The acid product must be used in a manufacturing process either on site or off site. The
Agency maintains that this approach will allow the legitimate processing of highly
halogenated secondary materials into usable products but will still clearly distinguish HAF
product acid from incinerator halogen acid scrubber water.
Upon review of other comments submitted on the 1987 and 1990 proposed rules,
the Agency has identified several issues pertaining to HAFs that require clarification in the
regulations. Specifically, these issues concern: (1) the regulation of chlorine emissions
from HAFs, (2) the operation of HAFs under the special operating requirements (SOR)
exemption for boilers, and (3) the designation of hazardous waste fed to HAFs as
inherently waste-like material.
One commenter to the 1987 proposed rule requested that the Agency clarify its
position on limiting inorganic halide salts in feedstocks to boilers and industrial furnaces.
The Agency has established limits on emissions of HC1 and C\2 from industrial furnaces,
and a HAF operator, like any other industrial furnace operator, must comply with these
HC1 and Cl2 emission standards. To demonstrate compliance under the Tier I feed rate
screening limits, a HAF operator must include inorganic chlorine as part of the total
chlorine fed to the device. The Agency believes that this requirement is justified because
recent testing indicates that even thermally stable compounds such as NaCl are converted
with high efficiency to HC1 under laboratory conditions that simulate incineration.5
Another commenter to the 1987 proposal stated that HAFs are unjustly excluded
from the automatic waiver of a trial burn to demonstrate 99.99% destruction and removal
efficiency (DRE) when operated under the special operating requirements (SORs). The
5 U.S. EPA, Laboratory Method to Estimate Hydrogen Chloride Emission Potential
Before Incineration of a Waste. February 1990.
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Agency acknowledges the commenter's concern, but notes that all industrial furnaces,
including HAFs, arc ineligible for the automatic DRE trial burn waiver. The Agency stated
in the preamble to the 1987 proposal that modified boilers that produce and export steam
(and thus meet EPA's definition of boiler in 260.10) would be regulated as boilers. In
such a case, the unit may be eligible for the automatic waiver of the DRE trial burn, which
applies only to boilers. Any halogen acid furnace that is a modified fire-tube boiler not
meeting the definition of a boiler in 260.10, however, would not be eligible for the
automatic waiver. The Agency's reasons for applying the automatic DRE trial burn waiver
only to boilers are discussed further in Section II.C.2.d of this preamble.
Several commenters expressed concern that the April 27,1990 proposal required a
minimum heating value of 5,000 Btu/lb for secondary materials fed to HAFs. Today's
final rule does not require a minimum heating value on secondary materials fed to HAFs.
Although the Agency understands that most wastes burned in HAFs have a heating value
greater than 5,000 Btu/lb and, so, the HAFs are engaged in energy recovery as well as
materials recovery, not all wastes meeting the minimum halogen limit also have a heating
value normally associated with energy recovery. The Agency believes that HAFs need not
be required to recover both material and energy values from every hazardous waste fed to
the device to meet the definition of an industrial furnace, and that the regulations adopted
today for HAFs ensure that they will be operated in a protective manner even if energy
values are not recovered.
Commenters1 misconceptions regarding a minimum heating value for secondary
materials may have arisen from the Agency's proposal pursuant to §261.2(d)(2) to list
hazardous waste fed to HAFs as inherently waste-like material. In today's rule, the
Agency is listing as inherently waste-like any secondary material fed to HAFs that is
identified or listed as a hazardous waste under 40 CFR Part 261, Subparts C and D.
Without such materials being designated as inherently waste-like, HAFs burning hazardous
wastes solely as ingredients (i.e., wastes that have low heating value and therefore, are not
burned partially for energy recovery) to produce an acid product might not be regulated
because the material they are burning might not be a solid waste pursuant to
§261.2(e)(l)(i). However, HAFs that burn hazardous wastes with high heating values
(i.e., greater than 5,000 Btu/lb), would be subject to today's rule even without listing them
as inherently waste-like because these wastes are considered under §261.2(e)(2)(ii) to be
burned at least partially for energy recovery. For reasons discussed in the April 27,1990
proposed rule (55 FR 17892), the Agency believes that such an inconsistent result would
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not provide adequate protection of human health and the environment (the wastes burned
by HAFs are some of the most toxic generated and regulation of emissions from burning
these wastes certainly is needed to protect human health and the environment). Moreover,
there are significant elements of treatment associated with burning in HAFs: toxic organic
compounds are destroyed rather than recovered, and the burning if conducted improperly
could become part of the waste disposal problem. Because the materials burned in HAFs
meet the criteria of §261.2(d) for inherently waste-like materials, EPA today is adding to
the list of inherently waste-like materials under §261.2(d)(2) secondary materials fed to
HAFs that are listed or identified as hazardous waste under Subparts C or D of Part 261.
While HAFs will not be precluded from burning secondary materials with low heating
values, today's listing will prevent the HAFs that burn this material and the material itself
from being unregulated. As a result, in all cases, hazardous waste fed to HAFs, and the
HAFs themselves, will be subject to hazardous waste regulations under today's final rule.
d. Basis for Designating HAFs as Industrial Furnaces. EPA has defined an
industrial furnace in §260.10 as any of the specifically-designated enclosed devices that are
integral components of a manufacturing process and that use thermal treatment to
accomplish recovery of materials or energy. To date, 11 types of devices have been
designated as industrial furnaces. The industrial furnace definition also provides criteria for
adding devices to the list. As discussed above, these criteria include: (1) the design and
use of the device primarily to accomplish recovery of material products; (2) the use of the
device to burn or reduce raw materials to make a material product; (3) the use of the device
to burn or reduce secondary materials as effective substitutes for raw materials in processes
using raw materials as principal feedstocks; and (4) the use of the device to burn or reduce
secondary materials as ingredients in an industrial process to make a material product. As
explained below, HAFs meet the definition of an industrial furnace as well as two of the
above criteria, (1) and (4), for designating additional devices as industrial furnaces.
HAFs are Integral Components of a Manufacturing Process. HAFs are commonly
located on-site at large scale chemical manufacturing processes that reclaim primarily
secondary materials generated on-site and that typically use the halogen acid product on-
site. In these cases, the Agency believes the device should clearly be considered an integral
component of the manufacturing process and, thus, eligible for designation as an industrial
furnace. The situation is less clear when the device receives halogen-bearing secondary
materials from off-site or if the halogen acid product is sent off-site. In these situations, the
Agency believes, nonetheless, that the device should be considered an integral component
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of a manufacturing process and, thus, eligible for consideration as an industrial furnace
provided that the device is located on the site of a manufacturing process and that the
halogen acid product is used by a manufacturing process.
HAFs Recover Materials and Energy. EPA believes that HAFs recover materials
and energy to produce a bona fide product Production of halogen acid (a 3 to 20 percent
halogen acid solution) from the combustion of chlorine-bearing secondary materials
constitutes materials recovery in the context of the designation of HAFs as industrial
furnaces, HAFs can also be considered to burn secondary materials as ingredients in an
industrial process to make a material product (i.e., the product halogen acid). As discussed
above, chlorine-bearing secondary materials are burned to produce the halogen acid product
for use in a manufacturing operation.
HAFs also recover energy. Most halogen-bearing secondary materials reclaimed in
HAFs are burned partially for energy recovery because substantial, usable heat energy is
released by the materials during combustion. The materials typically have an as-fired
heating value of approximately 9,000 Btu/lb, and the heat released results in the thermal
degradation of chlorinated organic compounds to form HC1. Although under definitions in
260.10, energy recovery in a boiler is characterized by the recovery and export of energy,
energy recovery in an industrial furnace need not involve any export of energy. Rather,
energy recovery in an industrial furnace is based on the burning of materials with
substantial heating values (greater than 5,000 Btu/lb) in a manner that results in the release
of substantial usable heat energy. See 50 FR 49171-49174 (November 29,1985).6
HAFs Meet Industrial Furnace Criteria. The Agency believes that HAFs meet two
of the above criteria (i.e., criteria (1) and (4)) for designating devices as industrial furnaces.
EPA believes that restrictions on the halogen content of waste streams fed to HAFs and on
the halogen content of the acid product ensure that the HAF is: (a) designed primarily to
recover halogen acid (and so is not engaged in incineration); and (b) used to bum
secondary materials as ingredients in the process of halogen acid production to produce a
material product (i.e., the product halogen acid).
Addition of HAFs to List of Industrial Furnaces. EPA believes that HAFs are
integral components of a manufacturing process and that they are designed and operated to
6 We note as discussed previously in the text that, although all hazardous wastes fed
to a HAF must have an as-generated halogen content of at least 20%, all such wastes need
not have a heating value of 5,000 Btu/lb.
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recover materials and energy. For these reasons EPA is today adding to the list of devices
designated as industrial furnaces under §260.10 HAFs defined as furnaces that: (1) are
located at the site of a manufacturing process; and (2) process hazardous wastes with a
minimum as-generated halogen content of 20 percent by weight to produce an acid product
with a minimum halogen content of 3 percent by weight and where the acid product is used
in a manufacturing process.
e. Interim Status for HAFs. HAFs that are in existence on the effective date of
today's rule are eligible for interim status like other boilers and industrial furnaces burning
for energy or material recovery. Although certain HAFs may technically have met the
amended definition of incinerator, EPA believes that there was legitimate confusion as to
such units' operating status. These devices would not have been incinerators under the
original 1980 definition of incinerator because their primary purpose was not destruction of
waste. When EPA amended that definition in 1985 to adopt a definition based on the unit's
design rather than its operating purpose, the Agency did not intend to regulate HAFs as
incinerators and noted that the regulatory change was not intended to (or expected to) affect
the number and identity of regulated incinerator units. See 50 FR 625 (Jan. 4, 1985).
Moreover, given that many HAFs met the definition of boiler, it would have been
anomalous and unintended for some HAFs to be subject to full regulation and others to be
unregulated (until the present rules were adopted). Given these circumstances, the Agency
is finding pursuant to §270.10(e)(2) that there was substantial confusion as to which HAF
owners and operators were required to submit a Part A application and that this confusion
is attributable to ambiguities in the subtitle C rules. Accordingly, such owners and
operators may submit Part A applications by the effective date of today's regulation.
We note that this policy on interim status eligibility date does not apply to other
devices that are currently subject to regulation as an incinerator but claim to be an industrial
furnace subject to the BIF rule and its interim status eligibility date. An example is an
aggregate kiln that currently burns hazardous waste for the purpose of treatment
(destruction) and, so, is subject to the incinerator standards of Subpart O, Parts 264 and
265. There is no ambiguity about the regulatory status of such a device given that the
Agency clearly intended for such burning to be subject to the incinerator standards, and the
Agency's rules have always so stated. Thus, the date for interim status eligibility for such
facilities is the 1981 date for incinerator interim status.
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D. SmeMng, Meliiag, and Refining Furnaces Burning Hazardous Waste to Recover
Metals
In the October 1989 supplement to the proposed rule, EPA solicited further
comment on an. appropriate regulatory regime for smelting furnaces burning hazardous
wasie far she exclusive purpose of material recovery. See 54 FR 43733. This issue was
closely connected witfc she qu .-stion of jurisdictional limitations on the Agency's authority
to regulate industrial furnaces burning secondary materials for material recovery, discussed
under the rubric of indigenous wastes. Id- at 43731-32. The Agency noted generally that
where it did not perceive jurisdictional limitations on its authority, it regarded regulation of
organic emissions from smelting furnaces as unnecessary given the normal absence of
organics in the material feed to the unit. We also indicated concern at the prospect of
regulating emissions of metals that were not attributable to the processing of hazardous
waste, and accordingly solicited comment as to a means of determining when burning of
hazardous waste resulted in emissions in excess of those from processing other materials in
the device. M- at 43733. With respect to a test for determining when wastes are
indigenous, the Agency reproposed a fairly broad test that would have had the effect of
excluding many wastes and devices from the Agency's jurisdiction, but would have
distinguished between wastes being burned for the purpose of conventional treatment, and
for the purpose of material recovery treatment
These proposals proved extremely controversial. Perhaps more importantly, after
the proposal was issued, the question of indigenous waste was the partial subject of the
District of Columbia Circuit Court of Appeals' decision API v. EPA. 906 F. 2d 726 (D.C.
Cir. 1990). In that decision, the court stated that the Agency had been overly restrictive in
interpreting the jurisdictional limitations imposed by the statutory definition of solid waste
based upon the court's earlier opinion in American Mining Congress v. EPA. 824 F. 2d
1177 (D.C. Cir. 1987). That earlier opinion, the court held, is limited to situations
involving continuous recycling processes that are not part of the waste disposal problem,
and certainly does not mandate the type of indigenous principle that the Agency discussed
in the 1989 notice. 906 F. 2d at 740-41. The court accordingly remanded and directed the
Agency to rethink whether any type of indigenous principle is warranted given the court's
clarification of its earlier opinion.7 Ii at 741.
7 Technically, the court remanded the Agency's decision not to formally adopt a
treatment standard under the land disposal restrictions program for the residue from
processing a waste the Agency had indicated would be indigenous to a particular type of
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The court's opinion, as well as the many comments on this !: sue, raise complex
issues that EPA has not yet resolved (In this regard, the Agency notes that the mandate in
section 3004(q) to regulate facilities burning hazardous waste for energy recovery as may
be necessary to protect human health and the environment does not apply to devices
burning for the purpose of material recovery, H. Rep. No. 198, 98th cong. 1st Sess. 40,
and so the court-ordered December 31.199C issuance fate does net apply.) In particular,
the Agency is presently studying the question of jurisdiction as part of a comprehensive
effort to determine if the Agency's rules on recycling should be amended (either as a
regulatory matter or as part of RCRA reauthorization). In the interim, however, the
Agency does not believe it prudent to apply regulations to a whole potential class of devices
and wastes that the Agency has not fully evaluated (since these situations would have been
excluded from regulation under the proposal). See provision for conditional deferral of
smelting, melting, and refining furnaces under §266.100(c). In addition, because EPA has
placed most of its efforts into issuing the mandated portion of these regulations as soon as
possible, the Agency has not resolved the questions of how to regulate raised in the 1989
notice even for the class of smelting furnaces where authority would have existed under the
proposed view of indigenous waste. The issue of whether material recovery is a form of
"treatment" is also presently submitted for decision to a panel of the D.C. Circuit in Shell
Oil v. EPA (No. 80-1532), and the Agency believes it prudent to await the Court's ruling.
Another reason for deferring regulation of these devices is that the Agency wishes
to study further whether regulation under the Clean Air Act may be more appropriate than
RCRA regulation. Smelting, melting, and refining furnaces have been traditional subjects
of Clean Air Act regulation, and with the advent of amended section 112 of the Clean Air
Act amendments of 1990, technology-based controls on toxic air emissions are likely to
apply to these devices. Given that in many instances the principal risks potentially posed
by air emissions from these devices would come from the nonhazardous waste portion of
feed (see 54 FR at 43733), and that Clean Air Act regulation may result in control of
individual toxics, the Agency believes that further study of the most appropriate means of
regulation is warranted. (The Agency specifically requests information on other devices
that may burn hazardous waste solely for metal recovery. EPA will use such information
metal recovery furnace. Id» at 740. EPA has since indicated, in motions filed with the
Court, that it views the interim treatment standard based on stabilization as applying in all
cases where the residue remains a hazardous waste.
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to consider whether the deferral for smelting, melting, and refining furnaces should be
broadened provided that the principles stated here apply to the other devices as well)
At the same time, EPA is concerned that this deferral not become a license for sham
recycling activities, or for operations motivated by conventional treatment objectives rather
than recovery purposes. Accordingly, the Agency has crafted this deferral narrowly.
First, only smelting, melting, and refining furnaces (as used in the §260.10 definition of
"industrial furnace") burning hazardous waste solely to recover metals would be eligible for
this deferral. In the unlikely event that one of these devices would be used to recover
organics or nonmetal inorganics, EPA believes that substantial amounts of organics would
be destroyed showing that the purpose of the activity was either conventional treatment or
energy recovery. (The Agency notes specifically that it intends to include as a smelting,
melting, or recovery furnace the types of high temperature metal recovery devices used as
the basis for the land disposal prohibition treatment standard for waste KO61, and other
similar devices.)
Second, sham recovery operations would be viewed as conventional treatment
operations and would require a permit to control emissions. Although it is difficult to
quantify when operations are sham, two fundamental notions are that any waste involved
must contain economically viable amounts of metals to recover (the best objective measure
would be the same or greater levels of metal as in normal nonhazardous feed stocks), and
that the person recovering the metal be in the business of producing metals for public sale
(whether to an ultimate user or for further processing or manufacture). See also 53 FR at
522 (Jan. 8, 1988). The limitations on Btu level and levels on toxic organics discussed
below are further efforts to ensure that only bona fide metal recovery activities be deferred
from emissions regulation at this time.
Third, today's regulations are deferred only when these devices burn (process)
hazardous waste exclusively for metal recovery and not partially for destruction or energy
recovery as well. To implement this policy, today's rule provides that a waste with a
heating value of 5,000 Btu/lb or more (either as-generated or as-fired) is burned (at least
partially) as a fuel. The heating value limit is based on the Agency's long standing sham
recycling policy (48 FR 11157 (March 16,1983)) that wastes with a heating value of 5,000
Btu/lb or more are considered to be fuels. See also 50 FR at 49171-173 (Nov. 29,1985)
(partial burning for energy recovery is covered by section 3004(q) and Btu-rich wastes are
burned at least partially for that purpose).
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Finally, only wastes that contain less than 500 ppm tr: toxic organic constituents
listed in Appendix Vffl, Part 261, will be considered to recover metals. EPA believes that
it is important to have an objective measure to determine when burning is for metal
recovery, and that a 500 ppm level is within the zone of reasonable values that the Agency
could select for this purpose. As noted in the supplemental proposal in a closely related
context, a 500 ppm level for total toxic organic constituents reasonably distinguishes
wastes destined for material recovery from wastes burned for nonrecovery purposes
because: (1) it represents a concentration of material far exceeding trace levels (generally
measured in single digit parts per million (ppm) or tens of ppm); (2) this level of hazardous
constituents could create an incremental health risk if burned inefficiently, or with
inadequate emission controls; and (3) this level is high enough to indicate that an objective
of burning is waste treatment ~ destroying nontrace level organics ~ as opposed to material
recovery. (The Agency's earlier proposal dealt with the question of when a waste might be
considered to be indigenous to an industrial furnace burning for material recovery, and
considered the issue of whether these devices were burning for a material recovery
purpose, and proposed the 500 ppm level adopted in this rule as a means of objectively
ascertaining that purpose. 54 FR 43731.)
In order to be informed of persons claiming this deferral, and in order to decrease
potential abuse of the deferral, the Agency is requiring that all persons notify the Agency if
they assert that their smelting, melting, or refining furnaces are deferred from regulation
when burning hazardous wastes because the purpose of the activity is metal recovery. In
addition, all such persons have to keep records documenting the basis for the claim (i.e.,
that the wastes meet the Btu and total toxic organic constituent thresholds, the wastes
contain recoverable levels of metals, and the device is indeed engaged in producing a metal
product for public use). Sampling and analysis procedures specified in SW-846 must be
used to make these determinations. These conditions are consistent with existing §261.2(f)
which requires that all persons claiming to be exempt or excluded from regulation because
of a recycling activity to have the burden of proof demonstrating that they are entitled to the
exemption or exclusion. In addition, the Agency notes that a consistent recommendation of
state and regional officials at the Agency's recent public meetings on the regulatory
definition of solid waste was to provide notification and recordkeeping so that regulatory
officials know that a person is operating in an exempt status in order to verify their claim.
The Agency is acting on these recommendations in this rule.
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The Agency also notes that the derived from rule could apply to the residues from
metal recovery if metals are being recovered from listed hazardous wastes. EPA believes
this to be explicit from the remand in API v. EPA discussed earlier. The Court indicated
that the Agency's explanation for not establishing a treatment standard for the slag residue
from processing waste K061 was erroneous, and remanded the case to the Agency to
reconsider its explanation. 906 F. 2d at 740-42. Implicit (or perhaps explicit) in this
holding is the fact that the Court viewed the residue as a hazardous waste still coming under
the terms of the K061 land disposal prohibition (the Court referred repeatedly to "k061
slag" and mentioned the derived from rule as the basis for the slag being a hazardous
waste, id. at 742), at least until the Agency provides a different explanation as to why the
slag might not be a hazardous waste. Thus, because EPA has not yet provided a new
explanation regarding the indigenous principle (as explained above), at the present time,
EPA views residues from metal recovery of listed hazardous wastes are considered to be
derived from treatment of hazardous waste and thus hazardous themselves unless some
other principle (such as the Bevill amendment, or in some cases, status under an authorized
state program) operates to achieve a different result
Finally, the Agency notes that the deferral applies only to the furnace itself. The
hazardous waste is subject to transportation and storage controls prior to introduction into
the furnace. See §266.100(c).
The deferral of regulation of emission standards does not apply to cement kilns,
aggregate kilns, and HAFs that bum hazardous waste for purposes other than energy
recovery. The Agency has studied these devices carefully and determined that the
regulatory standards in today's rule are appropriate for these devices when they burn
hazardous wastes for a purpose other than energy recovery. Consequently, the Agency
sees no reason to defer emission standards for these types of units.
PART THREE: STANDARDS FOR BOILERS AND INDUSTRIAL
FURNACES BURNING HAZARDOUS WASTE
Today's rule establishes controls for emissions of paniculate matter, toxic organic
compounds, toxic metals, and hydrogen chloride and free chlorine. Those controls are
discussed below.
EPA notes that in some cases, today's rule potentially requires limitations on the
content of nonwaste input to a boiler or industrial furnace that is burning hazardous waste.
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For example, compliance with the limits for metals, PM, and HC1/C12 requires controls not
only on the hazardous waste input but also potentially controls on other fuels and industrial
furnace feedstocks. EPA has adopted this approach not to regulate the nonwaste input to
these devices, but rather to ensure that burning hazardous waste in the device does not pose
unacceptable risks to human health and the environment. These limitations function as
operating conditions on the unit to ensure compliance with the hazardous waste emission
standards. For example, unless limitations are established on nonwaste parameters,
owners and operators could initially demonstrate compliance by burning clean raw
materials along with hazardous waste, and then change their raw material input in a manner
that causes emissions to increase significantly. In addition, the approach adopted today
allows owners and operators maximum flexibility in demonstrating compliance with the
emission standards by allowing adjustments to nonwaste input as a means of achieving
compliance. The alternative of demonstrating compliance only through alteration of
hazardous waste feed is not only less flexible, but would create enormous administrative
difficulties (and add significant expense) for both regulated entities and Agency permit
writers. (For example, stack monitoring might no longer be a feasible means of
demonstrating compliance because one could not ascertain what portions of the emissions
are attributable to burning hazardous waste.) For these reasons, we think the approach
adopted today is the most sensible means of demonstrating compliance.
I. Emission Standard for Particulate Matter
Boilers and industrial furnaces that burn hazardous waste may emit substantial
quantities of paniculate matter (PM). (Emissions of paniculate matter can have adverse
effects on human health and the environment even if toxics are not adsorbed on the
paniculate matter. However, the Agency's chief concern in this rule is control of adsorbed
toxics.) Because toxic metals and organic compounds may adsorb onto smaller size PM
that can be entrained in the lungs, unregulated paniculate emissions could pose a significant
threat to human health. Although there may be limitations to the health-based standards,
the metals and organic emissions standards promulgated in today's rule provide protection
of public health based on current knowledge about toxic pollutants and available risk
assessment methodologies. The PM control standard promulgated today will provide
additional protection by ensuring that adsorbed metal and organics are removed from stack
gas with the PM.
In today's rule, EPA is establishing a standard for boilers and industrial furnaces
which limits paniculate emissions to 0.08 gr/dscf (grains/dry standard cubic foot) corrected
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to 7% oxygen. This limit was chosen because it provides a common measure of protection
from paniculate emissions from boilers, industrial furnaces, and incinerators burning
hazardous waste. This standard may be redundant for: (1) a new, large capacity facility
assigned to a specific source category which is governed by a New Source Performance
Standard (NSPS); (2) a waste burning facility located in a non-attainment area subject to
State Implementation Plan (SIP) standards; (3) a facility with standards for metals and HC1
emissions that result in particulate emissions below O.OS gr/dscf; and (4) a facility subject
to a stricter standard based on Best Available Control Technology (BACT) imposed
pursuant to the Clean Air Act's Prevention of Significant Deterioration (PSD) program. In
such cases, the device would be subject to the more stringent particulate matter standard,
not the RCRA 0.08 gr/dscf standard, and the additional burden of demonstrating
compliance with the applicable particulate matter standard concurrently with the applicable
emissions standards in today's rule for organic compounds, metals, and acid gases will not
be substantial. We believe, however, that there are many situations where a BIF is either
not currently subject to a particulate matter standard, or the standard is higher than the
RCRA 0.08 gr/dscf standard.
The Agency has considered lowering the particulate standard to take advantage of
technology advances made in air pollution control and to be consistent with the proposed
standard of 0.015 gr/dscf for municipal waste incinerators. (We note that the proposed
standard for MWIs also served as a surrogate to control emissions of toxic metals. 54 FR
52219. In contrast, today's rule has separate emission standards for each toxic metal.) We
are not prepared to do that at this time, however, because we have not conducted the
studies to establish an appropriate PM standard that represents best demonstrated
technology (BDT). Although many boilers and industrial furnaces may be able to achieve a
PM standard lower than 0.08 gr/dscf (in fact, the PM NSPS for specific types of BIFs is
lower than 0.08 gr/dscf), we are not certain that all BIFs can meet a standard of 0.015
gr/dscf. This is because some industrial furnaces have a very high (uncontrolled)
particulate loading due to entrained particles of raw materials. Examples are cement kilns
and light-weight aggregate kilns. Hence, a single PM standard of 0.015 gr/dscf cannot
now be promulgated.
The Agency firmly believes that the 0.08 gr/dscf PM standard, when used as a
supplement to the risk-based metal controls provided by today's rule, provides protection
of human health and the environment Given that hazardous waste burned in BIFs could
contain virtually unlimited concentrations of toxic metals, the Agency believes that risk-
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based standards are needed to supplement the PM standard for hazardous waste burning
irrespective of whether the PM standard represents best-demonstrated technology. Even
under a PM standard as low as 0.015 gr/dscf, a large fraction of the PM emitted from a
hazardous waste combustion device could be comprised of toxic metals that could result in
substantial health risk.
Nonetheless,, tS« Agency will consider if additional PM controls are warranted to
control enrissia-s of toxic metals. In that evaluation, the Agency will consider whether the
additional controls, if any, should be promulgated in the future under the new Clean Air
Act See discussion in section HI.A of Part One of this preamble. Finally, we note that
permit writers also could impose a lower PM standard where facts warrant, pursuant to the
omnibus permit authority in section 3005(c)(3).8
A. Basis for Final Rule
Paniculate matter (PM) is controlled from combustion sources to limit emissions of
toxic metals and PM per se (i.e., because of human health and ecological impacts
associated with PM that does not contain toxic metals). In the May 6,1987 proposed rule,
EPA suggested that a PM emission standard was not needed for boilers and industrial
furnaces because the risk-based metals controls provide adequate control of metals
emissions. The Agency reasoned that a standard intended to control PM per se would be
more appropriately applied to these sources under authority of the Clean Air Act rather than
RCRA.
EPA received numerous comments on the May 6,1987 proposed rule suggesting
the need for a paniculate standard for boilers and furnaces burning hazardous waste. Many
commenters believed that, notwithstanding the risk-based metals controls, unregulated PM
emissions with adsorbed toxic metals and organic compounds could pose a significant
health risk. In addition, three commenters suggested that EPA address the issue of
paniculate control during soot-blowing cycles when levels of paniculate emissions are 4 to
7.2 times the level of emissions under normal operation. The Agency carefully considered
these comments and subsequently determined that the risk-based metals standards should
8 EPA notes that permit writers choosing to invoke the omnibus permit authority of
§270.32(b)(2) to add conditions to a RCRA permit must show that such conditions are
necessary to ensure protection of human health and the environment and must provide
support for the conditions to interested parties and accept and respond to comment In
addition, permit writers must justify in the administrative record supporting the permit any
decisions based on omnibus authority.
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be sapptemenfed with a PM standard to provide a common measure of control for metals.
This decision was based in pan on a consideration of commenters' concerns about the
limitations of risk-based metals standards. See 54 FR 43720-21. Hence, the Agency
subsequently proposed a paniculate emissions standard of 0.08 gr/dscf (grains/dry
standard cubic foot) corrected to 7% oxygen in the October 26, 1989 supplement to the
proposed rule. The standard would be applicable to all boilers and industrial furnaces not
governed by a more stringent (NSPS or SIP) standard.
1. Alternatives Considered. In selecting the standard for boilers and industrial
furnaces, the Agency considered the following alternatives:. (1) apply the current NSPS
standard for steam generators burning waste; (2) apply the applicable NSPS; or (3) apply
the existing hazardous waste incinerator standard. These options are discussed in the 1989
supplemental notice (54 FR 43720).
Many commenters supported the proposed paniculate standard of 0.08 gr/dscf.
Several commenters, however, opposed this limit, arguing against imposing a standard
appropriate for incinerators on boilers and furnaces. Still other commenters suggested that
the 0.08 gr/dscf limit did not go far enough in protecting the public health. These
respondents argued for a lower limit comparable to that the Agency proposed for municipal
waste incinerators.
The Agency continues to believe that the 0.08 gr/dscf PM standard, when used as a
supplement to the risk-based metal controls provided by today's rule, provides substantial
protection of human health and the environment.
2. Basis for Standard. Today's rule promulgates the proposed paniculate emission
limit of 0.08 gr/dscf because, as a supplement to the risk-based metals controls, it provides
a common measure of protection from paniculate emissions from boilers, industrial
furnaces, and incinerators burning hazardous waste. In addition to providing control of
paniculate metals and adsorbed organic compounds, the 0.08 gr/dscf standard should also
ensure that the Clean Air Act's National Ambient Air Quality Standard (NAAQS) for
particulates is achieved in most cases. An analysis of existing sites shows that emissions
of particulates at 0.08 gr/dscf could result in MEI levels of up to 30% of the maximum
daily PMjQ (paniculate matter under 10 microns) NAAQS (150 mg/m^). If background
paniculate levels at a site are high (i.e., the site is in a non-attainment area), paniculate
emissions from the device should also be addressed as pan of the State Implementation
Plan (SIP) (as they are now for hazardous waste incinerators in paniculate non-attainment
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areas). Therefore, although the 0.08 gr/dscf standard may not ensure compliance with the
NAAQS in evay situation, this issue will be addressed by the SIP since the facility would
be, by definition, in a non-attainment area for paniculate emissions.
B. Interim Status Compliance Procedures
Facilities operating under interim status must comply with the PM emission
staodanl By the effective date of the rule, owners/operators must submit a certification of
precompliance that documents their use of engineering judgment to show that, considering
feed rates of ash from all feed streams, partitioning of ash to bottom ash or product, and the
PM removal efficiency of the air pollution control system (APCS), PM emissions are not
likely to exceed the 0.08 gr/dscf limit. Owners and operators must also establish and
provide with the precompliance certification limits on feed rates of ash in all feed streams
consistent with those used to determine that emissions of paniculate matter are not likely to
exceed the standard. The facility may not exceed these feed rates during interim status
(unless amended by a revised certification of precompliance). Further, within 18 months
(unless extended) of promulgation, owners/operators must conduct emissions testing and
certify that emissions do not exceed the limit. See section VII in Part Three of this
preamble for more information.
C. Implementation
Owners/operators must demonstrate compliance with the PM standard using
Methods 1-5 of 40 CFR Part 60, Appendix A. The compliance test for certification during
interim status and the trial burn for facilities applying for a RCRA operating permit must be
representative of worst-case operating conditions with respect to paniculate emissions that
will occur during operation of the facility (i.e., because limits on operating conditions
applicable for the remainder of interim status will be based on operating conditions during
the compliance test).
The PM standard is implemented by limiting the feed rate of ash from all feed
streams (i.e., hazardous waste, other fuels, raw materials) and by limits on APCS-specific
operating parameters. The limits are established during interim status based on the
compliance test, and in the operating permit based on the trial burn.
The final rule gives special consideration to cement and light-weight aggregate kilns
because their raw material feed streams contain the vast majority of the ash input and
resulting PM. Therefore, owners/operators of cement kilns and light-weight aggregate
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kilns are no! required to monitor ash feed rates of feedstreams. We emphasize, however,
that cement kOns and lightweight aggregate kilns, like all BIFs, are still required to
demonstrate oonformancc with the PM emission standard during a compliance test (under
interim status) or trial burn (under a Part B application). The Agency believes that the
capacity limit on the facility (expressed in appropriate units such as raw material feed rate)
and the limits on the air pollution control system (APCS) operating parameters applicable
during bosh interim states and under a subsequent operating permit will ensure that cement
and light-weight kflns continuously comply with the PM standard 9
IL Controls for Emissions of Toxic Organic Compounds
Burning hazardous waste that contains toxic organic compounds (i.e., organic
compounds listed in Appendix VIII of 40 CFR Part 261) under poor combustion
conditions can result in substantial emissions of the toxic compounds originally present in
the waste as well as other compounds, due to partial but incomplete combustion of the
constituents in the waste. The quantity of toxic organic compounds emitted depends on the
concentrations of the toxic compounds in the waste, the waste firing rate (i.e., the
percentage of total fuel provided by the hazardous waste to the boiler or industrial furnace),
and the combustion conditions under which the waste is burned. The risk posed by the
emissions depends on the quantity and toxicity of the compounds emitted and on the
ambient levels to which persons are exposed. Hypothetical risk assessments show that
under poor combustion conditions that achieve only 99 percent or 99.9 percent destruction
and removal efficiency (DRE) of organic compounds, risks to the maximum exposed
individual (MEI) from unburned carcinogenic organics found in hazardous waste can result
in increased lifetime cancer risks of 1(H.10
The Agency is controlling the emissions of toxic organic compounds from boilers
and industrial furnaces that bum hazardous waste with two performance standards. First, a
99.99 percent destruction and removal efficiency (DRE) standard for principal organic
hazardous constituents (POHCs) in waste feeds will ensure that constituents in the waste
9 We note, moreover, that some boilers and many industrial furnaces are already
subject to a paniculate matter (PM) standard under a NSPS, SIP, or PSD program and the
applicable PM standard is generally more stringent than the 0.08 gr/dscf standard provided
by today's rule. Thus, these devices are already under a regulatory compliance program
for a PM standard. We note further that the more stringent PM standard applies.
10 Engineering-Science, Background Information Document for the Development of
Regulations to Control the Burning of Hazardous Waste in Boilers and Industrial Furnaces.
Volume ffl, January 1987 (NTIS # PB 87 173845).
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are not emitted ax levels that could pose significant risk in virtually all scenarios of which
the Agency is aware.11 Second, limits on flue gas concentrations of carbon monoxide
(CO) and, where specified, hydrocarbons (HC) will ensure that combustion devices
operate continuously at high combustion efficiency and emit products of incomplete
combustion (PICs) at levels that will not pose adverse effects on public health and the
environment The basis for these standards is discussed below.
A. DRE Standard.
As proposed, the Agency is promulgating a 99.9999% DRE standard12 for those
acutely hazardous wastes listed because they contain dioxin13 (and waste mixed with those
wastes), and a 99.99 percent DRE performance standard for all other wastes. This
standard is protective, it can be readily achieved by boilers and industrial furnaces, and it
will ensure that the Agency's controls are consistent for all combustion devices (boilers,
industrial furnaces, and incinerators) that pose similar risks.
Hypothetical risk assessments have shown that a 99.99 percent DRE standard for
POHCs is protective of risks posed by emissions of organic constituents in the waste in
virtually every scenario of which the Agency is aware.14 (EPA considers elsewhere in this
notice the issue of products of incomplete combustion.) Increased lifetime cancer risks to
the maximum exposed individual (MEI) from an incinerator operating at 99.99 percent
DRE would generally be 10'6 or less. Threshold (i.e., noncarcinogenic) organic
compounds also would not be expected to be present in emissions from hazardous waste
burned in boilers and industrial furnaces at levels that could pose a health hazard under the
99.99 percent DRE standard.
EPA is aware, however, that the DRE standard does not directly control the mass
emission rate (e.g., pounds per hour) of unburned toxic organic constituents in the waste.
Although there are hypothetical situations in which risks from POHCs could be significant
under a 99.99 percent DRE standard (e.g., boilers or industrial furnaces located in urban
areas burning high volumes of waste with high concentrations of highly potent
carcinogenic organics), the Agency is not aware that any such situations are actually
11 Except that 99.9999% DRE is required for dioxin-listed hazardous waste.
12 The proposed formula for calculating DRE has been revised in the final rule (see
§266.104(a)) to make it mathematically correct considering use of significant figures.
!3 EPA Hazardous Wastes FO20, FO21, FO22, FO23, FO26, and FO27.
M Engineering Science, op. cit
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occurring. If, however, during the permit process, it appears that a high-risk scenario may
exist, permit officials may use the omnibus permit authority15 of Section 3005(c)(3) of the
Resource Conservation and Recovery Act (RCRA) codified at §270.32(b)(2) to develop
permit requirements, as necessary, to protect human health and the environment (e.g., by
requiring a 99.9999 percent DRE, by limiting the feed rate of particular toxic compounds,
or by setting a mass emissions rate).
1. Selection ofPOHCsfor DRE Testing. In the April 27, 1990 proposed rule to
amend the incinerator standards (55 FR 17890), EPA outlined the consideranons to be
made by applicants and permitting officials in selecting POHCs for DRE trial burns. Given
that the DRE implementation procedures for boilers and industrial furnaces (BIFs) are
identical to those for incinerators, the discussions in the incinerator proposed rule are
pertinent to this rule.
A major factor in selecting a POHC for DRE testing is its incinerability relative to
other toxic organic compounds. A number of indices can be used to predict incinerability
including heat of combustion, autoignition temperature, thermal stability under excess
oxygen conditions, and thermal stability under low oxygen (substoichiometric) conditions.
An incinerability ranking based on thermal stability at low oxygen concentrations
(TSLoO2) shows promise and is currently seeing widespread use in incinerator permits. A
number of commenters responded to EPA's request for comment on the use of the TSLoO2
index for POHC selection. In general, they raised no problems with use of the index.
Their main concern appeared to be that EPA choose one index and apply it consistently.
The Agency, however, is not requiring the use of a particular index. Due to the
various "failure modes" different organic compounds are susceptible to during the
destruction process in a combustion device, and the evolving state of knowledge in this
area, the Agency feels that the POHC selection process is technically complex, and that it
should involve a number of considerations, rather than simply one incinerability ranking.
Thus, EPA instead recommends that permit writers and applicants consider these indices
and other relevant factors and use their judgment and applicable guidance on a case-by-case
basis to select POHCs for the trial burn.
15 EPA notes that permit writers choosing to invoke the omnibus permit authority of
§270.32(b)(2) to add conditions to a RCRA permit must show that such conditions are
necessary to ensure protection of human health and the environment and must provide
support for the conditions to interested parties and accept and respond to comment In
addition, permit writers must justify in die administrative record supporting the permit any
decisions based on omnibus authority.
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2. Use ofPOHC Surrogates. A number of laboratory-scale, pilot-scale, and field-
scale tests have been conducted to investigate the use of nontoxic tracer surrogates (e.g.,
sulfur hcxafluoridc (SF$)) rather than POHCs selected from Appendix VIH of Part 261.
Sulfur hexafluoride, in particular, shows promise as a conservative tracer surrogate for
compounds which are susceptible to the thermal failure mode (i.e., it is difficult to destroy
unless sufficiently high temperatures are reached). It is readily available commercially, and
is inexpensive and nontoxic. POHCs that are listed on Appendix Yin, especially in
situations where spiking is required to increase concentrations in a waste for DRE testing,
are often difficult to obtain, are expensive, and are a health hazard to operators. Sampling
and analysis techniques for SFg are well documented because of its long use as a tracer gas
for monitoring ambient air and are more straightforward (simpler) and less expensive than
sampling techniques for Appendix VHI, Part 261, compounds (e.g., VOST and MM5).
Numerous commenters responded to EPA's request for information on an approach
for simplifying and standardizing DRE testing. Commenters supported standardization of
DRE testing provided the approach is equitable for all boilers, industrial furnaces, and
incinerators. Comments were received in support of all three approaches proposed by EPA
("POHC soup," surrogates, and specific waste analysis). Commenters generally supported
use of surrogates in lieu of extensive waste analysis for design of DRE tests. Other
commenters suggested using a limited number of major waste constituents as POHCs, such
as carbon tetrachloride, perchloroethylene, trichloroethylene, and monochlorobenzene,
until it can be shown that a universal surrogate, such as sulfur hexafluoride (SF$), is
comparable in demonstrating DRE performance. Sulfur hexafluoride was recommended by
some commenters as a good surrogate choice based on the high accuracy of results with the
compound and ease of use.
However, since the April 27 proposed rule, data have become available showing
cases where other organic compounds were more difficult to destroy than SFg under
conditions of low oxygen. This is consistent with theory, since SFfi can be destroyed
under conditions of high temperature and low oxygen relatively easily compared to
compounds which need oxygen to decompose. Thus, although SF$ appears to show
promise as a surrogate for testing the thermal failure mode because of its stability at high
temperatures, it does not appear to be adequate as a "universal" surrogate, since it does not
test for low oxygen or "mixing" failure.
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Nevertheless, today's rule explicitly allows the use of surrogate, nontoxic
compounds for selection as POHCs for DRE testing. As for any other type of POHC, the
use of such compounds must be approved on a case-by-case basis by permit officials based
on technical support provided by the applicant. The applicant's trial bum plan must
adequately document the correlation between the DRE of the surrogate compound and the
DREs of the Appendix Vffl compounds anticipated to be burned at the facility under the
facility's permit
3. Waiver of DRE Trial Bum for Boilers Operating Under the Special Operating
Requirements In 1987, the Agency proposed to waive the trial burn requirement to
demonstrate DREs for boilers that operate under special operating requirements (SOR).
The SOR required that, in addition to meeting the proposed 100 ppmv CO limit, a
qualifying boiler must: (1) burn at least 50 percent fossil fuel in the form of oil, gas, or
coal; (2) operate at a load of at least 25 percent of its rated capacity; (3) burn hazardous
waste fuel with an as-fired heating value of at least 8,000 Btu/lb; and (4) inject the
hazardous waste fuel through an acceptable atomization firing system.
The SOR were based on the results of nonsteady-state boiler testing. From these
results, the Agency believed that boilers operating under the SOR would maintain a hot,
stable flame conducive to maintaining high combustion efficiency, resulting in maximum
destruction of organic constituents in the hazardous waste fuel. The Agency believed that
these boilers would achieve at least 99.99 percent DRE, and therefore, a trial burn to
demonstrate DRE would not be necessary.
The Agency continues to believe that boilers operating under the SOR will achieve
99.99 percent DRE. However, based on comments received on the proposed SOR and on
further examination of the previous steady-state and nonsteady-state boiler test results, the
Agency has made the following modifications to the SOR:
(1) limit eligibility for the waiver to nonstoker, watertube boilers;
(2) revise the requirement that the boiler fire 50 percent fossil fuel or fuels derived from
fossil fuel to include tall oil, to allow permit officials to approve on a case-by-case
basis other nonhazardous fuels with combustion characteristics comparable to fossil
fuel, and to require for all such primary fuels (i.e., fossil fuels, tall oil, and other
fuels approved on a case-by-case basis) a ftijnimum heating value of 8,000 Btu/lb;
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(3) clarify that the hazardous waste fuel fired must have an as-fired heating value of
8,000 Btu/lb and require that each fuel fired in the burner where hazardous waste is
fired must have an as-fired heating value of 8,000 Btu/lb;
(4) increase the minimum load requirement from 25% to 40%; and
(5) eliminate the lower viscosity requirements for the hazardous waste and decrease the
upper viscosity limits for the hazardous waste to 300 seconds, Say bolt Universal
(SSU), measured at the as-fired temperature of the fuel.
As proposed in 1987, boilers with a trial burn waiver under the SOR must meet the
Tier I CO limit of 100 ppmv16 and must comply with all other requirements of the final
rule (e.g., metals standards, PM limit).
The revised SOR are presented below, along with the basis for the revisions.
a. The Boiler Must Be a Nonstoker, Watertube Boiler. Commenters stated that the
nonsteady-state testing of only three stoker and firetube boilers is insufficient to determine
whether 99.99 percent DRE would always be achieved under the SOR. Commenters also
maintained that the stoker and firetube boilers tested were not representative of all types and
sizes.
The Agency agrees that there is limited data demonstrating that stoker and firetube
boilers can achieve 99.99% DRE under the SOR. In the Agency's steady- and nonsteady-
state testing, only three firetube boilers and one stoker boiler were tested under steady-state
conditions, and one stoker boiler was tested under nonsteady-state conditions. The
remainder of the boilers tested were watertube boilers.
The results from one of the firetube boiler tests generally support the ability of
firetube boilers to achieve 99.99 percent DRE, but this boiler was specially designed to
combust hazardous waste. The Agency is concerned whether more conventionally
designed firetube boilers could easily achieve this level of DRE. DREs could not be
calculated at one of the other firetube boiler tests due to inadequate waste feed levels, and
sampling and analytical problems occurred at the third firetube boiler test The stoker boiler
tested under steady-state conditions did not demonstrate 99.99 percent DRE. In addition to
the limited data for these boiler types, a greater potential exists for poor distribution of
16 Boilers complying with the Tier n PIC controls where CO levels exceed 100 ppmv
are not eligible for the automatic waiver of the DRE trial bum. This is because the DRE test
data used to support the waiver was obtained for boilers operating at CO levels below 100
ppmv.
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combustion gases and localized cold spots in firetubc and stoker boilers that can result in
poor combustion conditions. This is because these boilers generally burn fuels with a large
and variable particle size on a bed, thus, making even distribution of combustion air
difficult Therefore, the final rule precludes stoker or firetube boilers from the automatic
waiver of a DRE trial bum.
b. A Minimum of 50 Percent of the Fuel fired to the Boiler Must Be High Quality
"Primary" Fuel Consisting of Fossil Fuels or Fuels Derived From Fossil Fuels, Tall Oil,
or, if Approved on a Case-By-Case Basis, Other Nonhazardous Fuel Comparable to Fossil
Fuel, and All Such Primary Fuels Must Have a Minimum As-Fired Heating Value of 8,000
Btu/lb. Thirteen commenters found the SO percent fossil fuel requirement to be overly
restrictive. In particular, one commenter proposed that the requirement be rephrased to
allow the burning of no more than 50 percent hazardous waste in mixtures such that
nonhazardous waste fuel supplements can be fired. Another commenter suggested
eliminating the fossil fuel requirement for wastes that have heating values comparable to
fossil fuels. Eleven commenters supported the burning of high quality non-fossil fuels,
such as tall oil (i.e., fuel derived from vegetable and rosin fatty acids) and the by-products
derived from the fractional distillation of tall oil Many of these commenters said they have
burned these materials and claimed they have heating values and combustion characteristics
similar to fossil fuels. Three commenters requested that the burning of wood wastes as a
primary fuel be allowed. One of these commenters presented the results from six trial
burns for wood waste boilers which demonstrated that combustion zone temperatures in
these types of boilers are consistent, and that a hot, stable flame conducive to the
destruction of organic constituents in the waste is present under these conditions.
Based on the comments and information presented regarding the use of tall oil (i.e.,
tall oil burns like commercial fuel oil), the Agency is revising the 50% primary fuel
requirement to include tall oil.. Also, the Agency believes that the combustion of other
nonhazardous fuels that have heating values of at least 8,000 Btu/lb (representing the lower
heating value range of most sub-bituminous coals), and combustion characteristics similar
to fossil fuels, will ensure a hot, stable flame conducive to the destruction of organic
constituents in the waste. An owner/operator who is planning to burn such a fuel
supplement must present information on the supplement's combustion characteristics for
the Director's review. Concerning wood wastes, the Agency continues to believe that these
wastes may not provide the hot, stable combustion zone conditions needed to achieve
99.99 percent DRE. Due to the higher flue gas moisture, excess air, CO levels, and lower
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furnace temperatures associated with wood firing, the potential for less than 99.99 percent
DRE exists. Therefore, boilers that fire wood wastes must demonstrate DRE capabilities
through a trial burn.
The 50 percent minimqm primary fuel requirement, on a total heat or volume input
basis, whichever results in the greater volume of primary fuel, also is needed to ensure
appropriate combustion zone conditions. This limit was based on the maximum levels of
hazardous waste burned in the boilers tested by EPA under nonsteady-state conditions.
Finally, the Agency recognized that the term "fossil fuel" can include peat or other
fuels with heating values below 8,000 Btu/lb. Because the test data used to support the
waiver were from boilers fired with primary fuels with heating values higher than 8,000
Btu/lb, the final rule applies the minimum 8,000 Btu/lb as-fired heating value limit to all
fuels, including fossil fuels, used to meet the minimum 50% primary fuel requirement.
c. Boiler Load Must Be at Least 40 Percent. Several commenters addressed the
proposed minimum load level of 25 percent. Only one commenter considered it to be too
low. This commenter advocated an 80 percent load requirement unless high efficiency
combustion can be demonstrated at the trial burn. One commenter considered the 25
percent requirement to be arbitrary, but within current practice. Another commenter
recommended that the level be more flexible for multiple burner boilers. One commenter
recommended that the requirement to maintain a boiler load of 25 percent be eliminated if
the Btu value of the wastes burned is equivalent to that of coal thereby providing the heat
input necessary to sustain normal combustion operations.
Boiler testing conducted at a load as low as 26 percent has demonstrated that certain
boilers can achieve 99.99 percent DRE when operated at low loads. However, due to
concerns related to flame stability, combustion control, and heat transfer effects associated
with load turndown on some boilers, the Agency has raised the boiler load limit from 25
percent to 40 percent of design load. Operation of some boilers at loads of less than 40
percent can result in significantly higher excess air levels and localized decreases in flame
temperatures. In addition, most of the boilers tested to develop the operating requirements
operated at loads above 40%. Therefore, limiting the boiler load to 40% is more consistent
with the available test data. If an owner/operator expects to operate a unit at a lower load
while firing hazardous waste, a trial burn to demonstrate 99.99 percent DRE is required.
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d. The Heating Value of the Hazardous Waste Fuel Must Be a Least 8,000 Btu/lb,
As-Fired, and Each Fuel Fired in a Burner Where Hazardous Waste Is Fired Must Have a
Heating Value of at Least 8,000 Btu/lb, As-Fired. Eleven commenters expressed concern
that the "as-fired" requirement proposed in 1987 will require the blending of wastes that
have heating values of less than 8,000 Btu/lb with other wastes and/or the primary fuel
before atomization. Four commenters documented a number of problems with blending
low Btu wastes, including immiscibility and other mixing problems, increased quantity of
materials requiring handling, difficulty of controlling feed during unit upsets, and
impracticality for coal-fired systems. Five commenters requested that the heating value be
determined on a total-burner basis, as a composite of primary fuel and waste. Three
additional commenters recommended that the minimum heating value of wastes be lowered
to 5,000 Btu/lb.
The Agency agrees that waste fuel blending can present problems in some
instances. However, the Agency is concerned that allowing low Btu wastes to be fired
separately from the fuel and then atomized in the flame region of the burner might make it
difficult to ensure good atomization, proper feed system operation, and, consequently,
adequate combustion of the hazardous waste. Therefore, the 8,000 Btu/lb requirement,
which represents the lower range of heating values of fossil fuels, applies to the as-fired
heating value of the hazardous waste and to the as-fired heating value of any other fuel fired
in the same burner with the hazardous waste.17
If hazardous waste with a heating value below 8,000 Btu/lb18 is mixed with the
"primary" fuel to meet the as-fired minimum heating value for hazardous waste of 8,000
Btu/lb, that quantity of primary fuel may not be counted toward the 50% primary fuel
requirement This is because the purpose of requiring 50% of the fuel to be "primary" fuel
is to ensure a hot, stable flame to combust the hazardous waste. If a portion of the primary
17 We note that the 8,000 Btu/lb minimum heating value also applies to the "primary"
fuel that must comprise at least 50% of the boiler's fuel requirements. However, the
remainder of the boiler's fuel requirements may be provided by hazardous waste and other
fuels. There are no restrictions on the other fuels unless they are fired in the same burner
with the hazardous waste. In that case, those other fuels, like the hazardous waste and
"primary" fuel, must have a minimum heating value of 8,000 Btu/lb.
1 ° We note that, as discussed elsewhere in the text, the sham recycling policy stays
into effect until an existing facility certifies compliance with the emissions standards (see
§6266.103(c)). Thus, until that time, hazardous waste burned in a BIF must have an as-
generated heating value of 5,000 Btu/lb, unless the waste is burned solely as an ingredient
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fuel is blended with the hazardous waste to increase the heating value of the hazardous
waste as-fired, then that portion of the primary fuel is not providing the hot, stable flame.
The following example shows how this requirement will work. Suppose a boiler is
fired with 70% primary fuel and 30% hazardous waste, and that half of the primary fuel is
blended with the hazardous waste to achieve an as-fired heating value of 8,000 Btu/lb.
This boiler would not be eligible for the automatic waiver of the DRE trial burn because it is
fired with only 35% primary fuel (half of the 70%) that is not blended with the hazardous
waste to meet the minimum as-fired heating value limit of 8,000 Btu/lb.
e. The Hazardous Waste Must Be Fired with an Atomization System. Seven
commenters argued that lower viscosity limits are unnecessary. Three commenters stated
that it is common to atomize wastes well below 150-200 SSU, and that No. 2 oil has a
viscosity of 32.6-37.9 SSU at 100°F. One commenter indicated that the upper viscosity
limits appear high for the atomization systems specified. One commenter disagreed and
said that the high limits are in the correct range. Six commenters expressed concern that the
particle size limits are overly restrictive. One commenter stated that diverse waste streams
can be handled to achieve good destruction without particle size limits. Another commenter
disagreed with EPA by stating that they are not familiar with nozzles designed for particle
sizes as small as 200 mesh. Three commenters said the waste viscosity should be left to
the discretion of the owner/operator since it is industry practice to operate at viscosities
which provide optimum atomization.
Based on the commenters' arguments, the Agency has eliminated the lower
viscosity requirements and reduced the upper limit to 300 SSU (Seconds, Saybolt
Universal) measured at the as-fired temperature of the hazardous waste. We eliminated the
lower level because, after consideration of comments and re-evaluation, we believe that the
concern stated at proposal — formation of a fog at low viscosity levels which could result in
poor combustion conditions - is not likely to occur. At proposal, the Agency established
upper viscosity limits ranging from 300 to 5,000 SSU, depending on the type of
atomization system. Commenters noted that, as a practical matter, wastes with as-fired
viscosities greater than 300 are not fired in an atomization system. These modifications
will give facilities the flexibility to preheat wastes before atomization and are consistent
with general industry practice for good atomization.
Regarding particle size limits the final rule establishes the proposed limits. When
high pressure air or steam atomizers, low pressure atomizers, or mechanical atomizers,
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70% of the waste must pass a 200 mesh (74 micron) screen. When a rotary cup atomizer is
used, 70% of the waste must pass a 100 mesh (ISO micron) screen. These mesh sizes are
consistent with the design droplet size of the atomizers.
Owners/operators of boilers who propose to fire hazardous waste outside these
viscosity and particle size limits must conduct a DRE trial bum.
B. PIC Controls.
The burning of hazardous waste, like virtually any combustion process, results in
emissions of incompletely burned organic compounds, or products of incomplete
combustion (PICs). PICs can be unburned organic compounds that were present in the
waste, thermal decomposition products resulting from organic constituents in the waste, or
compounds synthesized during or immediately after combustion. If a device is operated
under poor combustion conditions, substantial emissions of PICs can result (even if
99.99% DRE is demonstrated for POHCs; this just means that the POHC is not being
emitted in its original form). However, it should be noted that estimates of risk to public
health resulting from PICs, based on available emissions data, indicate that PIC emissions
do not pose significant risks when BIFs and incinerators are operated under good
combustion conditions.
Nonetheless, the Agency is concerned about the potential health risk from PICs
because the available information has serious limitations. It is very difficult to identify and
quantify emissions of thousands of different compounds, some of which are present in
minute quantities. Although elaborate and expensive sampling and analytical techniques
have been developed that can identify many PICs, many others cannot be identified and
quantified with current techniques. Further, health effects information adequate to conduct
a health risk assessment considering exposure via direct inhalation is not currently available
on many organic compounds that may be emitted from combustion.systems. Finally, the
available public health and environmental risk assessment tools are incomplete. Data are
currently available to conduct indirect exposure analyses (e.g., exposure via the food chain,
drinking water, dermal exposure) on only a few organic compounds, and it will be some
time before the Agency will be able to quantify impacts on ecological resources on a site-
specific basis for purposes of establishing emissions standards.
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Given the limited information about the hazards that PIC emissions may pose, EPA
believes it is prudent to require that boilers and industrial furnaces operate at a high
combustion efficiency to minimize PIC emissions.
EPA is promulgating today a two-tiered approach to control PICs as discussed in
the October 29,1989, supplemental notice (54 FR 43721-28). Under Tier I, CO is limited
to 100 ppmv. Under Tier n, the Agency is providing an alternative standard. The facility
need not meet the 100 ppmv CO limit provided the facility can demonstrate that the
hydrocarbon (HC) concentration in the stack gas does not exceed a good operating practice-
based limit of 20 ppmv. The alternative CO limit under Tier n must be established during
the test bum based on the average over all runs of the highest hourly rolling average for
each run.
1. Use of a CO Limit to Control PICs. Generally accepted combustion theory
holds that low CO flue gas levels combined with low excess oxygen levels indicate a
boiler, industrial furnace, or incinerator is operating at high combustion efficiency.
Operating under high combustion efficiency helps to ensure minimum emissions of
unburned (or incompletely burned) organics. In the first stage of the combustion of
hazardous waste fuel, the POHCs thermally decompose in the flame to form other, usually
smaller, compounds termed products of incomplete combustion. In this first stage of
combustion, these PICs also decompose to form CO.
The second stage of combustion involves the oxidation of CO to CC*2 (carbon
dioxide). The CO to CO2 step is the slowest (rate-controlling) step in the combustion
process because CO is considered to be more thermally stable (difficult to oxidize) than
other intermediate products of the combustion of hazardous waste constituents. Because
fuel is being fired continuously, these combustion stages occur simultaneously.
Thus, in the waste combustion process, the "destruction" of POHCs is independent
of flue gas CO levels. CO flue gas levels cannot be correlated with DREs for POHCs, and
may also not correlate well with PIC destruction. Although some emissions data indicate a
weak correlation between CO and PICs, the data generally indicate that there is a
relationship between the two parameters: when CO is low, PIC emissions are relatively
low. The converse may not hold: when CO is high, PICs may or may not be high.
Low CO is an indicator of the status of the CO to CO2 conversion process, the last
rate-limiting oxidation process. Because oxidation of CO to CO2 occurs after the
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destruction of a POHC and its (other) intermediates (PICs), the absence of CO is a useful
indication of POHC and PIC destruction. The presence of high levels of CO in the flue gas
is a useful indication of inefficient combustion, and at some level of elevated CO flue gas
concentration, is an indication of the failure of the PIC and POHC destruction process.
EPA believes it is necessary to limit CO levels to levels that are indicative of high
combustion efficiency because the precise CO level that indicates significant failure of the
PIC and POHC destruction process is not known. In fact, this critical CO level may
depend on site-specific and event-specific factors (e.g., fuel type, fuel mix, air-to-fuel
ratios, and the rate and extent of changes in these and other factors that affect combustion
efficiency). EPA believes that limiting CO levels is also reasonable because: (1) it is a
widely practiced approach for monitoring combustion efficiency - some boilers and
industrial furnaces are already equipped with CO monitors, and many are equipped with
flue gas oxygen monitors; (2) the monitors may pay for themselves through fuel savings
resulting from operation of the boiler or industrial furnace closer to maximum combustion
efficiency; and (3) well-designed and well-operated boilers and industrial furnaces can
readily be operated in conformance with either the 100 ppmv CO limit under Tier I, or the
20 ppmv HC limit under Tier IL
2. Tier I PIC Controls: 100 ppmv CO Limit.
a. Basis for the 100 ppmv CO Limit The May 6,1987 proposed rule would have
applied the same CO emission limits to all boilers and industrial furnaces: a lower limit of
100 ppmv over an hourly rolling average and a 500 ppmv limit over a 10-minute rolling
average. The hazardous waste feed would be shut off automatically if either limit was
exceeded. However, the hazardous waste would be cutoff immediately once the 500 ppmv
limit was exceeded while the waste feed would be cutoff within 10 minutes if the 100 ppmv
limit was exceeded. Further if the hazardous waste feed was cutoff more than 10 times in a
month, the proposed rule would have prohibited further hazardous waste burning pending
review and approval by enforcement officials. The lower limit of 100 ppmv was selected
as representative of steady-state high efficiency combustion conditions resulting in PIC
emissions that would not pose a significant risk. The higher limit of 500 ppmv was
proposed to limit the frequency of emission spikes that inevitably accompany routine
operational "upsets," such as load changes and start-ups of waste firing.
While two commenters stated that the proposed 100 ppmv CO limit is arbitrary, six
commenters supported the Tier I CO limit of 100 ppmv. One commenter supported both
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the 100 ppmv CO limit over an hourly rolling average, and the 500 ppmv CO limit over a
10-minute rolling average. Three additional commenters also expressed support for the
500 ppmv CO limit over a 10-minute rolling average. Three other commenters supported a
500 ppmv CO limit over an hourly rolling average, and stated that a maximum 1,000 ppmv
CO limit can be included in addition to a 10-minute average.
Many commenters opposed the CO trigger limits and associated limits on the
number of waste feed cutoffs proposed in May 1987. Primarily, commenters objected to
one set of CO emission limits as applicable to all boilers and industrial furnaces. Further,
they argued that PIC emissions will not be significant if, when the waste feed is cutoff, the
combustion chamber temperatures are maintained while the waste remains in the chamber.
Six commenters argued that the trigger limits will result in increased NOX emissions. One
commenter stated that NOX and CO cannot be lowered simultaneously, and added that
many low NOX boilers may not be able to meet these CO limits. As an alternative, one
commenter stated that a higher Tier I CO limit should be allowed for less toxic emissions;
however, this commenter did not provide an alternative approach for identifying the toxicity
of emissions. One commenter suggested that EPA retain two alternatives to the CO
standard: establishing an alternative standard based on nonmethane, ethane hydrocarbon
(NMEHC) emissions, and a case-by-case risk assessment approach.
As a result of these and other comments and further evaluation, EPA is
promulgating the Tier I limits based on a maximum hourly rolling average CO limit of 100
ppmv, corrected to 7 percent flue gas oxygen content If this limit is exceeded, the
hazardous waste feed must be automatically and immediately cutoff. The final rule does
not restrict the number of waste feed cutoffs because: (1) combustion chamber
temperatures must be maintained after a cutoff; and (2) the number of cutoffs will be
minimized by allowing CO concentrations to be averaged over a 60-minute period (i.e., the
hourly rolling average) and by the recommended use of pre-alarms to provide time to
remedy the problem or to allow a staged waste cutoff before reaching the CO limit.
Nonetheless, the Agency retains the authority to limit the frequency of cutoffs as the facts
warrant See §266.103(e)(7)(ii). The final rule does not include the proposed 500 ppmv
rolling average over a 10-minute limit on CO because we do not believe it is needed given
that the final rule requires immediate waste feed cutoff when the 100 ppmv hourly rolling
average limit is exceeded. In addition, several commenters argued that the 500 ppmv limit
was arbitrary.
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In addition, EPA is promulgating alternative (Tier II) standards (discussed below),
as discussed in the October 1989 supplemental notice, for control of PIC emissions from
boilers and industrial furnaces. The Agency believes that the alternative controls will allow
facilities flexibility in meeting both the PIC controls and NOX emissions standards
(imposed under different regulatory authorities) simultaneously. The Agency believes that
the alternative, Tier n standards for control of PIC emissions are needed to address issues
and concerns raised by commenters on the proposed rule.
The 100 ppmv CO limit promulgated today for Tier I is indicative of steady-state
(i.e., normal), efficient combustion conditions. The time-weighted average for the CO
limit is provided to accommodate the CO spikes that inevitably occur during routine
"upsets," such as when hazardous waste fuel firing starts, when there is a load change on
an industrial boiler, or when the composition of fuels varies. Given that CO is a sensitive
indicator of overall combustion conditions, and that it may be a conservative indicator of
POHC and PIC destruction, EPA is implementing CO control limits based on time-
weighted averages of exceedances rather than implementing fixed CO limits. Fixed limits
that do not acknowledge inevitable CO spikes and that do not give owners and operators
time to adjust combustion conditions actually could result in greater emissions of PICs
because each time hazardous waste firing is interrupted, CO concentrations increase, and
emissions of incompletely burned organics may also increase. (Note, however, that there
is a requirement to maintain combustion chamber temperature after a waste feed cutoff
while waste remains in the chamber that is intended to minimize HC emissions after a
cutoff.) Thus, any controls on CO must balance the effects of organic emissions that may
result from overly stringent CO limits that require frequent waste feed interruptions with the
effects of emissions resulting from less stringent controls that acknowledge inevitable CO
spikes.
The Agency has considered whether the 100 ppmv CO limit is, in fact, too stringent
given that we acknowledge the limit was chosen from within the range of reasonable values
that may be considered indicative of good combustion conditions - 50 to 250 ppmv. We
attempted to obtain CO/time profiles from a number of well-operated devices to determine
the percentage of time the facilities operated within particular CO ranges. ^ We thought to
use this data to predict the frequency of waste feed cutoffs that would be required at various
19 Energy and Environmental Research Corporation, "Guidance on Metal and PIC
Emissions from Hazardous Waste Incinerators", Final Report, September 21,1990.
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CO limits. Unfortunately, the analyses could not be conducted because the facilities we
evaluated were operating under specific CO limits and their CO levels never exceeded those
limits when burning hazardous waste. We found that the facilities learned to comply with
the CO limits they had to meet
Moreover, we believe that the 100 ppmv CO limit is reasonable for a number of
reasons. Not only is it within the range of CO levels that are indicative of good combustion
conditions, but the Agency believes that it is not too low because: (1) it is higher than the
technology-based 50 ppmv CO level EPA requires for boilers burning waste PCBs (see 40
CFR Part 761); (2) it is higher than the CO limits included in many hazardous waste
incinerator permits20; (3) the Agency explicitly encourages the use of pre-alarms to
minimize the frequency of automatic waste feed cutoffs21; and (4) the limit is implemented
on an hourly rolling average basis which allows and minimizes the effects of short-term CO
spikes.
We also note that the Agency may soon promulgate regulations for municipal waste
combustors (MWCs) that, among other controls, may limit CO concentrations to 50, 100,
or 150 ppmv (as proposed), depending on the type of MWC, over a four hour rolling
average and dry-corrected to 7% oxygen. The MWC limits are technology-based - they
represent levels readily achievable by well-designed and well-operated units. EPA does not
believe that the MWC limits present a conflict with the 100 ppmv (with provisions for an
alternative higher limit if HC concentrations are less than 20 ppmv) limit for BIFs under
today's rule. The Agency is confident that the BEF rule is protective because the Agency
has determined that, when CO levels are less than 100 ppmv, PIC emissions do not pose
significant risk. Thus, although the 100 ppmv limit is not a best demonstrated technology-
based limit (many BIFs (and hazardous waste incinerators) readily operate at CO levels
well below 100 ppmv), the 100 ppmv CO limit will ensure protection of human health and
the environment
As stated above, the CO limits are based on a flue gas oxygen content of 7 percent.
One commenter indicated that EPA's reasoning for using the CO correction of 7 percent
20 We note that the Agency proposed on April 27,1990 to apply to hazardous waste
incinerators the same CO/HC limits that today's rule applies to BIFs.
21 If the CO limit is "too low" for a given facility's design and operating conditions,
then frequent waste feed cutoffs may occur. Frequent waste feed cutoffs may actually
increase PIC emissions because the resulting perturbation to the combustion system may
upset the temperature, oxygen, fuel relationships needed for complete combustion.
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oxygen is not clear. The commenter believes the 7 percent correction factor is unfair for
thermal units which, under normal conditions, need to operate at oxygen levels greater than
7 percent, yet operate with low levels of CO and HCs. EPA believes that correcting CO
levels for flue gas oxygen content is necessary because without this correction, high CO
flue gas concentrations could be diluted by high rates of excess oxygen. In today's rule,
EPA is requiring that CO be corrected to a flue gas oxygen content of 7 percent because the
majority of boilers and industrial furnaces achieve high combustion efficiency at optimum
flue gas oxygen levels ranging from 3 percent to 10 percent The optimum oxygen level to
achieve high combustion efficiency for a given device will vary depending on factors such
as fuel mix and boiler load In general, large combustion devices (in terms of heat input
capacity) have optimum oxygen requirements on the low end of the range of oxygen
content, while smaller units require higher oxygen levels. EPA believes that a correction
level of 7 percent is reasonable since this oxygen level is in the middle of the range of
typical operation for all devices and since the majority of devices burning hazardous waste
fuels have moderate heat input capacities (e.g., 20-150 MM Btu/hr). In addition, 7 percent
oxygen is the reference level for the existing paniculate standard for hazardous waste
incinerators under 40 CFR 264.343(c).
Moreover, the oxygen level to which CO values are corrected is not significant
since the CO levels for all facilities are corrected to a common basis. If the oxygen
correction level were changed from 7% to some other value, then theoretically, the CO limit
would have to be adjusted accordingly, and the effect on individual facilities would remain
the same.
b. Implementation of the 100 ppmv CO Limit. The procedures used to implement
the 100 ppmv CO limit are discussed below, including oxygen and moisture correction,
format of the limit, and compliance with the limit
Oxygen and Moisture Correction. The CO limit under Tier I (and Tier II) is on a
dry gas basis corrected to 7 percent oxygen. The oxygen correction normalizes the CO data
to a common base, accounting for the variation in design and operation of the various
combustion devices. In-system leakage, facility size, and waste feed type are other factors
that cause oxygen concentrations to vary widely in flue gases and were considered in
selection of the oxygen correction factor. The correction for moisture normalizes the CO
data that results from the different types of CO monitors used at facilities (e.g., extractive,
in situ, etc.). EPA's evaluation indicates that application of the oxygen and moisture
corrections can change measured CO levels by a factor of two in some cases.
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Measured CO levels must be corrected continuously for the amount of oxygen in
the stack gas according to the formula:
= COmxl4/(E-Y)
where COC is the corrected concentration of CO in the stack gas, COm is the measured CO
concentration according to guidelines specified in Appendix 2.1 provided in Methods
MflnMl for Compliance with the BBF Regulations (Methods Manual)22, E is the percentage
of oxygen contained in the air used for combustion, and Y is the measured oxygen
concentration on a dry basis in the stack. Oxygen must be measured at the same stack
location at which CO is measured under procedures that are also provided in Appendix 2. 1
of the Methods Manual.
Format of the CO Limit. EPA proposed that the CO limits be implemented under
either of two alternative formats, the hourly rolling average format or the time-above-a-limit
format. Under this approach, applicants would select the preferred approach on a case-by-
case basis. Comments were received in support of both alternative formats. Based on
further evaluation of the two formats and for reasons explained below, EPA is requiring
use of the hourly rolling average format for compliance with this rule.
Under the hourly rolling average format, a facility must measure and record CO
levels as an hourly rolling average. This approach allows instantaneous CO peaks without
requiring a cutoff provided that at other times during the previous hour CO levels were
correspondingly below the limit This approach requires a CO monitoring system that can
continuously measure and adjust the oxygen correction factor and compute the hourly
rolling averages.
Under the proposed time-above-a-limit format, dual CO limits would be established
in the permit: the first as a never-to-exceed limit and the second as a lower limit for
cumulative exceedances of no more than a specified period of time in an hour. These limits
and the time duration of the exceedances would be established on a case-by-case basis by
equating the mass emissions (peak areas) in both the formats (time-above-a-limit and
hourly rolling average formats) so that the regulation would be equally stringent in both
cases. The instruments needed for the time-above-a-limit format would include a CO
22 U.S. EPA, Methods Manual for Compliance with the BIF Regulations. December
1990. Available from the National Technical Information Service (NTIS), 5285 Port Royal
Road, Springfield, VA 22161, (703) 487-4600. The document number is PB 91-120-006.
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monitor, a recorder, and a timer that could indicate the cumulative time of exceedances in
every clock hour, at the end of which it would be recalibrated (manually or electronically).
Oxygen would not be measured continuously in this format; instead an oxygen correction
factor would be determined from operating data collected during the trial burn.
Subsequently, oxygen correction factors would be determined annually or at more frequent
intervals specified in the facility permit
EPA has re-examined the time-above-the-limit format in light of several comments
received and has decided to delete this alternative in today's final rule because:.
1. Since a facility would not be required to measure oxygen continuously under this
format, there would be no assurance that a facility would be operated reasonably
close to the oxygen level at which it operated during the trial burn. Even with a daily
determination of an oxygen correction factor, there would be the possibility of
"gaming" by the facility (operating the facility at low oxygen levels during the short
test period when the oxygen is measured, getting a favorable correction factor
established on that basis, and thereafter letting the facility operate at high oxygen
levels). Since the major advantage of this format was the cheaper cost due to the
omission of the oxygen monitoring requirement, adding continuous oxygen
monitoring to this format would remove this advantage as well; and
2. The proposed computations for converting hourly rolling averages to this format
would be cumbersome, inexact, and above all, very restrictive. To obtain a
conservative conversion, a permit writer would have to assume that CO levels will
remain at the established never-to-exceed limit for the full specified time in the hour,
and at the lower established limit the rest of the time. The CO limits obtained by
these computations would be very restrictive. As an example, a conversion of a Tier
I limit of 100 ppmv hourly rolling average for a facility having a single CO excursion
of 4-minutes duration in which the peak level was 1,000 ppmv, would result in a
permit specifying that for the remaining 56 minutes, CO could not exceed 34 ppmv,
a very restrictive limit For example, a CO profile of 30 ppmv for 55 minutes and 40
ppmv for the remaining 5 minutes would result in a violation.
Compliance with the Tier I CO Limit. The Agency considered a number of
alternative approaches for evaluating CO readings during trial burns to determine
compliance with the 100 ppmv limit, including: (1) the time-weighted average (or the
average of the hourly rolling averages); (2) the average of the highest hourly rolling
averages for all trial burn runs; or (3) the highest hourly rolling average. The time-
weighted average alternative provides the lowest CO level that could reasonably be used to
determine compliance, and the highest hourly rolling average alternative provides the
highest CO level that could reasonably be used. EPA is requiring the use of the most
conservative of these approaches, the highest hourly rolling average approach, for
interpreting trial bum CO emissions for compliance with the 100 ppmv Tier I limit (This
approach is conservative because trial burn CO levels are compared to the nwcimqm CO
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allowed under Tier I -100 ppmv.) EPA believes this conservative approach is reasonable
since compliance with the Tier I CO limit allows applicants to avoid the Tier n requirement
of evaluating HC emissions to provide the additional assurance (or confirmation) that HC
emissions do not exceed levels representative of good operating practice.
3. Tier II PIC Consols: Limits on CO and HC.
a. Need for Tier n PIC Controls. Commenters indicated that several types of
boilers and many cement kilns will not be able to meet the (Tier I) 100 ppmv CO limit
proposed in May 1987 even though HC concentrations will not be high at elevated CO
levels. For example, boilers that burn residual oil or coal typically operate with CO
emission levels above the Tier 1100 ppmv CO limit because of inherent fuel combustion
characteristics, equipment design constraints, routine transient combustion-related events,
requirements for multiple fuel flexibility, and requirements for compliance with NOX
emission standards established under the Clean Air Act Attempts to reduce CO emissions
from these devices to meet the Tier I limit could prove unsuccessful. In addition, there is a
possibility that thermal efficiency could be adversely affected if these attempts are
successful.
Similarly, industry and trade groups for the cement industry voiced strong
opposition to the 100 ppmv CO limit for cement kilns. These commenters indicated that
some cement kilns, especially modem precalciners, routinely emit CO above the Tier 1100
ppmv limit. In general, commenters indicated that while the Tier I limit may be appropriate
for combustion devices in which only fuel (fossil or hazardous waste) enters the
combustion chamber, it is inappropriate for cement kilns and other product kilns in which
massive amounts of feedstocks are processed These feedstocks can generate large
quantities of CO emissions which are unrelated to the combustion efficiency of burning the
waste and fuel. Whereas all the CO from boilers and some industrial furnaces is
combustion-generated, the bulk of the CO from product kilns can be the result of process
events unrelated to the combustion conditions at the burner where wastes are introduced.23
Therefore, limiting CO emissions from these combustion devices to the Tier 1100 ppmv
level may be difficult and may not be warranted as a means of minimizing risk from PICs.
23 For example, CO can be generated from the trace levels of organic matter contained
in the raw materials as the materials move down the kiln from the "cold" feed end to die
"hot" end where the fuel and waste is fired and the product is discharged.
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In summary, commcnters argued that there are specific instances and classes of
combustion devices for which the Tier I CO limit would be difficult or virtually impossible
to meet, and thus this limit is inappropriate since EPA has not established a direct
correlation between CO emissions, PIC emissions, and health risks.
In light of these concerns, commenters suggested that EPA establish CO limits for
specific categories of combustion devices based on CO levels achieved by units operating
under best operating practices (BOP). The Agency considered this approach but
determined that equipment-specific CO trigger limits would be difficult to establish and
support and would not necessarily provide adequate protection from PIC emissions.
Nonetheless, EPA believes that the CO limits should be flexible to avoid major economic
impacts on the regulated community since no direct correlation has been established
between exceeding the 100 ppmv CO limit and increasing health risks from PIC emissions.
EPA believes, however, that at some elevated CO level PIC emissions would pose
significant risk. At this time, EPA is unable to identify a precise CO trigger level since the
trigger level may vary by the type and design of the combustion device and the fuel mix
used in the device. Consequently, EPA has established a two-tiered approach to control
PICs. Under Tier I, CO is limited to 100 ppmv or less, as discussed above. Under Tier
n, CO levels can exceed 100 ppmv provided that the owner or operator demonstrate that
the HC concentration in the stack gas does not exceed a good operating practice-based limit
of 20 ppmv (except that the Director may establish under §266.104(f) an alternative HC
limit for furnaces that feed raw material containing organic matter and, thus, cannot meet
the 20 ppmv limit).
Under Tier n, the CO limit for a facility is based on the levels achieved during a
successful compliance test The Agency originally proposed two alternative approaches for
establishing HC emission limits under the Tier n waiver a health-based approach and a
technology-based approach. These two alternatives and EPA's rationale for selecting the
technology-based approach for the final rule are discussed below. Before moving to those
discussions, however, it may be useful to summarize the conclusions of an evaluation by
EPA's Science Advisory Board of the proposed PIC controls.
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b. Comments by EPA's Science Advisory Board (SAB). We present below a
summary of SAB's conclusions24 on the scientific support for EPA's proposed PIC
controls and EPA's response:
• SAB: The Agency has not documented that PICs from hazardous waste combustion
can cause significant health risk to human health or the environment
- EPA Response: While the Agency agrees that available data do not show that
PICs are likely to pose a significant health risk, EPA's emissions testing to date
has been able to identify and quantify only as much as 60% of the organic
compounds being emitted during any test During many of EPA's tests, less than
5 to 10% of organic emissions were characterized. The Agency is concerned that
this large fraction of uncharacterized organic emissions could be comprised of
compounds that can pose significant health risk. Therefore, the Agency believes
that PICs have the potential to present a hazard and should be controlled.
• SAB: It is prudent to control PICs given the inability to show that they do not pose a
health risk because of limitations of sampling and analytical techniques and health and
environmental impact assessment data and methodologies.
- EPA Response: The Agency agrees. Additional emissions testing cannot be used
to determine if, in fact, PICs can pose significant risk because the sampling and
analytical techniques are not available to identify the unknown compounds.
Moreover, even if the techniques were available, health effects data are not likely
to be available for the compounds so that a risk assessment could not be
conducted.
• SAB: The use of CO and HC to ensure high combustion efficiency seems to be a
reasonable approach to control PIC emissions.
- EPA Response: The Agency agrees.
: Under the Tier H controls when CO exceeds 100 ppmv, HC should be
monitored continuously.
the Science Advisory Board", Report # EPA-SAB-EC-90-004, January 1990.
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- EPA Response: The Agency agrees. Today's final rule requires continuous HC
monitoring under the Tier n controls (see §266.104(c)) when CO levels exceed
100 ppmv, and for certain industrial furnaces irrespective of CO level (see
§§266.104(d) for permitted furnaces and 266.103(a)(5) for furnaces operating
under interim status).
• SAB: There is no scientific support for the health-based approach to establish HC
limits on a site-specific basis based on a calculated "unit risk" value for total HC and
stack gas monitoring of HC concentrations.
- EPA Response: The final rule does not allow the use of the proposed health-
based approach to control HC. HC are controlled under the technology-based
limit of 20 ppmv. See §266.105(c).
• SAB: The risk assessment procedures are adequate, however, to show that the
technology-based HC limit of 20 ppmv appears to be protective of human health.
- EPA Response: The Agency agrees.
• SAB: The Agency should show that the proposed limits for CO and HC do not result
in frequent automatic waste feed cutoffs that may increase PIC emissions.
- EPA Response: See discussion in section C.2.b.i above.
Thus, the SAB supported the overall reasonableness of the course adopted in this
rule to control potential risks from emissions of PICs.
c. Health-Based Approach for HC Limits. Under the Tier II health-based
approach, the Agency proposed to allow applicants to demonstrate that PIC emissions from
combustion devices pose an acceptable risk (i.e., less than 10~5) to the maximum exposed
individual (MET). Under this approach, EPA proposed to require that applicants quantify
HC emissions during trial burns and assume that all hydrocarbons are carcinogenic
compounds with a unit risk value that would be calculated based on available data. The HC
unit risk value would be 1.0 x 10~5 m^/ug and would represent the adjusted 95th percentile
weighted (i.e., by emission concentration) average unit risk of all the hydrocarbon
emission data in EPA's database of field testing of boilers, industrial furnaces, and
incinerators burning hazardous waste. The weighted unit risk value for HC considers
emissions data for carcinogenic PICs (e.g., chlorinated dioxins and furans, benzene,
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chloroform, and carbon tetrachloride) as well as data for PICs that are not suspected
carcinogens and are considered to be relatively nontoxic (e.g., methane, and other Cl as
well as C2 hydrocarbons).25
The Agency proposed to implement this provision by back-calculating an acceptable
HC emission rate (and, based on stack gas flow rates, a HC concentration) from the
acceptable ambient level based on the calculated "total HC" unit risk value discussed above
and allowing an incremental cancer risk of 1 in 100,000.
A number of commenters supported the health-based approach while several others
pointed out that the approach was seriously flawed. EPA's Science Advisory Board
reviewed the approach as discussed above and concluded that the site-specific, health-based
approach of controlling HC was not scientifically supportable.
Upon re-evaluation, EPA believes that basing the HC limit on a health-based
approach is not supportable and, thus, has not selected this approach for the final rule.
Given the limited data base on the types and concentrations of PICs emitted over a range of
operating conditions, we are concerned that the potency value that the proposed approach
would apply to the total mass of hydrocarbons emitted may not be appropriate. It is not
clear whether the proposed potency value may overstate or understate the risk posed by HC
emissions. In addition, we are concerned that we do not fully understand what types of
hydrocarbon emissions are actually detected by the continuous monitoring equipment For
example, as we discussed at proposal, certain halogenated compounds are under reported
by the HC detection system. Finally, as we noted at proposal, the proposed risk-based
approach could allow extremely high HC concentrations - concentrations clearly indicative
of combustion upset conditions.
d. Technology-Based Approach: 20 ppmv HC Limit Under the technology-based
approach, the Tier I CO limit of 100 ppmv will not have to be met if HC levels in the stack
gas do not exceed a good operating practice-based limit of 20 ppmv26 (measured on an
hourly rolling average basis, reported as propane, dry corrected to 7% oxygen). As noted
25 Additional information on the development of the unit risk factor can be found in
U.S. EPA, Background Information Document for the Development of Regulations for
PIC Emissions from Hazardous Waste Incinerators. October 1989.
26 A.S discussed at proposal, the 20 ppmv limit represents a demarcation between good
and poor combustion conditions based on HC emissions data from 24 facilities. The 20
ppmv limit is not based on best operating practice. A best operating practice limit would be
set a level on the order of 5 ppmv.
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above, EPA developed this technology-based approach because of current scientific
concerns (seconded by the SAB) related to a health-based approach. In addition, the
health-based approach could allow HC levels of several hundred ppmv, levels that are
clearly indicative of "upset" combustion conditions. The approach, as noted above, lacks a
firm scientific basis and could allow facilities to operate under upset conditions. EPA
would not authorize such operations unless reasonably certain they would not pose a
significant risk to human health and the environment Such reasonable certainty does not
exist here.
One commenter agreed that the PIC standard should be protective without imposing
a technology "fix." Although EPA believes the development of a health-based approach is
a step in the right direction, the Agency is concerned about whether the health-based Tier II
approach is adequately protective given the limited database on PIC emissions and the
uncertainty as to what fraction of organic emissions would be detected by the HC
monitoring system. Despite the limitations of the HC health risk assessment methodology,
EPA believes (and the SAB concurs) it is reasonable to use this methodology to predict
whether a technology-based limit appears to be protective. Accordingly, EPA used the
health risk assessment methodology to show that a 20 ppmv HC limit would not result in
an incremental lifetime cancer risk to the hypothetical maximum exposed individual greater
than 1 in 100,000..
The final rule establishes limits for both CO and HC under the Tier H PIC controls.
The CO limit is established as the average over all runs of the highest hourly rolling average
for each run of the compliance test or trial burn. To demonstrate compliance with the HC
limit, the highest hourly rolling average HC level during the compliance test or trial bum
cannot exceed 20 ppmv (except as otherwise provided for furnaces feeding raw materials
containing organic matter), reported as propane, corrected to 7% oxygen on a dry basis.
The Agency considered whether to establish provision for a case-by-case waiver of
the 20 ppmv HC limit based either on health-risk assessment or technical feasibility (i.e.,
feasibility of providing combustion conditions to minimize fuel-generated HC). The final
rule does not provide for a waiver of the 20 ppmv HC limit as an indicator of good
combustion conditions and minimum fuel-generated PIC emissions. (The final rule does,
however, allow the Director to establish under the Part B permit proceedings an alternative
HC limit for industrial furnaces (e.g., cement kilns, light-weight aggregate kilns) to
account for hydrocarbons that are emitted from trace levels of organic matter in the raw
material. Any alternative HC limit established for a furnace will ensure that fuel-generated
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hydrocarbons (hazardous waste and other fuels) are less than 20 ppmv by establishing the
HC limit based on HC concentrations when the system is designed and operated under
good combustion conditions without burning hazardous waste.27 See section n.B.5 of
Part Three of this preamble for more discussion of the alternative HC limit for industrial
furnaces.)
EPA did not provide a waiver of the HC limit in the final rule because: (1) the
Agency believes, and SAB concurs, that a site-specific, health risk assessment approach to
establishing HC limits (e.g., a waiver of the 20 ppmv limit) is not scientifically
supportable; and (2) a technology-based waiver is not supportable because well-designed
and operated hazardous waste combustion devices can readily meet a 20 ppmv HC limit
Several commenters disagreed with EPA that both CO and HC should be
monitored, stating that it is unnecessary to monitor CO if HC is monitored. The Agency
continues to believe that it is reasonable to require both CO and HC monitoring when CO
levels exceed 100 ppmv. When CO levels exceed the Tier I level, the facility is not
operating at high combustion efficiency and the potential for high PIC emissions exists.
The Agency believes that, since CO monitoring is a widely practiced approach for
improving and monitoring combustion efficiency, and since CO emission levels may
respond more quickly to process upsets than HC levels, the apparent redundancy in
requiring both CO and HC monitoring is warranted to ensure protection of human health.
Another commenter added that HC monitoring could be supplemented by frequent
testing for common PICs that respond poorly to HC monitors, such as carbon
tetrachloride, formaldehyde, perchloroethylene, and chlorobenzene. At this time, the
Agency believes that continuous HC monitoring combined with CO monitoring is adequate
in most cases to detect when the facility is operating under combustion upset conditions
(this is another reason, however, that monitoring both CO and HC is reasonable when CO
levels exceed the level normally indicative of good combustion - 100 ppmv). We note
that, as discussed in section ILD below, the final rule requires a hot HC monitoring system
(i.e., unconditioned gas sample heated to a minimum of 150°C) which ensures minimum
loss of organic compounds. Nonetheless, the Agency is currently developing sampling
and analytical techniques to continuously monitor indicator organic compounds such as
those suggested by the commenter.
27 We note that this approach should limit fuel-generated hydrocarbon concentrations
to well below 20 ppmv because fuel-generated hydrocarbons from a well-designed and
operated cement or light-weight aggregate kiln should not exceed 5 ppmv.
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e. Basis for Final Rule. EPA believes that the 20 ppmv HC limit in the final rule
for the Tier n PIC controls is representative of an HC limit that distinguishes between good
and poor combustion conditions. (When a facility operates under poor combustion
conditions, PIC emissions can increase and may result in adverse health effects to exposed
individuals.) This HC limit is within the range of values reported in the Agency's data base
for hazardous waste incinerators, boilers, and industrial furnaces that burn hazardous
waste, and the limit is also protective of human health based on risk assessments conducted
for 30 incinerators. See 54 FR 43723. Under Tier II, HC must be monitored
continuously, recorded on an hourly rolling average basis, reported as ppmv propane, and
corrected to 7 percent oxygen on a dry basis. In addition, CO must be monitored
continuously, corrected to 7 percent oxygen on a dry basis, recorded on an hourly rolling
average basis, and may not exceed the limit established during the test burn (i.e., the
average over all runs of the highest hourly rolling average for each run).
4. Special Requirements for Furnaces. The final rule provides several special
requirements for industrial furnaces stemming from the fact that: (1) some industrial
furnaces, notably cement kilns, are not able to meet the 20 ppmv HC limit because trace
levels of organic matter in raw materials can emit substantial levels of hydrocarbons; and
(2) the PIC controls may not be protective for furnaces (e.g., cement kilns and mineral
wool cupolas) that feed hazardous waste at locations other than where normal fuels are
fired. These special requirements are discussed below.
a. Alternative HC Limit EPA requested comment on whether alternative HC limits
may be appropriate for certain industrial furnaces. See 54 FR 43724 (Oct. 26,1989). A
number of commenters28 requested that EPA allow cement kilns, light-weight aggregate
kilns, and lime kilns that cannot meet the 20 ppmv HC limit because of the hydrocarbons
generated by trace levels of organic materials in the normal raw materials to establish a site-
specific alternative HC limit that does not allow HC levels when burning hazardous waste
to be significantly higher than when burning normal fuels, processing normal raw
materials, and producing normal products in a system that is designed and operated to
minimize hydrocarbon concentrations in stack gas. Nineteen commenters pointed out that
28 ^ addition to comments on the October 26,1989 supplement to the proposed rule,
see minutes of the EPA meetings with the Cement Kiln Recycling Coalition of April 17,
1990; May 23,1990; June 4,1990;, June 20,1990; July 19,1990; and October 10,1990.
See also minutes of the EPA meeting with Southdown, Inc. on May 11,1990, and the
letter from the Cement Kiln Recycling Coalition to Bob Holloway, EPA, dated June 15,
1990.
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baseline HC emission levels from cement kilns can be attributed to the naturally-occurring
raw materials that are used in the production of cement Use of shale as a raw material, for
example, can result in HC emissions from kerogens in the shale. Use of fly ash as a
source of iron and silica could result in increased CO emissions from partial oxidation of
free carbon in the fly ash. Commenters claim that approximately 6 to 10 cement plants
may not be able to comply with the HC limit of 20 ppmv even though they generate
minimal HC from sources other than raw materials (e.g., hazardous waste fuels, other
fuels, organic compounds in slurry water). The organic compounds in normal raw
materials would not ordinarily be hazardous, so that their emissions (e.g., through
volatilization) would not raise the types of concerns normally addressed by RCRA.29
The Agency believes that it will be possible in some situations to develop an
approach on a case-by-case basis to effectively implement an alternative HC limit under the
principle stated above. (If the 20 ppmv HC limit were health-based, the Agency would be
more reluctant to develop an alternative to it. Given, however, that the limit is a measure of
combustion efficiency, the Agency believes it reasonable to develop an alternative means
for this class of furnaces to demonstrate combustion efficiency.) The Agency considered a
number of approaches to establish an alternative HC level and determined in the time
available that none appeared to be workable in all situations. The Agency is therefore
adopting a more individualized approach in the present rule that allows permit writers to
establish an alternative HC limit (i.e., a HC limit that exceeds 20 ppmv) in a facility's
operating permit, and allows permit writers to grant an extension of time to comply with the
HC limit during interim status, based on the following showings: (1) for cement kilns, the
kiln is not equipped with a by-pass duct that meets the requirements of §266.104(0(1); (2)
the applicant demonstrates that the facility is designed and operated to minimize
hydrocarbon emissions from fuels and raw materials; (3) the applicant develops an
approach to effectively monitor over time changes in the operation of the facility that could
reduce baseline HC levels — for example, changes in raw materials, fuels, or operating
conditions -- which could result in establishing a new baseline and corresponding
adjustment of the HC limit; and (4) the applicant demonstrates that the hydrocarbon
emissions are not likely to pose a significant health risk See §266.104(0(2). We explain
these provisions in more detail below, along with an explanation of which provisions apply
during interim status and which are part of permit application and issuance.
29 We note, however, that nonhazardous organic constituents in feedstreams may be
partially combusted to form hazardous products of incomplete combustion.
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Interim Status Facilities. Today's rule requires facilities operating in interim status
to comply with CO and, if required, a 20 ppmv HC limit within 18 months of the rule's
date of promulgation. The rule provides for a case-by-case extension from these
requirements (as well as the paniculate, metals, and HC1/C12 standards) "if compliance is
not practicable for reasons beyond the control of the owner or operator." See
§266.103(c)(7)(ii). The situation where a furnace may be unable to achieve the 20 ppmv
HC limit because of organics present at baseline conditions (i.e., when the facility is
designed and operated to minimize HC emissions from raw materials and fuels while
producing normal products under normal operating conditions and when no hazardous
waste is burned) may be eligible for the extension of time provided the following
conditions are satisfied:
1. The applicant for the extension of time must have submitted a complete Part B permit
application. The application must include the following information pertinent to the
question of an alternative HC limit: (a) documentation that the system is designed and
operated to minimize HC emissions from all sources when the baseline level is
established and when hazardous waste is burned; (b) documentation of the baseline
HC flue gas concentration when the facility is operated to minimize HC emissions
and when feeding normal raw materials and normal fuels to produce normal products
under normal operating conditions and when not burning hazardous waste; (c) a test
protocol to confirm the baseline HC (and CO) level; (d) a trial burn protocol to
demonstrate that, when hazardous waste is burned, HC (and CO) concentrations do
not exceed the baseline level; and (e) a procedure to show if and when HC emissions
from nonhazardous waste sources may decrease (in which case, the overall HC limit
might be adjusted downward after a new baseline is established). See §270.22(b).
(The substantive basis for these requirements is explained in more detail below.)
2. During interim status, the applicant must not only conduct emissions testing when
burning hazardous waste to certify compliance with all remaining emissions controls -
- dioxins and furans, PM, metals, and HQ/C12 ~ but also establish and comply with
interim limits on CO and HC presented in the Part B permit application as levels the
applicant has determined by testing (without burning hazardous waste) are baseline
levels. We note that the Director may not have time during the review of the
extension request (and a preliminary review of the Part B application) to confirm the
adequacy of the interim CO and HC limits proposed by the applicant. Moreover, to
do so would require the types of oversight of test protocols, emissions testing, and
review of data that will be applied under the permit process. Thus, the interim limits
are subject to revision based on (confirmation) testing in support of the operating
permit Nonetheless, EPA believes that establishing interim CO and HC limits and
requiring the owner/operator to comply with them until a permit is issued (or denied)
is reasonable and provides a measure of protection of human health and the
environment
It should be noted that the Agency does not believe that it is possible to establish an
alternative HC limit during interim status. This is because the level of interaction
between an applicant and permit writer over evaluation of the various protocols to
establish a HC baseline and determine when it should be reduced, plus conducting
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test burns to confirm the HC baseline and that HC levels do not increase when
hazardous waste is burned, plus conducting a health-risk assessment for organic
emissions when hazardous waste is burned are beyond the scope of interim status.
Consequently, the rule is structured so that the alternative HC limit (if warranted)
would be established as part of the permit, and die interim status certification of
compliance deadline can be extended, if the Director finds this is warranted, while the
permit is being processed. The Director may also may make the extension of time
conditional on die time estimated to process the permit application or other factors,
and can be conditioned on operating conditions than ensure the facility will operate in
a manner that protects human health and the environment Any such condition would
be embodied in an interim status extension determination that is enforceable as a
requirement of subtitle C (much as conditions in a closure plan are enforceable), and
would be documented in an administrative record for the determination.
3. Cement kilns with a by-pass duct are ineligible for an extension. The rule precludes
cement kilns operating with a by-pass duct from eligibility for the extension of the
certification of compliance date for compliance with the CO and HC limit, as well as
for obtaining an alternative HC limit in a permit
Fully Permitted Facilities. The Director may establish an alternative HC limit in the
facility's operating permit provided that the applicant meets the following requirements.
Information and data documenting compliance with these requirements must be included in
the Part B permit application. See §270.22(b). First, the applicant must document in the
permit application that facility is designed and operated to minimize HC emissions from all
sources, including raw materials and fuels. Examples of situations where the system is not
designed and operated to minimize HC (and CO) levels during baseline testing are when:
(1) coal is mixed with raw material which is fed into a cement kiln preheater such that the
coal can contribute to HC emissions; (2) cement kiln slurry water contains enough organic
compounds to significantly contribute to HC emissions; (3) waste fuels such as tires are
burned in a manner that could contribute to HC emissions; (4) die furnace is not operated
and designed to minimize emissions of hydrocarbons emitted from raw material (in general,
the more quickly the raw material is exposed to elevated temperatures, the lower the
hydrocarbon emissions); and (5) normal fuels are not burned under good combustion
conditions.
Second, the applicant must propose in the permit application baseline flue gas CO
and HC levels. These proposed baseline levels also serve as interim values under which
the facility must operate under a conditional time extension for certification of compliance
with the HC standard until permit issuance (or denial). The proposed baseline levels must
be supported by emissions testing under baseline conditions (i.e., when the facility is
designed and operated to minimize HC emissions from raw materials and fuels while
producing normal products under normal operating conditions and when no hazardous
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waste is burned). Baseline levels must be determined from test data as the average over all
valid runs of the highest hourly rolling average value for each run. This is the same
approach specified by the rule to determine limits on other operating parameters (e.g.,
maximum feed rate limits, maximum temperatures, etc). EPA believes that this approach is
workable for cement kilns30 given that commenters have asserted that when hazardous
waste is burned, hydrocarbon levels do not increase and often decrease. As discussed in
section HE of Part Three of the preamble, HC levels from a cement kiln with HC levels of
66 to 70 ppmv when burning coal decreased to 38 to 63 ppmv when burning hazardous
waste fuel. If the facility cannot install continuous monitors for HC (and CO and oxygen)
in time to conduct these baseline tests prior to submittal of the permit application (which
must be sufficiently prior to 18 months after promulgation of the rule to give the Director
time to consider whether to grant the time extension), the facility may use portable
monitors. We note that the HC monitoring system must be a hot, unconditioned system.
In addition, we note that different baseline values may be necessary for different modes of
operation if the baseline HC (or CO) level changes significantly under those modes of
operation. Examples are when the raw material mix is changed to make a different cement
product or when different fuels are burned.
Third, the applicant must develop emissions testing protocols to: (1) confirm the
baseline HC and CO levels proposed in the permit application (and under which the facility
must operate in interim status upon receipt of an extension of time to comply with the HC
limit and until an operating permit is issued (or denied)); and (2) to demonstrate that, when
hazardous waste is burned, HC and CO levels do not exceed baseline levels (and emissions
of other pollutants do not exceed allowable levels). If a baseline HC or CO level is to be
established for more than one mode of operation, a baseline confirmation test (comprised of
at least three valid runs) must be run for each mode.
Fourth, the applicant must develop an approach to effectively monitor over time
changes in the operation of the facility that could significantly reduce baseline HC or CO
levels. If baseline levels are significantly reduced, then the alternative HC and CO limits
that apply when burning hazardous waste must also be reduced. Such changes could
include: (1) changes in the concentration of organic matter in raw materials; (2) changes in
the concentration of organic matter in the raw material mix due to changes in the mixture of
30 Although any industrial furnace that cannot meet the 20 ppmv HC limit because of
organic matter in raw material is eligible to apply for an alternative HC limit, only one
commenter expressed concern that industrial furnaces other man cement kilns may not be
able to meet the 20 ppmv HC limit
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raw materials needed to produce different types of product; (3) changes in fuels; and (4)
changes in the concentration of organic compounds in slurry water used for a wet cement
kiln. The approach must be workable and enforceable.
EPA is requiring this condition in order to avoid establishing a high baseline which
is then reduced without also lowering the HC limit, potentially allowing the hazardous
waste to be burned under poor combustion conditions creating high, but undetected, HC
levels (i.e., hazardous waste could be burned under poor combustion conditions and could
be emitting high HC levels even though the HC limit was not exceeded). (The Agency
notes that the problem of establishing a HC baseline and for determining when the baseline
might change for this type of industrial furnace is more difficult than determining when the
raw material baseline changes in documenting when co-combustion of hazardous waste
with raw materials in a Bevill device might affect the composition of residues. See section
Xm of Part Three of the preamble. This is because, in the case of the HC baseline, not
only must the raw materials' and fuels' composition be monitored, but the units design and
operating conditions as well to determine whether the baseline has changed. Thus, the rule
provides for more interaction in establishing baseline conditions and determining when they
change for assessing alternative HC limits for cement kilns than it does when making
detenninations as to whether co-combustion of hazardous waste can remove residues from
eligibility for exclusion under the Bevill amendment)
Finally, EPA is concerned that hazardous waste burning may affect the type and
concentration of organic compounds emitted from an industrial furnace that has elevated
HC concentrations attributable to raw materials. For example, the chlorine in the hazardous
waste may result in higher concentrations of chlorinated organic compounds. Therefore,
the rule requires the owner or operator, as pan of the permitting process, to use state-of-
the-art emissions testing procedures and risk assessment to demonstrate that organic
emissions are not likely to pose unacceptable health risk. The owner or operator must
conduct emissions testing during the trial burn to identify and quantify the organic
compounds listed in Appendix Vm, Part 261, that may be emitted using test procedures
specified by the Director on a case-by-case basis. As noted above, although EPA does not
believe such risk-based approaches to be adequate as the basis for a national risk-based PIC
standard, we think the approach is part of the best means of assuring that cement kilns
combust hazardous waste fuels properly in those instances where HC levels are greater
than 20 ppmv as a result of organics in normal raw material feed.
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Two sampling and analysis approaches that the Director may use are discussed
below. One protocol involves the following steps to identify and quantity concentrations of
organic compounds in stack emissions:
1. Sample volatile organic compounds using the VOST train of Method 0030 as
prescribed in SW-846 Analytical work is conducted using GC/MS according to
Method 5040 in SW-846.
2. Sample semi-volatile organic compounds using the sampling train prescribed in
Method 0010 in SW-846. Analytical work is conducted using GC/MS according to
Method 8270 in SW-846.
3. Sample aldehydes and ketones using an impinger train with 2-4 di-nitro-phenyl
hydrazine (2-4 DNPH) in the impinger solution as prescribed in Method 0011 in the
Methods Manual, and analysis of impinger solution by high performance liquid
chromatography (HPLC) as specified in "Analysis for Aldehydes and Ketones by
High Performance Liquid Chromatography" in die Methods Manual
Another protocol is a screening approach that has been described in the literature31
that uses the following protocols as specified in SW-846:
1. Soxhlet extraction sample preparation;
2. Gas chromatography (GC) coupled with flame ionization detector (FID) or mass
spectrography (MS) screening;
3. Total chromatographic organics (TCO) and gravimetric (GRAY) procedures; and
4. High performance liquid chromatography-ultraviolet/MS (HPLC-UV/MS) screening
and compound identification.
To select an appropriate protocol, the Director will consider the state-of-the-art of
sampling and analytical techniques and the expected nature of organic emissions
considering emissions data or other information.
We note that, under this PIC risk assessment, emission rates must also be
determined for the 2,3,7,8-chlorinated tetra-octa congeners of chlorinated dibenzo-p-
dioxins and dibenzofurans (CDDs/CDFs) using Method 23, "Determination of
Polychorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans (PCDFs) from
Stationary Sources" in Methods Manual for Compliance with the BIF Regulations
3 1 Johnson, Larry, et al., "Screening Approach for Principal Organic Hazardous
Constituents and Products of Incomplete Combustion", JAPCA Journal, Volume 39, No.
5, May 1989.
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Manual^ (incorporated by reference in §261.1 1). The risks from these congeners
must be estimated using the 2,3 J,8-TCDD toxicity equivalence factor prescribed in
"Procedures for Estimating the Toxicity Equivalence of Chlorinated Dibenzo-p-Dioxin and
Dibenzofuran Congeners" in fofpthrvk Manual
The owner or operator must then conduct dispersion modeling to predict the
maximum annual average ground level concentration of each such organic compound. On-
site ground level concentrations must be considered if a person resides on-site; otherwise,
only off-site concentrations may be considered. Dispersion modeling must be conducted in
conformance with EPA's Guideline on Air Quality Models. EPA's "Hazardous Waste
Combustion Air Quality Screening Procedure" provided in Method^ Manual, or EPA's
Screening Procedures for Estimating Air Quality Impact of Stationary Sources. All three
documents are incorporated by reference in §260.1 1.
Stack heights exceeding good engineering practice (GEP, as defined in 40 CFR
51.100(ii)) may not be used to predict ground level concentrations. See section V.B.1.C of
Part Three of this preamble.
If the owner or operator applies for an alternative hydrocarbon limit for more than
one industrial furnace such that emissions from the furnaces are from more than one stack,
emissions testing must be conducted on all such stacks and dispersion modeling must
consider emissions from all such stacks.
To demonstrate that the noncarcinogenic organic compounds listed in Appendix IV
of the rule do not pose an unacceptable health risk, the predicted ground level
concentrations cannot exceed the levels established in that Appendix.
To demonstrate that the carcinogenic organic compounds listed in Appendix V of
the rule do not pose an unacceptable health risk, the sum of the ratios of the predicted
ground level concentrations to the levels established in the Appendix cannot exceed 1.0.
This is because the acceptable ambient levels established in Appendix V are based on a 10~5
risk level. To ensure that the summed risk from all carcinogenic compounds does not
exceed 10'5 (i.e., 1 in 100,000) the sum of the ratios described above must be used. (We
note that the 2,3,7,8-TCDD toxicity equivalency factor is to be used to estimate the risk
from 2,3,7,8-chlorinated CDDs/CDFs, and the risk from these congeners must be added to
the risk from other PICs to ensure that the summed risk does not exceed 1 in 100,000.)
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To demonstrate that other compounds for which the Agency does not have adequate
health effects data to establish an acceptable ambient level are not likely to pose a health
risk, the predicted ambient level cannot exceed 0.09 ug/m^. This is the 5th percentile
lowest reference air concentration for the compounds listed in Appendix IV of the rule.
b. Feeding Waste at Locations other than the Hot End. If hazardous waste is fed
into an industrial furnace at locations other than the "hot" end where the product is normally
discharged and where fuels are normally fired, the rule requires the owner/operator to
monitor HC irrespective of whether CO levels do not exceed the Tier I limit of 100 ppmv
and to comply with special restrictions during interim status. These provisions are
discussed below.
Mandatory HC Monitoring^. Except as indicated below, facilities that fire
hazardous waste into an industrial furnace at locations other than the "hot" end where the
product is normally discharged and where fuels are normally fired must comply with the
HC limit even if CO levels do not exceed the Tier I limit of 100 ppmv. See §266.105(d).
This is because the Agency is concerned that the hazardous waste could conceivably be
fired at a location in a manner such that nonmetal compounds in the waste may be merely
evaporated or thermally cracked to form pyrolysis by-products rather than completely
combusted. If so, little CO may be generated by the process and, thus, monitoring CO
alone would not ensure that HC emissions were minimized.
However, if hazardous waste is burned (or processed) solely as an ingredient, HC
monitoring is not automatically required because emissions of nonmetal compounds are not
of concern. This is because the metals emissions controls will ensure that metals emissions
do not pose a hazard. (The rule establishes the restrictions discussed below because we are
concerned that the interim status controls on organic emissions may not be protective when
hazardous waste is fed at locations other than the "hot" end of a furnace.) See discussion
in section VnH of Part Three of this preamble for when a waste is considered to be burned
solely as an ingredient33.
32 Continuous HC monitoring is required for a furnace if hazardous waste is fired at
any location other than the "hot", product discharge end where fuels are normally fired
irrespective of the CO level in stack emissions (i.e., irrespective if CO levels are lower than
the Tier I limit of 100 ppmv) and irrespective of whether furnace off-gas is passed through
another combustion chamber.
33 Regulated entities have indicated that there is substantial confusion over the terms
"use as an ingredient" and "material recovery". Under the RCRA hazardous waste
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Interim Status Restrictions. In addition to requiring HC monitoring when
hazardous waste is fed into a furnace at locations other than the "hot" end where the
product is discharged and where fuels are normally fired, today's rule applies other
restrictions to hazardous waste burning during interim status. See §266.104(a)(5). The
hazardous waste may not be fed at any location where combustion gas temperatures are less
than 1800°F, and the owner or operator must demonstrate that adequate oxygen is present
to combust the waste. In addition, for cement kilns, the hazardous waste must be fed into
the kiln itself. These requirements are provided to ensure adequate destruction of the waste
given that the DRE standard (which requires a demonstration by trial burn that organic
constituents in the waste are destroyed) is not applicable during interim status. Like the
requirement for mandatory HC monitoring, however, these restrictions do not apply if the
hazardous waste is burned (processed) solely as an ingredient. For further discussion, see
section Vn.H of Part Three of this preamble.
5. Special Considerations for Cement Kilns.
a. Monitoring in the By-Pass Duct of a Cement Kilns. The final rule provides that
cement kilns with by-pass ducts may monitor CO and, if required, HC concentrations in
the by-pass duct. Most precalciner and some preheater kilns are equipped with by-pass
ducts where a portion (e.g., 5-30%) of the kiln off-gas is diverted to a separate air pollution
control system (APCS) and, sometimes, a separate stack. A portion of the kiln gases are
so diverted to avoid a build-up of metal salts that can adversely affect the calcination
process. Dust collected from the by-pass APCS is usually disposed of while dust collected
from the main APCS is usually recycled back into the kiln to make the clinker product
Several comments were received regarding sampling at cement kilns. Five
commenters suggested that HC (and CO) measurements should be allowed in the bypass
duct rather than in the main stack because: (1) the by-pass gas is representative of the kiln
off-gas; and (2) this approach would preclude the problem of nonfuel HC emissions from
the raw material exceeding the 20 ppmv limit The raw material would be heated and
partially calcined in the precalciner or preheater and HC from that process would be emitted
regulatory program, EPA considers a hazardous waste to be burned or processed as an
ingredient if it is used to produce a product EPA considers a hazardous waste to be
burned or processed for material recovery if one or more constituents of the waste is
recovered as a product
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from the main stack. The by-pass duct draws the kiln off-gas prior to the precalciner or
prehcater and, so, would not be affected by that process.
Another commenter specifically supported monitoring CO (and HC, if required)
only in the bypass duct provided that hazardous waste is fed only to the kiln and not to the
preheater or precalciner.
The Agency conducted testing34 at a cement kiln to gather information relevant to
the issue of HC monitoring in the bypass duct for preheater and precalciner cement kilns.
The data showed that the gases in the bypass duct are representative of the combustion of
waste in the kiln.
Based on this test data and public comment, the final rule allows CO and, where
required, HC monitoring in the by-pass duct of a cement kiln provided that: (1) hazardous
waste is fired only into the kiln (i.e., not at any location downstream from the kiln exit
relative to the direction of gas flow); and (2) the by-pass duct diverts a minimum of 10% of
kiln off-gas. See §266.104(f)(l). The 10% diversion requirement is based on engineering
judgment that, at this level of kiln-gas diversion, the by-pass gas will be representative of
the kiln off-gas. Industry representatives indicate35 that the by-pass duct capacity of most
facilities actively involved in burning hazardous waste exceeds the 10% limit.
b. Use of Hazardous Waste as Slurry Water for Wet Cement Kilns. Some kiln
operators have inquired as to what regulatory standards apply, if any, if hazardous wastes
are used as slurry water. The Agency does not regard the practice as an excluded form of
recycling. The Agency has long been skeptical of claims that hazardous wastes are
"recycled" when they substitute for very commonly available and economically marginal
types of raw materials. In particular, the Agency has been skeptical that liquid hazardous
wastes serve as a substitute for water. Cf. 48 FR at 14489 (April 4,1983). In the case of
hazardous waste used as slurry water, die hazardous constituents in the waste are ordinarily
unnecessary to the claimed recycling activity and are being gotten rid of through the
slurrying process. Given the possibility of hazardous levels of air emission is high, the
practice certainly can be part of the waste disposal problem. Consequently, the Agency
34 U.S.EPA, "Emissions Testing of a Precalciner Cement Kiln at Louisville,
Nebraska", November 1990.
35 Letter dated August 16,1990, from Dr. Michael von Seebach, Southdown, Inc., to
Dwight Hlustick, EPA.
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regards such practice as a form of waste management subject to regulation under today's
rule.
EPA considered prohibiting the use of hazardous waste as slurry water for wet
cement kilns because of concern that toxic organic constituents in the waste could be
volatilized and emitted without complete combustion. The final rule does not prohibit using
(or mixing) hazardous waste with slurry water because we believe that the controls
provided by the rule both during interim status and under a RCRA operating permit
adequately addresses the hazard that the practice may pose.
If hazardous waste is fed into any industrial furnace during interim status at a
location other than the hot, product discharge end, combustion gas temperatures must
exceed 1800°F at the point of introduction, and the owner or operator must document that
adequate oxygen is present to combust organic constituents in the waste. See discussion
above. EPA believes that these restrictions will, as a practical matter, preclude use of
hazardous waste in slurry water during interim status.
Although these restrictions on hazardous waste burned at locations other than the
hot end of an industrial furnace do not apply under a RCRA operating permit, the permit
proceedings will ensure that organic constituents in a hazardous waste that is fed into the
kiln in slurry water (or in the slurry itself) will be destroyed The Director will require that,
toxic nonmetal constituents in the waste are destroyed to a 99.99% destruction and removal
efficiency, and that adequate oxygen is present to completely destroy the organic
compounds.
C. Automatic Waste Feed Cutoff Requirements.
Today's rule requires that boilers and industrial furnaces combusting hazardous
waste be equipped with automatic waste feed cutoff systems to limit emissions of
hazardous compounds during combustion "upset" situations and to ensure stable
combustion conditions. The automatic waste feed cutoff system must be connected to the
CO and HC monitoring system, such that an exceedance of a CO or HC limit would trigger
a cutoff of the waste feed. Additionally, the automatic waste feed cutoff system must
engage when other key operating conditions deviate from specified unit operating limits,
which are determined during compliance testing or which are based on manufacturer
specifications. See §§266.102(e)(7)(ii) and 266.103(h).
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Some commenters disagreed with the proposed automatic waste feed cutoff
requirements. One commenter argued against any waste feed cutoffs for light-weight
aggregate kilns. Six commenters expressed concern that waste feed cutoffs would increase
the instability of the combustion conditions and would possibly increase air emissions.
Three commenters requested a controlled waste feed reduction over several minutes rather
than an automatic waste feed shutoff. Three commenters suggested different levels of CO
emissions be set for waste feed cutoffs.
The Agency acknowledges that there can be performance and other problems
associated with automatic waste feed cutoffs, and recognizes that they may be undesirable
for some applications. For example, when the facility operates without the use of
hazardous waste fuel, use of fossil fuel is increased, and the opportunity is lost for safe
disposal of hazardous waste. Further, HC emissions may actually increase if the automatic
waste feed cutoff is triggered frequently even though combustion chamber temperatures
must be maintained while hazardous waste or residues remain in the combustion chamber.
However, the Agency continues to believe that automatic waste feed cutoff systems are
necessary to avoid adverse effect on human health and the environment that could result if
hazardous waste is fired into the device when it is operating under combustion upset
conditions.
To address the concerns raised by commenters, EPA recommends installing pre-
alarm systems that alert an owner/operator of potential problems and provide time either for
corrective measures to be taken or for a staged cutoff of the hazardous waste feed. Thus,
the use of pre-alarms should minimize waste feed cutoffs. In addition, we have included in
the rule some additional requirements related to waste feed cutoffs and restarts, as
discussed below.
One commenter stated that cutoffs are inappropriate for combustion devices where
the waste is destroyed immediately upon injection into the combustion chamber (e.g.,
devices that bum liquid wastes), or if the combustion conditions supported by the waste
fuel continue to destroy residual waste after waste feed cutoff. The Agency continues to
believe that the best method for returning a combustion system to good operating
conditions, thereby minimizing unacceptable emissions, is to stop the input of hazardous
waste. Further, the burden associated with automatic cutoffs should not be substantial
because frequent automatic waste feed cutoffs should not occur given that the parameters
tied into the automatic cutoff system may be monitored on a hourly rolling average basis
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(which allows high values to be off-set by low values) and that the Agency recommends
the use of pre-alarms to warn the operator of a pending cutoff (which may give the operator
time to take corrective measures to avoid an automatic cutoff).
In the event of a waste feed cutoff, monitoring for CO and HC (and other operating
parameters for which limits in the permit are based on a rolling average basis) must
continue, and the waste feed cannot be restarted until CO and HC levels (and levels of the
other parameters) come within allowable limits. See §266.102(e)(7)(ii). (For permit
operating conditions not established on a rolling average basis, the Director will specify, on
a case-by-case basis, an adequate period of time during which the parameters must remain
within permit limits to demonstrate steady-state operation prior to restarting the hazardous
waste feed.) In addition, consistent with the April 27, 1990 incinerator amendments
proposal, the provision of the final boiler and industrial furnace rule requiring compliance
with the permit operating conditions states that compliance must be maintained at any time
there is waste in the unit See §266.102(e)(l). This language clarifies that activation of the
automatic waste feed cutoff does not relieve the facility of its obligation to comply with the
permit conditions if there is waste remaining in the unit (such as in a rotary kiln). Thus, for
example, the air pollution control system must continue to be operated within the applicable
permit conditions.
Furthermore, after a cutoff, the temperature in the combustion chamber must be
maintained at levels demonstrated during the compliance test for as long as the hazardous
waste or residue remains in the combustion chamber. The Agency believes this
temperature requirement will help ensure that hydrocarbon emissions will be minimized
after a cutoff.
To comply with this requirement, the operating permit must specify the minimum
combustion chamber temperature after a waste feed cutoff while waste remains in the
combustion chamber. An uninterruptable burner using auxiliary fuel (i.e., nonhazardous
waste fuel) of adequate capacity may be needed to maintain the temperature in the
combustion chambers) and to allow destruction of the waste materials and associated
combustion gases left in the system after the waste feed is automatically cut off. The safe
startup of the burners using auxiliary fuel requires approved burner safety management
systems for prepurge, pilot lights, and induced draft fan starts. If these safety requirements
preclude immediate startup of auxiliary fuel burners and such startup is needed to maintain
temperatures (i.e., if the combustion chamber temperatures drop precipitously after waste
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feed cutoff), the auxiliary fuel may have to be burned continuously on "low fire" during
nonupset conditions.
Furthermore, §266.102(e)(7)(ii)(B) requires that the combustion gases must
continue to be routed through the air pollution control system as long as waste remains in
the unit One effect of this clarifying requirement, in combination with the requirement to
maintain compliance with permit conditions as long as there is waste in the unit, is that
opening of any type of air pollution control system bypass stack while there is waste in the
boiler or furnace would be a violation of the permit (unless the facility demonstrates
compliance with the performance standards during the trial burn, with the vent stack open).
Although we believe that such emergency bypass stacks are not prevalent on boilers
and industrial furnaces, our discussion of this topic in the preamble to the incinerator
amendments at 55 FR 17890 (April 27,1990) would also apply to any boiler or industrial
furnace with such a bypass or vent stack. We received a number of comments from the
incinerator industry expressing concern that use of a bypass stack for safety purposes
would be considered a violation. We agree that there can be mitigating circumstances to
discredit their use as a safety device. However, the Agency continues to believe that the
facility can and should implement measures to minimize situations where use of the
emergency vent stack is necessary.
One commenter stated that the use of hazardous waste should be prohibited during
startup or shutdown periods for a cement kiln until normal operating temperatures are
achieved. The final rule does not restrict hazardous waste burning during kiln startup or
shutdown provided that the compliance (or trial burn) covers those periods of operations.
In other words, hazardous waste may be burned during startup and shutdown if the facility
demonstrates conformance with the standards during those operations.
Another commenter argued that accurate measurement of combustion chamber
temperature for some combustion devices will be difficult Because of this difficulty, the
final rule does not require that this temperature be directly measured in the combustion
chamber if an owner/operator can demonstrate to permitting officials that the combustion
chamber temperature correlates with a more easily measured downstream gas temperature.
One commenter agreed with FJ>A's revised proposal not to limit the number of
automatic waste feed cutoffs, but disagreed with EPA's requirement that combustion
chamber temperatures must be maintained at the levels that occurred during the trial burn
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for the duration of time that the waste remains in the combustion chamber. This commenter
believed that electric utility boilers and other burning devices will have difficulty in
accurately measuring combustion chamber temperatures. For this reason, the commenter
suggested that waste feed cutoffs alone be used to control HC emissions rather than also
requiring that combustion chamber temperatures be maintained. EPA believes that the
flexibility that the final rule allows for monitoring combustion chamber temperature and in
setting the frequency of waste feed cutoffs as discussed above should address this
commenter's concerns.
Another commenter supported the proposed 10 times per month limit on the number
of automatic waste feed cutoffs and the proposed requirement that any facility exceeding
that frequency would be required to cease burning hazardous waste, to notify the Director,
and not to resume burning hazardous waste until reauthorized by the Director. Another
commenter supported monthly cutoff limits because they would provide an incentive for the
facility to take corrective measures to preclude frequent cutoffs. Some commenters stated
that this requirement is overly restrictive.
After careful consideration, EPA has decided to modify this requirement for the
following reasons: (1) the Agency does not have data indicating a specific frequency of
cutoffs which would be unacceptable at all boilers and furnaces given that the combustion
chamber temperature and other conditions are maintained as described above; (2) the
Agency believes that operating costs associated with cutoffs will provide sufficient
incentive to encourage owners/operators to minimise automatic waste feed cutoff incidents;
and (3) the recommended use of pre-alarm systems will reduce the number of waste feed
cutoffs. However, the final rule allows the Director to use his discretion to determine
whether a limit on the frequency of cutoffs is warranted at a specific facility.
Waste Feed Restarts. Today's rule provides that when the automatic waste feed
cutoff is triggered by a CO limit or when applicable, an HC exceedance, the waste feed can
be restarted only when the hourly rolling average CO/HC levels meet the permitted limits
(e.g., 100 ppmv for CO under Tier I).
The Agency proposed two alternative approaches for restarting the waste feed when
a cutoff is triggered by a CO exceedance: (1) restart the waste feed after an arbitrary 10-
minute time period to enable the operator to stabilize combustion conditions; or (2) restart
the waste feed after the instantaneous CO level meets the hourly rolling average limit Eight
commenters supported restarting the waste feed after the instantaneous CO level meets the
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permit limit Five commenters suggested that waste feed can be restarted once the
instantaneous CO level meets the hourly rolling average limit The Agency considered the
comments, but continues to believe that allowing a waste feed restart after the hourly rolling
average equals or falls below the permitted limit is preferable. After the waste feed is
cutoff, the facility will be burning nonhazardous waste (typically fossil fuel), which should
result in CO and HC levels well below the allowable limits. Therefore, the hourly rolling
average should fall below the permitted limit within a relatively brief period of time.
Allowing the waste feed to be restarted when the instantaneous CO level has dropped to the
permitted level may not be desirable, because restarting the waste feed immediately may
trigger another cutoff due to a CO spike when the waste feed is restarted.
Three commenters supported the proposed approach to require the HC hourly
rolling average to be met before restarting the waste feed cutoff because of a HC
exceedance. Three commenters opposed this approach. Instead, these commenters
suggested a 10-minute waiting period be used. EPA considered these comments but
continues to believe that meeting the hourly rolling average is a conservative approach and
is appropriate after a HC exceedance, because the HC is a better surrogate for toxic organic
emissions than CO.
D. CEM Requirements for PIC Controls.
The final rule promulgates the proposed performance specifications for
continuously monitoring CO, HC, and oxygen. See Methods Manual for Compliance with
the BDF Regulations, incorporated by reference in today's rule in §260.11. The
performance specifications for HC monitoring, however, include specifications for both
hot and cold monitoring. Although hot monitoring is generally required by the final rule,
cold monitoring may be used for interim status facilities if they certify compliance with the
emissions standards within 18 months of promulgation of the rule. Even if cold
monitoring is used to certify initial compliance, however, hot monitoring is required for
these facilities when they recertify compliance and when they are issued a RCRA operating
permit
One commenter stated that an HC monitoring system is readily available for
continuous emissions monitoring (CEM), while five commenters maintained that HC
analyzers have serious operational problems. Several commenters requested that alternate
HC CEM methods be allowed, specifically monitors with non-dispersive infra-red (NDIR)
detectors rather than the required flame ionization detector (FID). One commenter noted
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that EPA has not validated the FID method for HC analysis nor has it provided any critical
discussion of the current methods of HC analysis.
The Agency considered the use of NDIR detectors for HC monitoring but believes
that NDIR systems have limitations compared to FID systems. EPA believes that FID
systems are more sensitive than NDIR systems and that an equivalent response is not found
with NDIR detectors. The final rule requires the use of FID detectors for HC monitoring.
Four commenters recommended monitoring nonmethane hydrocarbons (NMOC) as
opposed to "total" HC because methane, which is predominantly emitted from fuel sources,
has a high FID response factor. Furthermore, these commenters would like EPA to require
testing for specific PICs that respond poorly to HC monitors during test burns. One
commenter stated that HC monitors can be varied easily to detect NMOC. EPA does not
agree with either suggestion. The Agency is requiring HC monitoring to indicate whether
the device is operating under good combustion conditions. We acknowledge that the
largest fraction of organic compounds that the HC monitoring system required by the final
rule will detect for facilities operating under good combustion conditions will be
compounds that are relatively nonhazardous (e.g., methane). In addition, some hazardous
compounds, particularly highly chlorinated compounds) will be under-reported. Thus,
although the promulgated approach would not be adequate for the purpose of assessing the
risk that HC may pose from a given facility, the approach is adequate for its intended
purpose -- a measure of whether the facility continues to operate within good combustion
conditions. This is because EPA's emissions testing has shown that when combustion
conditions deteriorate, the compounds that are readily detected by the promulgated HC
monitoring system increase correspondingly.
In addition, if a NMOC system were used, the 20 ppmv HC limit would have to be
lowered to account for the methane fraction that would no longer be counted. Commenters
did not provide support for so adjusting the proposed HC limit Further, the Agency is
concerned that NMOC detectors may not be able to provide continuous data due to the time
required for methane separation. The Agency has also found that HC CEMs are more
durable than NMOC CEMs, and thus less prone to reliability problems. As a result, the
Agency has concluded that HC CEMs are more likely to provide a continuous indication of
combustion conditions than is possible with an NMOC monitor.
Hot Versus Cold HC Monitoring Systems. Except as indicated below, the final
rule requires the use of a hot or unconditioned HC monitoring system that must be
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maintained at a temperature of at least 150°C until the sample gas exits the detector. See
performance specifications in Methods Manual for Compliance with the BIF Regulations
(incorporated by reference, see §260.11). Given, however, that the technology has just
recently been demonstrated36 to be continuously operational on hazardous waste
combustion devices, the final rule allows the use of a conditioned gas monitoring system
during the initial phase of interim status operations. Facilities in interim status that certify
compliance with the emission standards for metals, HC1, Cl2, paniculate matter, CO and
HC within 18 months of promulgation of the final rule may obtain an automatic waiver to
use a conditioned gas system. Facilities that elect to obtain the automatic 12-month
extension (or a case-by-case extension) of the 18-month certification deadline, however,
are not eligible for the waiver because the additional time provided by the extension will
also provide time to install an unconditioned HC monitoring system. These facilities must
demonstrate compliance with the HC limit using an unconditioned gas monitoring system.
Further, facilities that certify initial compliance using a conditioned gas (cold) system must
use an unconditioned gas (hot) system when they recertify compliance within three years of
certifying initial compliance.
EPA is requiring the use of a hot monitoring system because it represents best
demonstrated technology given that a larger fraction of HC emissions can be detected with
a hot system. As discussed at proposal, a hot HC monitoring system can detect a
substantially larger fraction of hydrocarbon emissions than a cold system. This is because
the cold system uses a gas conditioning system that removes semi- and nonvolatile
hydrocarbons and a substantial fraction of water-soluble volatile hydrocarbons.
EPA received numerous comments regarding gas conditioning (heated versus
unheated) for HC monitoring. Eight commenters are in favor of gas conditioning. The
purpose of gas conditioning is to remove moisture from the combustion gases that can
degrade instruments or plug sample lines. Sample conditioning, however, can also remove
some of the water soluble hydrocarbons and the semi and nonvolatile hydrocarbons in the
flue gas such that methane and other nonhazardous volatile hydrocarbons are frequently the
dominant constituents measured by the detector. Some commenters were concerned that
fewer PICs would be detected by a conditioned (i.e., cooled) monitoring system.
36 Entropy Environmental Inc., "Evaluation of Heated THC Monitoring Systems for
Hazardous Waste Incinerator Emission Measurement", Draft Final Report, October 1990;
and Shamat, Nadim, et al, Total Hydrocarbon Analyzer Study", Paper presented at the
63rd Water Pollution Control Federation Conference in Washington, D.C., October 8,
1990.
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However, one commenter stated that even though the constituents contributing most of the
hypothetical risk are relatively nonvolatile they are relatively nondetectable through an
unconditioned (heated) monitoring system because of their halogen content
As discussed at proposal, the Agency is using HC monitoring to implement the
technology-based HC limit of 20 ppmv as an indicator of good combustion conditions.
The HC monitor is not used in an attempt to quantify organic emissions for risk assessment
purposes. Emissions testing has shown that during combustion upset condition, both the
hot and cold HC monitoring systems detect an increase in HC levels because under upset
conditions there is a substantial increase in hydrocarbon compounds that are readily
detected by either monitoring system.37
One commenter suggested that, rather than specifying a range of 40-64°F for
operation on the conditioner as proposed, a specific conditioning temperature (32°F)
should be required to precisely define the conditioned sampling procedure. We agree that a
minimum temperature should be specified rather than the range. The final rule allows a
conditioned monitoring system during the initial phase of interim status, and requires that
the sample gas temperature must be maintained at a minimum of 40°F at all times prior to
discharge from the detector. EPA selected a minimum temperature of 40°F from the range
of 40 to 64°F to ensure that moisture was effectively removed from the gas sample to
preclude plugging and fouling problems with the monitoring system.
Three commenters suggested that the HC limit of 20 ppmv be re-examined because
gas conditioning temperatures or other changes in the measurement method may influence
the amount of HC measured. Given that the 20 ppmv limit is based primarily on test bum
data using heated (i.e., unconditioned) monitoring systems, the Agency considered
lowering the 20 ppmv limit when a cold (i.e., conditioned) monitoring system is used.
(Limited field test data indicate that a heated system would detect from 30% to 400% more
of the mass of organic compounds than a conditioned system.) We believe, however, that
the 20 ppmv HC limit is still appropriate when a conditioned system is used because: (1)
the data correlating heated vs conditioned systems are very limited; (2) the data on HC
emissions are limited (and there apparently is confusion in some cases as to whether the
37 EPA is requiring the use of a hot, unconditioned HC monitoring system (except
under certain circumstances during the initial phase of interim status) because hot systems
are, nonetheless, more conservative in that they detect a larger fraction of organic
compounds in emissions. Further, hot systems represent best demonstrated technology for
monitoring HC levels.
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data were taken with a conditioned or unconditioned monitoring system); and (3) the
Agency's risk methodology is not sophisticated enough to demonstrate that a HC limit of 5
or 10 ppmv using a conditioned system rather than an unconditioned system is needed to
protect human health and the environment The SAB38 also concurs with this view.
(More detailed responses to comments on this issue are found in a separate background
document.)
E. Control ofDioxin and Fur an Emissions.
For facilities that may have the potential for significant emissions of chlorinated
dibenzodioxins and dibenzofurans (CDD/CDF), the final rule requires emissions testing for
both interim status and new facilities to determine emissions rates of all tetra-octa
congeners, calculation of a toxicity equivalency factor, and dispersion modeling to
demonstrate that the predicted maximum annual average ground level concentration (i.e.,
the hypothetical maximum exposed individual) does not exceed levels that would result in
an increased lifetime cancer risk of more than 1 in lOO.OOO.39 The Agency considers a
facility to have the potential for significant CDD/CDF emissions if it is equipped with a dry
paniculate matter control device (e.g., fabric filter or electrostatic precipitator) with an inlet
gas temperature within the range of 450 to 750 °F, or if it is an industrial furnace that has
hydrocarbon levels exceeding 20 ppmv. See §266.104(0(2).
Dispersion modeling must be conducted in conformance with EPA's Guideline on
Air Quality Models (Revised), EPA's "Hazardous Waste Combustion Air Quality
Screening Procedure" provided in Methods Manual for Compliance with the BIF
Regulations, or "EPA SCREEN Screening Procedure" as described in Screening
Procedures for Estimating Air Quality Impact of Stationary Sources. All three documents
are incorporated by reference in today's final rule at §260.11. To evaluate potential cancer
risk from the CDD/CDF congeners, prescribed procedures must be used to estimate the
2,3,7,8-TCDD toxicity equivalence of the 2,3,7,8-chlorinated congeners. See "Procedure
for Estimating Toxicity Equivalent of Chlorinated Dibenzo-p-dioxin and Dibenzofuran
38 U.S. EPA, "Report of the Products of Incomplete Combustion Subcommittee of
the Science Advisory Board", Report # EPA-SAB-EC-90-004, January 1990.
39 EPA is not requiring that the estimated cancer risk from CDD/CDF be added to the
risk from metal emissions to demonstrate that the summed risk to the maximum exposed
individual is less than 10~5. The Agency believes that it is inappropriate to sum the
estimated health risk from metals that are known or probable human carcinogens with a
toxicity equivalency factor for CDD/CDF that is designed to be very conservative.
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Congeners" in Methods Manual for Compliance with the BIF Regulations incorporated in
the rule by reference in §260.11 (a).
Studies conducted by the Agency40 and others41 during development of
regulations for municipal waste combustors (MWCs) concluded that PM control devices
operated at temperatures greater than 4SO°F have the potential for emitting elevated levels of
ODD/CDF. At these temperatures, precursor organic materials and chlorine in the flue gas
can be catalyzed by PM captured in the PM collection device to form ODD/CDF. Based on
these findings, the Agency proposed to restrict the combustion of hazardous waste in BIFs
that operate with PM control device temperatures greater than 450°F.
A number of commenters opposed the proposed limitation on the flue gas
temperature to less than 450°F. Several commenters pointed out technical distinctions
among types of boilers and industrial furnaces that affect the ability of a unit to change flue
gas temperature and the potential of an ESP to form CDD/CDF. For example, many boiler
and industrial furnaces either combust wastes that are very low in chlorine or that have high
levels of chlorine capture within the process (e.g., cement kilns). As a result, the
CDD/CDF emission potential will vary for different boilers and industrial furnaces, as well
as between boilers and industrial furnaces and MWCs. Commenters also stated that there
is no direct evidence of CDD/CDF emissions from several types of boilers and industrial
furnaces, and that compliance testing to demonstrate 99.99 percent DRE of POHCs and
continuous monitoring of CO and HC levels is adequate to ensure minimal emissions of
organic compounds.
The Agency has reviewed the available data on the theory of CDD/CDF formation
as well as CDD/CDF emissions from BIFs. Based on this review, the Agency agrees that
most, but not necessarily all, BIFs burning hazardous waste have low CDD/CDF emission
rates. For example, EPA recently tested a cement kiln burning hazardous waste that
operates with an ESP at a temperature of 500-550°F and found it to have relatively high
CDD/CDF emissions.42 (EPA conducted a risk assessment, however, that estimated the
40 See U.S. EPA, "Municipal Waste Combustion Study: Combustion Control of
Organic Emissions", EPA/530-SW-87-021C, NTIS Order No. PB87-206090; U.S. EPA,
"Municipal Waste Combustion Study: Flue Gas Cleaning Technology", EPA/530-SW-87-
021D, NTIS Order No. PB87-208108; and 54 FR 52251 (December 20,1989).
41 Vogg H. and L. Stieglitz, "Thermal Behavior of PCDD/PCDF in Fly Ash from
Municipal Waste Incinerators", Chemosphere, pp. 1373-1378,1986.
4 2 U.S. EPA, Emissions Testing of a Wet Cement Kiln at Hannibal. MQ December
1990.
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increased lifetime cancer risk to the hypothetical mgximum exposed individual from the
CDD/CDF emissions ranged from 7 in 10,000,000 to 2 in 1,000,000 without burning
hazardous waste and from 2 in 1,000,000 to 4 in 1,000,000 when burning hazardous
waste, well under the 1 in 100,000 limit established in today's rule.) The Agency suspects
that the elevated CDD/CDF concentrations in the stack gas at this cement kiln are the result
of the ESP's operating temperature and the level of HC precursor material in the flue gas.
HC concentrations ranged from 66 to 70 ppmv (measured with a hot system, reported as
propane, and corrected to 7% oxygen, dry basis) without hazardous waste burning and
from 38 ppmv to 63 ppmv with hazardous waste burning. (We note that to continue
burning hazardous waste under today's rule, the Director must establish during the Part B
permit proceedings an alternative HC level for this loin based on a demonstration by the
applicant that HC levels are not higher when burning hazardous waste than under normal
conditions and that the facility is designed and operated to minimize HC emissions from all
sources - fuels and raw materials. At certification of compliance with the emissions
controls other than the HC limit, this facility must also propose a HC concentration limit for
the remainder of interim status (until that limit or another limit is established under permit
proceedings) that will ensure that HC levels when hazardous waste is burned will not be
higher than baseline levels (i.e., HC levels when the system is designed and operated to
minimize HC emissions from all sources, when burning normal fuels and feeding normal
raw materials to produce normal products, and when not burning hazardous waste)). In
addition, trial burn emissions testing must demonstrate that emissions of organic
compounds are not likely to result in an increased lifetime cancer risk to the hypothetical
maximum exposed individual exceeding 1 in 100,000. See §266.104(0 and discussion in
section n.B.S.b of Part Two of this preamble.) There may be other factors that influence
CDD/CDF levels at this facility (and other faculties), but this is uncertain. In addition, the
exact HC concentration in combustion gas below which elevated CDD/CDF concentrations
will not occur is unknown.
The Agency continues to believe that the operating temperature of the PM control
device (and HC concentrations in flue gas) plays a significant role in CDD/CDF emissions.
For a given HC concentration in the flue gas, the available data suggest that the potential for
elevated CDD/CDF emissions is low if the PM control device operates at temperatures of
less than 450°F or above 750°F. Consequently, today's rule does not require BIFs with
PM control devices operating at temperatures outside of the 450-750°F window to
determine CDD/CDF emission rates (unless it is an industrial furnace with HC levels
greater than 20 ppmv). Owners and operators of units operating within the temperature
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window, however, are required to conduct stack testing to determine CDD/CDF emission
rates and to conduct a risk assessment using prescribed procedures to demonstrate that the
estimated increased lifetime cancer risk to the hypothetical maximum exposed individual is
less than 1 in 100,000.
The Agency notes that the final rule for municipal waste combustors (MWCs) may
take a slightly different approach to control dioxin and furans by limiting temperatures at
the inlet of the PM air pollution control system to within 30°F of those achieved in a
dioxin/furan compliance test The preamble to that rule, however, will probably continue
to note the possibility of dioxin/furan formation in the temperature range of 230°C (450°F).
In today's rule, the Agency believes that using temperature and HC levels as a trigger to
dioxin/furan testing and risk assessment will be fully protective of human health and the
environment and somewhat easier to implement than the MWC approach.
in. Risk Assessment Procedures
The Agency uses assessment of health risk to develop and implement the final rules
for metals, hydrochloric acid (HC1), and chlorine gas (Cl2)- Specifically, the Agency has
used risk assessment to: (1) establish ambient air concentrations of Appendix VIII
compounds that do not pose an unacceptable health risk for purposes of this rulemaking;
and (2) establish risk-based, conservative feed rate and emissions Screening Limits for
metals and HC1. In addition, if facilities fail the Screening Limits or elect to conduct
dispersion modeling to obtain less conservative limits, the rule allows facilities to use site-
specific dispersion modeling to establish emission limits, and ultimately feed rate limits for
metals and chlorine.
To establish health-based acceptable ambient concentrations for noncarcinogenic
toxic metal and nonmetal compounds (except for HC1, Cl2 and lead), EPA converted oral
reference doses to reference air concentrations (RACs) by assuming average breathing
volumes and body weights, and by applying a safety and a background level factor. See
54 FR at 43756. Health-based concentrations for carcinogenic pollutants were derived by
converting cancer potency factors, or slopes (unique for each carcinogen), into Risk
Specific Doses (RSDs) at a risk level of 1 in 100.000.43 Since carcinogens are assumed to
43 We note that the cancer risk from the airdnogenic metals must be summed to
ensure that the summed risk is not greater than 1 in 100,000. Thus, when more than one
carcinogenic metal is emitted, the allowable ground level concentration for each
carcinogenic metal is less than the 10~5 Risk Specific Dose for that metal.
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pose a small but finite risk of cancer even at very low doses, the RSD reflects a certain risk
level, corresponding to 1 chance in 100,000, or 10~5 excess risk of cancer for the
maximally exposed individual if exposed continuously to multiple carcinogenic chemicals
for a 70-year lifetime. RACs for HC1 and Cl2 are based on inhalation data, and a RAC for
lead is based on the National Ambient Air Quality Standard (NAAQS).
To establish the Screening Limits for metals and HC1, air dispersion modeling was
applied to back-calculate maximum acceptable feed rates and stack emissions rates from
risk-based, acceptable ambient concentrations. These calculations were performed for
various terrain types, effective stack heights, and land use classifications. The resulting
permissible Screening Limits reflect plausible, reasonable worst-case assumptions about a
generic facility that are not site-specific. The Screening Limits process provides a rapid and
convenient risk-based mechanism to determine compliance. Conservative assumptions
used to estimate health impacts exposure in the Screening Limit process include: (1) use of
reasonable, worst-case estimate of dispersion of stack emissions; and (2) for the Tier I feed
rate Screening Limits, assuming that all metals and chlorine fed into the BIF in all
feedstreams are emitted (i.e., there is no partitioning to bottom ash or product, and not
removal by an air pollution control system).44 See 52 FR 17002 (May 6,1987) and 54
FR 43729 (October 26, 1989).) Thus, assumptions and the Screening Limits tend to err
intentionally on the side of protecting human health.45
If emission levels exceed the Screening Limits, (or if the owner/operator so elects)
the rule allows a facility to conduct its own site-specific air dispersion modeling in order to
establish metals, HC1, and Cl2 emission limits. Incorporation of site-specific information
allows less conservative assumptions (than the reasonable worst-case, nonsite-specific
defaults), to be used in the dispersion models. Consequently, site-specific air dispersion
modeling may predict lower ambient concentrations than the nonsite-specific modeling
reflected in the Screening Limits, thus allowing higher emissions and feed rate limits.
44 TO obtain credit for partitioning to residue or product and for APCS removal
efficiency, owners and operators must conduct emissions testing to demonstrate the overall
System Removal Efficiency (SRE) - partitioning plus APCS removal efficiency. The
Agency has not assumed an SRE in developing the Tier 1 feed rate Screening Limits
because there are many site-specific factors that can affect the SRE.
45 We note that the Screening Limits may not always be conservative, however.
Today's rule identifies criteria whereby the Screening Limits may not be used because they
may not be conservative. See §266.106(7). That paragraph in the rule also gives the
Agency authority to determine whether the Screening Limits may not be protective in a
particular situation. In that case, the owner and operator must use the Tier m procedures --
site-specific dispersion modeling.
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A. Health Effects Data.
1. Carcinogens. Health effects evaluations for carcinogens have been summarized
in Part Three, I. D, "Evaluation of Health Risk" in the April 27,1990 proposal (see 55 FR
17873). To summarize briefly, in contrast to noncarcinogens, carcinogens are assumed to
present a small but finite risk of causing cancer, even at very low doses. The slope of the
dose-response curve in the low dose region is assumed to be linear for carcinogens.
Because of this, the slope of the curve in the low dose region may be used as an estimate of
carcinogenic potency. The unit risk is defined as the incremental lifetime risk estimated to
result from exposure of an individual for a 70-year lifetime to a carcinogen in air containing
1 microgram of the compound per cubic meter of air (ug/m^). At an air concentration of 1
ug/m3, the cancer potency slope is numerically equivalent to the unit risk. Thus, at a
preselected risk level, the corresponding air concentration which would cause that risk may
be calculated by dividing the desired risk level by the unit risk value. Although the
resulting value represents an air concentration with units of ug/m^, this concentration is
referred to as the Risk Specific Dose (RSD).
When exposed to more than one carcinogen, the Guidelines for Carcinogenic Risk
Assessment (51 FR 33992 (September 24, 1986)) recommend adding risks from the
individual carcinogens to obtain the aggregate risk (i.e., cancer risks from exposure to
more than one carcinogen are assumed to be additive). For today's rule, the Agency has
proposed that an aggregate risk level for metals (i.e., arsenic, beryllium, cadmium, and
hexavalent chromium) of 10~5 is appropriate because it would limit the risk level for
individual carcinogens to the order of 10'^. The Agency points out, however, that in
selecting the appropriate risk level for a particular regulatory program, it considers such
factors as the particular statutory mandate involved, nature of the pollutants, control
alternatives, fate and transport of the pollutant in different media, and potential human
exposure. See, e.g., 54 FR at 38049 (Sept 14, 1989). Particular factors bearing on the
Agency's choice here include the wide array and potentially large volumes of carcinogenic
pollutants that can be emitted by these devices (unlike the situation in such rules as the
benzene NESHAP when a single pollutant with well-understood effects was at issue), the
need to guard against environmental harm as well as harm to human health, potential
synergistic effects of the carcinogens emitted by these devices (which effects are not
accounted for by the risk assessment), and legislative history indicating Congressional
preference for parity of regulation between BBFs burning hazardous waste fuels and
hazardous waste incinerators (S. Rep. No. 284, 98th Cong. 1st Sess. 38)). In addition,
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the increased recognition of the need to control net air emissions of toxic pollutants
generally, manifest in Title ID of the Clean Air Act Amendments of 1990, influences the
Agency's choice of a conservative risk target in this rule. These same factors can also
influence choice of a risk level where the Agency is making site-specific determinations.
The following section discusses comments on health effects data on carcinogens.
a. Unit Risk Factors/Risk Specific Doses. A few commenters argued for deletion
of category C carcinogens from consideration in the risk assessment process.
Given that the carcinogenic metals arsenic, beryllium, cadmium, and hexavalent
chromium are classified as either A or B carcinogens, this discussion pertains only to the C
nonmetal Appendix VIE compounds for which the Agency established 10'^ RSDs for
purposes of implementing the low risk waste exemption, risk assessments for cement kilns
with HC levels exceeding 20 ppmv, and health-based limits for Bevill excluded waste.
As a conservative element in the risk assessment process, and especially for
purposes of implementing an exemption from some of the emission controls, EPA does not
believe that exposure to category C carcinogens should be ignored at this time for those
chemicals with cancer potency slopes. The classification schemes categorize chemicals
based upon weight of the evidence, not carcinogenic potency. Therefore, a highly potent
carcinogen may be classified in the C category and present a threat to health.
b. Quality of the Toxicological Data Base. Several commenters questioned the
quality and extent of the toxicology data base and EPA's selection of specific studies used
to calculate the cancer potency factors and unit risk values for a particular chemical. For
example, one commenter noted that the molecular species of a metal compound emitted
from an incinerator may be markedly different from the metallic complex actually tested for
carcinogenicity and used to calculate that metal's cancer potency factor. This would distort
the risk assessment process. This same commenter argued that beryllium oxide, which
would be formed preferentially at the extreme temperatures of a furnace, is relatively inert
compared to the molecular complex of beryllium which forms the basis of the cancer
potency factor. Another commenter contended that, in general, the less water soluble (and,
therefore, less bioavailable) metallic oxides are emitted from incinerators whereas the
metallic species tested for cancer were more water soluble and bioavailable (i.e., absorbable
into the organism).
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EPA acknowledges the concern that the metal complex tested for carcinogenicity in
animals reflect that to which humans are exposed. However, the particular metal complex
being emitted may not have been tested in animals. In such cases, it is sometimes
necessary to use that lexicological data which is available (on the same metal but cotnplexed
with a different ligand), limitations notwithstanding, until appropriate data on the complex
of concern become available. EPA believes the use of the available data base will result in
risk assessment methodology that is protective of human health and the environment.
Moreover, EPA notes that soluble metallic salts may also be emitted under some
conditions (e.g., metallic chlorides). For screening purposes, the conservative assumption
that soluble (i.e., bioavailable) metallic complexes are emitted, is assumed to protect health.
For the site-specific risk assessment option, historical or test burn data may be used to
identify probable emitted metallic species. If permit officials conclude during the permit
process that appropriate fate, transport, and lexicological data exist for the actual emitted
complex to support risk assessment, this could then be used in the site-specific risk
assessment option.
c. High Dose to Low Dose Extrapolation. Several commenters questioned the
scientific merit of extrapolating from high dose experimental data to low dose cancer risks
using existing statistical models, asserting that the process is not biologically-based and is
extremely conservative (i.e., overly health-protective). Two commenters asserted that the
linearized multistage model should not be applied to non-genotoxic carcinogens because
such "carcinogens" promote rather than initiate cancer, thus acting as a classical toxicant
with a threshold. These commenters maintained that a chemical such as chloroform, which
they claim is non-genotoxic (i.e., has not tested positive in mutation assays), would have a
threshold below which there is no risk of cancer. Another commenter argued that
biological evidence indicates a threshold for arsenic-induced cancer due to its known
benefit as an essential trace element at low doses. This same commenter asserted that
hexavalent chromium (Cr+6) is quickly converted in the body to the essential trace element
Cr+3 and, therefore, should be treated as a "threshold carcinogen."
The Agency is following closely recent developments in scientific consensus
regarding the basic molecular biology of cancer. EPA will revise its Guidelines for
carcinogen risk assessment, and other guidance documents, to reflect developing scientific
theory on high to low dose extrapolation threshold effects, and other related issues. Until
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that time, EPA will continue to use its current approach, believing that a more conservative
approach is warranted in the face of uncertainty.
d. Chromium Oxidation State. Several commenters argued that the current
proposal does not differentiate chromium in the +6 oxidation state from chromium +3.
They contend that most chromium emitted from boilers, industrial furnaces, and
incinerators exists in the +3 state. Consequently, the proposed approach, which assumes
that all chromium is +6, may overstate risks drastically. The commenters recommended
that EPA assume that only a fraction of the chromium emitted by incinerators exists in the
+6 oxidation state.
EPA concludes that assuming that 100% of the chromium is in the hexavalent
oxidation state is a conservative assumption taken in the face of limited data. In a test46 of
hazardous waste incinerator emissions under varying levels of total chlorine in the waste
burned, a high percentage of the total chromium emitted was in the hexavalent state under
certain conditions. Until more data is available, showing consistently lower proportions of
Cr+6 under a variety of combustion conditions, EPA believes it is health-protective to
assume that chromium from incinerator emissions exists in the hexavalent state. Facilities
may elect to conduct emissions testing to determine the actual emission rate of Cr+6.
e. Additive Risks. One commenter criticized EPA's selection of 10"^ as the
acceptable aggregate risk level (for carcinogenic metals) for deriving screening limits, and
claimed the selection is arbitrary and inconsistent with other EPA policy. EPA policy, the
commenter notes, has traditionally embraced a range of risks from 10~7 to 10~4, with the
final EPA-selected risk level dependent upon site-specific conditions (i.e., characteristics
and size of the exposed population).
EPA's rationale for selecting 10*5 risk for the MEI is described in the October 26,
1989 supplemental notice (54 Federal Register 43754). In summary, EPA continues to
believe that the aggregate cancer risk to the MEI of 10*5 for metals is appropriate because:
(1) it provides adequate protection of public health; (2) it considers weight of evidence of
human carcinogenicity; (3) it limits the risk from individual Group A and B carcinogens to
risk levels on the order of 10~6; and (4) it is within the range of risk levels the Agency has
46 U.S. EPA, "Pilot Scale Evaluation of the Fate of Trace Metals in a Rotary Kiln
Incinerator with a Venturi Scrubber/Packed Column Scrubber, VoL I, Technical Results",
April 1989.
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used for hazardous waste regulatory programs. See also the discussion in section HI.A.I
of Part Three above.
2. Noncarcinogens. For toxic substances not known to display carcinogenic
properties, there appears to be an identifiable exposure threshold below which adverse
health effects usually do not occur. Noncarcinogenic effects are manifested when these
pollutants are present in concentrations great enough to overcome the homeostatic,
compensating, and adaptive mechanisms of the organism. Thus, protection against the
adverse health effects of a toxicant is Likely to be achieved by preventing total exposure
levels that would result in a dose exceeding its threshold. Since other sources in addition to
the controlled source may contribute to exposure, ambient concentrations associated with
the controlled source should ideally take other potential sources into account. Therefore,
the Agency has conservatively defined reference air concentrations (RACs) for
noncarcinogenic compounds that are defined in terms of a fixed fraction of the estimated
threshold concentration. The RACs for lead and hydrogen chloride, however, were
established differently, as discussed below. The RACs established in today's final rule are
identical to those proposed. (See Appendix H of the Supplement to Proposed Rule at 54
FR 43762 (October 26,1989)). (The Agency notes that it does not intend for RACs to be
used as a means of setting air quality standards in other contexts. For instance, the RAC
methodology does not imply a decision to supplant standards established under the Clean
Air Act)
We note, however, that the RACs proposed in Appendix H of the supplement to
proposed rule (and promulgated today as Appendix IV to the rule) included both Agency-
verified and unverified values. Unverified values are subject to revision as the Agency's
Reference Dose Workgroup continues to establish verified inhalation RfDs. (Occasionally,
the Agency may also revise verified values based on new and significant information.)
Since the supplemental notice, the Workgroup has established inhalation RfDs for eight
compounds on proposed Appendix H (and promulgated Appendix IV to the rule). The
basis for the newly-verified RfDs is set forth in the Health, Effects Assessment Summary
Tables, Fourth Ouarter-FY9Q. U.S. EPA, OERR 9200 6-303 (90-4), September 1990.47
Consequently, RACs based on those RfDs are different from the proposed and
promulgated RACs. The RACs based on verified inhalation RfDs are shown in the table
47 The document is available from the National Technical Information Service (NTIS),
5285 port Royal Road, Springfield, VA 22161, (703) 487-4600. The document number is
PB90-921-104.
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below. EPA will use the omnibus permit authority of §270.32(b)(2) to use these revised
RACs where the facts warrant.48
Compound RAC in RAC Based on
Appendix IV of Recently-
Final Rule Verified RfD
(ug/m2) (ug/m3.)
Acroelin (107-02-8) 20 0.03
Carbon Disulfide (75-15-0) 200 3
p-Dichlorobenzene (106-46-7) 10 200
Bromomethane (74-83-9) 0.8 2
Hydrogen Sulfide (7783-06-4) 3 0.2
Mercury (7439-97-6) 0.3 0.08
Methoxychlor (72-43-5) 50 4
Toluene (108-88-3) 300 500
RACs have been derived from oral reference doses (RfDs) for those
noncarcinogenic compounds listed in Appendix Vffl of 40 CFR Part 261 (except for lead,
HC1, and Cl2) for which the Agency considers that it has adequate health effects data. An
oral RfD is an estimate (with an uncertainty of perhaps an order of magnitude) of a daily
oral dose (commonly expressed with units of mg/kg-day) for the human population
(including sensitive subgroups) that is likely to be without an appreciable risk of deleterious
effects, even if exposure occurs daily for a lifetime. Since these oral RfDs are subject to
change, EPA will undertake rulemakings as necessary if the derivative RACs change in a
way that affects the regulatory standard (see also the discussion of this issue in the
Boiler/Furnace supplemental notice published on October 26,1989 at 54 FR 43718). We
note that, in the interim before any such rulemaking is complete, and as discussed above,
4 8 EPA notes that permit writers choosing to invoke the omnibus permit authority of
§270.32(b)(2) to add conditions to a RCRA permit must show that such conditions are
necessary to ensure protection of human health and the environment and must provide
support for die conditions to interested parties and accept and respond to comment In
addition, permit writers must justify in the administrative record supporting the permit any
decisions based on omnibus authority.
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permit officials may use the omnibus permit authority49 of the statute to consider revised
health effects data in establishing permit conditions.
The Agency's rationale for using oral RfDs as a basis for RAC-derivation is
described in 54 FR 43755 (October 26,1989). EPA believes the approach to derive RACs
is reasonable because: (1) the RfDs are verified by an EPA workgroup whose decisions
are subject to public review; (2) the verification process addresses long term (lifetime)
exposure; (3) the RfDs are based on the best available information meeting specific
scientific criteria; (4) the most sensitive individuals are considered; and (5) the RfD
determination takes into account the confidence in the quality of the information on which
they are based. Nevertheless, the Agency's Inhalation RfD Workgroup is developing
reference dose values (concentrations) for inhalation exposure for several chemicals, and
some are currently available. As reference concentrations are established by the
Workgroup, the Agency will consider the need to change the RACs established in today's
rule as discussed above.
The final rule regulates HC1 emissions based on an annual exposure (long-term)
RAC of 7 ug/m3.50 The RAC is based on the threshold of priority effects resulting from
exposure to HC1. Background levels were considered to be insignificant given that there
are not many large sources of HC1 and that this pollutant generally should not be
transported over long distances in the lower atmosphere.
The Agency also proposed a short-term (i.e., 3-minute exposure) RAC for HC1.
The Agency agrees with commenters, however, that the proposed RAC was not technically
supportable. See discussion in section V of Part Four of this preamble. Consequently, the
final rule does not establish a short-term RAC for HC1.
To consider the health effects from lead emissions, we adjusted the National
Ambient Air Quality Standard (NAAQS) by a factor of one-tenth to account for background
ambient levels and indirect exposure from the source in question. Thus, although the lead
NAAQS is 1.5 ug/nA for purposes of this regulation, sources could contribute only up to
4 9 EPA notes that permit writers choosing to invoke the omnibus permit authority of
§270.32(b)(2) to add conditions to a RCRA permit must show that such conditions are
necessary to ensure protection of human health and the environment and must provide
support for the conditions to interested parties and accept and respond to comment In
addition, permit writers must justify in the administrative record supporting the permit any
decisions based on omnibus authority.
50 U.S. EPA, Integrated Risk Information System (IRIS) Chemical Files.
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0.15 ug/m3. Given, however, that the lead NAAQS is based on a quarterly average, the
equivalent annual exposure is 0.09 ug/m3.
Finally, section 109 of the Clean Air Act (CAA) requires EPA to establish ambient
standards for pollutants determined to be injurious to public health, allowing for an
adequate margin of safety . Secondary NAAQS, also authorized by section 109, must be
designed to protect public welfare in addition to public health, and, thus, are more
stringent As discussed above, the Reference Air Concentration (RAC) used in today's
rule for Lead is based on the Lead NAAQS. As the Agency develops additional NAAQS
for toxic compounds that may be emitted from hazardous waste incinerators, we will
consider whether the acceptable ambient levels (and, subsequently, the feed rate and
emission rate Screening Limits) ultimately established under this rule should be revised.
We note again that the reference air concentration values (and risk-specific dose values for
carcinogens) presented here in no way preclude the Agency from establishing NAAQS as
appropriate for these compounds under authority of the CAA.
a. Derivation of Oral RfDs/RACs. Many commenters responded to the issue of
derivation of oral RfDs/RACs, questioning the scientific basis for the oral RfDs and
conversion of RfDs to RACs. Some commenters stated that use of oral RfDs do not factor
in differences in routes of exposure (e.g., absorption, first-pass effects) when extrapolating
from oral to inhalation routes of exposure. As discussed above, we acknowledge the
limitations of developing RACs from oral RfDs but continue to believe the approach used is
reasonable and the best available approach until the Agency's Inhalation RfD Workgroup
can provide inhalation values.
Other commenters directed their comments exclusively to lead, indicating that the
lead RAC was arbitrary. EPA has based the lead RAC on the National Ambient Air Quality
Standard (NAAQS). This was done in part because no reference dose or cancer potency
slope is currently available for this metal. The final rule uses 10%, rather than 25% as is
used for other compounds, as an apportionment factor (as proposed) because the Agency is
particularly concerned with: (1) the possible high contribution of lead exposure by indirect
pathways, particularly in urban environments; and (2) the growing concern of low level
lead exposure in children since the lead NAAQS was established. (The Agency currently
plans to propose to readjust the lead NAAQS in 1991.)
b. Apportionment Some commenters questioned EPA's proposal apportioning
75% of the RfD to other non-specified sources, thus causing the RAC to correspond to
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25% of the RfD. The commenters indicated that the figure of 75% from other sources was
arbitrary and could vary from one chemical to another. They suggested that unless other
sources of exposure were identified, the RAC should reflect 100% of the RfD.
EPA has chosen a fraction (25%) of the RfD to serve as the basis for the RACs
because indirect pathways, known to contribute to risks, are not quantified in these
regulations. Even apart from exposures contributed by sources separate from the boiler,
industrial furnace, or incinerator, indirect pathways from emissions from these devices
themselves may contribute 75% or more to risk. Such indirect (i.e., non-inhalation)
pathways include deposition of emitted chemicals on: (1) gardens and crops directly
consumed by humans; (2) meadows used for grazing by beef cattle and other edible
livestock; and (3) meadows and fodder used by dairy cattle (and subsequent milk
consumption by humans).
Such real exposures, which are not quantified in these rules, are accounted for by
the allowance for 75% contribution from other sources. Moreover, it is questionable
whether any single facility should be allowed to consume 100% of an individual's
exposure allowance, above which any further exposure might cause adverse health effects.
B. Air Dispersion Modeling
The Agency used air dispersion modeling to develop the Screening Limits and
dispersion modeling is available as the exposure assessment component of the site-specific
risk assessment option. A more extensive discussion of air dispersion modeling is
included in the 1989 supplemental notice (see 54 FR 43752-54). This discussion focuses
on derivation of Screening Limits, wherein the dispersion models are used to "back-
calculate" emission rates from acceptable ground level concentrations. The section is also
applicable to dispersion modeling used for the risk assessment option (where ground level
concentrations are predicted from estimated emissions rates). The reader is referred to this
discussion for further information about air dispersion modeling. It should be noted that
for the purposes of the risk assessment option, more site-specific information may be used
in place of some of the conservative default assumptions used to derive the Screening
Limits, generally resulting in lower predicted ambient air concentrations.
1. Option for Site-Specific Modeling. In responding to this provision in the
proposal, many commenters argued for procedures which would allow greater flexibility in
the air dispersion modeling process. Many commenters seemed to confuse the issues of
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dispersion modeling used for the Screening Limits, and modeling for the site-specific risk
assessment EPA concedes that many assumptions used to develop the Screening Limits
are, by design, conservative to ensure that the Limits are protective in most cases. These
assumptions do not apply, however, when an owner or operator conducts site-specific
dispersion modeling under the Tier in standards. For site-specific dispersion modeling,
procedures specified in EPA's Guideline on Air Quality Models must be used.
2. Terrain-Adjusted Effective Stack Height. Two commenters stated that in
adjusting the stack height to account for local terrain and differentiating for terrain in the
screening limits, EPA is "double counting" the influence of terrain unnecessarily. One
commenter added that such terrain adjustment of stack height is not supported by the
current EPA Guideline on Air Quality Models (Revised) and should be eliminated.
EPA acknowledged this "double counting" of terrain in the supplement to the
proposed rule (54 FR 43759), stating that this additional conservatism is necessary to
account for the wide range of terrain complexities encountered at real facilities. EPA
continues to believe that this double counting is necessary. Without this conservatism,
additional criteria would have to be added to the existing list (see §266.106(b)(7)) for
determining when the screening limits may not be conservative and, thus, may not be used.
Commenters did not propose (and provide support for) additional criteria for determining
when the use of less conservative screening limits would be appropriate. Further, EPA
believes that additional criteria would complicate and delay the implementation of the rule
by placing additional burden on regulatory officials. Moreover, if a facility cannot meet the
screening limits, then site-specific dispersion modeling may be used to demonstrate
compliance with the Tier in standards. Detailed, comprehensive dispersion modeling
generally costs less than $5,000 and, thus, should not pose a substantial burden. In fact,
many BIFs have already conducted such modeling to comply with applicable standards
under the Clean Air Act. Finally, the final rule minimizes the burden of dispersion
modeling by allowing the use of screening models.
3. Conservatism in Screening Limits. Five commenters stated that EPA's
approach to setting the screening limits is overly conservative and illustrated this by
calculating the difference in estimated ground level concentrations using site-specific
information as opposed to the default assumptions recommended for the Screening Limits.
It should be noted that the Agency would expect that the use of site-specific
information would lead to higher emission limits that under the screening limits. However,
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the Agency developed feed rate and emission rate screening limits with the intent of
minimizing the need for site-specific dispersion modeling and thus reducing the burden of
demonstrating compliance with the emissions standards. To ensure that the limits are
protective in most cases, however, the Agency derived the limits using conservative
assumptions. The Agency believes that, although the assumptions are reasonable, they
would likely limit emissions by a factor of 2 to 20 times lower than would be allowed by
site-specific dispersion modeling (54 FR 43758).
4. GEP Stack Height. Two commenters stated that EPA should not impose a GEP
stack height limitation for existing stacks. The commenters went on to state that EPA
should allow modeling of emissions at actual stack height for existing stacks or, at a
minimum, adopt a grandfather provision to exclude GEP from applying to stacks
constructed prior to December 31,1970. One commenter also indicated that EPA should
recognize that the stack height used for conducting a site-specific dispersion modeling
analysis may exceed GEP formula height, as allowed under Section 123 of the Clean Air
Act.
The Agency maintains that in complying with the metals and HC1/C12 controls
credit will not be allowed for stack heights greater than GEP. GEP stack heights are
determined in a manner consistent with the Guideline for Determination of Good
Engineering Practice Stack Height (Technical Support Document for the Stack Height
Regulations), Revised (EPA 450/ 480-023R).
EPA's position here is consistent with the prohibition on using physical stack
height in excess of GEP in the development of emission limitations under EPA's Air
Program at 40 CFR 51.12 and 40 CFR 51.18. Stack heights higher than GEP cannot be
used for compliance purposes because such stacks merely provide added dispersion and
dilution of ambient levels. EPA prefers that pollutants be removed from the stack gas to
avoid build-up of persistent pollutants (e.g., metals) in the environment and subsequent
indirect exposure through, for example, the food chain. In addition, better dispersion of
emissions of carcinogenic compounds can merely expose larger populations to (albeit
lower) concentrations of pollutants and may not decrease the aggregate population risk
(i.e., cancer incidents/year in the affected population).
5. Plume Rise Table. One commenter recommended that EPA extend Table F-2
(plume rise) and Tables E-l through E-10 (feed rate and emissions screening limits) of the
October 26,1989 supplemental notice to account for the high flow rates typical of many
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cement plant stacks. Another commoner stated that the effective stack height of most utility
boilers exceeds the maximum stack height contained in Tables E-l through E-10. One
commenter indicated that the plume rise values presented in Table F-2 are not conservative
for conditions of neutral atmospheric stability at average to high wind speeds or for stable
atmospheric conditions at all typical wind speeds. This commenter added that the screening
limits based on Table F-2 plume rise may not be conservative for regions having complex
terrain.
For the final rule, the plume rise values presented in Table F-2 of the supplement to
the proposed rule were revised and the table was expanded to include higher stack exit flow
rates indicative of cement kiln stacks (exit flow rates were increased up to a level of 200
m^/s). See Appendix VI to the final rule. The plume rise table values were originally
developed based on plume rise equations presented in the 1979 User's Guide to the
Industrial Source Complex (ISC) model. The plume rise formulation in the ISC model has
since been changed to correspond to the way other EPA models determine plume rise.
Consequently, the entire table was revised, based on conservative application of the
updated neutral and stable buoyant plume rise equations.51 The revised values of plume
rise represent the lowest value of conservative stable buoyant and neutral buoyant plume
rise for each flow rate/temperature level
The range of terrain-adjusted effective stack heights, shown in Tables E-l through
E-10 of the supplemental notice, was not increased beyond the height of 120 meters. This
height was determined to be the maximum terrain-adjusted effective stack height based on
the stack parameter and site location data used in the development of the dispersion
coefficients (as described in Appendix F of the proposed, supplemental rule). Facilities
with terrain-adjusted effective stack heights that exceed 120 meters have the option of
conducting site-specific dispersion modeling to demonstrate compliance.
6. Compliance by Manipulating Effective Stack Height. One commenter claimed
that facilities may elect to circumvent compliance by manipulating their effective stack
heights. This commenter added that additional exposures could result from the increased
dispersion from taller stacks. The Agency acknowledges that an owner or operator could
increase physical stack height up to the GEP maximum to achieve better dispersion and
hence a higher allowable emission rate. The Agency maintains, however, that it is more
51 Memorandum from Sue Templeman, Radian Corp., to Dwight Hlustick, EPA,
entitled "Derivation of Plume Rise Values for BIFs", dated November 30,1990.
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protective of human health and the environment (see discussion in section ffl.B.4 above)
and it may be more cost-effective to upgrade emission control equipment to state-of-the-art
control, rather than to increase stack height, particularly given that the Agency plans to
consider in the future whether additional controls are needed to better control metals
emissions. See discussion in section section I of Pan Three of this preamble.
7. Effect ofHCl Emissions on Acid Rain. One commenter disagreed with the use
of Screening Limits for HQ which are based solely upon effective stack height, terrain and
land use. This commenter maintained that this approach ignores the effects of HC1 in
atmospheric reactions and acid rain.
Addressing potential effects of HQ in atmospheric reactions and acid rain is beyond
the scope of this rule. The screening limits were developed to protect human health in the
vicinity of facilities burning hazardous waste.
8. Building Wake Effects. One commenter stated that emissions limits based on
effective stack height, terrain, and land use would not be conservative in cases where
stacks are subject to building wake effects. This commenter added that only consideration
of building wake effects will lead to conservative concentrations for stacks influenced by
nearby structures and recommended that site-specific dispersion modeling be required in all
cases where the "Guideline for Air Quality Models (Revised)" indicates the necessity for
consideration of building wake effects.
The development of the conservative dispersion coefficients incorporated an
eleventh hypothetical source in order to represent facilities whose release heights do not
meet good engineering practice and whose plumes would thus be subject to building wake
effects (54 FR 43752). In addition, the Agency acknowledges that the dispersion
coefficients used to establish the Tier I and n Screening Limits may not be conservative in
extremely poor dispersion conditions or when the ambient-air receptor is located close to
the source and has therefore defined five situations for which the permit writer should
require site-specific dispersion modeling (54 FR 43754). Furthermore, the Agency is
reserving the right to require that a site-specific dispersion modeling analysis be conducted,
irrespective of whether the facility meets the specific Screening Limits. Thus, the permit
writer has the option of overruling use of Tier I or n, if a probability exists that application
of this methodology would not be protective of the health-based standards. The Tier III
approach of conducting site-specific dispersion modeling requires incorporation of building
wake effects, as necessary, in the modeling analysis. The Tier I and n Screening Limit
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methodology was not further modified to account for these factors, as it already embodies
repeated use of conservative assumptions.
C. Consideration of Indirect Exposure and Environmental Impacts
1. Indirect Exposure. During the proposal stages of these regulations, a few
commenters recommended incorporating indirect exposure pathways into the risk
assessment process. Indirect exposure is defined, in these regulations, as any exposure
pathway other than direct inhalation of emissions from a boiler or industrial furnace. One
commenter maintained that emissions such as metals, chlorinated dioxins, and furans
would be environmentally persistent and able to enter the food chain after deposition on the
ground (including crops, pasture land, surface waters). Consequently, the commenter
argued that indirect exposures should be factored into the risk assessment
EPA recognizes that the contribution of indirect pathways may be significant.
However, the Agency believes that other conservative procedures, such as apportioning
75% of exposures to either indirect pathways or other emission sources (that can contribute
to background levels) in the calculation of RACs, will help offset the contribution of
indirect pathways. Another significant source of conservatism, offsetting the contribution
of indirect pathways, is represented by the inherent uncertainty, and consequent
conservatism, in the models used to estimate unit risk values. Use of the MEI in the
Screening Limits procedure comprises yet another conservative element in the risk
assessment process which would offset direct estimation of indirect pathway exposure.
Therefore, the Agency has not modified the risk assessment process to address indirect
pathways.
2. Non-human Health Related Environmental Impacts. One commenter noted that
for many pollutants, environmental standards for certain flora and fauna may be more
stringent than for humans. Therefore, the effect on non-human receptors should not be
ignored in the regulations and the environmental risks should be evaluated
EPA is concerned about the potential effects of BIF emissions on non-human
receptors. While some environmental standards are available for the protection of
environmental receptors (notably EPA water quality criteria for aquatic organisms),
methods for quantifying exposure and defining acceptable levels for non-human receptors
are still largely in the developmental stages. Thus, until these critical procedures are better
established, the Agency is not requiring such an evaluation at this time. However, as noted
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earlier, some of the conservatism in the human health risk assessment is designed to
compensate for the absence of direct environmental standards.
D. Acceptable Risk Level for Carcinogens
Today's rule limits the incremental lifetime cancer risk to the hypothetical maximum
exposed individual (MEI) to 10~5. This risk level is within the range of levels historically
used by EPA in its hazardous waste and emergency response programs - 1(H to 10~6.
Under the rule, we are limiting the aggregate risk to the MEI from carcinogenic
metals to 10~5, and the aggregate risk from carcinogenic organic compounds (dioxins and
furans and other PICs under provisions of the alternative HC limit) to 10~5. This will limit
in most cases the risk from individual carcinogenic compounds to levels on the order of
1(H> but below 10'^. The rule does not require that the risk from carcinogenic organic
compounds be added to the risk from carcinogenic metals. This is because the Agency
does not believe it is appropriate to sum the risk from metals (i.e., arsenic, beryllium,
cadmium, and chromium) that are known or probable human carcinogens (Group A or B
carcinogens under the weight-of-evidence approach) with the risk from organic
compounds, many of which are possible human carcinogens (Group C carcinogens).
In selecting a 10" 5 aggregate risk threshold level for this rule, we considered risk
thresholds in the range of 10~4 to 10'^, the range the Agency generally uses for various
aspects of its hazardous waste programs.
We considered limiting the aggregate risk to the MEI to 10*6 but determined that
this risk threshold would be unnecessarily conservative for the purpose of this rule. In
reaching this determination, we considered that, at an aggregate risk level of 1(H>, the risk
level for individual metals would be on the order of 10"^, which we believe is overly
conservative for this rule.
Alternatively, we considered limiting the aggregate risk to the MEI to 10"4. An
aggregate risk threshold of 1(H would result in limiting the risk level for individual
carcinogens on the order of 10~5. We did not select a 10*4 aggregate risk threshold for this
proposed rule for a number of reasons. In selecting the appropriate risk level for a
particular regulatory program, the Agency considers such factors as the particular statutory
mandate involved, nature of the pollutants, control alternatives, fate and transport of the
pollutant in different media, and potential human exposure. The Agency believes that a
10"5 risk level is appropriate for this rule because: (1) the rule limits emissions considering
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only direct exposure via inhalation of dispersed emissions. Other routes of exposure (e.g.,
soil ingestion, uptake through the food chain) are not accounted for by this methodology,
which means the risk is somewhat higher, (2) the carcinogenic metals that the rule controls
are Group A or B (i.e., known or probable) human carcinogens; (3) we are concerned
about the potential risks posed by the unknown pollutants these devices can emit ~ Le.,
products of incomplete combustion (PICs).52; and (4) the 10~5 risk level does not result in
a rule that poses a substantial burden on the regulated community given that it is neither a
major rule as defined by Executive Order 12291 nor will it significantly impact small
entities.
When the proposed regulations were published and comments were solicited from
affected parties, several commenters responded to the issue of acceptable risk levels for
exposure to carcinogens. These commenters questioned the basis of 10~5 as representing
an acceptable risk level. They maintained that the discussion in the rule, serving as the
rationale or justification for selecting this level of risk, was inadequate. Others asserted that
the selected acceptable level of cancer risk was not consistent with other regulations
(specifically, 10'4 cancer risk to the MEI was used to set a national emission standard
(NESHAP) for benzene, and 10'5 for individuals living "some distance from the source").
The Agency continues to believe that the aggregate cancer risk to the MEI of 10~5 is
appropriate here because: (1) it provides adequate protection of public health; (2) it limits
the risk from individual Group A and B carcinogens to risk levels on the order of 10~6; and
(3) it is within the range of risk levels the Agency has used for hazardous waste regulatory
programs. See also discussion in section IRA above.
E. Use of MEl/Consideration of Aggregate Risk
The Agency considered the use of aggregate population risk or cancer incidence
(i.e., cancer incidents per year) in developing the national emission limits and in site-
specific risk assessments. This approach could, in some situations, be more conservative
than considering only MEI risk because, even if the "acceptable" MEI risk level were not
exceeded, large population centers may be exposed to emission such that the increased
cancer incidence could be significant However, it would be difficult to develop acceptable
aggregate cancer incidence rates. Nevertheless, it is likely that many facilities that perform
52 This rule is, thus, unlike the Benzene NESHAP where EPA targeted one known
pollutant with known effects.
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a site-specific MEI exposure and risk analysis would also generate an aggregate population
exposure and risk analysis that could be considered by the Agency.
Several commenters addressed the issue of using the maximum exposed individual
(MEI) as a basis for risk estimation and recommended using population (aggregate) risks as
a more realistic alternative. They maintained that health risks are overstated if based only
on exposure of the Maximum Exposed Individual (MEI). Aggregate population-based
exposures, which are usually much lower would more realistically represent site-specific
health risks. Many commenters noted that using the MEI exposure implicitly assumes that
population risks are similar.
EPA believes that evaluation of the MEI only (and not aggregate population risk) is
usually a conservative feature of the risk assessment For screening purposes, a simplified
approach is necessary. While site-specific demographic data is usually readily available
from 1980 census data, its incorporation into a screen would complicate the screening
process unnecessarily. Calculation of screening limits based on the risk to the MEI
requires much less site-specific information, facilitating application of the screen to a broad
range of sites. If the facility does not meet the screening limits, the option of site-specific
risk assessment is still available. While MEI exposures are estimated routinely in a site-
specific risk assessment, aggregate population risks may also be estimated, if desired.
Several commenters also contended that even the risk estimates for the MEI may be
overly health-protective since the MEI is assumed to reside at this high exposure location
24 hours per day, 365 days per year, for a 70-year lifetime. A more fair evaluation of MEI
risk would account for the attenuating effects of time spent indoors and off-site, and
include estimates of average residence times and facility lifetimes. Moreover, some
exposure assessments assume the MEI is located at the point of maximum ground level
concentration predicted by the dispersion model, when in fact, no one may live at this site.
EPA acknowledges that use of the hypothetical MEI is a conservative feature of the
rule but maintains that it is reasonable to balance against the potentially nonconservative
features of the rule discussed below.
F. Risk Assessment Assumptions
As indicated in the above discussion, we have used a number of assumptions in the
risk assessment, some conservative and others nonconservative, to simplify the analysis or
to address issues where definitive data do not exist
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Conservative assumptions include the following:
• Individuals reside at the point of maximum annual average ground level
concentrations. Furthermore, risk estimates for carcinogens assume that the
maximum exposed individual resides at the point of maximum annual average
concentration for a 70-year lifetime.
• Indoor air contains the same levels of pollutants contributed by the source as outdoor
air.
• For noncarcinogenic health determinations, background exposure already amounts to
75% of the RfD. This includes other routes of exposure, including ingestion and
dermal. Thus, the BIF is only allowed to contribute 25% of the RfD via direct
inhalation. The only exception is for lead, where a BIF is only allowed to contribute
10% of the NAAQS. This is because ambient lead levels in urban areas already
represent a substantial portion (e.g., one-third or more) of the lead NAAQS. In
addition, the Agency is particularly concerned about health risks from lead in light of
health effects data available since the lead NAAQS was established. EPA is currently
reviewing the lead NAAQS to determine if it should be lowered.
• Risks are considered for pollutants that are known, probable, and possible human
carcinogens.
• Individual health risk numbers have large uncertainty factors implicit in their
derivation to take into effect the most sensitive portion of the population.
Nonconservative assumptions include the following:
• For carcinogenic compounds, indirect routes of exposure are not considered, such as
uptake of arsenic, beryllium, cadmium, and chromium through the food chain.
• Although emissions are complex mixtures, interactive effects of threshold or
carcinogenic compounds have not been considered in this regulation because data on
such relationships are inadequate.
• Environmental effects (i.e., effects on plants and animals) have not been considered
because of a lack of adequate information. Adverse effects on plants and animals may
occur at levels lower than those that cause adverse human health effects. (The
Agency is also developing procedures and requesting Science Advisory Board review
to consider environmental effects resulting from emissions from all categories of
waste combustion facilities.)
Many commenters responded broadly on the impact of assumptions and uncertainty
in risk assessment While generally supporting the concept of risk assessment, some
asserted that EPA's proposed assumptions were too conservative regarding estimated
emission levels, dispersion modeling, and health impact estimation. Further, they
maintained that assumptions were not well enough justified and the conservative bias used
for each of the multiple assumptions required in a risk assessment tends to accumulate,
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resulting in gross over-estimation of health impacts. Some of the specific assumptions that
commenters considered too conservative are discussed in the following paragraphs.
Two commenters asserted that emission control technology should not be assumed
absent when estimating emission levels. One commenter recommended that sensitivity
analysis be incorporated into the risk assessment process. This commenter also
recommended incorporation into the risk assessment of population mobility (i.e., time
spent away from the site), facility lifetimes less than 70 years, and an attenuation factor for
time spent indoors, rather than assume 24 hr/day, 70-year exposure.
Many of the respondents argued that economic impacts resulting from overly-
conservative risk assessments are substantial. To avoid some of the default assumptions is
also burdensome in the commenters judgment, requiring trial burns, emissions
measurements, slag and product assays, and detailed air quality dispersion modeling.
Although many of the assumptions discussed by the commenters are conservative
in nature, it is difficult to determine how less conservative assumptions could be used in
light of the considerable associated uncertainty. Much of the conservatism referred to
originates from assumptions used to derive screening levels. When screening levels arc
derived, either: (1) no site-specific information is available (nor may be assumed if the
procedure is intended to screen a variety of sites); or (2) incorporation of site-specific
information in the derivation of screening levels would so complicate the process as to
render it prohibitively time-consuming and defeat its utility as a screen. Thus, in light of
the uncertainty (i.e., no site specific information), conservative assumptions are used to
derive the screening limits that EPA believes to be protective of human health and the
environment
If the facility fails to meet the screening criteria, the option of site-specific risk
assessment is still available. For site-specific risk assessment, more realistic and less
conservative assumptions may be incorporated, reflecting actual site or facility conditions.
V. Controls for Emissions of Toxic Metals
The Agency has identified 12 toxic metals in Appendix VIII of 40 CFR Pan 261
that may pose a hazard to human health and the environment: antimony, arsenic, barium,
beryllium, cadmium, hexavalent chromium, lead, mercury, nickel, selenium, silver, and
thallium. Five of these metals (or their compounds) are known or suspected carcinogens:
arsenic, beryllium, cadmium, hexavalent chromium, and nickel.
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Many of these toxic metals are contained in hazardous waste that is burned in
boilers and industrial furnaces. Many hazardous waste fuels contain metals at levels orders
of magnitude higher than levels found in No. 6 fuel oil. Metal-bearing wastes typically
used as fuel in boilers and industrial furnaces include spent halogenated and
nonhalogenated degreasing solvents used for metals cleaning, paint manufacturing wastes,
and other organic liquid wastes with high heating values. Currently, metals emissions
from the burning of these wastes are not controlled under RCRA for boilers and the types
of industrial furnaces that burn hazardous wastes. Emissions of carcinogenic metals can
potentially result in increased lifetime cancer risks of greater than 1 x 1(H and emissions of
noncarcinogenic metals such as lead can result in ambient levels that result in adverse health
effects.
Today's final rule promulgates the controls as discussed in the October 1989
supplement to the proposed rule (see 54 FR 4372S-29).53 See §266.106. The rules
establish metals emission limits for 10 toxic metals54 listed in Appendix Vffl of 40 CFR
Part 261 based on projected inhalation health risks to a hypothetical maximum exposed
individual (MEI). The standards for the carcinogenic metals (arsenic, beryllium, cadmium,
and chromium) limit the increased lifetime cancer risk to the MEI to a maximum of 1 in
100,000. The risk from the four carcinogens must be summed to ensure that the combined
risk is no greater than 1 in 100,000. The standards for the noncarcinogenic metals
(antimony, barium, mercury, silver, and thallium) are based on Reference Doses (RfDs)
below which adverse health effects have not been observed. The standard for lead is based
on the National Ambient Air Quality Standard (NAAQS) for lead.
The owner and operator must analyze the hazardous waste to be burned and comply
with the standard for each of the 10 metals that could reasonably be expected to be in the
53 Given time constraints in developing the final rule for promulgation, response to
major comments could not be provided in the preamble. Responses to comments are
provided in the Comment Response Document for the BIF Regulation.
*4 AS proposed, the rule does not limit emissions of nickel and selenium (see 54 FR
43729). Limits cannot be established for selenium because the Agency has inadequate
health data to establish a reference air concentration. Nickel is not controlled because the
two nickel compounds suspected at this time of being potential human carcinogens, nickel
carbonyl and subsulfide, are not likely to be emitted from combustion devices, given their
highly oxidizing conditions. In the 1989 supplemental notice to the proposed rule, EPA
requested comments on whether the reduced carcinogenic forms of nickel were likely to be
emitted from hazardous waste burning devices, especially those furnaces that may not use
highly oxidized conditions. However, the Agency did not receive any comments on this
issue pertinent to boilers and industrial furnaces.
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waste. The metals excluded from analysis must be identified and the basis for their
exclusion explained to ensure that there is adequate justification for not analyzing for a
particular metal.
The standards are implemented through a three-tiered approach. Compliance with
any tier is acceptable. The tiers are structured to allow higher emission rates (and feed
rates) as the owner or operator elects to conduct more site-specific testing and analyses
(e.g., emissions testing, dispersion modeling). Thus, the feed rate limits under each of the
tiers are derived based on different levels of site-specific information related to facility
design and surrounding terrain. Under Tier I (see §266.106(b)), the Agency has provided
conservative waste feed rate limits in reference tables as a function of effective stack height
and terrain and land use in the vicinity of the stack. The owner or operator demonstrates
compliance by waste analysis, not emissions testing or dispersion modeling.
Consequently, the Tier I feed rate limits are based an an assumed reasonable, worst-case
dispersion scenario, and an assumption that all metals fed to the device are emitted (i.e., no
partitioning to bottom ash or product, and no removal by an air pollution control device
(APCD)).
Under Tier n (see §266.106(c)), the owner or operator conducts emissions testing
(but not dispersion modeling) to get credit for partitioning to bottom ash or product, and
APCD removal efficiency. Thus, the Agency has developed conservative emission rate
limits in reference tables, again as a function of effective stack height and terrain and land
use in the vicinity of the stack. The Agency also assumed reasonable, worst-case
dispersion under Tier n.
Under Tier m (see §266.106(d)), the owner or operator elects to conduct emissions
testing and site-specific dispersion modeling to demonstrate that the actual (measured)
emissions do not exceed acceptable levels considering actual (predicted) dispersion.
The metals controls apply both to facilities applying for a Part B operating permit
and to facilities operating during interim status. See section Vn of Part Three of this
preamble for discussion of how the standards apply during interim status.
A. Background Information.
The following sections summarize EPA's regulation of metals emissions from
boilers and industrial furnaces under other statutes, the 1987 proposed rule and comments
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received on that proposal, and the basis for the 1989 revision to the proposed rule and
comments received on that revised approach.
1. Metals Standards Under Other Statutes. As discussed below, EPA has
promulgated standards applicable to boilers and industrial furnaces under other statutes for
some but not all of the 10 toxic metals controlled by today's rule. Under the Clean Air Act
(CAA), EPA established National Emissions Standards for Hazardous Air Pollutants
(NESHAPS) for arsenic, beryllium, and mercury for certain categories of sources (40 CFR
Part 61). These emission standards were developed considering the quantities and types of
metals emissions from various source categories, current control practices, and the
economic impacts of reducing emissions. In addition, EPA has established National
Ambient Air Quality Standards55 (NAAQS) for lead and paniculate matter. These ambient
standards are implemented by states under the State Implementation Plan (SIP) program to
control major sources of lead and paniculate emissions. The Agency does not believe that
lead emissions standards have been established under the SIPs for any boilers and for
many industrial furnaces that bum hazardous waste fuels (e.g., cement and light-weight
aggregate kilns) because they are not major lead emitters as defined under the NAAQS.
Therefore, EPA believes that today's metals controls are not redundant to existing Agency
standards, and, thus, are necessary to ensure adequate protection of human health and the
environment.
Paniculate emission standards, however, established under the SIPs in
confonnance with the paniculate NAAQS, or by EPA as New Source Performance
Standards (NSPS), do apply to some boilers and industrial furnaces that burn hazardous
waste. The paniculate standards generally limit metals emissions to the extent that state-of-
the-art paniculate control technologies will allow. High efficiency electrostatic precipitators
(ESPs) or fabric filters are usually required to meet these standards. However, these
paniculate emission standards may not adequately control metals emissions from the
burning of hazardous wastes in many boilers and industrial furnaces for several reasons:
(1) the paniculate standards do not apply to gas and oil-fired boilers (which represent a
large number of hazardous waste fuel burners); (2) smaller coal-fired boilers are not subject
to NSPS standards and may not be required under the SIPs to be equipped with ESPs or
fabric filters; (3) large volumes of hazardous waste fuels are burned by light weight
55 We note that the reference air concentration values for noncarcinogens and risk-
specific dose values for carcinogens established by today's rale are not intended to, and in
no way, preclude the Agency from establishing NAAQS as appropriate for these
compounds under authority of the Clean Air ACL
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aggregate kilns that are equipped with low-pressure wet scrubbers that may not be highly
efficient at collecting particulates in the less than 1 micron range, the size range that
contains the bulk of the paniculate metals; and (4) the risks posed by metals emissions from
these boilers and industrial furnaces that are equipped with ESPs, fabric filters, and wet
scrubbers can increase substantially when hazardous waste fuel is burned since the levels
of some metals, particularly chromium and lead, can be much higher in hazardous waste
than in coal.
2. 1987 Proposed Rule. The 1987 proposed rule would have established a four-
tiered standard to control emissions of arsenic, cadmium, hexavalent chromium, and lead.
Each Tier represented a standard protective on its own, and demonstration of compliance
with any Tier would have been sufficient Tiers I through in established hazardous waste
metals concentrations, feed rates, and emission screening limits, respectively, as a function
of device type and thermal capacity. Tier IV would have provided for site-specific
dispersion modeling to demonstrate that, when the screening limits were exceeded,
emissions would nevertheless not pose an unacceptable health risk. Data available to the
Agency indicated that only four of the 12 toxic metals listed in Appendix Vm of Part 261
were likely to be present in hazardous waste burned in boilers and industrial furnaces at
levels posing a significant health risk. The permit writer would have determined on a case-
by-case basis if any of the other toxic metals were present at levels posing a significant
risk.
Public comments submitted on the 1987 proposal stated that EPA's database on the
metals composition of hazardous waste was both limited and out of date in light of the
Agency's data collection efforts at that time and the HSWA statutory requirement to pretreat
waste that heretofore had been land disposed. As a result of HSWA, more hazardous
waste is being burned, and pretreatment operations are often likely to involve combustion.
The hazardous waste burned currently and in the future in boilers and industrial furnaces
may include toxic metals other than the four targeted for regulation in the 1987 proposal.
Therefore, the Agency requested comment in the October 1989 supplemental notice on
expanding die list of regulated metals to include all 10 Appendix Vm metals. (Nickel and
selenium were not included as discussed above.) In addition, if standards for all of the
toxic metals were included in the rule, the burden on permit writers would actually be
reduced because explicit standards would be provided for all metals of potential concern.
Without explicit standards, permit writers would have to rely on the omnibus permit
authority of the statute to add permit conditions as necessary to protect human health and
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the environment. Using the omnibus permit authority can involve a lengthy and
cumbersome interaction between permit officials and the applicant
3. 1989 Supplement to Proposed Rule. Based on public comments submitted on
the 1987 proposed rule and on additional evaluation of the risk assessment approach used
for the proposal, the Agency discussed in the 1989 supplemental notice whether to (1)
expand the list of metals for which emissions standards would be established in the rule to
include all the toxic metals listed in Appendix Vm of Part 261 (except nickel and selenium,
for the reasons discussed above); (2) establish the screening limits as a function of effective
stack height, terrain, and land use rather than as a function of device type and capacity; and
(3) rather than provide the screening limits in the rule itself as proposed in 1987, provide
them in a guidance document that would be entitled "Risk Assessment Guideline (RAG) for
Permitting Hazardous Waste Thermal Treatment Devices".
a. Expanded List of Metals. In the 1989 supplemental notice, EPA proposed to
expand the list of metals for which emissions standards would be established in the rule to
include antimony, arsenic, barium, beryllium, cadmium, hexavalent chromium, lead,
mercury, silver, and thallium. Thus, of the 12 toxic metals listed in Appendix Vm, only
selenium and nickel would not be controlled for reasons discussed above. Today's final
rule establishes standards for all 10 metals. We note that the controls apply only to metals
that are present in the hazardous waste feed at detectable levels using procedures specified
inSW-846. See §266.106(a).
b. Revised Basis for Screening Limits. In the 1989 supplemental notice, EPA also
proposed to revise the bases for the feed rate and emission rate screening limits to correlate
them with stack height and terrain and land use in the vicinity of the facility because these
parameters more directly relate emission controls to key parameters that affect the
dispersion of emissions, and ultimately, ambient levels (i.e., more so than the proposed
approach of correlating the screening limits to device type and heat input capacity). When
developing the Tier I through Tier ffl screening limits proposed in 1987, the Agency made
a simplified assumption that effective stack height correlated with thermal capacity (e.g., if
the thermal capacity of one device was 10 percent greater than the thermal capacity of
another, the effective stack height was also 10 percent greater). The Agency acknowledges
that this assumption may not always hold. Stack height is often more a function of the
height of nearby buildings and surrounding terrain than a function of the heat input capacity
of the device. Thus, the final rule correlates the Tier I and Tier n screening limits to stack
height, terrain, and land use.
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c. Establishing the Screening Limits in the Rule. As originally proposed in 1987,
the final rule incorporates the Tier I feed rate screening limits and the Tier n emissions rate
screening limits in the rule itself rather than in a separate guidance document. Our concern
(and many commenters concurred) is that a guidance document would not carry the weight
of a regulation ~ permit writers would be free to accept or reject the guidance (i.e., in this
case, the screening limits and the reference air concentration (RACs) and risk-specific dose
(RSD) values used to develop the limits). In addition, permit writers would be obligated to
justify use and appropriateness of the guidance on a case-by-case basis. This would place
a substantial burden on the permit writer and result in inconsistent, and perhaps,
inappropriate permit conditions. Finally, implementing the emission standards during
interim status as required by the final rule would be virtually impossible without
incorporating the screening limits and RACs and RSDs in the rule.
We note that revisions to the RACs and RSD values will undoubtedly need to be
made over time as the Agency obtains additional health effects information on the regulated
pollutants, and corresponding revisions to the screening limits, will be made by formal
rulemaking (i.e., proposed revisions, opportunity for public comment, and promulgation
of final revisions). In the interim, however, permit writers may apply stricter limits than
contained in the rule (if the facts justify it) pursuant to the omnibus permit authority56 in
Section 3005(c)(3).
In the 1989 proposal, as a possible alternative to monitoring waste feed rates and
compositions, EPA requested comment on using the results of analyses of emission control
residues to monitor compliance with the metals emission standards. Several commenters
supported this approach. The final rule allows for this or other alternative approaches to
implement the metals controls. See section V.C.4 of Part Three of the preamble.
B. How the Standards Work.
1. Tier III Standards. Tier DI standards are discussed first because the Agency
believes that the majority of facilities will elect to comply with these standards rather than
5 6 EPA notes that permit writers choosing to invoke the omnibus permit authority of
§270.32(b)(2) to add conditions to a RCRA permit must show that such conditions are
necessary to ensure protection of human health and the environment and must provide
support for the conditions to interested parties and accept and respond to comment In
addition, permit writers must justify in the administrative record supporting the permit any
decisions based on omnibus authority.
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the Tier I or Tier n screening limits to obtain more flexible permit limits. The Tier m
standards (see §266.106(d)) require: (1) emissions testing to determine actual emissions
taking into account partitioning of metals to combustion gas versus ash or product; and
removal of metals from flue gas by the air pollution control system (APCS); and (2) site-
specific dispersion modeling to take into account actual, predicted dispersion conditions at
the facility.
To comply with the Tier in standards, predicted ambient concentrations of the
carcinogenic metals, arsenic, beryllium, cadmium, and hexavalent chromium at the
hypothetical maximum exposed individual (MEI) may not result in an increased cancer risk
of more than 1 in 100,000. The risk from each metal must be summed to ensure that the
summed risk does not exceed 1 in 100,000. As proposed, the final rule establishes a risk-
specific dose (RSD) for each metal at the 10~5 (i.e., 1 in 100,000) risk level. If a person is
exposed to the 10" 5 RSD (an ambient air concentration) over a lifetime, the probability of
increased cancer incidence is not expected to exceed 1 in 100,000. To ensure that the
summed risk from the four carcinogens is no greater than 1 in 100,000, the ratios of the
predicted ambient concentration to the 10~5 RSD must be summed for all metals to
demonstrate that the sum does not exceed l.O.57
For the noncarcinogenic metals, antimony, barium, mercury, silver, and thallium,
predicted MEI ambient air concentrations may not exceed the reference air concentrations
(RACs), as proposed. The RAC for lead is based on 10% of the National Ambient Air
Quality Standard (NAAQS) for lead, as proposed. One commenter stated that the lead
RAC may be appropriate for facilities in urban areas but that it is not appropriate for rural
areas with low background lead levels. This commenter suggested a waiver of the lead
RAC where a facility can show that measured ambient air lead levels do not exceed the
NAAQS. Although this approach is reasonable, the final rule does not include a waiver
provision for the lead RAC based on site-specific ambient air monitoring58 because: (1)
57 TO implement the metals controls, metals feed rates are limited to levels during the
compliance test or trial bum. Thus, if the owner/operator would like to have the flexibility
to bum wastes with varying (higher) levels of carcinogenic metals, he/she may choose to
develop two or more operating modes with varying feed rates of carcinogenic metals. If
so, a compliance test or trial bum would be required for each mode of operation to
demonstrate that the summed risk from the carcinogenic metals does not exceed 1 in
100,000. Under this approach, the operator is required to identify the mode of operation at
any time, and to comply with the metal feed rate limits for that mode of operation.
*° We note, however, that EPA's Guideline on Air Quality Models a^"ws the use of
ambient air monitoring to develop site-specific dispersion models.
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the lead NAAQS may not be protective given that the Agency has been developing for some
time a proposal to lower the NAAQS (perhaps by as much as 50%) based on health effects
data obtained since the NAAQS was established initially (the Agency plans to propose a
lower lead NAAQS in the fall of 1991); (2) the time and cost of conducting ambient
monitoring in conformance with procedures established by EPA's Office of Air Quality
Planning and Standards (OAQPS) would make this approach impracticable; (3) a waiver
provision would add extra complexity to the rule; and (4) such a waiver could make
eventual further regulation under amended section 112 of the Clean Air Act more likely.
a. Emissions Testing. Stack emissions testing for metals must be conducted in
conformance with "Methodology for the Determination of Metals Emissions in Exhaust
Gases from Hazardous Waste Incineration and Similar Combustion Processes" (Multiple
Metals Train) provided in section 3.1 of Methods Manual for Compliance with the BIF
Regulations (incorporated by reference in §260.11).
b. Dispersion Modeling. Dispersion modeling must be conducted in conformance
with EPA's Guideline on Air Quality Models (Revised), EPA's "Hazardous Waste
Combustion Air Quality Screening Procedure" provided in Methods Manual for
Compliance with the BIF Regulations, or "EPA SCREEN Screening Procedure" as
described in Screening Procedures for Estimating Air Quality Impact of Stationary Sources.
All three documents are incorporated by reference in today's final rule at §260.11. The
Guideline on Air Quality Models is the Agency's primary guide for dispersion modeling.
The "Hazardous Waste Combustion Air Quality Screening Procedure" is included in EPA's
Guidance on Metals and Hydrogen Chloride Controls fPF Hazardous Waste Incinerators.
Draft Final Report, August 1989. The derivation of this procedure, which was developed
specifically for hazardous waste combustion facilities, is also included in that document
The data base used in the derivation is the same as that used for deriving the Tier I and Tier
n screening limits as summarized in the October 26,1989 supplement to the proposed BIF
rule (54 FR 43752). Finally, the EPA SCREEN screening procedure has been in general
use since 1988 when it was developed by EPA's Office of Air Quality Planning and
Standards. It has been used by Regional Offices, States, and sources for air dispersion
modeling required by EPA air regulations.
If a user determines that there is an inconsistency between either of the screening
procedures discussed above and EPA's Guideline on Air Quality Models, the Guideline
shall have primacy.
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c. GEP Stack Height. As proposed, stack heights used to demonstrate
conformance with the final rule may not exceed Good Engineering Practice (GEP) as
defined in 40 CFR Part 51.100(ii).
d. MEL As proposed, the hypothetical MEI concentration is the maximum annual
average ground level concentration at an off-site location. On-site MEI locations need not
be used to demonstrate conformance with the standards, unless a person resides on-site.
e. Bubble Approach for Multiple Stacks. Given that the standards for metals (and
HQ and Cl2) are health risk-based, the final rules are implemented using a limited "bubble"
approach as proposed. Under the limited bubble approach, emissions from all hazardous
waste combustion stacks at a facility subject to metals and chlorine feed rate limits must be
considered in demonstrating conformance with the acceptable ambient levels. This includes
all boilers and industrial furnaces regulated under today's rule, and also those RCRA-
regulated incinerators and thermal treatment units where feed rate or emission limits have
been established for metals, chlorine, HQ, or Cl2 by EPA. (The Agency considered
expanding the bubble to consider other stack emissions such as from nonhazardous waste
incinerators or process stacks, but believes that effective implementation would be difficult
given the different types and levels of regulatory control and procedures applicable to a
variety of stack emission sources.)
To implement the bubble approach, dispersion modeling must consider emissions
from all regulated stacks (see discussion above) to predict the maximum annual average
off-site ground level (i.e., MEI) concentration of each metal. The MEI location will
generally vary for each metal
2. Tier II Standards. See §266.106(c). The final rule incorporates the Tier II
emission rate screening limits (see Appendix I of the final rule) as presented in the 1989
supplemental notice as a function of terrain adjusted effective stack height, and noncomplex
versus complex terrain and urban versus rural land use in the vicinity of the facility. The
limits were back-calculated from the RACs and 10~5 RSDs established by today's rule
using reasonable, worst-case dispersion scenarios. Conformance with the Tier n emission
rate screening limits is demonstrated by emissions testing (i.e., the facility's actual
emissions are compared to the maximum allowable screening limits).
The methodologies for determining terrain adjusted effective stack height and terrain
type are established in §§266.106(b)(3) and (4), and the methodology for determining land
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use in the vicinity of the stack are provided in "Simplified Land Use Classification
Procedures for Compliance with Tier I and Tier n Limits in Appendix VI of Methods
Manual for Compliance with the BIF Regulations (incorporated by reference in today's
rule, see §260.11).
a. Special Requirements for Carcinogens. We note that the Tier n emission rate
screening limits for the carcinogenic metals arsenic, beryllium, cadmium, hexavalent
chromium, are back-calculated from the 10*5 RSD for each metal. Thus, if the actual
emission rate of one of those metals was at the Tier n screening limit, the resulting risk to
the MEI is estimated to be 1 in 100,000. Given that the rule requires that the summed risk
for all carcinogenic metals cannot exceed 1 in 100,000, the ratios of the actual emission rate
to the Tier n allowable emission rate for all of the carcinogenic metals must be summed and
the sum cannot exceed 1.0.
b. Bubble Approach for Multiple Stacks. Although we believe that most facilities
will use Tier m dispersion modeling to demonstrate conformance with the metals (and HC1
and Cl2) controls when they have multiple stacks to obtain credit for actual dispersion
conditions, Tier n (or Tier I) may be used. To use the Tier I feed rate limits or Tier n
emissions rate limits for multiple stacks, the owner/operator must conservatively assume
that all hazardous waste is fed to the source with the worst-case stack (i.e., considering
dispersion). The worst-case stack must be determined from the following equation59 as
applied to each stack:
K = HVT
where:
K = a parameter accounting for relative influence of stack height and plume rise;
H = physical stack height (meters);
V = flow rate (m-Vsecond); and
T = exhaust temperature (Kelvin).
The stack with the lowest value of K must be used as the worst-case stack.
c. Facilities Ineligible to Use the Tier n (and Tier I) Screening Limits. The
screening limits were back-calculated from the RACs and 10~5 RSDs established by
today's rule using dispersion modeling scenarios that the Agency considers reasonable,
59 This equation was proposed at 54 FR 43762 (Oct. 26,1989). It is derived from a
similar equation on pp. 2-3 of Screening Procedures for Estimating Air Quality Impact of
Stationary Sources, EPA-450/4-88-010, August 1988.
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worst-case dispersion scenarios. However, dispersion characteristics at a particular facility
may, in fact, provide worse dispersion of emissions than used to calculate the screening
limits. Consequently, die final rule, as discussed in the 1989 supplemental notice,
establishes criteria for facilities that are ineligible to use the screening limits. See
§266.107(b)(7).
3. Tier I Standards. See §266.106(b). The final rule incorporates the Tier I feed
rate screening limits (see Appendix I to the rule) as presented in the 1989 supplemental
notice as a function of terrain adjusted effective stack height, and noncomplex versus
complex terrain and urban versus rural land use in the vicinity of the facility. Conformance
with the Tier I feed rate screening limits is demonstrated by sampling and analysis of all
feed streams (hazardous waste, other fuels, and raw materials).
By complying with the conservative Tier I feed rate screening limits, applicants
burning hazardous waste with very low concentrations of metals would not have to conduct
emissions testing. The feed rate limits are back-calculated from the emission screening
limits, assuming that all metals present in feedstreams are emitted to the atmosphere. Thus,
no metals are assumed to partition to the bottom ash or product, and no allowance is made
for removal of metals from the stack gas by an air pollution control system. Consequently,
the Tier I feed rate screening limits are equivalent to the Tier n emission rate screening
limits and are provided in the same table in Appendix I to the rule. (At proposal, the feed
rate and emission rate screening limits were provided in separate tables because the Agency
presented the limits in different units - Ib/hr (pound per hour) for feed rate limits, and g/s
(grams per second) for emission rate limits. To avoid confusion and for simplicity,
however, the final rule combines the Tier I and n screening limits and presents the limits in
g/hr (grams per hour)).
The Tier n discussions above on special requirements for carcinogens also applies
to the Tier I feed rate limits. Thus, to demonstrate confonnance with the feed rate limits for
the carcinogenic metals, the sum of the ratios of the actual feed rate to the Tier I allowable
feed rate for all of the carcinogenic metals must be summed, and the sum cannot exceed
1.0.
In addition, the Tier n discussions above on the bubble approach for multiple
stacks and criteria for facilities that are ineligible to use the screening limits apply to the Tier
I feed rate screening limits as well
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Finally, we note that the Tier I feed rate limits may be adjusted upward to reflect
site-specific dispersion modeling. This is a hybrid of Tiers I and EQ. See §266.106(e).
Under this approach, site-specific dispersion modeling may be conducted using the
procedures discussed above to back-calculate allowable emission rates for each metal.
These allowable emission rates then become the adjusted feed rate limits. Given that
emissions testing is not conducted under this modified Tier I approach, no credit is given
for partitioning of metals to bottom ash or product, or removal by the air pollution control
system.
C. Implementation.
As discussed above, EPA developed a three-tiered standard to ensure that metals
emissions do not pose an unacceptable risk to human health and the environment Tier I
consists of conservative feed rate screening limits, Tier n establishes conservative emission
rate screening limits, and Tier HI allows the use of site-specific air dispersion modeling to
demonstrate compliance. The decision of which tier to use depends on the physical
characteristics of the facility and surrounding terrain, on the anticipated waste compositions
and feed rates, and on the level of resources available for conducting the analysis. It is
acceptable to use different tiers to comply with the standards for different metals.
1. Tier I Implementation. The Tier I feed rate limits are implemented by sampling
and analysis as necessary and flow rate monitoring of each feedstream (i.e., hazardous
waste, other fuels, and raw materials) to ensure that the total feed rate of each metal does
not exceed the Tier I limit on either an hourly rolling average or instantaneous basis (i.e., at
any time), except as provided for the carcinogenic metals and lead as discussed below.
a. Special Procedures for Carcinogenic Metals. Given that, for the carcinogenic
metals, the sum of the ratios of the actual feed rates to the Tier I allowable feed rates cannot
exceed 1.0, there are no fixed feed rate limits for individual carcinogenic metals. Rather,
the operator must insure that on an hourly rolling average or instantaneous basis (or as
allowed below for carcinogenic metals and lead) that the mixture of carcinogenic metals fed
into the BEF does not exceed allowable levels. To demonstrate conformance with this
standard, the operator must: (1) know the concentration of metals in each feedstream and
the flow rate of each feedstream; (2) calculate on an hourly rolling average or instantaneous
basis (or as allowed below for carcinogenic metals and lead) the sum of the ratios of the
actual feed rate to the allowable feed rate; and (3) ensure that the sum of the ratios for all
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carcinogenic metals (on an hourly rolling average or instantaneous basis or as allowed
below) does not exceed 1.0.
b. Averaging Periods. As discussed in the 1989 supplemental notice, the final rule
provides an alternative averaging period to the hourly rolling average or instantaneous basis
for the carcinogenic metals arsenic, beryllium, cadmium, and chromium, and for lead. For
these metals, an averaging period not to exceed 24 hours (i.e., 24-hour rolling average)
may be used provided that the feed rate at any time (i.e., instantaneously) does not exceed
10 times the feed rate on an hourly rolling average basis. The Agency believes that an
averaging period greater than an hourly rolling average is reasonable given that the metals
controls are based on lifetime exposures. However, the Agency is concerned that
averaging periods greater than 24 hours may be difficult to enforce. A ten-fold higher
emission rate should not pose adverse health effects from short-term exposures for the
carcinogenic metals because the 24-hour rolling average would not exceed the level that
could pose a 10~5 health risk over a lifetime of exposure and the threshold (i.e., noncancer)
health effect would not be likely at exposures only ten times higher than the 10~5 RSD. A
ten-fold higher instantaneous ambient level for lead should not pose adverse health effects
given that the acceptable ambient level for long-term exposure to lead (i.e., the lead RAC)
is based on only 10% of the National Ambient Air Quality Standard.
We do not believe that a similar approach for the other noncarcinogenic metals
would be appropriate given the uncertainty in the level of protection provided by the long-
term acceptable ambient levels (e.g., the RACs are based on oral RfDs converted 1 to 1 to
inhalation values).
2. Tier II Implementation. Conformance with the Tier II emission rate screening
limits is based on emissions testing (see section IV.B.l.a) using the Multiple Metals Train
prescribed in Methods Manual for Compliance with the BIF Regulations (incorporated by
reference in §260.11 (a)). The Tier n emission limits are implemented by permit limits on
the following parameters based on operations during the trial bum:
• Maximum feed rate of each metal in total feedstreams (e.g., hazardous waste, raw
material, other fuel), except as discussed below;
• Maximum feed rate of each metal in total hazardous waste feedstreams;
• Maximum feed rate of each metal in all pumpable hazardous waste feedstreams;
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• Maximum feed rate of total hazardous waste and pumpable hazardous waste;
• Maximum feed rate of chlorine in total feedstreams;
• Maximum capacity in appropriate units (e.g., total heat input, pounds of steam
produced, raw material feed rate);
• Maximum temperature at the inlet to the air pollution control system (APCS);
• Maximum combustion chamber temperature; and
• Key parameters to ensure proper operation of the APCS.
The approach that must be used to measure these parameters and the approach to
establish limits on each parameter based on trial bum data is specified in §266.102(e)(6).
In addition, the permit must specify sampling and analysis procedures for all
feedstreams and all flow rates of all feedstreams must be continuously monitored and
recorded.
The final rule establishes limits on these parameters because they can affect metals
emissions. The feed rate of metals in both total hazardous waste feeds and pumpable
hazardous waste feeds is limited because the physical form of the waste (e.g., solid vs
liquid) can affect the partitioning of the metal between bottom ash (for a boiler) or product
(for a furnace) and combustion gas entering the PM control system. Metals partition to the
combustion gas more readily when fired in a liquid or pumpable form.
The rule limits the metal feed rate from total feedstreams to account for metals in
raw materials and nonhazardous fuels. When added to the emissions from hazardous
waste, noncarcinogenic metals from these sources can cause the MEI concentration to
exceed the threshold level for health effects and carcinogenic metals from these sources can
cause the MEI concentration to exceed the incremental Ufetime cancer risk limit for the rule
of 1 in 100,000. Thus, there controls ensure that burning hazardous waste does not result
in unacceptable risks.
The rule limits the chlorine feed rate because chlorine can increase the volatility of
metals, thus increasing the rate of partitioning to the combustion gas and, in some cases,
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resulting in smaller metal particulates in flue gas that can be more difficult to control with a
PM collection system.
The rule limits the maximum capacity of the device to ensure that, during the
compliance test (under interim status) or the trial bum (under a Part B permit application)
the device is feeding raw materials and nonhazardous fuels at a rate that will not be
exceeded after the compliance test or trial burn. Thus, the gas flow rate and paniculate
loading are maximized during the compliance test or trial bum, which tests the ability of the
PM collection system to control metals.
The rule limits the mayi"n"" temperature at the inlet to the PM collection system
because temperature affects the volatility of a metal - some metal species may be partially
(or totally in the case of mercury) in the vapor form at high temperatures at the inlet to the
PM collection system which will reduce the amount of the metal collected. Limiting the
inlet temperature to that occurring during the compliance test or trial burn will ensure that
the temperature cannot be increased later which could result in an increase in metals
emissions.
Finally, the rule limits key operating parameters of the PM air pollution control
system to ensure that it continues to operate as efficiently as it did during the compliance
test or trial bum.
3. Tier III Implementation. Confonnance with Tier HI is demonstrated by
emissions testing and site-specific dispersion modeling showing that ambient levels of
metals do not exceed allowable levels. Permit limits are established for the same
parameters as required for Tier n.
4. Special Requirements for Furnaces that Recycle Collected Paniculate Matter.
Metal emissions are not feasibly monitored on a continuous basis. Thus, some other
means of demonstrating compliance is necessary. For most types of BEFs, compliance is
demonstrated by monitoring feed rates of metals from all feedstreams. EPA requested
comment on whether approaches other than monitoring feed rates of metals may be more
appropriate to implement the metals controls. See 54 FR 43760 (Oct. 26, 1989). A
number of commenters argued that the material balance approach for implementing the
metals controls was impractical and nonconservative for cement kilns. The material balance
approach for metals limits the feed rate of each metal in three types of feeds: (1) pumpable
hazardous waste; (2) total hazardous waste; and (3) total feedstreams. Although limiting
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the feed rate of each metal in the total hazardous waste feed and the pumpable hazardous
waste feed was workable, commenters argued that limiting the feed rate of metals in total
feedstreams was impractical for cement kilns because of the variety of raw materials they
feed. Raw materials to a cement kiln are a blend of several components including calcium
sources such as limestone, sea shells, marl, or chalk, silica sources such as clay, shale,
slate, or sand, and iron sources such as iron ore or mill grindings. The proportions of the
components of the blend are changed frequently according to the type of cement desired
and the composition of the sources. This can make it very difficult to accurately determine
the metals feed rate in the blended raw materials.
Of even more concern to the Agency, however, is the fact that the material balance
approach is not likely to be conservative (i.e., protective) for furnaces, like cement kilns,
that recycle collected PM back into the furnace. Because the dust is recycled, an increase in
the feed rate of a metal in one of the feedstreams ~ such as spiking during a compliance test
(under interim status) or a trial burn (under a Part B permit application) - leads to a gradual
increase in the concentration (and feed rate) of the metal in the recharged kiln dust which
leads to a gradual increase in the metal emissions. Several recharge cycles may be
necessary for the kiln to reach steady state condition. Thus, until the system reaches
equilibrium, metals feed rates do not correlate with metals emissions.
EPA considered a number of alternatives to address the problem that the recycled
dust creates a system that is out of equilibrium when a metal is spiked. We considered
handling the recycled dust as another feedstream. Under this approach, the feed rate of
metals in the recycled dust would be considered along with those from other feedstreams.
(Or alternatively, the feed rate of metals in the recycled dust would be considered as a
fourth level of metals feed rate controls - that is, the feed rate of metals in pumpable
hazardous waste, total hazardous waste, recycled dust, and total feedstreams would be
limited.) We did not adopt this approach because: (1) the recycled dust is an internal
recycled stream so that limits on the recycled dust coupled with limits on other feedstreams
would probably correlate with metals emissions in the kiln off-gas, but not necessarily with
stack emissions; and (2) during an emissions test when metals are spiked, the system will
not be in equilibrium and we do not know enough about metal behavior in the system to
determine whether the metals feed rate in the dust would be higher or lower after reaching
equilibrium (Le., we did not know whether this approach would be conservative).
To address this concern that the material balance approach to implementing metals
controls is not likely to be conservative (i.e., protective) for furnaces that recycle dust,
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today's rule requires owners and operators of such devices to comply with one of three
alternatives: (1) daily monitoring of collected PM to ensure that metals levels do not exceed
limits that relate concentration of the metal in the collected PM to emitted PM; (2) daily
stack sampling for metals; or (3) conditioning of the furnace system prior to compliance
testing to ensure that metals emissions are at equilibrium with metals feed rates. We
discuss each of these procedures below.
We note first, however, that today's rule gives owners and operators the option of
selecting one of these methods only during interim status. The Director will determine
under the Part B permit application proceeding which of these methods (or whether another
method) may be more appropriate on a case-by-case basis considering the facts. See
§266.106(f). In addition, we note that experience with these methods during interim status
may indicate the need to refine them for use under a RCRA operating permit. Finally, we
note that this provision of the permit standards is not limited to furnaces that recycle
collected PM. (However, the methods discussed below may be used during interim status
only by furnaces that recycle collected PM.) The permit standards provide this flexibility
because, although we believe that these methods (as they may be refined with experience)
or other methods that adequately address the concerns described below must be required
for systems that recycle collected PM, the first two methods (i.e., monitoring collected PM
or daily stack sampling) may be preferable for other types of devices as well. This is
because these first two alternative methods address not only the special problem caused by
recycled PM but also the problem of the difficulty (and imprecision) associated with
limiting metals emission rates by the material balance approach given the variability of
waste and raw material matrices and variability of the concentrations of metals in
feedstreams, a problem that also exists for these furnaces and will exist for other devices as
well.60
a. Monitoring Metals in Collected PM This approach will control metals emission
rates by establishing limits on all of the parameters discussed above for implementing the
Tier n and Tier in controls, except for limits on the feed rate of each metal in total
feedstreams. In lieu of that parameter, the final rule limits the concentration of each metal
in collected PM. See "Alternative Methodology for Implementing Metals Controls " in
Method Manual for Compliance with the BIF Regulations (incorporated by reference in
§260.11). The concentration limit is calculated by determining the maximqm allowable
60 We also note that these methods may be preferrable to the material balance approach
in some situations for implementing the metals controls for hazardous waste incinerators.
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concentration of each metal in the emitted PM and by empirically relating the concentration
of the metal in the emitted PM to the concentration of the metal in collected PM (i.e., the
enrichment factor). The maximum allowable concentration of each metal in the emitted PM
is determined by dividing the allowable emission rate for the metal in pounds per hour by
the applicable PM standard61 in pounds per hour. The enrichment factor (i.e.,
concentration of a metal in emitted PM divided by the concentration in collected PM) is
determined initially by a series of 10 emissions tests over a two-week period. Quarterly
testing is required thereafter to determine if the enrichment factor changes substantially. If
so, the series of 10 emissions tests must be conducted again to establish the revised
enrichment factor.
EPA acknowledges certain potential limitations to this approach: (1) the Agency
has limited data to support the main assumption of this approach — that the enrichment
factor will remain constant over the range of normal operating conditions that occur
between the initial series of 10 tests to establish the enrichment factor and the quarterly
confirmation tests; and (2) that a problem with emissions is detected after the fact.
However, we have built into the approach conservative features that should address
concern about whether the enrichment factor may change over time. First, the approach
assumes that the facility is always operating at its maximum allowable PM emission limit
Although allowable metal concentrations in collected PM would be higher when the facility
operates at lower PM emission levels, the limits do not change. Thus, for example, for
every 10% the facility operates under its PM standard, the limit on metals concentrations in
collected PM are conservative Gower than necessary) by 10%. Second, the enrichment
factor is statistically determined based on test data as the lower of: (1) twice the enrichment
factor at the 95% confidence level; or (2) the enrichment factor at the 99% confidence level.
Where there is significant scatter in the data, twice the enrichment factor at the 95%
confidence level is likely to govern. Thus, when the enrichment factor varies significantly
during the 10 tests, not only is the enrichment factor based on the 95% confidence level,
but an additional margin of safety is provided by doubling the factor at the 95% confidence
level for purposes of determining the metal limit in collected PM.62
61 The applicable PM standard is 0.08 gr/dscf or any more stringent standard that may
apply under the NSPS or SIP.
62 m addition, the methodology requires that a "safe enrichment factor" of 100 be used
when a metal is at nondetect levels in the collected PM. Mercury, for example, may be at
nondetcct levels because it is likely to be in the vapor form (and not collected as PM) in an
ESP or baghouse.
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As for detection after the fact, sampling of collected dust is required every eight
hours to form a daily composite sample. The operator is allowed up to 48 hours to analyze
the daily composite63 given that the analytical procedures can take 24 to 48 hours even for
on-site laboratories. In addition, if the sample fails the concentration limit for a metal, the
operator may analyze two duplicate samples that he may have elected to obtain to determine
if the failed sample is an outlier. Analyses of these back-up samples will also take up to 48
hours. Thus, it could take up to four days to confirm that a dust sample has failed the
concentration limit and that a violation of the metals emissions controls may have
occurred.64
Notwithstanding this provision of the method, EPA expects that owners and
operators that want to comply with the spirit of the controls and to operate in a manner that
is protective of human health and the environment will conduct triplicate analyses of
samples for those metals that may exceed the "conservative" metal limit to avoid the time
delay of subsequently analyzing back-up samples if the initial sample fails the concentration
limit Owners/operators should use historical data to determine whether a metal may be
close to exceeding a concentration limit and, thus, routinely analyze "back-up" samples
concurrently with the "required" sample for such metals. Further, EPA expects that
enforcement officials will consider whether the owner/operator has taken such precautions
to minimize the time during which they may be operating under violation conditions (if the
dust concentration actually exceeds the "violation" limit) in determining appropriate
enforcement action.
63 Except for "noncritical" metals where 30 continuous days of analyses demonstrate
that the dust concentration for die metal does not exceed 10% of the concentration limit.
For these metals, weekly composite samples must be analyzed If a weekly composite
exceeds 10% of the dust concentration limit, however, daily analyses would be again
required.
64 The methodology requires that two dust concentration limits be established for each
metal: a "conservative" limit and a "violation" limit For example, die conservative limit is
based on die safe enrichment factor of twice die enrichment factor at die upper 95%
confidence level, while die violation limit is based on die enrichment factor at die upper
95% confidence level If die conservative limit is failed more dian 3 times out of 60 times,
die owner/operator must notify die Director and he may bum hazardous waste for a total of
720 hours during which: (1) die series of 10 emissions tests must be conducted to revise
die enrichment factor and die dust concentration limits; and (2) die maximum feed rate of
each metal in die hazardous waste is reduced by 50% (except during die duee compliance
tests). If die violation limit is exceeded, however, die operator is in violation of die metals
controls (and he must also notify die Director, reduce die feed rate of metals in hazardous
waste, and conduct die series of 10 tests to calculate die revised concentration limits).
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Notwithstanding these potential limitations, EPA believes that this methodology is
preferable to the material balance approach. Rather than attempt to limit emissions by
limiting metal feed rates and extrapolating through a number of not well-understood
processes for furnaces that recycle dust, the methodology in the final rule goes to the
material that is closest to what is being emitted, collected PM, to extrapolate to emissions.
Limits on the operating parameters discussed above will be established under this
methodology during a minimum of three "compliance tests" of the first five of the ten
emissions tests required to establish the enrichment factor for each metal. Consequently,
during three of the ten runs, feed rates of metals in total hazardous waste and pumpable
hazardous waste will be at the maximum level that the facility may operate during the
remainder of interim status. Although the feed rate of metals in the hazardous waste during
the other tests need not be at the maximum level established during the three "compliance
tests", the feed rate must be at least 25%65 of the compliance test level, and the facility
must operate at the compliance test capacity (i.e., the maximum capacity at which the
facility may operate during the remainder of interim status). The owner and operator must
demonstrate compliance with the applicable PM standard and the metals emissions
standards of §266.106(c) or (d) during all ten tests required to establish enrichment factors.
The rule requires that the ten emissions tests to determine enrichment factors be conducted
in a two week period with not more than two tests per day, and that the three compliance
tests (when metals feed rates from the hazardous waste will be maximized to establish
limits for the remainder of interim status) be among the first five tests. EPA is providing
these restrictions to ensure that the enrichment factors are representative of operations over
several days when operating conditions can vary, and to ensure that any effect on
enrichment factors from the high metals loading from spiked hazardous waste during the
three compliance tests will be detected during the subsequent tests.
The testing and operating requirements for this methodology are prescribed in detail
in "Alternative Methodology for Implementing Metals Controls" in the Methods Manual.
6$ We are not requiring the facility operate at the maximum (i.e., compliance test)
metals feed rate from hazardous waste (or other feedstreams) during all ten emissions tests
because the purpose of the remaining tests is to obtain data to statistically determine the
enrichment factor. Thus, it is important to determine how the enrichment factor may
change as the feed rate of metals from various feedstreams varies. Nonetheless, the metal
feed rate in the hazardous waste must me a minimum of 25% of compliance test limits
during the remaining 7 enrichment factor determination tests.
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b. Daily Emissions Testing. Under this option, the owner or operator must
conduct daily emissions testing to confirm that the metals emissions limits are not
exceeded. Sampling must be conducted for a minimum of 6 hours each day when
hazardous waste is burned. To ensure that sampled emissions are representative of normal
emissions that day, the testing must be conducted when burning normal hazardous waste
for that day (i.e., considering metals content, point of introduction into the system, and
physical form of the waste) at normal feed rates for that day and when the air pollution
control system is operated under normal conditions. See §266.103(c)(3)(ii)(B).
Given that actual emissions sampling is used under this option to determine
compliance with emission standards, those operating conditions that apply to other BIFs
after certification of compliance that are designed to control metals emissions are not
necessary. See §266.103(c)(l). The operating parameters that need not be limited at
certification of compliance under this method are:
• Maximum feed rate of each metal in total feedstreams, total hazardous waste
feedstreams, or pumpable hazardous waste feedstreams;
• Maximum feed rate of pumpable hazardous waste;
• Maximum feed rate of chlorine in total feedstreams;
• Maximum combustion chamber temperature and temperature at the inlet to the air
pollution control system (APCS); and
• Key parameters to ensure proper operation of the APCS.
This approach has one drawback — there is a time delay before a violation of the
emissions limits is determined given that it normally takes a week or more to obtain the
results of the stack sampling. To minimize the impact of this problem, the operator is
required to know the metals concentration and feed rate of hazardous waste at all times and
must determine if a change in metal feed rate from the hazardous waste is likely to result in
exceedance of a metal emission limit
c. Conditioning Prior to Compliance Testing. Under this approach (see
§266.103(c)(3)(ii)(C)), the operator must condition the furnace to ensure that metals
emissions are in equilibrium with metals fed into the system from all feedstreams. The
owner or operator must determine using engineering judgment when the system has
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reached equilibrium (Le., how long the system must be conditioned). During conditioning,
hazardous waste and raw materials having the same metals content as will be fed during the
compliance test must be fed at feed rates that will be fed during the compliance test
Under this method, limits for all operating parameters under §266.103(c)(l) must
be established during the compliance test
5. Trial Burns. A trial burn, or data in lieu of the trial bum (e.g., emissions data
from interim status compliance testing) is required to demonstrate the performance
capabilities of a system and to establish the operating limits of a facility for the duration of
the operating permit. Compliance limits will be based on the operating conditions and
emission rates observed during the trial burn. Therefore, to obtain the most flexible
compliance limits, an owner/operator should conduct test burns and the trial burn under
worst-case conditions (those that maximize emissions without exceeding the established
limits). These conditions include feeding the waste used in the trial bum at a feed rate and
metals concentration that reflect the highest levels expected in present or future operations.
Spiking with Metals. To achieve the maximum allowable concentrations of metals,
the owner/operator may wish to spike the waste to artificially high concentrations of the
metals during the pre-trial burn period and during the trial burn. However, the
owner/operator may not feed metals at levels higher than those documented in the Part B
permit application as those not likely to result in emissions exceeding allowable levels.
Permit officials will consider this documentation in establishing pre-trial bum permit
conditions for new permits.
6. Monitoring and Analysis Requirements.
a. Emissions Testing. Emissions testing and analysis for metals must be
conducted using "Methodology for the Determination of Metal Emissions in Exhaust Gases
from Hazardous Waste Incineration and Similar Combustion Processes" provided in
Mfflhods Msnu3! fa*" Compliance with the BIF Regulations^, incorporated by reference in
§260.11. The methodology describes the use of a multiple metals sampling train. The
methodology also describes and provides references to the appropriate analytical techniques
in Test Methods for Evaluation Solid Wastes (SW-8461. incorporated by reference in
§260.11, that must be used to analyze samples.
"° U.S. EPA, Methods Manual for Compliance with the BIF Regulations. December
1990, EPA/530-SW-91-010. NTIS publication number PB91-120-006.
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b. Analysis of Feedstreams. Feedstreams must be analyzed for each of the 10
regulated metals that could reasonably be expected to be in the hazardous waste. If a
particular metal is excluded from the analysis, the basis for exclusion must be documented
and included in the operating record. Methods for sampling and analysis of feedstreams
for metals are prescribed in SW-846.
D. Interim Status Compliance Requirements
As prescribed in §266.103, and discussed in section VII of Pan Three of this
preamble, boilers and industrial furnaces operating under interim status must comply with
the metals emissions standards during interim status.
V. Controls for Emissions of Hydrogen Chloride and Chlorine Gas
Today's final rule uses a three-tiered regulatory approach to limit HC1 and C\2
emissions (see §266.107), an approach identical to that used to control noncarcinogenic
toxic metals emissions.
A. Background Information
In the 1987 proposed rule, EPA stated its intention to develop risk-based HC1
emission standards in the same format and for the same reasons as the proposed metals
emission limits. The HC1 emission limits for a particular device would have been based on
the device type and capacity, and on the type of surrounding terrain. In the 1989
supplemental notice, EPA discussed an alternative approach to make the standards a
function of stack height, terrain, and land use rather than a function of device type and
capacity. The reasons for the change were the same as those described above in the
discussion of the metals standards.
Controls on Cl2 were proposed on April 27,1990 (55 FR 17866) because Cl2 can
be emitted from devices burning chlorinated wastes if insufficient hydrogen is available
(i.e., from other hydrocarbon compounds or water vapor) to react with all of the chlorine
present in the waste. In recent tests67 of a cement kiln, EPA found that approximately
50% of gaseous chlorine emissions were in the form of Cl2 (and me omer 50% was in the
form of HC1). In the April 1990 proposal, the Agency proposed a C\2 RAC of 0.4 ug/m3.
67 U.S. EPA, Emission Testing of a Precalciner Ccmpnf Kilp qt ^yi^yijle. Nebraska,
November 1990. Document No. EPA/530-SW-91-016.
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In the 1989 supplemental notice, EPA also discussed the possibility of using
continuous HCI monitors in lieu of the waste feed analysis approach for monitoring HCI
emissions when emissions are likely to be close to allowable emissions. The Agency
continues to believe that this is a reasonable approach and believes that it can be effectively
implemented during the permit process as necessary using the omnibus authority.68
B. Response to Comments
The Agency received a number of comments on the proposed HCI and Cl2 controls
as discussed below.
1. Short-Term HCI RAC. A number of commenters stated that the Agency's
support for the proposed 3-minute RAC for HCI was inadequate. The Agency is currently
developing a new methodology for evaluating health effects data to develop a no-adverse-
effect short-term exposure level.69 Given that the new methodology has not been
approved by the Agency, today's final rule does not establish a short-term RAC for HCI.
We note that the Tier I chlorine feed rate limits proposed in the 1989 supplemental
notice were based on the short-term HCI RAC because the short-term exposure RAC
provided more restrictive feed rate limits than the long-term RAC. Consequently, the 1989
proposed chlorine feed rate limits are not included in today's final rule. In establishing the
Tier I feed rate limits for chlorine in today's final rule, the Agency considered both the
long-term HCI RAC (i.e., 7 ug/m3) and the Cl2 RAC (i.e., 0.4 ug/m3), and the
partitioning between the two pollutants in stack gases. Given that the Agency has tested for
Cl2 emissions at only two facilities, and at one of the facilities more than 50% of the
chlorine partitioned to Cl2, the Agency conservatively assumed in calculating feed rate
limits that 100% of the chlorine would be partitioned to &2- Because the Cl2 RAC is more
than an order of magnitude lower than the HCI RAC, the Tier I chlorine limits were based
on 100% conversion of chlorine to Cl2- If applicants believe that this assumption is too
conservative, they may conduct emissions testing to document Cl2 and HCI emission rates.
68 EPA notes that permit writers choosing to invoke the omnibus permit authority of
§270.32(b)(2) to add conditions to a RCRA permit must show that such conditions are
necessary to ensure protection of human health and the environment and must provide
support for the conditions to interested parties and accept and respond to comment In
addition, permit writers must justify in the administrative record supporting the permit any
decisions based on omnibus authority.
69 Memorandum dated September 18 from Susan Griffin, EPA, to Bob Holloway,
EPA, entitled "Derivation of Short-Term RAC for HCI".
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2. Need for C/2 Controls. Many commenters stated that Cl2 controls are
unnecessary. One commenter believed that very little hydrogen is needed to react with Cl2
to form HQ. Another commenter believed that operating conditions for boilers and
industrial furnaces are not conducive to the formation of C\2- Another commenter stated
that the proposed limits to control HC1 emissions will provide adequate control of C\2
emissions as well.
The Agency does not agree with these commenters. As discussed above, emissions
testing indicates that a substantial fraction of gaseous chlorine can be emitted in the form of
C\2. In addition, the HC1 controls may not be adequate to control Cl2 emissions. Because
C\2 has a much lower solubility in water than does HC1, the use of wet scrubbers as the
principle emissions control device for HC1 is not likely to significantly reduce emissions of
C\2- C\2 emissions can be controlled, however, by increasing the hydrogen content of
feed streams (e.g., by adding steam) or by decreasing the feed rate of chlorine. Moreover,
EPA does not believe that high C\2 emissions relative to HQ emissions is a widespread
occurrence.
3. HCl Emission Test Procedures. A number of commenters who own or operate
cement kilns expressed concern that EPA's HQ stack sampling and analysis procedure (see
section 3.3 in Methods Manual for Compliance with the BIF Regulations') was
inappropriate because it counted as HQ chlorine in inorganic chloride salts and chloride
ions that are emitted as ammonium chloride. The Agency has determined70 that the filter in
the sample probe, in fact, effectively removes fine particulate chloride salts so that they do
not interfere with the HQ determination. The Agency agrees, however, with commenters
that the procedure may consider as HQ chloride ions that are emitted as ammonium
chloride.71 Although the Agency has not developed a sampling and analysis procedure
that would correct this problem, we do not believe that any such over-reporting of HQ will
cause a cement kiln to exceed the HQ standard. This is because the highly alkaline
particulate matter resulting from the limestone raw materials effectively neutralizes much of
the chlorine generated from hazardous waste fed into the kiln.
70 U.S. EPA, Emission Testing of a Precalciner Cement Kiln at Louisville. Nebraska.
November 1990. Document No. EPA/530-SW-91-016.
71 U.S. EPA, Emissions Testing of a Wet Cement Kiln at Hannibal. MQ. December
1990. Document No. EPA/530-SW-91-017.
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4. Technology-Based HCl Controls. Several commenters stated that technology-
based HC1 emission controls applicable to hazardous waste incinerators (i.e., 99%
reduction of emissions in the stack gas) should also apply to BIFs. As discussed in the
proposed rule, the Agency continues to believe that a 99% reduction standard for BIFs to
control HCl emissions may be neither technically feasible nor necessary to protect human
health and the environment The Agency believes that the process chemistry of some
industrial furnaces (e.g., cement kilns) generally results in low HCl emissions and
concerns about tube corrosion generally limit HCl concentrations in boiler emissions.
Given the low uncontrolled HCl concentrations in many BIFs, a 99% reduction standard in
addition to the health-based standard required by today's final rule, may not be cost-
effective. Commenters did not provide data or information that would support the need
for, and the cost-effectiveness of a technology-based standard in addition to the health-
based standard provided by the final rule.
We note that the Agency is currently developing health effects data for two other
acid gases: hydrogen fluoride and hydrogen bromide.
C. Implementation
Procedures for implementing the HCl and Cl2 controls are virtually identical to
those for the metals controls discussed above.
1. Emissions Testing, Collection and analysis of HCl and Cl2 in stack gas
emission samples must be conducted according to the procedures prescribed in section 3.3
of the Methods Manual for Compliance with foe BIF Regulations. (Methods Manual)
incorporated by reference in §260.11. The Methods Manual describes two procedures for
sampling emissions for HCl and Cl2: Methods 0050 and 0051. Method 0050 collects a
sample isokinetically and is, therefore, particularly suited for sampling at sources emitting
acid paniculate matter (e.g., HCl dissolved in water droplets), such as those controlled by
wet scrubbers. Method 0051 uses a midget impinger train sampling method designed for
sampling sources of HCl and Cl2 emissions not in paniculate form. Samples collected
using either method must be analyzed using Method 9057 which is also described in the
Methods Manual
2. Wastes Analysis* Methods for sampling and analysis of feedstreams for total
chlorine and chloride are described in detail in SW-846.
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3. Interim Status Compliance Requirements. As discussed in section VII of Part
Three of this preamble, boilers and industrial furnaces operating under interim status must
comply with the HC1 and Cl2 emissions standards during interim status.
VI. Nontechnical Requirements
As proposed, the final rule requires BIFs to comply with the nontechnical standards
applicable to other hazardous waste treatment, storage, and disposal facilities. These
nontechnical standards address the potential hazards from spills, fires, explosions, and
unintended egress; require compliance with the manifest system to complete the cradle to
grave tracking system; ensure that hazardous wastes (and hazardous residues) are removed
from the site upon closure; and ensure that the owners and operators are financially capable
of complying with the standards. BIFs burning hazardous waste fuels that operate storage
facilities must already comply with these standards under existing §266.35(c).
We also note, in particular, that owners and operators of BIFs are subject to the
waste analysis requirements of §§264.13 and 265.13 by reference. See
§§266.102(a)(2)(ii) for permitted facilities, and 266.103(a)(4)(ii) for interim status
facilities. Before a waste is stored or burned, the owner or operator must obtain a detailed
chemical and physical analysis of a representative sample of the waste sufficient to enable
the owner or operator to comply with today's rule.
The nontechnical standards provided in today's rule are identical to those that
currently apply to hazardous waste incinerators. In today's rule, §266.102(a)(2) applies
these standards to permitted BIFs and §266.103(a)(4) applies these standards to BIFs
operating in interim status.
Finally, we note that, as proposed, today's rule applies the same controls on
fugitive emissions that currently apply to hazardous waste incinerators. The controls apply
to facilities operating under a permit (see §266.102(7)(i)) and, on the effective date of the
rule, to facilities operating under interim status (see §266.103(h)). The controls provide
for alternative control strategies including: (1) keeping the combustion zone where
hazardous waste is burned (or where emissions from such burning may migrate) totally
sealed; and (2) maintaining the combustion zone pressure lower than atmospheric pressure.
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Vn. Interim Status Standards
In addition to the nontechnical standards discussed above, today's final rule
requires facilities with interim status to comply with substantive emissions controls for
metals, HC1, Cl2, particulates, and CO (and, where applicable, HC and dioxins and
furans). Owners and operators must certify compliance with the emissions controls under
a prescribed schedule, establish limits on prescribed operating parameters, and operate
within those limits throughout interim status.
Given that interim status requirements are self-implementing, the Agency has
developed comprehensive interim status requirements to ensure that the standards are
implemented effectively. To assist the regulated community in complying with the
requirements, EPA is developing a guidance document entitled Interim Status Guidance
Document for JSjFs (ISGD). The guidance document will be available shortly after
publication of the final rule in the Fsdejaj Register. The ISGD will summarize the
provisions of the rule, provide example forms that may be used to submit data and
information required by the certifications of precompliance and compliance (see discussions
below), and provide guidance on developing a compliance test protocol. To provide
further assistance to the regulated community, EPA plans to conduct a series of workshops
open to the public to explain how the interim status standards work. The workshops are
scheduled to begin shortly after publication of the final rule in the Federal Register. To
obtain a copy of the ISGD or information on the dates and locations of the workshop,
contact the sources identified at the beginning of this preamble under "FOR FURTHER
INFORMATION CONTACT'.
The following sections summarize how the interim status standards work.
A. Certification Schedule.
1. Certification of Precompliance. The BEF rule is effective 6 months after the date
of promulgation. By the effective date, an owner/operator must submit a certification of
precompliance providing prescribed information supporting a determination that emissions
of individual metals, HC1, Q2, and particulates are not likely to exceed allowable levels.
See §266.103(b)(2). For certification of precompliance, the owner/operator must use
engineering judgment to evaluate available information and data (or must use EPA-
prescribed default data provided in sections 8.0 and 9.0 of Methods Manual for
Compliance with the BIF Regulations, incorporated by reference in §266.11) to determine
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that, under the operating limits (for EPA-prcscribed parameters) that the owner/operator
establishes, emissions are not likely to exceed the allowable emissions provided by
§§266.105,266.106, and 266.107. The owner and operator must then comply with these
operating conditions (see discussion in section VII.B below) submitted in the
precompliance certification during the interim status period of operation until a revised
precompliance certification is submitted or until a certification of compliance is submitted as
discussed below.
In addition, by the effective date of the rule, the owner or operator must submit a
notice for publication in a major local newspaper of general circulation providing the
general facility information prescribed by §266.103(b)(5). The information that must be
provided in the notice includes: the name and address of the owner and operator of the
facility, the type of facility, the type and quantity of hazardous waste burned; the location
where the operating record of the facility can be viewed; a notification that a facility mailing
list is being established so that interested parties may notify the Agency that they wish to be
placed on the mailing list to receive future information and notices about the facility, a brief
summary of the RCRA regulatory system for BIFs; and the address of the EPA Regional
Office where additional information on the RCRA regulatory system may be obtained.
EPA is requiring this public notice to ensure that the local citizenry is aware that the BIF is
burning hazardous waste and that, to the extent desired, the local citizenry may become
better informed about the facility operations through site inspections and review of data in
the operating record. In turn, this opportunity for local involvement in facility operations
should provide an added incentive for the owner and operator to comply with the spirit and
letter of the interim status standards.
EPA notes that facilities that meet the definition of "in existence" of
§266.103(a)(l)(ii) but that are not burning hazardous waste on the effective date of the rule
must nonetheless submit a certification of precompliance based on planned operations. The
certification may be revised at any time in the future if necessary. See §266.103(b)(8).
2. Certification of Compliance. Within 18 months of promulgation, the
owner/operator must conduct compliance testing72 and submit a certification of compliance
H We note that compliance testing may be conducted only under operating conditions
for which the facility has submitted a certification of precompliance. This is because the
facility may only operate after the effective date of die rule and prior to submittal of a
certification of compliance under conditions for which it has certified precompliance. If
any applicable emission standard is exceeded during the compliance test (or during
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with the standards for individual metals (§266.106), HC1 and Cl2 (§266.107), particulates
(§266.105), and CO, and, where applicable, HC and dioxins/furans (§266.104(b) through
e)). The certification of compliance is based on emissions testing and establishes operating
limits for EPA-prescribed parameters based on the compliance test. See §266.103(c)(l).
If the owner/operator cannot submit the certification of compliance within 18
months of promulgation, however, he must either (1) notify the Director that he is taking
an automatic 12-month extension under which hazardous waste burning is limited to a total
of 720 hours; (2) obtain a case-by-case extension of time for reasons beyond his control; or
(3) stop burning hazardous waste and begin closure of the hazardous waste portion of the
facility. See §266.103(c)(6).
The case-by-case time extension will be provided by the Director if he determines
that the owner or operator has made a good faith effort to comply with the requirements in a
timely manner but, for reasons beyond his/her control, are not able to meet the certification
of compliance deadline. Reasons could include inability to complete modifications to an air
pollution control system in time to conduct the compliance test to support the certification,
or a major, unplanned outage of the facility (e.g., need to replace refractory in a kiln) just
prior to scheduled compliance testing, or as discussed earlier, HC levels attributable to
organics in raw materials. The Director may use his discretion to determine the length of
the extension.73 The Director also may impose conditions that ensure that the boiler or
industrial furnace will be operated in a manner that protects human health and the
environment, provided that the Director documents the basis for adding such a condition
and provides the applicant opportunity to comment on it
In addition, we note that a case-by-case extension may be requested and granted for
any interim status certification deadline. A case-by-case extension may be granted after an
owner/operator has elected to take the 12-month automatic extension, an extension may be
granted if the owner/operator cannot comply with the recertiflcation schedule (see
discussion below), and an existing extension may be extended
pretesting), the facility must immediately submit a revised certification of precotnpliance
establishing revised (i.e., more stringent) operating limits.
73 We would not expect for the Director normally to limit the hours that hazardous
waste may be burned under a case-by-case extension given that the owner/operator must
support the need for the extension and, if granted, the extension must be for a legitimate
need In contrast, the hours of burning are limited for the automatic 12-month extension
because there is no judgement by the Director that, in fact, the extension is warranted
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3. Recertification. Owners and operators must periodically conduct compliance
testing and recertify compliance with the standards for individual metals, HC1 and Cl2,
particulates, and CO, and, where applicable, HC and dioxins/furans within three years of
the previous certification while they remain in interim status (i.e., until an operating permit
is issued under §270.66). See §266.103(d). EPA is requiring recertifications primarily to
ensure that air pollution control systems do not deteriorate over time.
4. Failure to Comply with the Certification Schedule. If the owner or operator
does not comply withe the certification schedule, all hazardous waste burning must cease as
of the date of the missed deadline, and closure must commence. See §266.103(e). Any
burning of hazardous waste by such a device after failure to comply with the certification
schedule must be under a RCRA operating permit. See §270.66.
To comply with the certification schedule, complete and accurate certifications of
precompliance and compliance must be submitted by the applicable deadlines. (Although
the deadline for certification of compliance may be extended (see §266.103(c)(7)), the
deadline for certification of precompliance may not be extended.) In addition to terminating
interim status if the owner and operator do not comply with the certification schedule, EPA
will also take appropriate enforcement action.
When closing a BIF, all hazardous waste and hazardous waste residues, including,
but not limited to, ash, scrubber water, and scrubber sludges, must be removed from the
affected BIF. In addition, the owner/operator must comply with the general interim status
closure requirements of §§265.111-265.115, as amended. These requirements, which are
incorporated by reference into today's rule, specify closure performance standards;
submission of and compliance with a written closure plan; disposal or decontamination of
equipment, structures, and soils; and certification procedures for closure.
We note that under amended §265.112(d)(2), for an owner or operator who fails to
submit a complete certification of compliance by the applicable compliance deadline
(including the automatic 12-month extension or the case-by-case extension under
§266.103(c)(6)(i)(B)), the date that he "expects to begin closure" is within 30 days after the
applicable deadline. Therefore, for example, for an owner who takes the automatic 12-
month extension, the closure notification requirements of §265.112(d)(l) or the closure
activity requirements of §265.113 would not be triggered unless and until the owner fails to
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submit a complete certification of compliance by the 12-month extended deadline and a
case-by-case extension beyond the 12-month extension was not obtained.
For any other BIF owner or operator closing during interim status operation (i.e.,
one who closes between the effective date of the rule but before the interim status
compliance deadline of 18 months after promulgation of the rule, or one who submits a
complete certification of compliance by the applicable 18-month compliance deadline, the
12-month automatic extension, or case-by-case extension, and closes during interim
status), the date when he "expects to begin closure" under 265.112(d)(2) will remain either
within 30 days after the date on which any hazardous waste management unit receives the
known final volume of hazardous waste, or if there is a reasonable possibility that the unit
will receive additional hazardous waste, no later than one year after the date on which the
unit received the most recent volume of hazardous waste.
5. Development of the Certification Schedule. In the 1989 supplemental notice, the
Agency requested comment on alternative schedules for requiring compliance with the
emissions standards during interim status. The Agency selected a certification deadline of
18 months (with provision for extensions) because we believe that most facilities will be
able to install the necessary monitoring equipment, conduct any precompliance testing that
may be necessary, and conduct compliance testing within that time period. Although 18
months from the date of promulgation is a fairly short period of time, we note that Agency
staff have made numerous public presentations and have had numerous discussions74 with
the regulated community, including, in particular, the development of interim status
compliance procedures. Thus, facility owners/operators have had some advance indication
of the general regulatory approach taken in the final rule.
The Agency received a comment that the air emission standards for cement kilns
should be instituted more quickly than the schedule proposed. The commenter believed
that accelerating the schedule will not place an excessive burden on these facilities because
the regulations were proposed far enough in advance for cement kilns to come into
compliance. The Agency has considered this comment and: (1) sees no compelling reason
to single out cement kilns from other BIFs for an accelerated schedule; and (2) continues to
believe that an 18-month compliance period is representative of the time required to
74 See the public docket for this rulemaking for summaries of meetings held with
groups including: Cement Kiln Recycling Coalition, Chemical Manufacturers Association,
National Solid Waste Management Association, Council of Industrial Boiler Operators, and
Hazardous Waste Treatment Council
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implement necessary plant design or process modifications, install monitoring and
compliance equipment, conduct facility compliance testing, and submit a certification of
compliance testing that documents key operating limits during the remainder of the interim
status period. In fact, the Agency is concerned that in some situations, where, for
example, the air pollution control system may need to be modified, an 18-month deadline
may not provide enough time to complete modifications, "shake-down" the system,
conduct pre-testing75, conduct compliance testing, and analyze test data and submit a
certification of compliance. Thus, the final rule includes provisions for time extensions to
all certification deadlines.
B. Limits on Operating Parameters
Limits on operating parameters during interim status are established at certification
of precompliance and at certification of compliance following emissions testing 18 months
(unless extended) after promulgation of the rule. The operating conditions can be revised
prior to certification of compliance by submitting a revised certification of precompliance.
The operating conditions can be revised after certification of compliance by conducting
emissions testing and submitting a revised certification of compliance.
After the effective date of the rule and prior to certification of compliance with the
emissions standards based on emissions testing, a facility may operate only under those
conditions for which the facility has submitted a "precompliance" certification
demonstrating that emissions of individual metals, HC1, Cl2, and participates are not likely
to exceed allowable levels. The operating conditions for which limits are established by
precompliance are (see §266.103(b)(3»:
• Feed rate of each of the 10 metals in:
- Total feed streams, except for furnaces that recycle collected paniculate matter (see
discussion in section VII.I below)
- Total hazardous waste feed streams
- Total pumpable hazardous waste feed streams;
• Total feed rate of chlorine in all feed streams;
• Total feed rate of ash in all feed streams, except for cement and light-weight aggregate
facilities for which ash content of feed streams is not an operating parameter,
75 Although pretesting is not required, EPA believes that most facilities will conduct
pretesting before conducting the formal compliance testing with all its attendant QA/QC
requirements.
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• Total feed rate of hazardous waste and feed rate of pumpable hazardous waste; and
• Maximum capacity in appropriate units such as heat input, steam production, or raw
material feed rate.
In addition, the following parameters must be considered in demonstrating
precompliance and must be continuously monitored (and records maintained in the
operating log) when monitoring systems are installed (see §266.103(b)(6)):
• Maximum combustion zone temperature;
• Maximum flue gas temperature entering the PM APCS; and
* Limits for APCS-specific operating parameters.
Once a facility has conducted compliance testing and certified compliance with the
emissions standards, limits for all of the above parameters, as well as for CO (and, where
applicable, HC) are established based on the compliance test and remain in force until
recertification under new conditions. See §266.103(c)(l).
C. Automatic Waste Feed Cutoff
Upon certification of compliance, an automatic hazardous waste feed cutoff system
must engage when the limits (established in the certification) for the following operating
parameters are exceeded (see §266.103(h)):
• Total feed rate of hazardous waste and feed rate of pumpable hazardous waste;
• Limits on CO and, where applicable, HC;
• Maximum capacity in appropriate units such as heat input, steam production, or raw
material feed rate;
• Maximum combustion zone temperature;
• Maximum flue gas temperature entering the PM APCS; and
• Limits for APCS-specific operating parameters.
Facilities operating during interim status after certification of compliance must test
the automatic waste feed shutoff system once every 7 days to ensure that it is operating
properly, unless an owner/operator can document that weekly testing will result in unsafe
conditions. See §266.103(k)(iii). In all cases, testing at least every 30 days is required.
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Owners/operators are required to document the results of these tests and all automatic waste
feed shutoff s that occur during normal operations.
D. Sham Recycling Policy
The BIF rules supersede the Agency's sham recycling policy (see 48 FR 11157
(March 16, 1983)) after the owner or operator certifies during interim status compliance
with the emissions standards for metals, HCI, Cl2, particulates, and CO (and, where
applicable, HC and dioxins and furans). Thus, after certification of compliance, a BIF may
burn hazardous waste (other than waste fed solely as an ingredient or solely for material
recovery) with a heating value lower than the 5,000 Btu/lb limit generally considered
heretofore to be the minimum for a legitimate hazardous waste fuel. Although the Agency
considers such burning to be treatment, we believe that conformance with the emissions
standards upon certification of compliance under §266.103(c) will ensure protection of
human health and the environment (Prior to today's rule, BIFs burning a hazardous waste
that was not considered to be a legitimate fuel were subject to the Subpart O incinerator
standards of Parts 264 and 265, assuming burning was not for some other legitimate
recycling purpose, such as material recovery.)
Although we indicated above that a BIF may burn hazardous waste for the purpose
of treatment upon certification of compliance, today's rule allows BIFs to burn such
hazardous waste for a total period of time not to exceed 720 hours prior to certification of
compliance. See §266.103(a)(6). The rule allows such burning only for purposes of
compliance testing (and pretesting to prepare for compliance testing) to determine that the
device can comply with the emissions standards while burning waste for treatment The
rule limits such burning to a total of 720 hours because we believe that period of time is
adequate to complete any pretesting and compliance testing, and it is the same period of
time that new BIFs may burn hazardous waste during the pretrial burn period under
§270.66(b)(l).
The Agency discussed three options in the 1989 supplemental notice for
superseding the sham recycling policy: rescinding the sham recycling policy on the
effective date of the final rule; rescinding the sham recycling policy when a facility comes
into compliance with the interim status emission standards; or leaving the sham recycling
policy in effect until a RCRA operating permit is issued
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The Agency received comments supporting all three of the options. Eight
commenters supported the first option, rescinding the sham recycling policy on the
effective date of the final rule, because the policy is considered guidance. Eight
commenters supported the second option, rescinding the sham recycling policy when
facilities come into compliance with the interim status emission standards, because the
standards are protective of human health and the environment Five commenters supported
the third option, leaving the sham recycling policy in effect until a facility is issued a RCRA
operating permit, because the permit writer oversight during the permit process is necessary
to ensure that a facility complies with the appropriate regulations.
The Agency believes that the procedures required for certification of the interim
status emissions standards are adequate to ensure effective implementation and enforcement
of the standards. The only emissions standard applicable to permitted facilities that is not
required during interim status is the destruction and removal efficiency (DRE) standard
requiring a trial burn to demonstrate 99.99% DRE. The Agency does not believe that this
is necessary because emissions testing of boilers and industrial furnaces indicates that
facilities with CO and HC levels within the limits established by today's rule also are likely
to achieve 99.99% DRE.
It should be noted that in rescinding the sham recycling policy for these types of
regulated boilers and industrial furnaces, the Agency is not altering in any way what
secondary materials are defined as solid and hazardous wastes when burned for legitimate
energy recovery. Thus, all spent materials, sludges, and by-products are solid wastes
when burned for recovery, as are off-specification commercial chemical products which are
burned as fuels (or used as a component of fuels) in lieu of their original intended use. See
§§261.2(c)(2) and 261.33. (Non-listed hazardous commercial chemical products (i.e.,
those that exhibit a characteristic but are not listed in §261.33) are likewise solid wastes
when they are recycled in ways that differ from their normal use. 50 FR at 14219 (April
11,1985).) With respect to the issue of what constitutes a normal manner of use for an
off-specification commercial chemical product that has some Btu value, or the issue of
when such a material is used "in lieu of [its] original intended use" (§261.33) and so is a
solid and hazardous waste, the Agency notes that not every type of burning ostensibly for
energy recovery is considered to qualify. Inappropriate modes of burning thus do not
render such materials non-wastes. For example, if ignitable off-specification natural gas
condensate is burned as a motor fuel, or reactive jet fuel (U 133, hydrazine) is burned as
conventional fuel oil, such materials are solid and hazardous wastes and subject to subtitle
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C controls. This is because the mode of burning is not at all like these materials' original
intended use.
E. Submitted of Pan B Applications
Permit writers will require owners and operators to submit Part B applications for
operating permits on a schedule considering the relative hazard to human health and
environment the facility poses compared to other storage, treatment, and disposal facilities
within the Director's purview.
F. ORE Testing
As proposed, testing to demonstrate 99.99% destruction and removal efficiency
(DRE) of organic compounds in the waste is not required under interim status. The
complexity and costs of DRE testing, as well as the substantial interaction needed between
owners/operators and regulatory officials, make such testing impracticable during interim
status. EPA expects that the control requirements for CO and HC will result in low levels
of emissions of organic compounds.
G. Chlorinated Dioxins and Furans
As proposed, hazardous waste containing or derived from any of the following
dioxin-listed wastes cannot be burned in a boiler or industrial furnace operating under
interim status: EPA Hazardous Waste Nos. F020, F021, F022, F023, F026, and F027.
Burning these dioxin-containing wastes during interim status is prohibited because boilers
and industrial furnaces cannot be assumed to achieve the 99.9999 percent DRE required for
these wastes.
Even though these wastes may not be burned during interim status, chlorinated
dioxins and furans may be emitted as PICs under certain conditions (i.e., when the PM
control device is operated within the temperature range of 450-750°F, or when HC
concentrations exceed 20 ppmv) as discussed in section H.E of Part Three of the preamble.
EPA believes that the emissions testing and risk assessment requirements of §266.104(e)
can be effectively implemented during interim status without significant EPA interaction.
Thus, the rule requires the owner or operator to certify compliance with those
requirements, as applicable.
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H. Special Requirements for Furnaces
Today's rule provides special interim status requirements industrial furnaces that
feed hazardous waste, except hazardous waste fed solely as an ingredient76, at locations
other than the "hot" end where the product is discharged and fuels are normally fired to
ensure adequate combustion of hazardous waste prior to conducting a trial burn during the
Part B permit process (see §266.103(a)(5)) as follows: (1) the combustion gases must
have a minimum temperature of 1800°F at the point where the waste is introduced77; (2)
the owner or operator must determine (and include such determination in the operating
record) that there is sufficient oxygen present to combust the waste; (3) the continuous
hydrocarbon monitoring controls provided by §266.104(d) apply; and (4) for cement kilns,
hazardous waste must be fed into the kiln itself;
EPA established a minimum temperature of 1800°F for the location of hazardous
waste firing and is requiring that the owner/operator demonstrate that adequate oxygen is
present to sustain combustion given that it is generally accepted that organic compounds are
readily destroyed at temperatures above 1800°F in the presence of adequate oxygen. The
demonstration of adequate oxygen is particularly important for cement kilns because they
are operated close to stoichiometric oxygen levels (i.e., with little excess oxygen in the
kiln) to efficiently maintain the high temperatures necessary to calcine and sinter the raw
materials. Although higher excess oxygen levels would better ensure more complete
combustion of fuels, operating at higher oxygen levels is less thermally efficient and
reduces the kiln production capacity.
76 Hazardous waste is burned solely as an ingredient if it is burned for neither energy
recovery (i.e., it has a heating value less man 5,000 Btu/lb) nor treatment or destruction
(i.e., it contains a total of less than 500 ppm toxic organic constituents listed in Appendix
Vffl, Part 261).
77 EPA is aware that cement companies have experimented with feeding containerized
waste into the upper, raw material feed end of the kiln using feed chutes that propel the
containers down into the kiln before they rupture and expose the waste to the combustion
gas (and begin to release hydrocarbons). In such a situation, the temperature limit applies
at the point that the waste may begin to release hydrocarbons - the point where the
container impacts the charge bed The temperature limit does not apply to the point where
the container is actually charged into the kUn. (If, however, a noncontainerized waste is
fired into the kiln at the upper end, the 1800°F temperature limit applies at the location
where the waste exits die firing system.) Although this discussion pertains to cement kilns,
EPA notes mat the subject requirements apply to any industrial furnace that feeds hazardous
waste at a location other than the "hot" end as described in the text
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In addition, continuous hydrocarbon (HC) monitoring is required to demonstrate
that HC levels do not exceed the regulatory limit of 20 ppmv on a hourly rolling average
basis (or alternative level established under §266.104(f)) irrespective of whether the CO
level is less than 100 ppmv where HC monitoring is not normally required. See
§266.103(a)(6). EPA is requiring HC monitoring because of the concern that CO
monitoring alone may not be an adequate indicator of good combustion conditions when
hazardous waste is fed at locations other than where (nonhazardous) fuels are normally
fired. See discussion in Part Two, section II.A.4.a of this preamble. Continuous
monitoring of HC and compliance with the applicable operating limit is required upon
certification of compliance (or, for furnaces that feed raw materials containing organic
matter and that receive a time extension to certify compliance, upon receipt of the time
extension78).
The Agency considered whether the hydrocarbon controls were redundant to the
operating requirements specified above and concluded that HC monitoring is needed to
effectively implement and enforce the controls on organic emissions. Although the
operating requirements alone should be adequate to limit organic emissions, absent HC
monitoring there would be no continuous verification that the operating requirements were,
in fact, adequate and that the owner/operator maintained compliance with the operating
requirements.
Finally, the rule requires that hazardous waste be fired into a cement kiln itself to
ensure that the waste is not introduced at a location that may not be conducive to complete
combustion of the waste. For example, cement companies have considered burning
hazardous waste in the precalciner of a cement kiln. Although such practices may prove
during the permit process to be acceptable, EPA has not tested emissions from a kiln
burning waste at locations other than in the kiln itself, and is concerned that complete
combustion of organic constituents may not be ensured. Thus, burning hazardous waste in
a cement kilns precalciner is not allowed during interim status. (This restriction is limited
to cement kilns because this is the only type of kiln of which the Agency is aware where
hazardous waste may be fired at a location that is clearly not designed for optimum
combustion conditions. A cement kiln precalciner is designed primarily to achieve
calcining of raw materials and may not provide adequate combustion of hazardous waste.)
78 We note, as discussed elsewhere in the text, the time extension will be conditional
on, among other things, HC (and CO) levels not exceeding an interim limit established in
the extension.
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The special requirements do not apply to hazardous waste that is burned
(processed) solely as an ingredient79 because such waste does not contain significant levels
of hazardous nonmetal constituents (i.e., compounds listed in Appendix VJH, Part 261)
and, thus, nonmetal emissions will not pose significant risk to human health and the
environment (Metal emissions will be adequately controlled by today's rule irrespective if
where the waste is fed into the system because metals are controlled by a PM control
device.) Thus, emissions of nonmetal compounds are not of concern when a waste is
burned (processed) solely as an ingredient EPA considers a waste to be burned solely as
an ingredient in a kiln if if is not burned partially as a fuel or for conventional treatment
(i.e., destruction). The Agency considers a waste that is fed to boilers and industrial
furnaces to be burned at least partially for energy recovery and not as an ingredient if it has
a heating value of 5,000 Btu/lb or greater, as-generated, and at least partially for treatment
(i.e., destruction) if it contains more than a total of 500 ppm (by weight) of Appendix Vm,
Part 261, nonmetal hazardous constituents. See 54 FR at 43731-32 where EPA discussed
use of a 500 ppm standard for distinguishing between recycling activities tantamount to
production and those constituting conventional treatment
The Agency notes in addition that it ordinarily does not consider metal-bearing
wastes hazardous wastes to be used as ingredients when they are placed in industrial
furnaces purportedly to contribute to producing a product. (The use of metal-bearing
wastes for material recovery is discussed earlier in the preamble, and this discussion does
not deal with the issue of when such wastes are burned for legitimate material recovery in
industrial furnaces.) To be considered legitimate use as an ingredient, it would normally
need to be demonstrated to EPA (or an authorized State) pursuant to §261.2(f) that the
hazardous metal constituents in the waste are necessary for the product (i.e., are
contributing to product quality) and are not present in amounts in excess of those necessary
to contribute to product quality. See 50 FR at 638 (Jan. 4,1985). This would normally
require some demonstration that these hazardous metal constituents do not render the
product unsafe for its intended use. (The other sham recycling criteria discussed frequently
by EPA would also have to be satisfied. See, e.g., 53 FR at 522 (Jan. 8, 1988). The
79 Under the RCRA hazardous waste regulatory program, EPA considers a hazardous
waste to be burned or processed as an ingredient if it is used to produce a product EPA
considers a hazardous waste to be burned or processed for material recovery if one or more
constituents of the waste is recovered as a product Nonetheless, the criteria are the same
for determining when a waste is burned (or processed) as an ingredient or for materials
recovery versus when it is burned for the partial purpose of energy recovery or
conventional treatment
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types of uses of hazardous wastes in industrial furnaces to produce waste-derived products
of which the Agency is aware, such as using hazardous wastes to produce aggregate or
cement (the Agency is not actually aware of cement kilns using hazardous wastes
ostensibly as ingredients, although some facilities have contemplated engaging in the
practice) do not appear to satisfy these criteria. In addition, the Agency notes the
discussion earlier in this preamble (in the context of hazardous waste used as slurry water)
to the effect that the more common and less valuable the raw material the hazardous waste
is replacing, the more likely the activity is to be some form of surrogate treatment
/. Special Metals Consols for Furnaces that Recycle Collected Paniculate Matter
For reasons discussed in section V.B.4 of this preamble, the final rule requires
owners and operators of furnaces (e.g., cement kilns, light-weight aggregate kilns with dry
paniculate matter (PM) control systems) that recycle collected PM back into the furnace to
implement the metals emissions controls of §266.106(c) or (d) under one of the three
alternative methods. The discussion in section V.B.4 of the preamble summarizes
procedures for certification of compliance under the methods. For certification of
precompliance, the standard procedures will be used for both the "daily emissions testing"
option, and the "conditioning prior to compliance testing" option. Precompliance
procedures are different, however, for the "monitoring metals in collected PM" method, as
discussed below.
Under the "monitoring metals in collected PM" method, operating limits will be
established for the all of the parameters listed in section VILB. above except for the feed
rate limit on each metal in total feedstreams. In lieu of that parameter, the special
procedures limit the concentration of each metal in collected PM. See "Alternative
Methodology for Implementing Metals Controls " in Method Manual for Compliance with
the BIF Regulations (incorporated by reference in §266.11).
For certification of precompliance, the owner/operator must estimate the enrichment
factor for each metal using engineering judgment or EPA prescribed default values. EPA
default values are 100 for mercury and 10 for all other metals. The enrichment factors are
then used to calculate precompliance dust metal concentration limits using the allowable
emission rate for each metal and the applicable PM standard using the same procedures
applicable for certification of compliance. Daily (or weekly for noncritical metals) analysis
of dust samples is required. If more than 3 of the previous 60 samples fail, the
owner/operator must notify the Director. The owner/operator is then allowed to bum
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hazardous waste for up to 720 hours before a revised certification of precompliance must
be submitted that revises the estimated enrichment factors and establishes revised
precompliance dust metals concentration limits. The revised enrichment factors must be
based on testing or engineering judgment using data or information not considered in the
original estimate.
/. Recordkeeping
Over the period of interim status, facilities will be required to generate and maintain
data and records designed to demonstrate routine compliance with established limits on
operating parameters. These records must be sufficient to allow a RCRA inspector to
review and evaluate recent and past operation of the facility for compliance purposes.
Records must be maintained for a period of three years or until an operating permit is
issued under §270.66, whichever is later.
VIII. Implementation of Today's Rule
There are three types of treatment, storage, and disposal facilities (TSDFs) which
may be affected by today's rule: (1) facilities which are subject to RCRA permit
requirements for the first time as a result of today's rule; (2) facilities which are already
operating under interim status; and (3) facilities that have been issued a RCRA permit. The
following sections describe the compliance obligations for facilities that have units subject
to permitting due to today's rule.
A. Newfy Regulated Facilities
Prior to receiving a permit, newly regulated facilities (i.e., facilities which only
contain the types of units newly regulated by today's final rule) must qualify for interim
status by the effective date of the rule in order to continue managing hazardous wastes in
units newly regulated by today's rule To obtain interim status, the eligible facility must
meet three criteria: (1) on the date of promulgation of the BIF rule, the facility must be "in
existence" with respect to hazardous waste burning or processing activities; (2) within 90
days of the date of promulgation, the owner or operator must notify EPA or an authorized
State (if not previously required to do so) of the facility's hazardous waste burning or
processing activities; and (3) within 180 days of the date of promulgation, the owner or
operator must submit Part A of the permit application.
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1. Definition of "In Existence". To meet the definition of an existing facility, the
boiler or industrial furnace must either be in operation burning or processing hazardous
waste on or before the effective date of the rule, or construction of the facility (including the
hazardous waste burning or processing equipment) must have commenced on or before the
effective date of the rule. See §266.103(a)(l)(ii). A facility has commenced construction if
the owner or operator has obtained the Federal, State, and local approvals or permits
necessary to begin physical construction; and either
(a) A continuous on-site, physical construction program has begun; or
(b) The owner or operator has entered into contractural obligations - which cannot be
cancelled or modified without substantial loss ~ for physical construction of the
facility to be completed within a reasonable time. See §270.2.
2. Section 3010 Notification. BIF owners and operators burning hazardous waste
fuels have already been required to notify of their hazardous waste fuel activities under
existing §266.35 and need not renotify. (See section 3010(a) which allows EPA to waive
notification if the information is considered unnecessary.) Although today's rule requires
small quantity burners and owners and operators of smelting, melting, and refining
furnaces to notify, this notification is not a section 3010 notice and so is not a prerequisite
to obtaining interim status.
Facilities which have not submitted a section 3010 notification form to EPA must
do so by rinsert date 90 days after publication in the FEDERAL REGISTER!. This is done
by completing a section 3010 notification form and sending it to the appropriate EPA
Regional Office. (See EPA form 8700-12, dated 7/90. See 55 FR 31389, August 2,1990
for a copy of the form. Notification instructions are set forth in 45 FR 12746.)
3. Pan A Permit Application. Newly regulated facilities must also submit a Part A
permit application to the appropriate EPA Regional Office by rinsert date 6 months after
publication in the FFDF.R AT. REGISTER!, which is the effective date of today's rule. (See
270.70(a) and EPA Form 8700-23, dated 1/90.)
B. Interim Status Facilities
Interim status facilities that contain units newly regulated by today's rule must file
an amended Part A permit application under 40 CFR 270.10(g) if they are to continue
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managing hazardous waste in these newly regulated units. The facilities must file the
necessary amendments to EPA by finsert date 6 months after publication in the FEDERAT.
REGISTER!, the effective date of the rule, or they will have to cease management of
hazardous waste in these units. In authorized states, the facility should also send a copy of
the submission to the State program.
Today's rule amends §270.72 to allow interim status facilities to add newly
regulated units as a change in interim status without prior Agency approval. The current
procedures for the addition of new units in §270.72(a)(3) require Agency approval prior to
making the change. Section 270.72(a)(l) allows the addition of newly listed or identified
wastes, and any newly regulated units associated with them, to be added to the Part A
application without prior Agency approval. Today's addition of §270.72(a)(6) extends this
ability to any newly regulated unit Today's rule also eliminates the reconstruction limit for
the addition of newly regulated types of units. (As noted earlier, the Agency proposed this
specific change for boilers and industrial furnaces, but realized in the course of
implementing the proposal that the problem was more endemic and called for a general
solution.) This provision is located in §270.72(b)(7).
In order to add a unit as a change in interim status under the new §270.72(a)(6), the
owner or operator must file the amended Part A permit application by the effective date of
the rule that subjects the unit to regulation.
Technical Correction to §270.73(f), (g). In the course of developing today's rule,
the Agency discovered that particular regulatory provisions dealing with loss of interim
status are miscodified. See §§270.73(f), (g). We are amending these provisions in
today's notice to match the implementing statutory language. The result will be that neither
boilers nor industrial furnaces, nor other units which achieve interim status after Nov. 7,
1984, are subject to the automatic statutory loss of interim status provisions.
The 1984 HSWA amendments provided that each facility which achieved interim
status prior to the effective date of the amendments would automatically lose its interim
status on a specified date, unless by an earlier specified date the facility applied for a final
determination regarding the issuance of a permit (i.e., submitted Part B of its permit
application). See RCRA sections 3005(c)(2), (e)92). The dates for Part B submission and
loss of interim status vary according to whether the facility is a land disposal facility,
incinerator, or other facility. M- Of relevance to today's technical correction, HSWA
provided that interim status for incinerators would terminate five years after the enactment
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of HSWA (i.e., on November 8,1989), unless the Pan B application was submitted within
two years after the enactment (i.e., by November 8, 1986); interim status for other non-
land disposal facilities would terminate eight years after the HSWA amendments (i.e.,
November 8, 1992) unless the Part B application was submitted within four years (i.e.,
November 8,1988). See RCRA section 3005(c)(2).
EPA amended its regulations on July 15, 1985 to incorporate these and other
HSWA changes. See 50 FR at 28702. EPA's intention in promulgating these amendments
was simply to reflect the new statutory provisions; for the most part, the Agency simply
codified into the regulations the new HSWA language. M. at 28703. In light of the largely
ministerial nature of the regulations, and in view of the need to move quickly to incorporate
HSWA, EPA published these 1985 regulations without opportunity for public comment.
M- (The D.C. Circuit eventually sustained the legality of these procedures in United
Technologies Corp. v. EPA. 821 F. 2d at 714 (D.C. Cir.1987).)
Section 270.73(f), (g) sets forth the dates on which interim status for incinerators
and other non-land disposal facilities terminates if the facilities fail to submit their Part B
applications. However, in contrast to the HSWA amendments, the sections by their terms
apply to all incinerator and other non-land disposal facilities, instead of being limited only
to those facilities which had obtained interim status on November 8,1984, the date of the
HSWA amendments. In fact, it is impossible for units newly subject to regulation after the
specified dates for submission of Part B permit applications (such as the boilers and
furnaces regulated by today's rule, or certain facilities newly subject to regulation under the
recent Toxicity Characteristic rule) to comply with the rules as codified. EPA did not
intend for these rules to deviate from statutory language. As the preamble to the 1985
codification regulations stated, the Agency simply intended for section 270.73(0, (g) to
reflect the HSWA termination-of-interim status provisions. M- at 28723.
The Agency is today making a technical correction to these sections to correct this
mistake, and to avoid the unintended (and possibly illegal) result that large classes of newly
regulated units are ineligible for interim status because they failed to submit Part B
applications at a time they were unregulated. EPA is proceeding without proposing the
correction for public comment, and believes that public comment is unnecessary, for the
following reasons: (1) this correction simply conforms the language of the regulations to
the Agency's original expressed intent in promulgating the 1985 regulations, which
themselves were validly promulgated without the opportunity for comment; (2) this
correction simply conforms the regulations to HSWA's plain language; (3) the amendment
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conforms the regulations to the Agency's actual practice in implementing the regulations
and RCRA 3005(c)(2); (4) the amendment is necessary to avoid rendering units newly
regulated after specified Part B permit application submittal dates from being ineligible for
interim status even though they meet all of the statutory interim status eligibility criteria; and
(5) the amendment can be viewed as an interpretative rule, which does not require prior
notice and public comment
C. Permitted Facilities
Some permitted facilities contain boiler and furnace units that are newly subject to
Subtitle C regulation as a result of today's rule. These permitted facilities must therefore
submit permit modifications to EPA Regional offices, and comply with federal permit
modification procedures in order to continue to manage hazardous waste in these units.
The modification will be processed under Federal permit modification procedures rather
than authorized state procedures because this rule is promulgated under HSWA
authority.80 However, because the permit undergoing modification is most likely a jointly
issued EPA-state RCRA permit, a copy of the modification request should also be
submitted to the state if it is an authorized state.
1. Amendment to §270.42(g). Today's rule contains a new permit modification
procedure in §270.42 for the addition of any newly regulated waste management units used
to manage hazardous wastes (see §270.42(g)). This two-step procedure essentially allows
the permittee to notify the Agency of its newly regulated boilers and furnaces using the
Class 1 permit modification procedures, and to continue to handle hazardous wastes.
Subsequently, the permittee must submit a Class 2 or 3 permit modification request to
initiate a permanent change to the permit The self-implementing interim status standards of
§266.103 would apply until the permit was modified using the Class 2 or 3 modification
procedures. This new permit modification provision only applies to newly regulated units
that were not previously subject to the permitting requirements of Subtitle C of RCRA.
Today's new permit modification provision for newly regulated units is essentially
identical to the special procedure in §270.42(g) for newly regulated wastes. The purpose
of today's amendment is to extend the same opportunities and procedures that are available
for newly regulated waste streams (and any units used to manage them) to those situations
80 Except, however, the provisions for sludge dryers, carbon regeneration units,
infrared incinerators, and plasma arc incinerators are not promulgated under HSWA
authority.
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where the unit becomes newly regulated in absence of a new waste identification. (See 53
FR 37922, September 28,1988.) EPA believes that the same rationale applies to newly
regulated types of units, and is therefore clarifying this provision in today's rule.
Without the procedure in §270.42(g), the facility would need to obtain an approved
permit modification if the facility were to continue managing hazardous wastes past the
effective date of today's rule, which establishes management standards for boilers and
industrial furnaces. If the modifications were not approved within six months, these
facilities would be barred from handling hazardous wastes, disrupting the ongoing
operations of many of these facilities as well as other RCRA facilities that would then need
to manage the wastes. As discussed below, EPA believes that the addition of a boiler or
industrial furnace to a facility's permit is a Class 3 modification. Because of the time
allowed for preparation of the modification request by the facility and public participation in
the permit modification procedures, the Agency would be unable to review and make a final
determination on the modification request in the six month period.
Today's technical correction rectifies a potential inequity between permitted facilities
and newly regulated facilities. Newly regulated facilities are required only to submit Part A
of the permit application, and submit the RCRA section 3010 Notification form, if
necessary, to obtain interim status. Both activities can be easily completed by the effective
date of today's rule, allowing them to continue operations, while permitted facilities, who
have undergone the scrutiny of the permitting process, would likely be barred from doing
so.
2. Procedures to Modify Permits. Under today's new procedures in §270.42(g), a
unit that is "in existence" as a unit by managing hazardous waste on or before the effective
date of today's rule must submit a Class 1 modification by that date. Essentially, this
modification is a notification to the Agency that the facility is managing hazardous wastes in
these newly regulated units. It could consist of a revised Part A application form clearly
indicating all activities that are newly regulated as a result of today's rule. As part of the
Class 1 procedure, the permittee must also notify the public regarding the modification
within 90 days of submittal to the Agency.
Next, within 180 days of the effective date, the permittee must submit a Class 2 or
3 modification request to the Agency. It is at this time that the detailed Part B information
must be submitted The Agency believes that the Class 3 permit modification procedures
are most likely applicable to the addition of boilers or industrial furnace units. The Qass 3
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modification requires an initial public notice by the facility owner of the modification
request, a 60 day public comment period, and an informal meeting between the owner and
the public within the 60 day period. After the end of the 60 day public comment period, the
Agency will develop a draft permit modification, open a second public comment period of
45 days and hold a public hearing. After the public comment period, the Agency will make
a final decision on the modification request
Today's rule also amends Appendix I to §270.42 to classify the permit
modifications for boilers and industrial furnaces. Section L is revised to include boilers
and industrial furnaces with incinerators, and to specify additional permit conditions to
conform with today's rule (and the conditions added to incinerator permits under the
omnibus authority of §270.32(b)(2). For more information on these permit modification
procedures, see 53 FR 37912, September 28,1988.
D. Addition of Storage Units at Direct Transfer Facilities That Obtain Interim Status
As discussed in section XII.C of Part Three of this preamble, the requirements for
boilers and industrial furnaces are being promulgated under section 3004(q) of RCRA,
which is a HSWA provision. As a result, under section 3006(g), EPA will implement
these requirements in both authorized and unauthorized States until the State is authorized
to implement these requirements in lieu of EPA. Based on comments received during the
rulemaking, EPA is aware that many interim status facilities newly-regulated under this rule
may wish to add storage units to their facilities in the future rather than continue direct
transfer operations (direct firing of the burner from the transport vehicle). Furthermore,
EPA recommends that facilities install tanks and reduce or eliminate direct transfer practices
because of the additional hazards associated with the practice. As discussed in more detail
below, EPA believes that such units can be added to the facility without awaiting complete
permitting.
1. Unauthorized States. Facilities that wish to shift to storage from direct transfer
operations and that are located in unauthorized states, will generally be able to add such
units to the facility as a change in interim status under 40 CFR 270.72(a)(3). In order to
qualify for addition of units under this provision, the facility must: (1) obtain interim status
for the boiler or industrial furnace; and (2) submit a revised Part A application to the EPA
Regional Office prior to adding the storage units with a justification for the change.
Because EPA strongly encourages the discontinuation of direct transfer operations at
boilers and industrial furnaces, EPA believes that the addition of storage units at such
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facilities constitutes a change necessary to meet federal requirements under 40 CFR
270.72(a)(3)(ii). The Regional Office must approve the interim status change, unless it is
covered by amended §270.72(a)(6) just discussed. Although 40 CFR 270.72(b) limits the
extent of an addition that can be made during interim status, the addition of associated
storage units under today's rule would be exempt from this limitation pursuant to
§270.72(b)(2).
2. Authorized States. Interim status facilities located in authorized states that wish
to discontinue direct transfer operations will also generally be able to add such units to the
facility pursuant to 40 CFR 270.72(a)(3). In states which are not authorized to implement
the HSWA storage requirements for boilers and industrial furnaces, the procedure for
adding storage units at new interim status boilers or industrial furnaces is the same as
described above for facilities located in unauthorized states. Because EPA is implementing
both the rule promulgated today and the associated storage requirements in such states, the
federal rules governing changes in interim status apply to both the boilers and industrial
furnaces and the addition of associated storage facilities.
In states which have been authorized to implement the HSWA storage requirements
for boilers and industrial furnaces, facilities newly regulated under today's rule must
comply with the authorized state requirements concerning the addition of associated storage
units. In some cases, the authorized state may require the facility to obtain a permit prior to
constructing or operating such storage units.
E. Compliance with BIF Versus Incinerator Rules.
Existing rules (see §266.3 l(c)) require that cement kilns burning hazardous waste
that are located in urban areas must comply with the hazardous waste incinerator standards.
In addition, existing rules allow owners/operators of any boiler or industrial furnace to
obtain an incinerator permit These provisions exist because the Agency had not yet
established regulatory controls for BIFs. In fact, the statutory provision (Section
3004(q)(2)(c)) requiring that cement kilns in urban areas be regulated as incinerators states
that the "...regulations remain in effect until the Agency develops substantive standards for
cement kilns burning hazardous waste." Therefore, on the effective date of the BIF rule,
both of these regulatory provisions will be rescinded except as discussed below.
Commenters questioned what regulations should more appropriately apply under
three scenarios: (1) if a BIF is operating in interim status under the Subpart O, Part 265,
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incinerator standards; (2) if a BIF has already been issued an incinerator operating permit
under Subpart O, Part 264; and (3) if a BIF has previously submitted a Part B application
for an incinerator permit and the permit review process has progressed substantially by the
effective date of the BIF rule. A BIF currently operating under the interim status
incinerator regulations must comply with the BIF regulations on their effective date in lieu
of the incinerator regulations so that it is subject to the more stringent BIF rule. A BIF
currently operating under an incinerator permit will continue under that permit until it is
reviewed or the permit term otherwise expires. At that time, the BIF rule will apply.
Although the Agency's general policy is that BIFs are to be regulated only under the BIF
rules, we believe permit officials should use their discretion to determine whether to grant
exceptions for the third situation given the protectiveness of the standards, and the
desirability of avoiding further delay and expense by having to duplicate the permit process
under these BIF rules. For example, if a BIF is operating under the incinerator interim
status standards but has submitted Part B of the incinerator permit and the permit
proceedings have progressed substantially, the Director may continue processing the permit
(and issue it) under the incinerator standards and use omnibus authority81 to add
conditions to the permit as necessary to conform with the BIF rule.
IX. Permit Procedures
A. Pcart E Information
As proposed on May 6, 1987 (52 FR 17015), § 270.22 provides specific
information requirements for Part B of the permit application. Paragraph (a) requires a trial
burn to demonstrate conformance with the performance standards of §§266.104 through
266.107, except where the trial burn is waived. Although the regulatory language is
substantively the same as proposed, it has been restructured for clarity, by specifying the
documentation required to support a waiver from each type of trial burn: DRE trial burn,
paniculate matter trial bum, metals trial burn, and HC1/C12 trial burn.
In addition, the rule specifies under §270.22(a)(6) that owners and operators may
submit data from previous compliance testing of the device, or from testing of similar
81 EPA notes that permit writers choosing to invoke die omnibus permit authority of
§270.32(b)(2) to add conditions to a RCRA permit must show that such conditions are
necessary to ensure protection of human health and the environment and must provide
support for the conditions to interested parties and accept and respond to comment In
addition, permit writers must justify in the administrative record supporting the permit any
decisions based on omnibus authority.
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boilers or industrial furnaces burning similar wastes, in lieu of a trial bum provided that the
data is determined adequate and sufficient documentation of similarity is provided.
Paragraphs (b) through (d) were added to §270.22 to provide information
requirements related to other regulatory provisions being promulgated today for boilers and
industrial furnaces. Paragraph (b) requires information describing the automatic waste feed
cutoff system. Paragraph (c) requires owners and operators using direct transfer
operations to feed hazardous waste from transport vehicles directly to the boiler or
industrial furnace to submit information supporting conformance with the direct transfer
standards at § 266.111. Under paragraph (d), owners and operators that claim their
residues are excluded from regulation under § 266.112 must submit information adequate
to demonstrate conformance with those provisions.
B. Special Forms of Permits
As proposed, the final rule adds § 270.66 to Subpart F of Part 270. This section
establishes special forms of permits (see discussion below) for new boilers and new
industrial furnaces, and sets forth requirements for the various periods of operation under
which a boiler or industrial furnace operates, depending on applicable trial burn
requirements. This section also establishes trial bum procedures. Finally, this section
discusses special procedures for permitting existing facilities. Although these provisions
were described in the preamble to the proposal, at 52 FR 17016, they are described briefly
below, in order to highlight minor changes from the proposed requirements.
1. Permits for New Boilers and Industrial Furnaces. Paragraph (b) specifies four
operating periods of a permit for a new facility. The provisions have been restructured
from those proposed in recognition of die fact that all boilers and industrial furnaces subject
to a permit must undergo some type of trial burn. Although a facility could conceivably
meet the requirements for a waiver of the DRE trial burn, paniculate matter trial burn,
metals trial burn, and HC1/C12 trial burn, all regulated facilities must demonstrate
conformance with the carbon monoxide, and where applicable, hydrocarbon limits of
§266.104.
In addition, minor revisions to this section have been made to make the permit
process for new boilers and industrial furnaces consistent with the way the hazardous
waste incinerator permitting process is implemented, i.e., one permit with four periods of
operations rather than an individual permit for each period of operation.
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Thus, the final rule provides for permits addressing four periods of operation for all
boilers and furnaces: the pre-trial burn period, the trial burn period, the post-trial burn
period, and the final permit period
Conditions addressing compliance with each performance standard (or
corresponding waiver requirement) will be set in the permit for each period of operation.
Applicants must submit a statement with Part B of the permit application that suggests the
conditions necessary to operate in conformance with the performance standards of
§§266.104 through 266.107. For those performance standards for which a trial burn is
required, the Director will use his engineering judgment, and consideration of the
applicant's proposal, in setting operating conditions in the permit sufficient to meet the
performance standards. Once the trial bum data are available, they will be used to modify,
if necessary, the final operating conditions in the permit. For those performance standards
for which a trial bum demonstration is not required (for example, when the applicant has
chosen to comply with Tier I of the metals limitations under § 266.106(b)), appropriate
conditions (in the above example, metals feed rate limits specified under § 266.102(e)(4))
will be set for all periods of operation.
The pre-trial bum period begins with initial introduction of hazardous waste into the
boiler or industrial furnace and extends for the minimum time required, not to exceed 720
hours of hazardous waste burning, to bring the device to a point of operational readiness to
conduct a trial burn. This period may be extended once by the Director if good cause is
shown. The trial burn period covers the period when the trial bum is conducted. This
period is followed by the post-trial burn period, which extends for the minimum time
necessary to allow analysis, data computation, and submission of the trial burn results and
modification of the permit by the Director if necessary to reflect the trial bum results. Such
modifications will proceed under the permit modification provisions at § 270.42.
Paragraph (c) specifies information that must be included in the trial bum plan.
Paragraph (d) establishes trial burn procedures, including criteria for approval of trial bum
plans and requirements for submission of trial burn data. Paragraph (e) establishes
procedures for selection of POHCs when a DRE trial burn is required. Finally, paragraph
(f) establishes the determinations that the applicant must make based on the trial burn
results — the data, analyses, and computations that must be submitted to support
conformance with the applicable emissions standards.
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2. Permit Procedures for Interim Status Facilities. Applicants owning or operating
existing boilers or industrial furnaces will be permitted under § 270.66(g). This paragraph
addresses submission of trial burn plans and trial burn data for existing boilers and
furnaces. These provisions differ from the proposal in that they specifically require that the
applicable trial burn data be submitted and considered prior to permit issuance. This
language conforms with the January 30, 1989 change to the hazardous waste incinerator
regulations, promulgated at 54 FR 4286 providing clarification of this point.
X. Exemption of Small Quantity Burners
Section 3004{q)(2)(B) of RCRA provides EPA with explicit authority to exempt
from regulation facilities that burn small quantities of hazardous wastes if the wastes are
burned at the same facility at which they are generated. The Administrator is to ensure that
such waste fuels are burned in devices designed and operated in a manner sufficient to
ensure adequate destruction and removal to protect human health and the environment.
The Agency has carefully evaluated the risks posed by small quantity burning and
concluded that a conditional exemption for small quantity burners should be allowed where
hazardous waste combustion poses insignificant risk. A discussion of the original May
1987 proposal and the subsequent October 1989 proposed revisions is presented below.
On May 6,1987 (52 FR 17034), the Agency proposed to exempt facilities that bum
small quantities of hazardous waste that they generate on site because even in the absence
of regulatory control, the health risk posed by such burning would not be significant.
Eligibility for the exemption would have been based on the quantity of waste burned per
month, established as a function of device type and thermal capacity. In order to be
exempt, in addition to restricting the quantity of waste burned, a facility was required to
notify the Regional Administrator that it is a small quantity burner, limit the maximum
instantaneous waste firing rate to 1% of total fuel burned, and refrain from burning acutely
toxic waste containing dioxin.
On October 26,1989 (54 FR 43730), the Agency proposed several revisions to the
exemption in the 1987 notice. Rather than establish hazardous waste quantity limits as a
function of device type and capacity, EPA proposed quantity limits that vary as a function
of effective stack height. The exempt quantities proposed in October 1989, and
promulgated today, include several changes to the risk assessment methodology. In
particular, the quantities are based on evaluation of risks from hydrocarbon (HQ emissions
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instead of a PIC/POHC ratio as originally proposed. This change was made to better
account for organic emissions from combustion. In addition, the procedures for evaluation
of facilities with multiple stacks were revised to reduce over-regulation in these situations.
A. Response to Comments
Numerous commenters to the 1987 and 1989 proposals objected to the
conservatism of the calculated quantity limits and/or the 1% limit on hazardous waste
firing. The commenters stated that the assumptions used in calculating the exempt limits
are overly conservative, and that the 1% limit on firing of hazardous waste is based on
unrealistic and unjustifiable conclusions. The commenters, however, did not provide data
or analysis to support their arguments that assumptions used in the small quantity burner
exemption (SQBE) calculations and conditions (including limits on the waste to be burned)
for exemption eligibility were too restrictive. Absent technical support for alternate
approaches, the Agency continues to believe that the approach proposed in October 1989 is
reasonable and appropriate. In addition, using less conservative assumptions to derive the
exempt quantities could allow relatively large amounts of hazardous waste to be burned, a
result somewhat at odds with the statutory language referring to small "quantities" of
hazardous waste. See §266.108 (a)(2) which limits the maximum hazardous waste firing
rate at any time to 1% of the total fuel requirements of the device on a volume basis. See
also §266.108(a)(3) which requires the hazardous waste to have a minimum heating value
of 5,000 Btu/lb, as-generated, to ensure that the exemption is limited to fuels as intended
by section 3004(q)(2)(B) and to ensure adequate destruction of toxic organic constituents.
One commenter requested credit for the presence of air pollution control devices
(APCDs). The Agency believes that it is not appropriate to allow credit for APCDs
because, without requirements for and oversight of the operation and maintenance of the
devices, there is no assurance that collection efficiencies are being met
Four commenters to the 1987 proposal urged EPA to delete the small quantity
burner exemption. These commenters were concerned that the large number of boilers and
industrial furnaces burning hazardous waste that do not have to meet any design
requirements would have a detrimental effect on human health and the environment The
Agency continues to believe that the exemption is protective of human health and the
environment because it is health-based, incorporating quantity limits and conservative
assumptions designed to be protective regardless of size and location of the device, or
conditions of operation.
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Two commentcrs stated that the exemption should apply to facilities that generate
hazardous waste at off-site facilities under the same ownership and operational control.
The Agency is concerned, however, that contrary to Congress's intent, this approach could
allow a large quantity generator to distribute their hazardous wastes in small quantities to
TSDFs (including entities that are parent corporations, joint ventures, subsidiaries of the
generator, etc.) that would then bum the wastes without regulation. Consequently, the
final rule limits the exemption to facilities that bum only hazardous waste generated on-site.
One commenter to the 1987 proposal urged the Agency to clarify that the 1% limit
on the hazardous waste firing is to be applied only to unmixed hazardous waste fuel, not to
a mixture of hazardous and non-hazardous fuel. The Agency acknowledges the ambiguity
in the proposed rule language and intended the proposal to require that the quantity
determination take into account only the hazardous waste fuel prior to mixing with a
nonhazardous waste fuel. Today's final rule contains language to that effect and requires
the exempt facility to keep records to document that the quantity of hazardous waste prior to
mixing with a nonhazardous fuel complies with the quantity limitations.
Six commenters to the 1989 proposal suggested that quantity limits be based on 1%
of the total fuel burned and not the stack height, which relies upon dispersion only. The
Agency, however, continues to believe that terrain-adjusted stack height is the important
criterion, because it is possible that even a 1% limit, with large dispersion and low stack
height, could pose a threat to human health and the environment.
B. Basis for Today's Final Rule
In order to calculate allowable exempt quantities under today's rule, worst-case
dispersion coefficients (based on incinerator modeling), and an HC unit risk factor of 2 x
10'5 m^/ug (based on a 10~5 risk limit) were assumed, as proposed in the October 1989
supplemental notice. Allowable emission rates of hydrocarbons (HCs) were then back-
calculated as a function of effective stack height, terrain type, and land use. The
assumption used in this back-calculation was an HC concentration in the stack gas of 150
ppmv at 99.99% DRE. Finally, the exempt quantities were calculated using the HC
emission rates and an empirically-derived ratio of combustion gas volume to mass of
waste. The most conservative allowable emission rates calculated for each stack height
were then used as the established quantity limits.
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A detailed description of the methodology used to derive quantity limits for the
exemption is available in the docket for the supplemental notice.
As mentioned above, the use of effective stack height to determine eligible quantity
limits reflects one of the revisions proposed in the October 26,1989 supplemental notice.
The Agency notes that we have not established separate exempt quantity limits for the
different terrain types and land use classifications. Rather, the revised quantities are based
on assumptions of terrain and land use that result in the lowest (i.e., most conservative)
exempt quantities. We believe that this conservative approach is appropriate given that
there would be no EPA or State agency oversight of an operator's determination of a
facility's terrain and land use classification. Some key assumptions used to arrive at the
quantity limits are described below.
EPA evaluated the risks posed by emissions of organic compounds, metals, and
hydrogen chloride, the parameters controlled in the substantive regulations promulgated in
today's rule.82 The analysis demonstrates that the risks posed by organic emissions from
waste-as-fuel activities are overwhelmingly dominated by the risks posed by carcinogenic
(as opposed to noncarcinogenic) waste constituents. Accordingly, the initial evaluation
performed in support of the small quantity burner exemption focused exclusively on
carcinogenic risks, on the assumption that controls ensuring insignificant risks from
organic carcinogenic emissions will ensure protection against non-carcinogenic releases.
This assumption was confirmed by evaluating the potential risks from metals and hydrogen
chloride that would result when those quantities of waste indicated by the risk analysis for
organic carcinogens were burned.
The risks from burning small quantities of hazardous waste are determined
primarily by the following factors:
• Composition of the waste stream being burned;
• Toxicities and concentrations of hazardous constituents in the waste stream;
• Destruction and removal efficiency achieved by the device;
• Local meteorology, which influences the amount of dispersion of stack emissions;
• Clustering and size of sources; and
• The effective stack height of the device.
82 U.S. EPA, "Analysis for Calculating a de Minimis Exemption for Burning Small
Quantities of Waste in Combustion Devices", August 1989.
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The values of these parameters can and do vary widely. Reasonable, worst-case
assumptions were made for these parameters in the Agency's calculations of exempt
quantities and evaluation of risks. In the risk analysis, EPA assumed an acceptable cancer
risk level of 1.0 x 10*5 to an individual residing for 70 years at the ground level point of
maximum exposure to reasonable, worst-case stack emissions. Reasonable, worst-case
dispersion coefficients based on effective stack heights were used. The dispersion
coefficients were those developed in the risk analysis for the proposed amendments to the
hazardous waste incinerator regulations (See 54 FR 43752 and 55 FR 17871). The
dispersion coefficients differ by terrain type, land use, and effective stack height Separate
calculations were made for noncomplex and complex terrain and urban and rural land use,
resulting in three different sets of quantity eligibility limits for each effective stack height.
The rationale for the assumptions used in the risk analysis is discussed below.
1. Composition of Hazardous Waste Stream, Composition data on hazardous
waste-derived fuels is scarce. Information gathered by the mail questionnaire survey and
other industry contacts indicate that most of the materials burned are organic solvents that
are usually classified as hazardous based on ignitability and/or toxicity. The actual
concentrations of carcinogens in wastes burned by 21 facilities during EPA's field testing
program for boilers and industrial furnaces ranged from 0 to 17% with an average of
approximately 4%.
The quantity of PICs measured in EPA test burns was found to be independent of
specific POHC species and was a function of hydrocarbon (HC) content of the fuel only.
This is supported by comparisons made by MRI of PICs from hazardous waste and fossil
fuel combustion. Since it is impossible to differentiate between the PICs from fuel and
those from hazardous waste during most tests, it was assumed that the boilers in the EPA
test burns were using fuels of 100% HC and all PICs are the result of hazardous waste
burning. Additionally, HC emissions are presumed to be an acceptable measurement of
PICs; historic data indicate that HC measures from 75 to 95% of all PICs emitted.
The hazardous waste was assumed to contain concentrations of cadmium,
chromium, nickel, and lead that were obtained from the state sampling reports of the
Keystone Cement Company. Arsenic, barium, and mercury concentrations were based on
90th percentile levels from the Engineering Science Background Document
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2. Toxicity of Hazardous Constituents. The average unit risk of those PICs that
were identified during EPA trial bums was 1.0 x 10~5 m^/ug. However, it is likely that the
PICs resulting from incineration under the 99% DRE assumption for the small quantity
burner analysis would have a higher toxicity than those measured under the 99.99% DRE
in the EPA boiler tests. EPA therefore estimates the unit risk for total HCs to be 2.0 x 10~5
m^/ug. This corresponds to a carcinogenic potency of Qj* = 0.07 for hydrocarbons (HC).
As explained in the October 1989 notice, this potency factor was used rather than a Qj*
value of 1.0 for products of incomplete combustion as originally proposed in the May 6,
1987 proposed rule because the Agency was concerned about possible nonconservative
features of PIC estimation. (See 54 FR 43730).
3. Destruction Efficiency. The burner destruction efficiency determines the
quantity of unburned hazardous wastes that will be emitted from the stack. Assumed
values for boiler and furnace performance were selected based upon a review of test data
generated in support of this rule and based on the professional judgment of Agency staff
members familiar with the destruction and removal efficiencies (DRE) typically achieved by
boilers. It was assumed that, in the worst case, boilers and furnaces would only achieve
99% DRE83 of organic constituents. This represents a very poorly performing combustion
device. In fact, as explained previously, most boilers and furnaces can be expected to
achieve 99.99% DRE of organic waste constituents even when operated under less than
optimal conditions.
4. Assumptions Regarding Metals and Chlorine in Waste Fuels,. A similar
reasonable, worst-case analysis was performed to evaluate the potential risks posed by
emissions of toxic metals (including carcinogens) and hydrogen chloride from small
quantity burners. As a result, it was determined that, at the volume cut-offs specified by
the exemption and the assumed waste concentrations as discussed above, metals emissions
caused by cofiring of hazardous wastes would not pose a significant risk. The analysis
also considered hydrogen chloride emissions assuming a chlorine content of 50% in the
hazardous waste fuel The chlorine content in actual hazardous wastes seldom exceeds 3%;
however, the highest chlorine content measured in a hazardous waste fuel fired in a boiler
83 We note that we assumed 99% DRE to derive the small quantity burner exempt
quantities rather than the 99.9% that the owner/operator must assume under the low risk
waste exemption of §266.109 because monitoring of CO is not required for the small
quantity burner exemption to ensure that good combustion conditions are maintained. CO
monitoring is required under the low risk waiver of the DRE trial burn.
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of which EPA is aware was 43%. Predicted ground level concentrations of HQ also did
not exceed the reference air concentrations.
The assumptions used to determine the effect of local meteorology/dispersion and
the clustering of sources (stacks at the facility) are discussed in the following section.
C. How the Exemption is Implemented
1. Use of Terrain-Adjusted Effective Stack Height. In the 1987 proposal, the
Agency used a set of assumptions about local meteorology, dispersion modeling, terrain
conditions, etc., to determine eligible quantity limitations. As mentioned above, today's
rule uses terrain-adjusted effective stack height along with the most conservative
assumptions of terrain and land use to determine quantity limits for exemption eligibility.
See §266.108.
2. Multiple Stacks,. As explained in the October 1989 notice, in today's final rule
the exempt quantities for a facility with multiple stacks from boilers or industrial furnaces
burning hazardous waste are limited according to the following equation:
£^
Actual Quantity Burned/i) i.o
i = 1 Allowable Quantity Bumed(i)
Where:
N means the number of stacks
Actual Quantity Burned, means the waste quantity per month burned in stack "i"
Allowable Quantity Burned, means the maximum allowable exempt quantity for stack
For example, if a site had two stacks with effective stack heights (ESH) of 30 and
10 meters, the following equation would hold:
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+ _X * 1.0
. 140 40
Where:
• 140 and 40 are the exempt quantities from §266.108 for stack heights of 30 and 10
meters, respectively
• X is the waste quantity burned in the device with the 30 meter stack
• Y is the waste quantity burned in the device with the 10 meter stack
In this example, if Y is burning 15 gallons/month, then X could burn no more than
87.5 gallons/month.
D. Wastes Ineligible for Exemption
Boilers and furnaces burning hazardous waste fuels containing or derived from any
of the following dioxin-containing hazardous wastes are not eligible for the exemption:
EPA Hazardous Waste Nos. F020, F021, F022, F023, F026, and F027. See
§266.108(a)(4). Given the toxicity of these wastes, EPA does not believe it is appropriate
to exempt facilities burning them from regulation. Hazardous waste fuels containing or
derived from these dioxin-containing wastes must be burned at a 99.9999% destruction and
removal efficiency (DRE). We cannot expect boilers and furnaces to achieve that level of
DRE when operating outside of the Agency's regulatory system.
E. Exemption of Associated Storage
Hazardous fuel storage practices prior to burning vary from site to site. Many
facilities burning relatively large quantities of hazardous waste fuels hold the fuels in a
storage system and then pump the waste fuels through a dedicated line into the combustion
zone of the boiler. Other facilities mix hazardous waste fuels with other fuels (typically
virgin fuel oil) in a storage/mixing tank prior to burning the blended material. These tanks
are not feasibly emptied of hazardous waste every 90 days and so are in most cases
ineligible for the generator accumulation provisions in §262.34.
Under today's rule, facilities storing unmixed hazardous waste fuels are responsible
for complying with all applicable standards for the storage of the hazardous waste fuel.
Owners and operators that are eligible for the small quantity burner exemption and who mix
toxic hazardous waste fuels with other fuels would, however, be exempt from the storage
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standards after such mixing, as proposed. See §266.101(c)(2). The basis for this
exemption is discussed below.
The Agency is promulgating an exemption for storage of such storage/mixing tanks
(for small quantity burners) in order for the small quantity burner exemption in Section
3004(q)(2)(B) to have practical application. Congress evidently envisioned a class of
facilities capable of burning small amounts of hazardous wastes safely absent regulation
and viewed such burning as a superior means of managing these small amounts of waste.
Furthermore, assuming that small quantity waste storage is conducted safely, the Agency
assumes that Congress also envisioned exemption of the storage since permitting storage
would discourage safe on-site burning just as much as regulating the burning itself.
We believe that storage of small amounts of hazardous wastes mixed with virgin
fuels would pose no significant incremental risks over storage of the virgin fuels. The
monthly volumes of hazardous waste fuel covered by the small quantity burner exemption,
for example, represent less than 1% of the fuel flow rate through these tanks. Under these
circumstances, we think the statutory exemption can reasonably be read to encompass this
limited class of storage practices as well.
We note further that the Agency is studying other situations where hazardous
waste-containing mixtures may not be appropriately subject to regulation and will consider
whether to issue rules addressing the issue generically. It appears to us justifiable to
address the question for the limited class of burning facilities in advance of other types of
situations because Congress has singled out small quantity burning facilities for exemption
where appropriate. We note further that to the extent these small quantity waste-virgin fuel
tanks are underground storage tanks (as defined in section 9001(1)), they would be subject
to regulation under Subtitle I if they contain petroleum.
F. Notification and Recordkeeping Requirement
As proposed in the October 26,1989 supplemental notice, the final rule requires
(conditionally) exempt small quantity burners to provide a one-time written notification to
EPA (see §266.108(c)) of their status as a small quantity burner and a certification that they
are in compliance with the requirements of §266.108. To assist enforcement efforts, the
owner or operator must also indicate in the notification the maximum allowable quantity
that may be burned per month as provided by §266.108(a)(l). In addition, the final rule
requires small quantity burners to keep records to document that they comply with the
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conditions of the exemption including: quantities of hazardous waste burned per month;
quantities of hazardous waste and other fuels burned at any time to demonstrate
conformance with the 1% hazardous waste firing rate limit; and heating value of the
hazardous waste.
XI. Exemption of Low-Risk Waste from ORE Standard and Particulate
Matter Emission Standard
The final rule defines two types of "low-risk" wastes: (1) waste that is low risk
with respect to feed rate of hazardous (i.e., Appendix Vffl, Part 261) nonmetal constituents
and, thus, is exempt from the requirement to demonstrate 99.99% DRE; and (2) waste that
is low risk with respect to both nonmetal constituents and metals (i.e., the waste meets the
Tier I feed rate limits for metals provided by §266.106(b)) and, thus, is exempt from both
the DRE standard and the 0.08 gr/dscf paniculate standard. See §266.109.
The following sections explain these exemptions and how they operate.
A. Exemption from Compliance with the DRE Standard
In the May 6,1987 proposed rule, the Agency proposed a risk-based, site-specific
waiver of the DRE trial burn and the flue gas CO limits for facilities burning waste that
poses insignificant health risks absent those controls (52 FR 17002). Today's final rule
retains the exemption from the DRE standard, but requires the facility to monitor CO
continuously and to comply with the Tier I PIC controls of §266.104(b) (i.e., CO cannot
exceed the 100 ppmv limit on an hourly rolling average basis).
In the 1987 proposal, EPA explained the basis for the DRE exemption for boilers or
industrial furnaces that burn low-risk waste (52 FR 17002). After further consideration,
however, the Agency believes that controls on emissions of PICs are needed. This is
because a waste with low levels of toxic organic constituents can nonetheless pose
significant health risk if it is burned under poor combustion conditions conducive to
formation of PICs. Toxic PICs can form from poor combustion of nontoxic organic
compounds.
The final rule does not allow a burner to operate under the alternative CO limit
provided by §266.104(c), which allows higher CO levels provided that HC levels do not
exceed 20 ppmv, because the Agency believes that only those devices operating under best
demonstrated technology combustion conditions should be granted an exemption from the
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DRE requirement (We note that this is consistent with the CO restriction for the automatic
waiver of the DRE trial bum for boilers operating under the special operating conditions
provided by §266.110.) Devices operating at CO levels above 100 ppmv on an hourly
rolling average are not operating under best demonstrated technology combustion
conditions even if they can show that hydrocarbon levels do not exceed 20 ppmv (or the
HC limit established under §2666.104(f)). As discussed at proposal (see 54 FR 43723
c.3), the 20 ppmv HC level represents a demarcation between good and poor combustion
conditions. HC levels under best demonstrated technology combustion conditions would
generally be less than 5 ppmv on an hourly rolling average basis.
B. Exemption from Compliance with the Paniculate Standard
Today's final rule also provides a waiver of the paniculate standard for facilities that
both obtain the DRE standard waiver and meet the Tier I requirements for all metals.
(Because the PM standard guards against risks from both adsorbed organic compounds and
metals, only facilities with waste that is low risk for both organic constituents and metals
are eligible for the PM waiver.)
The basis for imposing a paniculate standard on boilers and industrial furnaces
firing hazardous waste, as explained in the October 26,1989 supplemental notice (54 FR
43719), is primarily the concern over adsorption of toxic organics and metals onto the
emitted particulates. Consequently, the Agency believes that an exemption from the
paniculate standard for boilers and industrial furnaces is appropriate provided that the
facility can demonstrate that emissions of toxic organics and metals do not pose
unacceptable human health risks.
C. Eligibility Requirements
Three eligibility requirements for the low-risk waste exemption were detailed in the
1987 proposed rule. Many commenters objected to the first of these requirements, that 50
percent of the fuel fired in the boiler or industrial furnace must consist of oil, natural gas,
coal, or other fossil fuels derived from these fuels. These commenters requested that EPA
allow the cofiring of various other fuels, including tall oil, off-specification fuel oils, and
wood chips.
Although some of these fuels may provide a hot, stable flame that will support good
combustion, the Agency is concerned that others may not In today's rule, the Agency is
requiring for this exemption the same conditions on the primary fuel as required for the
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special operating requirements for boilers seeking the automatic waiver from a DRE trial
burn (see section 13.A.3 of Part Three of this preamble): a minimum of 50% of the fuel
fired to the boiler must be high quality "primary" fuel consisting of fossil fuels or fuels
derived from fossil fuels, tall oil, or, if approved by the Director on a case-by-case basis,
other nonhazardous fuel comparable to fossil fuel, and all such primary fuels must have a
minimum as-fired heating value of 8,000 Btu/lb.
The two remaining eligibility requirements, that the hazardous waste must have an
as-fired heating value of at least 8,000 Btu/lb, and that the waste must be fired into the
flame zone of the combustion chamber, are being promulgated as proposed in 1987. The
reasons for these requirements are the same as discussed in section II. A3 of Part Three of
this preamble in the context of the automatic waiver of the DRE trial burn for boilers.
D. How the Low-Risk Waste Exemption Works
1. Constituents of Concern. The low-risk waste exemption is intended to exempt a
waste from either or both the DRE standard and the paniculate standard if the
owner/operator demonstrates that, absent regulatory controls (i.e., under a reasonable,
worst-case emissions scenario), emissions from the facility will not result in ambient levels
of toxic organic compounds and/or metals that exceed acceptable levels. The organic
constituents of concern are the hazardous organic compounds listed in Appendix VIE of 40
CFR Part 261 and the metals of concern are the 10 regulated metals. See section E of this
preamble.
2. Estimation of Worst-Case Emissions. The requirements for estimating worst-
case emissions were discussed in the May 1987 proposed rule and are being promulgated
in today's rule with slight modifications.
To estimate reasonable, worst-case emissions of toxic organic constituents in
hazardous waste fuel, an owner or operator must: (1) identify every nonmetal Appendix
Vm constituent that could reasonably be expected to be found in the waste; and (2) assume
a reasonable, worst-case destruction and removal efficiency (DRE) for each constituent of
99.9 percent in calculating the worst-case emissions (by considering waste concentration
and feed rate) from the stack for each constituent This assumed DRE of 99.9 percent is
less conservative than the proposed 99 percent assumption in the 1987 notice. The Agency
is making this change in response to the many commenters who objected to the 99 percent
DRE assumption. Specifically, the commenters' objection was that 99.9 percent was the
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worst DRE measured by the Agency in its nonsteady-state testing of boilers operated under
intentionally upset (i.e., high CO and smoke) conditions. The Agency believes that
changing the assumed DRE from 99 percent to 99.9 percent is justified because today's
rule, unlike the 1987 proposal, does not provide a waiver of the continuous CO emission
monitoring (CEM) requirements. Compliance with continuous CO monitoring
requirements will ensure that these devices do not operate under upset conditions and will
achieve a DRE of at least 99.9 percent
The Agency has eliminated the proposed requirement that emissions of products of
incomplete combustion (PICs) be estimated using a ratio of PICs to principal organic
hazardous constituents (POHCs). As explained in the April 1989 notice (54 FR 43730),
use of the PICrPOHC ratio may not be a conservative method for estimating PIC
emissions.
An estimate of worst-case emissions is not necessary for metals. To be eligible for
the exemption from the paniculate standard, the waste must be low-risk with respect to
organic compounds and must meet the Tier I metals feed rate limits. See §266.106(b).
Those metals feed rate limits assume that all metals fed into the device are emitted.
3. Dispersion Modeling. Dispersion modeling must be used to predict the
maximum annual average ground level concentration of each toxic nonmetal compound in
the waste using procedures identical to those required to implement the Tier m metals
controls. See 266.109(a)(2)(iii)(A).
4. Acceptable Ambient Levels. Predicted maximum annual average ground level
concentrations of each toxic nonmetal compound may not exceed levels the Agency
proposed as acceptable for purposes of this rule. The acceptable ambient concentrations
were developed for carcinogenic and noncarcinogenic compounds using the same
procedures used to develop the RACs and 10~5 RSDs for the 10 toxic metals.
To demonstrate that the noncarcinogenic nonmetal compounds listed in Appendix
IV of the rule do not pose an unacceptable health risk, the predicted ground level
concentrations cannot exceed the levels established in that Appendix.
To demonstrate that the carcinogenic nonmetal compounds listed in Appendix V of
the rule do not pose an unacceptable health risk, the sum of the ratios of the predicted
ground level concentrations to the levels established in the Appendix cannot exceed 1.0.
This is because the acceptable ambient levels established in Appendix V are based on a 10~5
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risk level. To ensure that the summed risk from all carcinogenic compounds does not
exceed 10*5 (i.e., 1 in 100,000), the sum of the ratios described above must be used.
To demonstrate that other compounds for which the Agency does not have adequate
health effects data to establish an acceptable ambient level are not likely to pose a health
risk, the predicted ambient level cannot exceed 0.09 ug/nA This is the 5th percentile
lowest reference air concentration for the compounds listed in Appendix IV of the rule.
5. Constituents with Inadequate Health Effects Data. At the time of the 1987
proposal, the Agency had data adequate for establishing RACs and RSDs for only about
150 of the over 400 compounds listed in Appendix VIE, Part 261. In the preamble to the
May 1987 proposal, EPA stated that, to be eligible for the exemption, health effects data
(i.e., RACs and RSDs) must be available for each constituent in the waste. In response to
comments concerning the inadequacy of current health effects data to establish a RAC or
RsD for a large number of compounds, we have established in today's rule a conservative
RAC value for such constituents determined as the 5th percentile lowest RAC for all of the
nonmetal Appendix Vin, Part 261, constituents - 0.09 ug/m^ (see note to Appendix V of
the final rule). EPA believes that this approach will be protective of human health and the
environment and will not unreasonably restrict owners/operators from eligibility for the
exemption.
XII. Storage Standards
A. Permit Standards for Storage
Under the administrative controls for hazardous waste marketers, burners, and
blenders of hazardous waste burned in boilers and industrial furnaces promulgated on
November 29,1985, and codified in Subpart D of Part 266, EPA subjected existing burner
storage facilities (effective May 29,1986) to only the interim status standards of Part 265.
The permit standards of Part 264 were not applied to existing storage facilities in order to
avoid two-stage permitting, given that today's rule for permitting boiler and industrial
furnace facilities was under development at that time. The Agency wanted to avoid
requiring a boiler or industrial furnace owner or operator to obtain a permit for their
hazardous waste fuel storage facility and to soon thereafter obtain another permit for
operation of the boiler or industrial furnace under today's rule.
Today's rule does, therefore, subject such existing burner storage facilities to the
permit standards of Part 264. See §266.101 (c).
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Numerous comments on the May 6,1987 proposed rule to subject burner storage
units to the permit standards of Part 264 agreed that the interim status standards currently in
force are not adequate and permit standards are needed. Several commenters were
concerned about the potential mishandling of waste fuels stored on-site in and around
residential areas. One commenter requested that preburn transport and storage regulations
for hazardous waste apply to all hazardous waste blends, mixtures, or diluted hazardous
materials.
With the promulgation of today's rule, all hazardous waste storage units will be
subject to applicable Pan 264 and 265 standards. Since hazardous waste storage units
standards are designed to be protective of human health and the environment regardless of
the location of the facility, on-site storage associated with boilers and industrial furnaces
burning hazardous waste is not restricted to areas in or around residential areas. These
standards apply to the storage of any hazardous waste blends, mixtures, or dilutions that
will be burned at these facilities, due to the "mixture rule" of 40 CFR 261.3. Whereas
nonindustrial boilers were previously prohibited from burning hazardous wastes unless
they were operated in confbrmance with the incinerator standards of Subpart O of Parts 264
or 265, today's rule eliminates the distinction between industrial and nonindustrial boilers.
Consequently, today's rule establishes standards that are protective when hazardous waste
is burned in any boiler.
One commenter recommended that the final rule allow the 90-day "on-site"
accumulation provision to include wastes received at the BIF from off-site, company-
owned locations. The 90-day accumulation provision referred to by the commenter is
contained in 40 CFR 262.34(a) and only applies to generators of hazardous wastes. The
Agency does not intend to apply this provision to hazardous waste treatment, storage, or
disposal facilities.
B. Consideration of Requirement for Liquid Waste Fuel Blending Tanks
In the October 26,1989 supplemental notice, the Agency requested comment on a
requirement that all boiler and industrial furnaces use blending and surge storage tanks
(i.e., other than other modes of waste fuel transfer) to avoid flow interruptions and waste
stratification which could affect the ability of a combustion device to meet performance
standards. The majority of commenters opposed requiring blending and surge storage
tanks for BIFs and suggested that such a requirement would not be necessary to ensure
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compliance with performance standards. Several commenters believed that a uniform
requirement for tanks, containers, and/or surge tanks may not be universally appropriate.
These commenters noted that some secondary materials such as lead acid batteries, flue
dust, and various scraps and slags cannot be transferred to furnaces from a tank or
container system. Another commenter suggested that in some instances, such as feeding
incompatible wastes, direct transfer may be preferable due to health and safety concerns. A
few commenters concurred with this view, but felt that storage and blending tanks should
be required in all other instances. One commenter suggested that storage tanks should be
required only if transport vehicles do not meet Department of Transportation requirements,
secondary containment is not used in transfer operations, and if operations are not covered
by site-specific contingency or SPCC plans. One commenter agreed that hazardous wastes
should generally be fed from storage tanks and supported a final rule that would allow a
"window of opportunity" to install storage tanks, thus providing an incentive for a
company to reduce their reliance on direct burning from transport vehicles.
In today's rule, the Agency is not requiring storage and blending tanks for boilers
and industrial furnaces burning hazardous waste because we continue to believe that such
tanks are not requisite to demonstrating conformance with the emission standards of
§§266.104 through 266.107. However, as indicated in the supplement to the proposed
rule, EPA believes that facilities that install blending and storage tanks may be better able to
control flow interruptions and waste stratification. Consequently, boilers and industrial
furnaces with blending and/or storage tanks may operate with greater efficiency and thereby
may more readily meet performance standards for emissions.
We also note that, once an owner/operator is in interim status, the Part A application
may be revised to convert from direct transfer operations to the use of storage units.. See
discussion in section Vffl of Part Three of the preamble.
C. Standards for Direct Transfer Operations
In the October 26, 1989, supplement to the proposed rule, EPA identified
permitting authorities' concerns about the practice of feeding hazardous waste fuels directly
from transport vehicles to boilers and industrial furnaces. These concerns included: (l)the
potential for fires, explosions, and spills during transfer operations; and (2) the
stratification of waste in the transport container and the potential for waste fuel flow
interruptions which, in turn, could affect the ability of the burner to consistently provide
efficient combustion of the waste. EPA requested comment on two approaches to regulate
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direct transfer operations. One approach was for permit writers to use the RCRA omnibus
authority to establish additional permit conditions as necessary to ensure adequate
protection of human health and the environment from such operations The other approach
was to require that facilities burning hazardous waste use blending and surge storage tanks
to avoid the flow interruptions and waste stratification, which would address permit
writers' concerns.
In the April 27, 1990 Federal Register notice, EPA noted that commenters on the
October 1989 notice stated that controls on transfer operations were needed during interim
status. As a result, the Agency requested comment on the need and appropriateness of
regulating direct transfer operations under interim status standards for containers and tank
systems of Subparts I and J of Part 265. EPA received numerous comments in response to
these solicitations. The majority of commenters recommended that EPA allow direct
transfer with proper controls and restrictions, such as: (1) allow direct transfer approval
for facilities granted interim status or a RCRA operating permit; (2) establish direct transfer
standards similar to Subparts I and J of 40 CFR Part 265 for facilities with a contingency
or SPCC plan; and (3) allow direct transfer during test burns alone. Some respondents
suggested that instead of allowing direct transfer, EPA should require storage and blending
tanks for all facilities burning hazardous waste.
The Agency is today promulgating standards regulating direct transfer operations.
See §266.111. The Agency believes that these standards will adequately address potential
risks to human health and the environment.
EPA considers direct transfer operations to be a part of the hazardous waste firing
system, not a storage activity. Hence, facilities that are not subject to the burner standards
of §§266.102 (permit standards) or 266.103 (interim status standards) are not subject to the
direct transfer standards. Examples of facilities not subject to the direct transfer standards
are small quantity burners exempt from regulation under §266.108, metals reclamation
furnaces deferred under §266.100(c), and coke ovens exempt under §266.101(b)(4).
These direct transfer standards reference extensively the Subpart I container
standards and the Subpart J tank standards of Parts 264 and 265 and will apply equally to
facilities operating under a permit as well as those operating under interim status. The
regulations address the area in which transport vehicles are located and piping and other
ancillary equipment (termed "direct transfer equipment in today's rule) used to transfer
waste from the vehicle to the burner. The standards provide general operating requirements
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and controls on equipment integrity, containment and detection of releases, response to
leaks or spills, design and installation of new direct transfer equipment, and closure.
1. General Operating Requirements. Facilities that directly transfer hazardous
waste to boilers and industrial furnaces from transpon vehicles must comply with general
operating requirements that specify safe management practices for handling incompatible
wastes, spill prevention controls, and automatic waste feed cutoffs. These general
operating requirements apply to both containerized and bulk hazardous waste. General
performance standards for safe operation in today's rule include measures for conducting
direct transfer operations such that fire, explosion, violent reactions, and other conditions
that could threaten human health or the environment do not occur. Direct transfer from
open-top containers is prohibited. Direct transfer equipment, which is any device that
distributes, meters, or controls hazardous waste flow between a transport vehicle and a
BIF, must also be closed except when necessary to add or remove the waste. Safe
management practices for handling incompatible wastes are also required. Transport
vehicles or direct transfer equipment holding ignitable or reactive hazardous waste must be
located at least 50 feet from the receiving facility's property line.
2. Inspections and Recordkeeping. All equipment and areas where direct transfer
occurs must be inspected hourly for leaks during direct transfer operations. Control
equipment, direct transfer equipment monitoring data, and other equipment ensuring
compliance with direct transfer standards must also be inspected hourly. Finally, the rule
provides recordkeeping requirements to document results of inspections.
We note that only daily inspection is required under Subpart J of Parts 264 and 265
for tank systems (i.e., piping, valves and other direct transfer equipment). EPA is
requiring hourly inspections of direct transfer operations because, unlike tank systems that
use hard piping, direct transfer operations use flexible hoses and quick change coupling
devices that have a greater potential for leaks or spills.
3. Equipment Integrity. Equipment integrity requirements address direct transfer
equipment (e.g., piping or conveyors from the transport vehicle to the burner). The
standards promulgated today require the transfer of waste to other equipment if equipment
holding hazardous waste leaks or is in poor condition, and specify safe management
practices for transferring wastes to other containers or transport vehicles. An assessment is
required of existing direct transfer equipment that does not meet the secondary containment
requirements discussed below to determine if the direct transfer equipment is leaking or
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unfit for use and must be certified by a qualified, registered professional engineer. If
equipment is found to be leaking or unfit for use, the owner/operator must comply with the
requirements addressing responses to leaks or spills.
4. Containment and Detection of Releases. The rule requires secondary
containment for underground direct transfer equipment.. See §266.111(e)(l). Inspections
and leak tests of direct transfer equipment and recordkeeping requirements are also
required. Existing direct transfer equipment subject to the secondary containment
requirements of §265.193 (by reference in §266.1 ll(e)(l) of today's rule) must comply
with those secondary containment requirements within two years after the effective date of
the rule. EPA believes that two years (30 months from promulgation) is a reasonable
amount of time to enable owners and operators to retrofit existing equipment with
secondary containment as necessary given that direct transfer operations generally do not
involve the use of extensive equipment subject to secondary containment
5. Response to Leaks or Spills. Action required to be followed in the event of a
leak or spill are based on those required in Subpart J, Part 265. See §266.111 (e)(5).
Should a leak or spill occur, equipment use must cease (to prevent the flow or addition of
wastes into the direct transfer equipment or secondary containment system) and the system
must be inspected to determine the cause of the release. The waste must be removed from
the direct transfer equipment or secondary containment system and visible releases to the
environment must be contained. In the event of a leak or spill, the Director must be notified
of the incident in writing. Secondary containment, repair, or closure of the leaking
equipment, and certification of major repairs must be provided
6. Design and Installation of New Equipment. New direct transfer equipment must
meet the design and installation standards specified in today's rule as defined in §265.192
for tank systems. See §266.111 (e)(4) in today's rule referencing that section. The
standards include: specifications for assessing the design of new direct transfer equipment;
backfill requirements for new underground direct transfer equipment; tightness tests;
equipment support and protection requirements; corrosion protection; and written
certification that these requirements have been met
7. Closure. Today's rule applies by reference the closure requirements for direct
transfer equipment provided by §265.197 (except paragraphs (c)(2) through (c)(4)). See
§266.11 l(e)(6). That section requires the removal or decontamination of waste residues,
system components, and contaminated soils, structures, and equipment
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Applicability of the Bevill Exclusion to Combustion Residues When
Burning Hazardous Waste
Under the Agency's existing regulations, wastes that are derived from the treatment
of listed hazardous wastes are also considered to be hazardous unless and until they are
delisted (see 40 CFR 261.3(c)(2) and (d)(2)). The combustion or processing of hazardous
waste in a device that uses elevated temperatures as the primary means to change the
chemical, physical, or biological character or composition of the hazardous waste, is a type
of treatment no matter what type of device is used in the process, or for what purpose the
waste is burned or processed. Accordingly, under the Agency's existing rules, residues
from thermal combustion (or processing) of listed hazardous wastes remain the listed
hazardous wastes until they are delisted.
When the device burning hazardous waste is (1) a boiler burning primarily coal or
other fossil fuels, (2) an industrial furnace processing primarily ores or minerals, or (3) a
cement loin processing primarily raw materials, the applicability of the Bevill exclusion
must be considered (see RCRA Section 3001(b)(3)(A)(i-iii)). The Bevill exclusion refers
to residues resulting from burning or processing certain materials whereby the residues are
not considered to be hazardous waste at this time because they require special study to
determine whether they should be regulated under Subtitle C.
To determine whether the Bevill exclusion continues to apply when the devices
described above burn or process hazardous waste, today's final rule promulgates the case-
by-case determination involving a two-part test as discussed in the October 1989
supplement to the proposed rule. See §266.112. Under this test, owners and operators
must determine on a site-specific basis whether the co-combustion of hazardous waste has
significantly affected the character of the residue. The residue is considered to be
significantly affected if both: (1) concentrations of toxic (Appendix Vm, Part 261)
compounds in the waste-derived residue are significantly higher than in normal (i.e.,
without burning/processing hazardous waste) residue; and (2) toxic compounds are present
in the waste-derived residue at levels that could pose significant risk to human health. If
the case-by-case determination demonstrates that the residue has been significantly affected
(or if the owner or operator does not obtain data and information adequate to support a
demonstration that the residue has not been significantly affected), such derived-from
residues are subject to regulation as hazardous waste because the residues are no longer the
type of material Congress commanded the Agency to study before regulation. Such
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residues are no longer deemed to be from processing ores or minerals, burning fossil fuels,
or making cement Rather, they are from treating hazardous waste.
The following sections discuss the basis for applying the Bevill exclusion to
derived-from residues, the evolution of the Agency's interpretations on the applicability of
the Bevill exclusion to waste-derived residues, and how today's case-by-case determination
works.
A. Basis for Applying the Bevill Exclusion to Derived-Prom Residues
A number of commenters questioned whether the Agency has the legal authority to
determine that some residues from coprocessing hazardous waste with Bevill raw materials
could remain excluded under the Bevill amendment pending completion of the section 8002
studies. Because the Agency's previous determination of this question (50 FR 49190
(Nov. 29,1985)) could have been more fully explained, the Agency has decided to reopen
the question in this rule and to respond to the public comments.
The Agency's consistent position on this issue is that so long as the processing of
hazardous waste does not significantly affect the character of the waste residues as high
volume/low hazard, then those wastes can remain excluded under the Bevill amendment.
Put another way, the wastes can potentially remain the type of material that Congress told
the Agency to study before imposing subtitle C regulation.
Instead of focusing on the question of whether coprocessing hazardous waste
affects the composition of the residues from a Bevill device, some commenters would have
it that the mixture and derived-from rules apply to the residues, so that the residues are
subject to subtitle C (assuming listed wastes are coprocessed) regardless of the actual effect
of burning hazardous waste. At the least, the statute does not compel this result In the
case of utility boilers burning fossil fuels, the statute states explicitly that wastes "generated
primarily from the combustion of coal or other fossil fuels" is to be excluded. See section
3001(b)(3)(A)(i). Thus, some type of co-combustion is expressly authorized. With
respect to the two remaining categories of Bevill waste (wastes from processing ores and
minerals and cement kiln dust), the Bevill amendment (section 3001(b)(3)(A)) does not use
the term "primarily", but does not expressly address the question of whether the exemption
applies when the residues are produced in part from burning hazardous waste. Thus, read
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literally, dust from a cement kiln that bums hazardous waste along with normal raw
materials could be termed "cement kiln dust".84
If there were doubt on this point, the Agency is convinced that it is dispelled by the
1984 amendments. Sections 3004(q)(l) and 3010(a) both state explicitly that "(nothing in
this subsection shall be construed to affect or impair the provisions of section 3001(b)(3)"
(the Bevill amendment). This language would be meaningless unless it allowed some
residues from Bevill devices burning hazardous wastes (specifically hazardous waste fuels)
to remain within the scope of the Bevill amendment Although commenters argued, based
on passages from the legislative history, that the provision should not be given this natural
meaning, the Agency does not find the argument persuasive. Rather, the legislative history
appears to state that Bevill devices burning hazardous waste fuels will be subject to the
emission standards developed pursuant to section 3004(q). See H . Rep. No. 198, 98th
Cong. 1st Sess. 41; S. Rep. No. 284, 98th Cong. 1st Sess. 37. Today's rules accomplish
that result
At the same time, the Agency is concerned about reading the Bevill amendment in a
manner that gives it undue scope, such as by allowing Bevill devices to serve as a dumping
ground for other hazardous wastes. We do not view the interpretation adopted today as
allowing the exemption to have undue scope. In the first place, emissions from the Bevill
device itself are regulated. Second, the facility becomes subject to the facility-wide
corrective action provisions of sections 3008(h) and 3004(u) by virtue of regulation of the
combustion activity. Thus, potential problems relating to mismanagement of waste
residues must be evaluated and addressed no later than during the permitting process.
Most importantly, the Agency believes that the reading adopted strikes a reasonable
balance between the terms of the Bevill amendment and other provisions and regulations
relating to hazardous waste management A reading that would disqualify residues from
the Bevill amendment if any hazardous waste is burned in the device would exalt form over
substance by barring from Bevill eligibility a residue that was not discernably affected by
$4 EPA does not accept the argument that the omission of the word "primarily" in
regard to ore/mineral processing wastes and cement kiln dust means that the residues must
come exclusively from processing raw materials exclusively. This type of negative
inference is not a compelled reading of the statute, and the legislative history to the
provision in fact indicates that Congress used the term "primarily" with respect to utility
wastes to overrule a 1978 EPA proposed regulation on the scope of utility wastes, rather
than to affect the scope of the remaining two Bevill categories. 126 Cong. Rec. 3363
(1980).
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burning hazardous waste. Given that such material could be exactly the high volume/low
hazard residue that Congress told the Agency to study before regulating, EPA does not
agree with an interpretation that automatically forecloses it from Bcvill status.85 In
addition, use of Bevill devices for combusting hazardous wastes provides needed treatment
capacity for a number of hazardous wastes, and the Agency would be reluctant to adopt an
interpretation that discouraged safe processing of hazardous waste by necessarily imposing
hazardous waste disposal costs on residues that might not be affected by the hazardous
waste combustion.
For all of these reasons, therefore, the Agency is reading the statute in a way that
does not automatically disqualify residues from coprocessing hazardous wastes in Bevill
devices from eligibility for Bevill exempt status.
B. Evolution of Interpretations
To determine whether the Bevill exclusion continues to apply when the devices
described above86 burn hazardous waste fuel, the Agency stated in 1985 (see 50 FR 49190
(Nov. 29, 1985)) that the exclusion continues to apply as long as the hazardous waste is
burned for energy recovery (i.e., not for destruction). The underlying principle for this
determination was that when hazardous waste is used as fuel, the character of the residue
would continue to be determined by the Bevill material (e.g., coal, ores or minerals, or
cement raw materials) being burned or processed. Thus, the residue should remain within
the Bevill exclusion pending special study before it could be regulated under Subtitle C.
In the May 6, 1987 proposed rule (52 FR 17012-013), the Agency suggested
refining these determinations to address residues from industrial furnaces processing ores
or minerals and that also process hazardous waste for materials recovery, and residues
from cement kilns that may process hazardous waste as an ingredient. Under that
proposal, such residues would remain within the Bevill exclusion provided that at least 50
percent of the raw material fed to the device consisted of a virgin ore, mineral, or normal
85 EPA notes that in assessing whether residues have been affected by hazardous
waste burning it is using a somewhat more rigorous test for assessing inorganic
contamination - use of the TCLP rather than the synthetic acid rain leaching procedure -
than it used in making the high volume/low hazard determination for mineral processing
wastes. 54 FR at 36630 (Sept 1,1989). The Agency views this as an additional
safeguard to assess the possible effect coprocessing of hazardous waste may have had on
the residues.
86 That is, a boiler burning primarily coal, an industrial furnace processing primarily
ores or minerals, or a cement kiln processing primarily raw materials.
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raw material. However, residues from devices burning hazardous waste for the purpose of
destruction (i.e., for neither energy nor materials recovery) would not qualify for the Bevill
exclusion.
The Agency has evaluated these interpretations of the applicability of the Bevill
exclusion to waste-derived residues in light of its stated principle that residue that results
from coburning hazardous waste and Bevill raw materials should remain within the Bevill
exclusion provided that the character of the residue is determined by the Bevill material
(i.e., the residue is not significantly affected by the hazardous waste). As discussed in the
October 1989 supplement to the proposed rule (54 FR 43733-36), the Agency does not
believe that its data base for making these interpretations is sufficient to ensure that, in
every case, the residue would not be significantly affected by the hazardous waste.
Further, the Agency has reconsidered whether the interpretation that residues generated by
the subject devices when burning waste for destruction are not within the Bevill amendment
is consistent with the stated principle. Consequently, the Agency proposed in the
supplemental notice to require case-by-case determinations of the effect of burning
hazardous waste on residuals. That case-by-case approach is promulgated in today's rule.
C. Case-By-Case Determinations
We discuss below which devices are eligible for the Bevill exclusion of residues
and how the two-part test works for determining whether combustion of the waste has
significantly affected the residue.
1. Eligible Devices. Until further studies were completed, Congress intended to
exclude from Subtitle C regulation residues from: (1) devices that bum primarily fossil
fuel; (2) industrial furnaces that process ores or minerals; and (3) cement kilns. As the
Agency reads these provisions, to be eligible for exclusion from Subtitle C regulation under
the Bevill amendment, the waste-derived residue must be generated from: (1) a boiler
burning primarily coal87; (2) an industrial furnace processing primarily ores or minerals
(otherwise, residues could not be said to come from processing ores and minerals, but
rather from processing other materials), or (3) a cement kiln processing primarily raw
87 The Agency has determined that residues from cofiring hazardous waste with oil or
gas are not excluded under the Bevill amendment because the character of the residue
would be determined by the hazardous waste. This is because oil and gas generally
produce little residue when burned and, thus, toxic constituents from the hazardous waste
can significantly affect any residue generated. See 50 FR 49190 (Nov. 29,1985). The
Agency is not reopening mis determination in today's rule.
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materials. To implement the provision that, to be eligible for the Bevill exclusion the device
must burn primarily Bevill material, EPA is requiring that a boiler must burn at least 50
percent coal, an industrial furnace must process at least 50 percent ores or minerals, and at
least 50 percent of the feed stock to a cement kiln must consist of normal raw materials.
This requirement also confirms the Agency's long-standing interpretation that the Bevill
exclusion applies only to primary facilities and not to secondary facilities such as secondary
smelters.** See §266.112(a).
2. Two-Part Test. Today's rule requires a case-by-case determination as to
whether the hazardous waste being burned or processed significantly affects the character
of the residue with respect to inorganic and organic toxic (i.e., Appendix Vffl, Part 261)
constituents. The residue is considered to be significantly affected if both: (1)
concentrations of toxic (Appendix VIII) compounds in the waste-derived residue are
significantly higher than in normal (i.e., without burning/processing hazardous waste)
residue; and (2) toxic compounds are present in the waste-derived residue at levels that
could pose significant risk to human health. Part One of the test need not be conducted if
the waste-derived residue passes Part Two of the test (i.e., if the health-based concentration
limits are not exceeded). Such a waste would still meet the high volume/low hazard Bevill
threshold.
a. Pan One - Comparison with Normal Residues. Part One of the test requires a
comparison of hazardous waste-derived residues with normal residues to determine if toxic
compounds are present at statistically significant higher levels. See §266.112((b)(l). The
toxic compounds of concern are any compound listed on Appendix Vffi, Part 261, that
may reasonably be expected to be a constituent in the hazardous waste plus the list (see
Appendix Vm to the rule) of 31 organic compounds that are common products of
incomplete combustion (PICs) from burning hazardous waste. The total concentration of
each compound of concern in the residues is to be determined.89 Analytical procedures are
provided in Test Methods far Evaluating Solid Waste. Physical/Chemical Methods (SW-
846) incorporated by reference in §260.11 (a).
88 in support of mis reading, one court has held that residues from a secondary lead
smelter are not covered by the Bevill amendment. Deo Co. v. EPA (WD. Ala. 1986).
89 We note mat Part One of the test considers the total concentration of each
compound, while Pan Two of the test considers, for metals, the concentration in an extract
generated from the Toxicity Characteristic Leachate Procedure (TCLP).
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The rule requires the use of a statistical test to compare the concentrations of toxic
constituents in samples of normal (without burning/processing hazardous waste) residues
with samples of waste-derived residues. In the statistical test, the 95th percent confidence
interval about the mean of the normal residue concentrations (using a "t" distribution) is
used to determine the upper 95th percent confidence interval about the mean. Procedures
that must be used to determine the upper 95th percent confidence interval about the mean
are prescribed in "Statistical Methodology for Bevill Residue Determinations" in Methods
Manual for Compliance with the BIF Regulation, incorporated by reference in §260.11 (a).
A minimum of ten composite samples must be obtained and analyzed to represent the
normal residue in order to effectively calculate the upper 95th percent confidence interval
about the mean. This is the concentration that the waste-derived residue may not exceed to
pass Part One of the test The waste-derived residue must be characterized by composite
samples with a composite period not to exceed 24 hours to ensure that residues are
managed properly and promptly (i.e., as exempt residues or hazardous waste) and to
provide for effective enforcement The sampling approach must be based on (and be
consistent with) representative sampling protocols described in SW-846 and must be
documented by recordkeeping.
If operating conditions change so that concentrations of toxic compounds in nonnal
residue may (would have) decrease(d), the owner and operator must re-establish the
"baseline" concentrations in nonnal residue and use the lower baseline levels for the test.
This is necessary to ensure that owners/operators do not use the most contaminated raw
materials in order to bum more hazardous waste, and then switch back to their normal raw
materials.
i
b. Part Two.— Comparison with Health-Based Limits. Part Two of the test
requires a comparison of the concentration of toxic constituents in the waste-derived
residues with health-based limits the Agency has established in Appendix VHI to the rule.
The comparison is made to determine if toxic compounds in the waste-derived residue are
present at levels higher than the health-based limits. The toxic compounds of concern are
the same as for Part One of the test - any compound listed on Appendix Vm, Part 261,
that may reasonably be expected to be a constituent in the hazardous waste plus the list (see
Appendix DC to die rule) of 31 organic compounds that are common products of incomplete
combustion (PICs) from burning hazardous waste. The total concentration of each
nonmetal compound of concern in the waste-derived residue must be compared with the
health-based limit. In addition, the concentration of each metal of concern in an extract
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from the Toxicity Characteristic Leaching Procedure (TCLP) must not exceed the health-
based limits.
The Agency does not have adequate health effects data (e.g., MCLs, RfDs, unit
risk values) to establish health-based limits for many compounds listed in Appendix VIE,
Part 261. Consequently, we have conservatively established a health-based limit for such
compounds based on the 5th lowest percentile value of the health-based values for
nonmetal compounds established in Appendix VII to the rule. That value is 0.002 mg/kg.
This is the same approach EPA used to establish a RAC for compounds where insufficient
health effects data were available to establish a RAC or RsD for the compound.
The rule requires the use of total concentrations of nonmetal compounds rather than
extract concentrations for the test of health significance because the purpose of burning
toxic nonmetal compounds in these devices should be to destroy the compounds. (Use of
total nonmetal concentrations thus serves as a partial check that combustion is being
conducted properly.) The health-based limits for the metals in Appendix Vm of the rule
are the Toxicity Characteristic (TC) limits (see §261.24) for those metals for which TC
limits have been established. To establish health-based limits for the other metals, the
Agency applied the same 100 fold dilution factor to leachate concentrations used to
establish the TC limits. The Agency has also used this same dilution factor in assessing
whether mineral processing wastes satisfy the low hazard prong of the Bevill test. See 54
FR 36630 (Sept 1,1989).
To determine if the concentrations of toxic compounds in the waste-derived
residues are higher than the health-based limits, owners and operators must obtain and
analyze composite samples of waste-derived residues with a composite period not to exceed
24 hours. The sampling approach must be based on (and be consistent with) representative
sampling protocols described in SW-846 and must be documented by recordkeeping.
D. Recordkeeping
Owners and operators must maintain for a period of three years or until the facility
is issued a permit, whichever is longer, records of sampling and analyses of residues to
support claims that the waste-derived residue retains the Bevill exclusion.
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E. Other Considerations
1. Generic Determinations, In the October 26,1989 supplement to the proposed
rule, the Agency requested data and information that it could use to support: (1) generic
determinations of levels of toxic constituents in normal (i.e., generated without
burning/processing hazardous waste) residues; and (2) generic determinations that certain
waste-derived residues are not significantly affected by burning/processing hazardous
waste, and, thus, remain excluded without the need to make the case-by-case
demonstration.
a. Normal Residues. After review of comments on the 1989 supplemental notice,
the Agency concluded that it is not practicable to establish generic concentrations of toxic
constituents in normal residues. Commenters noted that there were so many site-specific
variables that affect the concentration of toxic constituents in normal residues that this
approach was not workable. Variables include the type of industrial furnace, type of fuels
burned, and type and source of raw materials used by industrial furnaces. The Agency
initially considered establishing generic concentration levels in normal residues to avoid
giving an advantage to facilities that use fuels or raw materials with high (i.e., higher than
normal for the industry) levels of toxic constituents. Normal residues from such facilities
would have high levels of toxic constituents. Thus, waste-derived residues from such
facilities could also have high levels of toxic constituents. Consequently, such facilities
could burn/process hazardous waste with high levels of toxic constituents without losing
the Bevill exclusion of residues. We note that enforcement officials will give priority
consideration to those facilities whose residues fail Part 2 (health-based limits) of the test to
determine Bevill applicability and rely on Part 1 (comparison with normal residues) to
retain the exclusion. Owners and operators must be able to support, at any time, that the
nonhazardous waste feedstreams being fed into the device when hazardous waste is fired
are the same (or would not decrease the concentrations of toxic constituents in residues) as
those fired when the concentrations of toxic constituents in normal residues were
determined. If the concentrations of toxic constituents in nonhazardous feedstreams
decrease significantly from those concentrations when the normal residue was generated for
purposes of establishing normal concentrations of toxic constituents (or if design or
operating conditions change such that levels of toxic constituents in normal residue could
decrease significantly), then the owner/operator must establish new, lower, concentrations
for normal residue.
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b. Excluded Residues. The Agency also concluded that it is not practicable to
make generic determinations that certain waste-derived residues are not significantly
affected by burning or processing of hazardous waste and, so, remain excluded. This
approach is not workable given that the exclusion would have to be conditioned on a
number of factors including: (1) the composition, feed rate, and method of feeding the
hazardous waste; (2) the type of device; (3) the composition, feed rate, and method of
feeding any other fuels; and (3) the composition, feed rate, and method of feeding any raw
materials. The data base to support such determinations is not available. Moreover, any
such generic exclusion that is necessarily conditioned on so many factors would be of little
practical use to the regulated community given the variability of normal operations.
2. Burning for Destruction, The case-by-case approach to determine the effect of
coburning on residues from Bevill devices focuses on the residues that are actually
generated rather than on the purpose for which the hazardous waste is burned. Thus,
residues generated from burning hazardous waste in boilers and industrial furnaces for the
purpose of destruction90 are eligible to retain the Bevill exclusion. The Agency's historic
approach to the issue of cogenerated residues has been to focus on the character of the
residues to ascertain what determines their character - the Bevill material or the hazardous
waste being burned/processed (see 50 FR 49190 (November 29,1987)). The statute itself
does not directly specify that the purpose of the burning is a relevant criterion, but instead
states that certain types of waste are excluded from Subtitle C regulation pending
completion of required special studies. Since the Bevill devices would still be engaged in
the Bevill activity, and composition of the residues would potentially be unaffected, the
Agency sees no absolute bar to allowing Bevill status for such residues.
90 i^. example, wastes with low heating value that are not burned for materials
recovery or as an ingredient are burned for destruction. We note that such wastes may be
burned only by new facilities as incinerators under an operating permit or by those existing
facilities operating under interim status that also have certified compliance with the
applicable emissions standards.
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PART FOUR: MISCELLANEOUS PROVISIONS
I. Regulation of Carbon Regeneration Units
A. Basis for Regulating Carbon Regenerating Units as Thermal Treatment Units
In today's rule, EPA is clarifying the regulatory status of carbon regeneration91
units. Since 1980, controlled flame (direct flame) carbon regeneration units which destroy
organic contaminants adsorbed onto activated carbon have met the definition of incinerator
and were subject to regulation as such, while carbon regeneration nonflame thermal units
were treated as exempt reclamation units. Today's rule defines carbon regeneration unit
and incinerator (see §260.10) to ensure that both direct flame and nonflame thermal carbon
regeneration units are regulated as thermal treatment units under the interim status standards
of Part 265, Subpart P, and the permit standards of Part 264, Subpan X.
One commenter expressed concern that the thermal treatment standards of Subpart
X were vague. EPA disagrees and points out that Subpart X, Part 264 covers
miscellaneous hazardous waste management units that do not or may not fit the description
of any of the units covered by other Part 264 regulations. Without Subpart X, these
unregulated units could only operate as interim status facilities and could not be fully
permitted, thereby preventing the construction of new units or some expansions of existing
units. EPA recognized that some types of new units that were not previously allowed to be
constructed could reduce risks to human health and the environment from the management
of hazardous waste. Promulgation of Subpart X generic permitting standards was intended
to allow such construction and flexibility for technical development and innovation and to
cover diverse technologies and units. The Subpart X standards specify that health and
environmental safety must be a primary concern during the management of hazardous
wastes in miscellaneous units. If the need arises, the Agency may develop specific
technology standards in the future (see 52 FR 46964, December 10, 1987). Although
several commcnters supported the application of Part 264, Subpan O incinerator standards
to direct flame and nonflame devices, EPA has decided against this since demonstration of
confonnance with the ORE standards (and the proposed CO/THC standards) may not be
achievable or warranted for carbon regeneration units considering the relatively low levels
of toxic organic compounds adsorbed onto the activated carbon.
The term "regeneration" includes reactivation of used carbon for reuse.
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B. Definition of Carbon Regeneration Unit and Revised Definition of Incinerator
Several commenters requested that EPA consider revising the definition of a carbon
regeneration unit so that certain units used for air emissions control, wet oxidation, and
general recycling, would not be regulated. Activated carbon units used as air emission
control devices of gaseous industrial process emissions will not necessarily be regulated
because trapped organics in such columns are not hazardous wastes because the gas
originally being treated is not a solid waste (it is an uncontained gas92), and therefore any
condensed organics do not derive from treatment of a hazardous waste. (The nongas
residues from these devices could be hazardous wastes if they are listed or if they exhibit a
characteristic, however.) However, regeneration or reactivation of carbon used to control
air emissions from hazardous waste treatment, storage, or disposal facilities (e.g., under 40
CFR 265 and 265, Subpart H, June 21, 1990, 55 FR 25454) is subject to regulation as a
RCRA thermal treatment unit
We considered whether other units truly are engaged in reclamation, or whether the
regeneration of the carbon is just the concluding aspect of the waste treatment process that
commenced with the use of activated carbon to adsorb waste contaminants, which are now
destroyed in the "regeneration" process (just as rinsing out a container of hazardous waste
is a stage in the storage process and does not constitute recycling of the container).
Irrespective of whether these units are better classified as waste treatment or recycling units
(or whether the units are flame or nonflame devices), we are concerned, as indicated above,
that emissions from the regeneration process can pose a serious hazard to public health if
not properly controlled, and therefore are clarifying today that they are regulated as thermal
treatment units.
We note that this revision also applies to those carbon regeneration units that, while
in active service treating wastewater, meet the definition of wastewater treatment units in
§260.10. Such units are exempt from RCRA permitting standards while treating
wastewater. However, these units are not exempt from RCRA regulation when they are
being regenerated because they are not treating wastewater during the regeneration process.
Rather, the activated carbon columns themselves are being treated thermally. The thermal
regeneration unit is subject to Part 265, Subpart P (existing units) or Part 264, Subpart X
(new units).
92 See 47 FR at 27530 (June 30,1982) and 54 FR at 50973 (Dec. 11,1989).
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C. Units in Existence on the Effective Date of the Rule are Eligible for Interim Status
Although certain carbon regeneration units may technically have met either the 1980
or 1985 definitions of incinerator, the Agency believes that there has been legitimate doubt
as to these units' regulatory status (which is why the Agency undertook this rulemaking to
clarify the status). The units might potentially have been classified as incinerators, thermal
treatment units, or perhaps exempt recycling units. It would also have been confusing to
interpret the rules in a manner that carbon regeneration units were not all regulated in the
same way, given that there functions and activities are roughly identical whether or not the
units are direct-fired. In fact, the most natural classification of these units, and the one the
Agency intended, is as thermal treatment units. (EPA does not believe that these are
recycling units, but rather that regeneration is a continuation of the waste treatment process,
that process consisting of removal of pollutants by adsorption followed by their
destruction. Nor does the Agency believe that incinerator standards make technical sense
for these devices, as noted above.) In addition, few if any of these units have actually been
regulated as incinerators in practice.
For these reasons, EPA is finding pursuant to §270.10(e)(2) that there was
substantial confusion as to which owners or operators of carbon regeneration units were
required to submit a Part A application and that this confusion is attributable to ambiguities
in the subtitle C rules. Accordingly, such owners and operators may submit Part A
applications by the effective date of today's regulations and be eligible for interim status
under Part 265, Subpart P (assuming they meet remaining requirements for interim status
eligibility, and the facility is not already subject to interim status for other units).
IL Sludge Dryers
In today's rule, the Agency is clarifying the regulatory status of sludge dryers. In
particular, the rule adds a definition of "sludge dryer" to §260.10 and amends the definition
of "incinerator" in §260.10 to specifically exclude sludge dryers.
On November 17, 1980 (45 FR 76074), EPA suspended the applicability of the
RCRA permitting requirements (40 CFR Pan 122, which is now codified as part 270) and
hazardous waste management facility standards (40 CFR Parts 264 and 265) to owners and
operators of devices meeting the definition of "wastewater treatment unit" in 40 CFR
260.10 and 270.2.
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Since promulgation of this wastewater treatment unit exclusion from RCRA
permitting requirements, the Agency has received numerous requests to determine if certain
types of units satisfy the definition of "wastewater treatment unit" and, therefore, would
not require a RCRA permit. Many of these requests have concerned the regulatory status
of thermal treatment units, particularly sludge dryers. Commenters have also requested
clarification of the regulatory status of sludges from thermal treatment units. Most of the
requests have been from owners and manufacturers of sludge dryers. The Agency believes
that approximately 40 sludge dryers are currently being used in the metal finishing industry
to dehydrate metal hydroxide sludges (EPA Hazardous Waste F006) generated in the
treatment of wastewater.
In response to these inquiries, EPA distributed policy memoranda to the Regional
offices explaining that a sludge dryer is included within the scope of the wastewater
treatment tank exclusion, provided that it meets the definition of "wastewater treatment
unit." (See OSWER Policy Directives 9503.52-1 A and 9503.51-1 A, available upon
request from the RCRA Hotline.) In addition, with respect to the status of the sludges
themselves, they are hazardous waste if identified or listed (including by application of the
mixture and derived-from rules) and are subject to regulation when removed from the
tanks.
Despite the original November 17, 1980 preamble discussion and the policy
clarification, the regulatory status of sludge dryers has continued to be unclear. One reason
for the confusion is because it is not clear whether a sludge dryer satisfies the third
component of the definition of wastewater treatment unit (i.e., whether it meets the
definition of a "tank" or "tank system"). The Agency has determined that sludge dryers
that are integrally equipped with feed or discharge hoppers that provide for an accumulation
of waste satisfy the definition of "tank system."93 Based on information available to EPA
at this time, it appears the most sludge dryers are so equipped. (Those sludge dryers that
are not so designed may still be considered tanks, but a case-by-case decision must be
made.) The Agency has also determined that other types of equipment not obviously
meeting the "tank" definition, such as presses, filters, sumps, and other types of
93 We note that sludge dryers that are a part of a wastewaster treatment facility that is
subject to regulation under either section 402 or 307(b) of the Clean Water Act) and that fa
not meet the definition of a tank system are subject to RCRA regulation as thermal treatment
units, just like sludge dryers that are not a part of a wastewater treatment system.
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processing equipment, are covered within the meaning of the term "tank" or "tank system"
when used in die context of this exclusion (see OSWER Policy Directive 9503.52-1 A).
Another reason that the regulatory status of sludge dryers has been the subject of
many questions may be because some sludge dryers technically meet the current definition
of an "incinerator," although EPA never intended to regulate direct-flame (or nonflame)
sludge dryers as incinerators. When EPA amended the definition of "incinerator" to use
physical design criteria rather than a primary purpose test (i.e., purpose of burning) to
define an incinerator, it did not intend to bring sludge dryers under regulatory control as
incinerators. (See SO FR 625, January 4,1985, indicating that the revised definition would
not bring large numbers of devices other than incinerators under incinerator standards.)
Under the former primary purpose definition, sludge dryers were not incinerators.
Although under die 1985 revised definition of incinerator sludge dryers could be classified
as incinerators, this was not EPA's intention. The Agency is clarifying this ambiguity by
clearly regulating all nonexempt sludge dryers (i.e., those not meeting the definition of
"wastewater treatment unit" under today's rule, as discussed below) under the interim
status standards of Part 265, Subpart P ("Thermal Treatment"), and the permit standards of
Part 264, Subpart X ("Miscellaneous Units"). See 55 FR 17866 (April 27, 1990) for
details. Given that such units managing hazardous waste always were subject to some type
of regulation, they are not newly eligible for interim status as a result of today's
clarification.
Even though as a result of this amendment sludge dryers are potentially subject to
regulation under Subpart P of Part 265 and Subpart X of Part 264 as other thermal
treatment units, sludge dryers that meet the § 260.10 definitions of "wastewater treatment
unit" and "tank" or "tank system" continue to be exempt wastewater treatment units under
§§264.1(g)(6) and 265.1(c)(10). The Agency believes that virtually all sludge dryers meet
the tank/tank system definition and, therefore, would be exempt when used as part of a
wastewater treatment system.
A. Jufy 1990 Proposal
To better clarify the regulatory status of sludge dryers, the Agency proposed on
July 18,1990 (55 FR 29280) a definition for "sludge dryer" to clearly distinguish them
from other thermal treatment units: Sludge dryer means any enclosed thermal treatment
device that is used to dehydrate sludge and that has a maicim^im total thermal input of 1,500
Btu/lb of sludge treated on a wet-weight basis.
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In the same notice, the Agency also proposed to amend the definition of a
wastewater treatment unit to say that sludge dryers were the only thermal treatment devices
(heretofore) meeting the definition of a wastewater treatment unit that were exempt from
regulation.
Today's rule clarifies that sludge dryers meeting the definition of a wastewater
treatment unit are exempt from regulation (by promulgating a definition of sludge dryer and
revising the definition of incinerator to exclude sludge dryers). EPA also proposed a
further clarification that other devices that use heat to treat wastewaters were not to be
considered eligible for the wastewater treatment tank exemption. The Agency indicated,
without discussion, that it had not intended for such units to be eligible for the exemption
and that the proposal was a simple clarification which reflected common understanding
within the Agency and the regulated community.
Commenters disagreed with this assessment of the regulations, and the Agency has
since studied the issue in more depth. It appears that the Agency was mistaken in its
assessment both of the current intended scope of the rule and of common understanding of
what the rule covers. With respect to such devices as evaporators and steam strippers used
in wastewater treatment, the Agency has in fact traditionally regarded such units as eligible
for the wastewater treatment exemption. See 55 FR at 25467 (June 21, 1990).
Commenters likewise indicated their understanding that current rules exempt such devices.
Given the narrow scope of the proposal, the clear indication that any change would
not be a clarification of existing rules (as indicated) but rather a potentially far-reaching
alteration, and the absence of any discussion (or study) of whether a substantive change in
regulatory status of these devices is warranted, EPA cannot go forward. Consequently, we
are not adopting any other pan of the definition of wastewater treatment unit discussed in
the 1990 notice.
B. Summary of Public Comments
EPA received comments regarding the status of sludge dryers in response to the
April 27,1990 BEF notice and the July 18,1990 notice discussed above.
Many of the Commenters to these notices supported the inclusion of sludge dryers
in the wastewater treatment unit (WWTU) definition. The Commenters, however,
requested clarification on whether units similar to sludge dryers (e.g., evaporators) would
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also be eligible for the WWTU exclusion. As discussed above, other devices using heat
that meet the definition of wastewater treatment unit would continue to be exempt from
RCRA regulation (except, of course, an incinerator, boiler, or industrial furnace burning
hazardous waste).
Eleven commenters to these proposals stated that the maximum 1,500 Btu/lb
thermal input requirement in the sludge dryer definition is too low. Citing low thermal
efficiencies (especially for indirect-fired dryers), these commenters recommended thermal
input requirements ranging from 1,700 to 3,300 Btu/lb.
After consideration of the commenters' concerns and further review of the technical
background information on the thermal input limit, the Agency is today revising the thermal
input limit to 2,500 Btu/lb wet sludge. The Agency believes that depending on the nature
of the treatment system, the thermal input to a bona fide sludge dryer (i.e., a device that is
not an incinerator) can be as high as 2,500 Btu/lb.
Several commenters also requested that EPA clarify that the total thermal input limit
was not to include the heating value of the sludge itself given that a number of sludges that
are dried have as-fired heating values of 1,000 to 2,700 Btu/lb. The Agency agrees. The
final rule explicitly excludes the heating value of the sludge from the 2,500 Btu/lb limit on
thermal input With this clarification, however, we note that the primary purpose test ~
dehydration - is the primary distinction between a sludge dryer and an incinerator. This is
because a sludge incinerator can readily meet the thermal heat input limit of 2,500 Btu/lb
when the heating value of the sludge itself is not included. However, the primary purpose
of a sludge dryer is dehydration while the primary purpose of an incinerator is volume
reduction to produce an ash residue. Thus, we believe that the definition in today's rule
adequately distinguishes between sludge dryers and incinerators. Nevertheless, it should
be noted that any person claiming the wastewater treatment unit exemption for a sludge
dryer must have documentation to support that the primary purpose of the device is to
dehydrate sludge, not to destroy sludge to produce an ash residue.
The Agency received many responses to its request for comments on whether it is
necessary to specify a minimum percent volume reduction in the definition of a sludge
dryer. Although one commenter stated that a percent volume reduction should be specified
in the sludge dryer definition, twelve of the commenters stated that such a requirement
would be arbitrary, confusing, unworkable, and costly to enforce. Two of the commenters
stated that a minimum percent weight reduction would be more appropriate. In today's
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rule, the Agency has decided not to specify a minimum percent volume (or weight)
reduction in the definition of a sludge dryer. The Agency believes that such a specification
would be difficult to support and would not be needed to distinguish sludge dryers from
incinerators.
Several commenters stated that the Agency should address emissions of volatile
organics from units such as sludge dryers. In addition, two commenters recommend a
1,000 Btu/lb thermal input limit for the device to control volatile emissions from sludge
dryers. EPA recognizes the need to address volatile emissions from sludge dryers and
intends to evaluate alternatives for regulating these units at a later date. However, because
this rule simply clarifies that EPA intended for sludge dryers that meet the definition of a
wastewater treatment unit to be exempt from the RCRA rules, it would be inappropriate to
address volatile organic emissions at this time. Nonetheless, sludge dryers that do not meet
the definition of a wastewater treatment unit (e.g., sludge dryers that are not a part of a
wastewater treatment facility that is subject to regulation under either section 402 or 307(b)
of the Clean Water Act) are subject to regulation as thermal treatment units under Subpart X
of Part 264. Under those standards, the Agency may apply controls on volatile organic
(and other) emissions as necessary to protect human health and the environment
After considering comments on the proposed sludge dryer definition, EPA is today
promulgating the following definitions:
Sludge dryer means any enclosed thermal treatment device that is used to dehydrate
sludge and that has a maximum total thermal input, excluding the heating value of the
sludge itself, of 2,500 Btu/lb of sludge treated on a wet-weight basis.
Incinerator means any enclosed device that: (1) uses controlled flame combustion
and neither meets the criteria for classification as a boiler, carbon regeneration unit, or a
sludge dryer, nor is listed as an industrial furnace; or (2) meets the definition of infrared
incinerator or plasma arc incinerator.
HI. Classification of Coke and By-Product Coal Tar
A. AISI Petition
The American Iron and Steel Institute (AISI) petitioned EPA with respect to the
practice of recycling tar decanter sludge by the following means:
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1. Applying the sludge to coal prior to or just after charging the coal into the coke
oven; and,
2. Combining the sludge with coal tar prior to its being sold.
The coke and the coal tar are often used as fuel and so have been classified as solid
wastes and hazardous wastes since they are fuels produced or otherwise containing a
hazardous waste — EPA Hazardous Waste No. K087, tar decanter sludge. See
§261.2(c)(2)(i)(B). These hazardous waste fuels have been exempt from regulation under
§ 261.6(a)(3)(vii) and 50 FR 49170-171 (November 29,1985). The AISI has requested
that EPA not classify such coke or coal tar as solid wastes. AISI submits that recycling the
decanter sludge in this manner does not significantly affect the concentration of toxic metal
and organic constituents of the coke or coal tar. EPA has indicated that waste-derived fuels
could be classified as products under such circumstances, "since the more waste-derived
fuels from a process are like products from the same process produced by virgin materials,
the less likely EPA is to classify the waste-derived fuel as a waste." 50 FR 49169 (Nov.
29, 1985). To support its request, the AISI submitted data on the metals and organic
constituents in coke, coal tar, and tar decanter sludge both with and without sludge
recycling. The data and the Agency's response are discussed below.
B. Process Description
Coke used for making iron is manufactured through the destructive distillation of
coal in ovens. A typical oven holds approximately 13 tons of coal which is heated to a
temperature of about 2000°F. Generally 20 to 100 ovens are located adjacent to each other
in a "coke oven battery." The destructive distillation or "coking" process takes about 15-18
hours. During that time period, about 20-35 percent of the coal is converted to coke oven
gas (COG) consisting of water vapor, tar, light oils, heavy hydrocarbons, and other
chemical compounds. The COG is collected from the top of the coke oven and, in most
cases, sent to the by-product plant via the coke battery main. The COG is then cleaned by
removing wastes and by-products prior to being burned, generally in the coke oven under-
firing system. As a first step in the COG cleaning process, the coal tars, consisting of
heavy hydrocarbons, are condensed from the gas. In addition, most of the paniculate that
escapes from the ovens is collected in the tar. This paniculate is believed to consist
principally of coal fines. The paniculate or solids are then removed from the tar in the tar
decanter. The coal tar is then burned as fuel or sold for use in various products such as
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roofing cement The sludge has been listed as EPA Hazardous Waste No. K087 and is
disposed of or recycled either by mixing with coal prior to being charged to the coke oven
or mixing with coal tar after physical processing (grinding) prior to sale.
Approximately 8-12 gallons of tar are produced per ton of coke. In addition,
approximately one pound of tar decanter sludge is produced for every 40 pounds of tar
produced.
C. Basis for Approval of the AISI Petition
The AISI submitted data from metal and organic chemical analyses for the coke,
coal tar, and tar decanter sludge from four plants. The Agency reviewed these results and
determined the following:
1. The recycling of tar decanter sludge by application to the coal charge does not
appear to have a significant effect on the chemical composition of coke;
2. The organic chemical composition of the tar decanter sludge does not appear to
be significantly different from the coal tar, and,
3. The concentration of one metal, lead, in the sludge appears to be slightly higher
than in the coal tar. However, the increase does not appear to be statistically
significant due to the high variability of the concentration values.
Based on the above and the fact that there is such a small quantity of sludge relative
to the quantity of coke and coal tar produced by the coking process, EPA believes that
sludge recycling, as described here, does not significantly affect the concentration of toxic
metals and organic constituents in coal tar or coke. Furthennore, coke, coal tar, and the
decanter tank tar sludge are similar materials formed in a single process and contain the
same contaminants. In this circumstance, when the coke and the decanter tank tar sludge
are very nearly the identical substance and, moreover, come from a single process, the
Agency is warranted in exercising its discretion to determine that this management of the
sludge is "not part of the waste disposal problem", and hence that the coke product is no
longer a RCRA solid waste. American Mining Congress v. EPA. 907 F. 2d 1179, 1186
(D.C. Cir. 1990). Therefore, in today's rule, EPA is classifying such coke and coal tar as
products, not wastes. As a result, the coke and coal tar will be excluded under 40 CFR
261.4 from the definition of solid waste and not subject to RCRA hazardous waste
management regulations when used as a fuel A necessary corollary to this action is also to
exclude the coking process from regulation when K087 is used as an ingredient to produce
coke. Given that K087 is for practical purposes just like other materials used to produce
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coke and comes from the same process as these other materials, it would be anomalous to
assert RCRA control over the coking process. Again, this form of sludge management -
which is the same as raw material management — does not appear to EPA to be part of the
waste disposal problem.94 (In addition, coke ovens are subject to a special regulatory
regime under amended section 112(i)(8) of the Clean Air Act, and RCRA regulation of this
particular practice could disrupt the Clean Air Act regulatory scheme. Thus, the Agency
views RCRA regulation of this practice as inappropriate in any case.)
This exemption applies only to the waste-derived fuels and only when derived from
tar decanter sludge, K087. Thus the tar decanter sludge, K087, is subject to full RCRA
regulation prior to recycling. In addition, the exemption does not extend to coke or coal tar
produced from hazardous waste (e.g., spent solvents) other than tar decanter sludge, EPA
Hazardous Waste K087.
IV. Regulation of Landfill Gas
In the November 29,1985 final rules regulating hazardous waste burned for energy
recovery, the Agency indicated that gas recovered from hazardous waste landfills that is
burned for energy recovery hi boilers or industrial furnaces is not regulated under the
waste-as-fuel rules. 50 FR 49171. EPA took this action in order to study further the extent
to which there might be jurisdictional limits on the Agency's authority under section
3004(n) of RCRA to regulate gaseous emissions from hazardous waste. Id. In today's
rule, we are amending this language slightly by indicating that the exemption also applies to
gas recovered from solid waste landfills. Therefore, gas recovered from a solid waste
landfill that exhibits a hazardous characteristic would also be exempt from today's rule
when burned for energy recovery in a boiler and industrial furnace.
In addition, the Agency solicited comment, in the May 6,1987 proposed rule, on
whether the hydrocarbon phase of the condensate removed from recovered gas should also
be exempt from regulation when burned as fuel (52 FR 17021). Two commenters
responded that the condensate contains chemical constituents similar to fossil fuels such as
kerosene or gasoline and that the handling and burning of the gas condensate poses no
significant hazard to human health. The commenters encouraged the Agency not to regulate
9* The Agency is not aware of any other hazardous wastes that are burned in coke
ovens as an ingredient that are just like other materials used to produce coke. If such
materials are used, the Agency would encourage the industry to provide the necessary
information in order to determine whether the exclusion should be modified.
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the hydrocarbon phase of the landfill gas condensate unless the hydrocarbons exhibit a
Subtitle C characteristic of a hazardous waste. However, data on condensate composition
provided by one respondent was vague and represented only one source of condensate.
Absent adequate data, EPA is not promulgating an exemption from regulation of the
hydrocarbon phase of the landfill gas condensate at this time. Facilities that wish to bum a
landfill gas condensate may consider whether they are eligible for the small quantity burner
exemption promulgated in this rule.
V. Definitions of Infrared and Plasma Arc Incinerators
Today's rule establishes definitions for infrared and plasma arc incinerators and
revises the definition of incinerator to explicitly include these devices. As discussed in the
April 27, 1990 proposed amendments to the incinerator standards (55 FR at 17869-70),
EPA is clarifying that these devices are incinerators rather than (other) thermal treatment
units subject to regulation under Subpart X of Part 264 (or Subpart P of Part 265 for
interim status units) because: (1) although these devices use nonflame sources of thermal
energy to treat waste in the primary chamber, they invariably employ controlled flame
afterburners to combust hydrocarbons driven off by the primary process (and, thus, they
meet the definition of an "incinerator" under §260.10); and (2) the incinerator standards are
workable and protective for these units.
We note that today's action merely clarifies the regulatory status of these devices. It
does not subject them to regulation for the first time; they have been regulated since 1980.
Thus, interim status is not reopened for these devices.
PART FIVE: ADMINISTRATIVE, ECONOMIC, AND ENVIRONMENTAL
IMPACTS, AND LIST OF SUBJECTS
L State Authority
A. Applicability of Rules in Authorized States
Under Section 3006 of RCRA, EPA may authorize qualified States to administer
and enforce the RCRA program within the State. (See 40 CFR Part 271 for the standards
and requirements for authorization.) Following authorization, EPA retains enforcement
authority under Sections 3008,7003 and 3013 of RCRA, although authorized States have
primary enforcement responsibility.
Prior to the Hazardous and Solid Waste Amendments of 1984 (HSWA), a State
with final authorization administered its hazardous waste program entirely in lieu of EPA
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administering the Federal program in that State. The Federal requirements no longer
applied in the authorized State, and EPA could not issue permits for any facilities in the
State which the State was authorized to permit. When new, more stringent Federal
requirements were promulgated or enacted, the State was obliged to enact equivalent
authority within specified time frames. New Federal requirements did not take effect in an
authorized State until the State adopted the requirements as State law.
In contrast, under Section 3006(g) of RCRA, 42 U.S.C. 6926(g), new
requirements and prohibitions imposed by HSWA take effect in authorized States at the
same time that they take effect in nonauthorized States. EPA is directed to carry out those
requirements and prohibitions in authorized States, including the issuance of permits, until
the State is granted authorization to do so. While States must still adopt HSWA-related
provisions as State law to achieve or retain final authorization, the HSWA applies in
authorized States in the interim.
The majority of today's rule is promulgated pursuant to Section 3004(q) of RCRA,
a provision added by HSWA. (The provisions that are not promulgated pursuant to
HSWA are the provisions for sludge dryers, carbon regeneration units, infrared
incinerators, and plasma arc incinerators.) Therefore, the Agency is adding the
requirements (except the non-HSWA provisions) to Table 1 in §271.1 (j) which identifies
the Federal program requirements that are promulgated pursuant to HSWA and that take
effect in all States, regardless of their authorization status. States may apply for either
interim or final authorization for the HSWA provisions identified in Table 1, as discussed
in the following section of this preamble.
B. Effect on State Authorizations
As noted above, EPA will implement the majority of the provisions of today's rule
in authorized States until they modify their programs to adopt these rules and the
modification is approved by EPA. Because these provisions of the rule are promulgated
pursuant to HSWA, a State submitting a program modification may apply to receive either
interim or final authorization under Section 3006(g)(2) or 3006(b), respectively, for these
provisions on the basis of requirements that are substantially equivalent or equivalent to
EPA's. The procedures and schedule for State program modifications for either interim or
final authorization are described in 40 CFR 271.21. It should be noted that all HSWA
interim authorizations will expire January 1,1993. (See §271.24(c).)
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The provisions of today's rule that are not promulgated pursuant to HSWA -
provisions for sludge dryers, carbon regeneration units, infrared incinerators, and plasma
are incinerators - are not effective in authorized States. Thus, these requirements will be
applicable only in those States that do not have final authorization. In authorized States, the
requirements will not be applicable until the State revises its program to adopt equivalent
requirements under State law.
40 CFR 271.21(e)(2) requires that States that have final authorization must modify
their programs to reflect Federal program changes, and must subsequently submit the
modifications to EPA for approval. The deadline by which the State must modify its
program to adopt the HSWA portion of today's rule is July 1,1993 if a statutory change is
not needed, or July 1, 1994 if a statutory change is needed. The deadline by which the
State must modify its program to adopt the non-HSWA portion of today's rule is July 1,
1992 if a statutory change in not needed, or July 1, 1993 if a statutory change is needed.
These deadlines can be extended in certain cases (40 CFR 271.21(e)(3)). Once EPA
approves the modification, the State requirements become Subtitle C RCRA requirements.
States with authorized RCRA programs may already have requirements similar to
those in today's rule. These State regulations have not been assessed against the Federal
regulations being promulgated today to determine whether they meet the tests for
authorization. Thus, a State is not authorized to implement these requirements in lieu of
EPA until the State program modification is approved. Of course, States with existing
standards may continue to administer and enforce their standards as a matter of State law.
In implementing the Federal program for the HSWA portion of today's rule, EPA
will work with States under cooperative agreements to minimize duplication of efforts. In
many cases, EPA will be able to defer to the States in their efforts to implement their
programs, rather than take separate actions under Federal authority.
States that submit their official applications for final authorization less than 12
months after the effective date of these standards are not required to include standards
equivalent to these standards in their application. However, the State must modify its
program by the deadlines set forth in §271.21(e). States that submit official applications
for final authorization 12 months after the effective date of these standards must include
standards equivalent to these standards in their application. 40 CFR 271.3 sets forth the
requirements a State must meet when submitting its final authorization application.
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n. Regulatory Impacts
A. Cost Analysis
1. Background. Prior to publication of the proposed regulations in May 1987, the
Agency examined the projected compliance costs, economic impacts, and risk reductions
associated with the proposed rules. This effort consisted of a detailed examination of the
pre-proposal draft as it was drafted in mid-1986 and a supplement prepared in late 198695
that examined several changes in tax policy and regulatory approach that occurred after the
first analysis was completed.96
The analyses estimated that of the approximately 1,000 BIFs identified as firing
hazardous wastes, approximately 20 percent were likely to discontinue burning hazardous
wastes because of the rules, 60 percent would burn small amounts of waste and would
qualify for the small quantity burner exemption (SQBE), and the remaining 15 percent
would obtain full permits. Because the final 15 percent of devices represent large facilities,
however, the impact on the total quantity of waste burned would be small. For example,
under the "base case" scenario, although 20 percent of the devices would discontinue
burning hazardous wastes and a number of other devices would reduce the quantity of
hazardous waste they combust in order to qualify for the SQBE, only 3 percent of the
quantity of waste combusted in the absence of regulations would be diverted to other
devices. The mid-1986 analysis estimated that under this scenario, the aggregate after-tax
cost of compliance to individual firms would be $5.2 million per year and that the before-
tax social cost would be $8.2 million per year. Under other sets of assumptions (i.e., other
scenarios), these costs were likely to be higher, but in all cases were estimated to be less
than $100 million per year.
Based on these analyses, the Agency concluded that the total social costs, impact on
market competition, and the impact on small businesses were such that the proposed
regulations did not constitute a major rule, and that a formal Regulatory Impact Analysis as
described in Executive Order 12291 was not required.
95 U.S. EPA, "Regulatory Analysis for Waste-As-Fuel Technical Standards", Draft
Report, October 1986.
96 U.S. EPA, "Effects of Recent Changes on the Estimated Costs and Benefits of the
Proposed Waste As Fuel Technical Standards", January 1987.
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A number of comments on the economic analysis were received from affected
businesses and other groups. Most of these commenters contended that the cost of
compliance had been underestimated by the Agency. Based on these comments, as well as
changes made in the final regulation compared to the proposed requirements, the Agency
has reexamined and updated the earlier analyses.
2. Revised Cost Analysis. As indicated earlier, there have been a number of
changes made in the regulations that are expected to increase the cost of compliance. In
addition, the Federal tax code was changed in late 1986, the cost of goods and services to
the economy as a whole has increased due to inflation, and the estimated cost of specific
requirements associated with the BIF regulations have been reexamined. The new analysis
focused on assessing the impact of changes in compliance costs on typical facilities, and
did not reexamine the impact of these changes on the selection of regulatory options by
individual facilities. In addition, no effort was made to explicitly examine the impact of the
final rules on the economic competitiveness of individual firms or industries, nor on the
reduction in public health risks.
The primary changes that have occurred in the regulations subsequent to proposal
have been revised requirements for continuous emission monitoring of CO and HC;
addition of the PM standard, interim status compliance procedures, and limits on emissions
of several additional metals and C\2\ and increases in recordkeeping, sampling, and
analysis requirements. The impact of these changes plus the impact of tax code changes
and inflation on the before- and after-tax costs of the BIF regulations are summarized in
Table 1. When combined with the original "base case" cost estimates prepared in 1986, the
revised cost estimate for the promulgated rule is $15.2 million per year before taxes and
$10.3 million per year after-taxes.
The increased cost for CO and HC monitoring reflects the costs for installation of a
more comprehensive CO monitoring system than was originally estimated and the cost of
installing HC monitors on an estimated 20 devices (primarily cement kilns) that will operate
under the Tier n CO and HC limits. The zero cost increase associated with the PM
emission standard reflects the expectation that BIFs complying with the metals standards
will achieve the 0.08 gr/dscf standard, and that most existing industrial furnaces and some
boilers are already subject to this emission level (or a more stringent level) as the result of
State Implementation Plans or New Source Performance Standards. As a result, no
incremental increase for compliance with the PM emission limit is projected.
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The additional costs for interim status compliance reflects the increase in annualized
costs (over a 10 year period) for preparation' of the precompliance and compliance
certification packages (including compliance testing) by approximately 150 BIFs. The
additional cost for the C\2 standard is based on the incremental cost of analysis for C\2
beyond that already required to determine HC1 emissions.
The increase in annual recordkeeping, sampling, and analysis costs reflects a
reassessment of the estimated costs in the 1986 analysis. These increased costs reflect a
before-tax increase of approximately $2.4 million for recordkeeping and $0.6 million for
sampling and analysis.
The impact of the 1986 tax code changes was to reduce the marginal tax rate
imposed on before-tax profits and, thus, has the affect of increasing the impact of
compliance costs on after-tax profits. As a result, the change in the 1986 tax code is to
increase the after-tax cost of the regulations by an estimated $0.6 million per year. The
increase in costs due to inflation reflects an estimated increase in compliance cost of 20
percent between the time of the initial analysis (based on 1985 dollars) and 1990.
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Cost Element
CO and HC Monitoring
PM Standard
Interim Status Compliance
Cl2 Standards
Recordkeeping/Sampling &
Analysis
Tax Code Changes
Inflation
TABLE 1
Before Taxes
1,930,000
0
980,000
30,000
3,050,000
0
1.640.000
7,630,000
After Taxes
1,200,000
0
590,000
20,000
1,700,000
600,000
980.000
Not
1
2
3
4
5
6
7
5,090,000
Notes:
1. Based on installing 20 CO monitors using capital and O&M costs from the revised
ICR.
2. No incremental costs because BIFs already meet standard by meeting metals limits and
existing SIP and NSPS limits.
3. Assumes all not small quantity burner BIFs submit precompliance and compliance
certification packages, 50% of BIFs submit a revised certification of precompliance,
and 75% of compliance test can be used in lieu of the trial burn to obtain an operating
permit, thus reducing the cost of the Part B permit.
4. Assumes all BIFs complying with emissions limits (and not Tier I feed rate limits)
conduct 02 testing during compliance certification and trial burn tests ($165/sample).
5. Increases waste sampling and analysis costs over those estimated at proposal for all
non-small quantity burners by $300/month. Provides an additional 16 hours per
month for all non-small quantity burners and 2 hours per month for small quantity
burners for additional recordkeeping.
6. The 1986 revisions to the Federal tax code reduced the Federal marginal tax rate
(MTR) from 48% to 34%. The 1986 analysis assumed a MTR of 50% (48% Federal
plus 2% State). The revised analysis assumes a MTR of 40% (34% Federal plus 6%
State).
7. Adjustment for 20% inflation between 1985 and 1990 ($8.2 million before tax cost
estimate in 1985 dollars, adjusted to after-tax basis assuming a marginal tax rate of
40%.
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B. Regulatory Flexibility Act
The Regulatory Flexibility Act (RFA) requires Federal regulatory agencies to
evaluate the impacts of regulations on small entities. The RFA requires an initial screening
analysis to determine whether the proposed rule will have a significant impact on a
substantial number of small businesses. As indicated at proposal (52 FR 17030), the
Agency estimates that a substantial number of small entities will not be significantly
impacted by the rule. Although the Agency estimates that changes to the rule since
proposal and re-evaluation of some cost estimates made during the initial impact analysis
will result in a higher cost to the regulated industry, the Agency continues to believe that a
substantial number of small entities will not be significantly impacted by the rule.
C. Paperwork Reduction Act
The information collection requirements in this rule have been submitted for
approval to the Office of Management and Budget (OMB) under the Paperwork Reduction
Act 44 U.S.C. 3501 el seq.
in. List of Subjects
Administrative practices and procedures, Confidential business information,
Hazardous materials transportation, Hazardous waste, Indian lands, Insurance,
Intergovernmental relations, Packaging and containers, Penalties, Recycling, Reporting
and recordkeeping requirements, Security measures, Security bonds, Water pollution
control, Water supply.
Dated: /*'?/-"JO
F. Henry Habicht, H
Deputy Administrator AND
ACTING ADMINISTRATOR
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PART 260-HAZARDOUS WASTE MANAGEMENT SYSTEM: GENERAL
I. In Part 260:
1. The authority citation for Pan 260 continues to read as follows:
Authority: 42 U.S.C. 6905, 6912(a), 6921 through 6927, 6930, 6934, 6935,
6937, 6938,6939, and 6974.
2. Section 260.10 is amended by: (1) revising the introductory sentence; (2)
revising the definition of "incinerator"; (3) revising die definition of "industrial furnace" by
revising the introductory text and redesignating paragraph (12) as (13) and by adding new
paragraph (12); and (4) adding, in alphabetical order, definitions for "carbon regeneration
unit', "infrared incinerator", "plasma arc incinerator" and "sludge dryer" to read as follows:
§ 260.10 Definitions.
When used in Parts 260 through 266 and 268 of this chapter, the following terms
have the meanings given below:
Carbon regeneration unit means any enclosed thermal treatment device used to
regenerate spent activated carbon.
Incinerator means any enclosed device that
(1) Uses controlled flame combustion and neither meets the criteria for classification
as a boiler, sludge dryer, or carbon regeneration unit, nor is listed as an industrial furnace;
or
(2) Meets the definition of infrared incinerator or plasma arc incinerator.
Industrial furnace means any of the following enclosed devices that are integral
components of manufacturing processes and that use thermal treatment to accomplish
recovery of materials or energy;
(12) Halogen acid furnaces (HAFs) for the production of acid from halogenated
hazardous waste generated by chemical production facilities where the furnace is located on
the site of a chemical production facility, tile acid product has a halogen acid content of at
least 3%, the acid product is used in a manufacturing process, and, except for hazardous
waste burned as fuel, hazardous waste fed to the furnace has a minimum halogen content of
20% as-generated.
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Infrared incinerator means any enclosed device that uses electric powered resistance
heaters as a source of radiant heat and which is not listed as an industrial furnace.
Plasma arc incinerator means any enclosed device using a high intensity electrical
discharge or arc as a source of heat and which is not listed as an industrial furnace.
Sludge dryer means any enclosed thermal treatment device that is used to dehydrate
sludge and that has a maximum total thermal input, excluding the heating value of the
sludge itself, of 2,500 Btu/lb of sludge treated on a wet-weight basis.
3. Paragraph (a) of § 260.11 is amended by adding the following references in
alphabetical order
§ 260.11 References.
(a) * * *
U.S. EPA, Guideline on Air Quality Models (Revised) (1986) and Supplement A
(1987), available from the National Technical Information Service (NTIS), 5285 Port
Royal Road, Springfield, VA 22161, (703) 487-4600. The document numbers are: PB86-
245-248 (Guideline) and PB88- 150-958 (Supplement A).
U.S. EPA, Methods Manual for Compliance with the BTF Regulations. December
1990, available from the National Technical Information Service (NTIS), 5285 Port Royal
Road, Springfield, VA 22161, (703) 487-4600. The document number is PB91-120-006.
U. S. EPA, Screening Procedures for Estimating Air Quality Impact of Stationary
. August 1988, Available from the National Technical Information Service (NTIS),
5285 Port Royal Road, Springfield, VA 22161, (703) 487-4600. The document number is
PB89- 159-396.
PART 261-IDENTIFICATION AND LISTING OF HAZARDOUS WASTE
n. In Part 261:
1. The authority citation for Pan 261 continues to read as follows:
Authority: 42 U.S.C 6905, 6912(a), 6921, 6922, and 6938.
2. Section 261.2 is amended by redesignaring paragraph (dX2) as (dX3) and adding
new paragraph (d)(2) to read as follows:
§261.2 Definition of solid waste.
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(d) * * *
(2) Secondary materials fed to a halogen-acid furnace that exhibit a characteristic of
a hazardous waste or are listed as a hazardous waste as defined in subparts C or D of this
part
3. Section 261.4 is amended by adding paragraph (a)(10) and revising paragraphs
(b)(4), the first sentence of (b)(7), and (b)(8) to read as follows:
§ 261.4 Exclusions.
(a) * * *
(10) When used as a fuel, coke and coal tar from the iron and steel industry that
contains or is produced from decanter tank tar sludge, EPA Hazardous Waste K087. The
process of producing coke and coal tar from such decanter tank tar sludge in a coke oven is
likewise excluded from regulation.
(b) * * *
(4) Fly ash waste, bottom ash waste, slag waste, and flue gas emission control
waste, generated primarily from the combustion of coal or other fossil fuels, except as
provided by §266.112 of this chapter for facilities that bum or process hazardous waste.
(7) Solid waste from the extraction, beneficiation, and processing of ores and
minerals (including coal, phosphate rock and overburden from the mining of uranium ore),
except as provided by §266.112 of mis chapter for facilities that bum or process hazardous
waste.
(8) Cement kiln dust waste, except as provided by §266.112 of this chapter for
facilities that bum or process hazardous waste.
4. Section 261.6 is amended by deleting paragraph (a)(3)(vii) and renumbering
paragraphs (a)(3Xviii) and (ix) as (aX3Xvii) and (viii) respectively.
PART 264-STANDARDS FOR OWNERS AND OPERATORS OF
HAZARDOUS WASTE TREATMENT, STORAGE, AND DISPOSAL
FACILITIES
m. In Part 264:
1. The authority citation for Part 264 continues to read as follows:
Authority: 42 U.S.C. 6905, 6912(a), 6924, and 6925.
2. § 264.112 is amended by revising paragraph (d)(l) to read as follows:
\
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§ 264.112 Closure of plan; amendment of plan.
(d) Notification of partial closure and final closure. (1) The owner or operator must
notify the Regional Administrator in writing at least 60 days prior to the date on which he
expects to begin closure of a surface impoundment, waste pile, land treatment or landfill
unit, or final closure of a facility with such a unit The owner or operator must notify the
Regional Administrator in writing at least 45 days prior to the date on which he expects to
begin final closure of a facility with only treatment or storage tanks, container storage, or
incinerator units to be closed. The owner or operator must notify the Regional
Administrator in writing at least 45 days prior to the date on which he expects to begin
partial or final closure of a boiler or industrial furnace, whichever is earlier.
3. § 264.340 is amended by revising paragraph (a) to read as follows:
§ 264.340 Applicability.
(a) The regulations of this subpart apply to owners and operators of hazardous
waste incinerators (as defined in § 260.10 of this chapter), except as § 264.1 provides
otherwise.
PART 265--INTERIM STATUS STANDARDS FOR OWNERS AND
OPERATORS OF HAZARDOUS WASTE TREATMENT, STORAGE, AND
DISPOSAL FACILITIES
IV. In Part 265:
1. The authority citation for Part 265 continues to read as follows:
Authority: 42 U.S.C. 6905, 6912(a), 6924, 6925, and 6935.
2 § 265.112 is amended by revising paragraphs (a), (d)(l), and (d)(2) to read as
follows:
§ 265.112 Closure plan; amendment of plan.
(a) Written plan. By May 19,1981, or by six months after the effective date of the
rule that first subjects a facility to provisions of this section, the owner or operator of a
hazardous waste management facility must have a written closure plan. Until final closure
is completed and certified in accordance with §265.115, a copy of the most current plan
must be furnished to the Regional Administrator upon request, including request by mail.
In addition, for facilities without approved plans, it must also be provided during site
inspections, on the day of inspection, to any officer, employee, or representative of the
Agency who is duly designated by the Administrator.
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(d) Notification of partial closure and final closure. (1) The owner or operator must
submit die closure plan to the Regional Administrator at least 180 days prior to the date on
which he expects to begin closure of the first surface impoundment, waste pile, land
treatment, or landfill unit, or final closure if it involves such a unit, whichever is earlier.
The owner or operator must submit the closure plan to the Regional Administrator at least
45 days prior to the date on which he expects to begin partial or final closure of a boiler or
industrial furnace. The owner or operator must submit the closure plan to the Regional
Administrator at least 45 days prior to the date on which he expects to begin final closure of
a facility with only tanks, container storage, or incinerator units. Owners or operators with
approved closure plans must notify the Regional Administrator in writing at least 60 days
prior to the date on which he expects to begin closure of a surface impoundment, waste
pile, landfill, or land treatment unit, or final closure of a facility involving such a unit
Owners or operators with approved closure plans must notify the Regional Administrator in
writing at least 45 days prior to the date on which he expects to begin partial or final closure
of a boiler or industrial furnace. Owners or operators with approved closure plans must
notify the Regional Administrator in writing at least 45 days prior to the date on which he
expects to begin final closure of a facility with only tanks, container storage, or incinerator
units.
(2) Except for boilers and industrial furnaces that operate under interim status as
specified by §266.103(c)(7)(i)(B) or (C), the date when he "expects to begin closure" must
be either within 30 days after the date on which any hazardous waste management unit
receives the known final volume of hazardous wastes, or, if there is a reasonable
possibility that the hazardous waste management unit will receive additional hazardous
wastes, no later than one year after the date on which the unit received the most recent
volume of hazardous waste. If the owner or operator of a hazardous waste management
unit can demonstrate to the Regional Administrator that the hazardous waste management
unit or facility has the capacity to receive additional hazardous wastes and he has taken, and
will continue to take, all steps to prevent threats to human health and the environment,
including compliance with all interim status requirements, the Regional Administrator may
approve an extension to this one-year limit For boilers and industrial furnaces that operate
under interim status as specified by § 266.103(c)(7)(i)(B) or (C), the date when he
"expects to begin closure" must be within 30 days after failure to submit a complete
certification of compliance by the applicable deadline under § 266.103(c)(7)(i)(B) or (C).
3 §265.113 is amended by revising paragraphs (a) and (b) to read as follows:
§ 265.113 Closure; time allowed for closure.
(a) Within 90 days after receiving the final volume of hazardous wastes at a
hazardous waste management unit or facility, or within 90 days after approval of the
closure plan, whichever is later, or, for a boiler or industrial furnace that does not submit a
complete certification of compliance by the applicable deadline under §266.103(cX7Xi)(B)
or (C), within 90 days after the applicable deadline, the owner or operator must treat,
remove from the unit or facility or dispose of on-site, all hazardous wastes in accordance
with the approved closure plan. The Regional Administrator may approve a longer period
if the owner or operator demonstrates that:
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(b) The owner or operator must complete partial and final closure activities in
accordance with the approved closure plan and within 180 days after receiving the final
volume of hazardous wastes at the hazardous waste management unit or facility, or 180
days after approval of the closure plan, if that is later, or, for a boiler or industrial furnace
that does not submit a complete certification of compliance by the applicable deadline under
§ 266.103(c)(7)(i)(B) or (C), within 180 days after the applicable deadline. The Regional
Administrator may approve an extension to the closure period if the owner or operator
demonstrates that:
4. § 265.340 is amended by revising paragraph (a) to read as follows:
§ 265.340 Applicability.
(a) The regulations of this subpart apply to owners and operators of hazardous
waste incinerators (as defined in § 260.10 of this chapter), except as § 265.1 provides
otherwise.
PART 266--STANDARDS FOR THE MANAGEMENT OF SPECIFIC
HAZARDOUS WASTES AND SPECIFIC TYPES OF HAZARDOUS
WASTE MANAGEMENT FACILITIES
V. In Part 266:
1. The authority citation for Pan 266 continues to read as follows:
Authority: Sees. 1006, 2002(a). 3004, and 3014 of the Solid Waste Disposal
Act, as amended by the Resource Conservation and Recovery Act of 1976, as amended (42
U.S.C. 6905, 6912(a), 6924, and 6934).
2. Subpart D is hereby removed and reserved and Subpart H is added to read as
follows:
Subpart H - Hazardous Waste Burned in Boilers and Industrial Furnaces
Sec.
§ 266.100 Applicability.
§ 266.101 Management prior to burning.
§ 266.102 Permit standards for burners.
§ 266.103 Interim status standards for burners.
§ 266.104 Standards to control organic emissions.
§ 266.105 Standards to control paniculate matter.
§ 266.106 Standards to control metals emissions.
§ 266.107 Standards to control hydrogen chloride (HC1) and chlorine gas (Cl2)
emissions.
§ 266.108 Small quantity burner exemption.
§ 266.109 Low risk waste exemption.
§ 266.110 Automatic waiver of DRE trial bum for boilers.
§ 266.111 Standards for direct transfer.
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§ 266.112 Regulation of residues.
§ 266.100 - Applicability.
(a) The regulations of this subpart apply to hazardous waste burned or processed in
a boiler or industrial furnace (as defined in §260.10 of this chapter) irrespective of the
purpose of burning or processing, except as provided by paragraphs (b), (c), and (d) of
this section. In this subpart, the term "burn" means burning for energy recovery or
destruction, or processing for materials recovery or as an ingredient The emissions
standards of §§266.104, 266.105, 266.106, and 266.107 apply to facilities operating
under interim status or under a RCRA operating permit as specified in §§266.102 and
266.103.
(b) The following hazardous wastes and facilities are not subject to regulation under
this subpart:
(1) Used oil burned for energy recovery that is also a hazardous waste solely
because it exhibits a characteristic of hazardous waste identified in Subpart C of Part 261 of
this chapter. Such used oil is subject to regulation under Subpart E of Part 266 rather than
this subpart;
(2) Gas recovered from hazardous or solid waste landfills when such gas is burned
for energy recovery.
(3) Hazardous wastes that are exempt from regulation under §§261.4 and
261.6(a)(3)(v - viii) of this chapter, and hazardous wastes that are subject to the special
requirements for conditionally exempt small quantity generators under § 261.5 of this
chapter.
(4) Coke ovens, if the only hazardous waste burned is EPA Hazardous Waste No.
K087, decanter tank tar sludge from coking operations.
(c) Owners and operators of smelting, melting, and refining furnaces (including
pyrometallurgical devices such as cupolas, sintering machines, roasters, and foundry
furnaces, but not including cement kilns, aggregate kilns, or halogen acid furnaces burning
hazardous waste) that process hazardous waste solely for metal recovery are conditionally
exempt from regulation under this subpart, except for §§266.101 and 266.112.
(1) To be exempt from §§266.102 through 266.111, an owner or operator must:
(i) Provide a one-time written notice to the Director indicating the following:
(A) The owner or operator claims exemption under this paragraph;
(B) The hazardous waste is burned solely for metal recovery consistent with the
provisions of paragraph (c)(2) of this section;
(Q The hazardous waste contains recoverable levels of metals; and
(D) The owner or operator will comply with the sampling and analysis and
recordkeeping requirements of this paragraph;
(ii) Sample and analyze the hazardous waste and other feedstocks as necessary to
comply with the requirements of this paragraph under procedures specified by Test
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Methods for Evaluating Solid Waste. Physical/Chemical Methods. SW-846, incorporated
by reference in §260.11 of this chapter, and
(iii) Maintain at die facility for at least three years records to document compliance
with die provisions of this paragraph including limits on levels of toxic organic constituents
and Btu value of the waste, and levels of recoverable metals in the hazardous waste
compared to normal nonhazardous waste feedstocks.
(2) A hazardous waste meeting either of the following criteria is not processed
solely for metal recovery:
(i) The hazardous waste has a total concentration of organic compounds listed in
Part 261, Appendix Vffl, of this chapter exceeding 500 ppm by weight, as-generated, and
so is considered to be burned for destruction; or
(ii) The hazardous waste has a heating value of 5,000 Btu/lb or more, as-generated
or as-fired into the furnace, and so is considered to be burned as fuel
(d) The standards for direct transfer operations under §266.111 apply only to
facilities subject to the permit standards of §266.102 or the interim status standards of
§266.103.
(e) The management standards for residues under §266.112 apply to any boiler or
industrial furnace burning hazardous waste.
(Approved by the Office of Management and Budget under control number )
§ 266.101 - Management prior to burning.
(a) Generators. Generators of hazardous waste that is burned in a boiler or
industrial furnace are subject to Part 262 of this chapter.
(b) Transporters. Transporters of hazardous waste that is burned in a boiler or
industrial furnace are subject to Part 263 of this chapter.
(c) Storage facilities. (1) Owners and operators of facilities that store hazardous
waste that is burned in a boiler or industrial furnace are subject to the applicable provisions
of Subpaits A through L of Pan 264, Subparts A through L of Part 265, and Part 270 of
this chapter, except as provided by paragraph (c)(2) of this section. These standards apply
to storage by the burner as well as to storage facilities operated by intermediaries
(processors, blenders, distributors, etc.) between the generator and the burner.
(2) Owners and operators of facilities that burn, in an on-site boiler or industrial
furnace exempt from regulation under the small quantity burner provisions of § 266.108,
hazardous waste that they generate are exempt from regulation under Subparts A through L
of Pan 264, Subparts A through L of Pan 265, and Part 270 of this chapter with respect to
the storage of mixtures of hazardous waste and the primary fuel to the boiler or industrial
furnace in tanks that feed the fuel mixture directly to the burner. Storage of hazardous
waste prior to mixing with the primary fuel is subject to regulation as prescribed in
paragraph (c)(l) of mis section.
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§ 266.102 - Permit standards for burners.
(a) Applicability. (1) General. Owners and operators of boilers and industrial
furnaces burning hazardous waste and not operating under interim status must comply with
the requirements of this section and §§ 270.22 and 270.66 of this chapter, unless exempt
under the small quantity burner exemption of § 266.108.
(2) Applicability of Part 264 standards. Owners and operators of boilers and
industrial furnaces that burn hazardous waste are subject to the following provisions of Part
264 of this chapter, except as provided otherwise by this subpart:
(i) In Subpart A (General), § 264.4;
(ii) In Subpart B (General facility standards), §§ 264.11-264.18;
(iii) In Subpart C (Preparedness and prevention), §§ 264.31-264.37;
(iv) In Subpart D (Contingency plan and emergency procedures), §§ 264.51-
264.56;
(v) In Subpart E (Manifest system, recordkeeping, and reporting), the applicable
provisions of §§ 264.71-264.77;
(vi) In Subpart F (Corrective Action), §§ 264.90 and 264.101;
(vii) In Subpart G (Closure and post-closure), §§ 264.111 - 264.115;
(viii) In Subpart H (Financial requirements), §§ 264.141, 264.142, 264.143, and
264.147-264.151, except that States and the Federal government are exempt from the
requirements of Subpart H; and
(ix) Subpart BB (Air emission standards for equipment leaks), except
§264.1050(a).
(b) Hazardous waste analysis. (1) The owner or operator must provide an analysis
of the hazardous waste that quantifies the concentration of any constituent identified in
Appendix Vm of Part 261 of this chapter that may reasonably be expected to be in the
waste. Such constituents must be identified and quantified if present, at levels detectable
by analytical procedures prescribed by Test Methods for the Evaluation of Solid Waste.
Physical/ Chemical Methods (incorporated by reference, see §260.11 of this chapter). The
Appendix VIH, Part 261 constituents excluded from this analysis must be identified and the
basis for their exclusion explained. This analysis will be used to provide all information
required by this subpart and § 270.22 and § 270.66 of this chapter and to enable the permit
writer to prescribe such permit conditions as necessary to protect human health and the
environment Such analysis must be included as a portion of the Part B permit application,
or, for facilities operating under the interim status standards of this subpart, as a portion of
the trial bum plan that may be submitted before the Pan B application under provisions of
§270.66(g) of this chapter as well as any other analysis required by the permit authority in
preparing die permit Owners and operators of boilers and industrial furnaces not operating
under the interim status standards must provide the information required by §§270.22 or
270.66(c) of this chapter in the Part B application to the greatest extent possible.
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(2) Throughout normal operation, the owner or operator must conduct sampling
and analysis as necessary to ensure that the hazardous waste, other fuels, and industrial
furnace feedstocks.fired into the boiler or industrial furnace are within the physical and
chemical composition limits specified in die permit
(c) Emissions standards. Owners and operators must comply with emissions
standards provided by §§ 266.104 through 266.107.
(d) Permits. (1) The owner or operator may burn only hazardous wastes specified
in the facility permit and only under the operating conditions specified under paragraph (e)
of this section, except in approved trial bums under the conditions specified in § 270.66 of
this chapter.
(2) Hazardous wastes not specified in the permit may not be burned until operating
conditions have been specified under a new permit or permit modification, as applicable.
Operating requirements for new wastes may be based on either trial burn results or
alternative data included with Part B of a permit application under §270.22 of this chapter.
(3) Boilers and industrial furnaces operating under the interim status standards of
§266.103 are permitted under procedures provided by §270.66(g) of this chapter.
(4) A permit for a new boiler or industrial furnace (those boilers and industrial
furnaces not operating under the interim status standards) must establish appropriate
conditions for each of the applicable requirements of this section, including but not limited
to allowable hazardous waste firing rates and operating conditions necessary to meet the
requirements of paragraph (e) of this section, in order to comply with the following
standards:
(i) For the period beginning with initial introduction of hazardous waste and ending
with initiation of the trial bum, and only for the minimum time required to bring die device
to a point of operational readiness to conduct a trial bum, not to exceed a duration of 720
hours operating time when burning hazardous waste, the operating requirements must be
those most likely to ensure compliance with the emission standards of §§ 266.104 through
266.107, based on the Director's engineering judgment If the applicant is seeking a
waiver from a trial burn to demonstrate cpnformance with a particular emission standard,
the operating requirements during this initial period of operation shall include those
specified by the applicable provisions of §266.104, §266.105, §266.106, or §266.107.
The Director may extend the duration of this period for up to 720 additional hours when
good cause for the extension is demonstrated by the applicant
(ii) For the duration of the trial burn, the operating requirements must be sufficient
to demonstrate compliance with the emissions standards of §§ 266.104 through 266.107
and must be in accordance with die approved trial bum plan;
(iii) For the period immediately following completion of the trial bum, and only for
the minimum period sufficient to allow sample analysis, data computation, submission of
the trial bum results by the applicant, review of the trial bum results and modification of the
facility permit by the Director to reflect the trial burn results, the operating requirements
must be those most likely to ensure compliance with die emission standards of §§ 266.104
through 266.107 based on the Director's engineering judgment
(D) For the remaining duration of the permit, the operating requirements must be
those demonstrated in a trial bum or by alternative data specified in § 270.22 of this
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chapter, as sufficient to ensure compliance with the emissions standards of §§ 266.104
through 266.107.
(e) Operating requirements. (1) General. A boiler or industrial furnace burning
hazardous waste must be operated in accordance with the operating requirements specified
in the permit at all times when there is hazardous waste in the unit
(2) Requirements to ensure compliance with the organic emissions standards, (i)
DRE standard. Operating conditions will be specified either on a case-by-case basis for
each hazardous waste burned as those demonstrated (in a trial bum or by alternative data as
specified in § 270.22) to be sufficient to comply with the destruction and removal
efficiency (DRE) performance standard of § 266.104(a) or as those special operating
requirements provided by §266.104(a)(4) for the waiver of the DRE trial bum. When the
DRE trial burn is not waived under §266.104(a)(4), each set of operating requirements will
specify the composition of the hazardous waste (including acceptable variations in the
physical and chemical properties of the hazardous waste which will not affect compliance
with the DRE performance standard) to which the operating requirements apply. For each
such hazardous waste, the permit will specify acceptable operating limits including, but not
limited to, the following conditions as appropriate:
(A) Feed rate of hazardous waste and other fuels measured and specified as
prescribed in paragraph (e)(6) of this section;
(B) Minimum and maximum device production rate when producing normal
product expressed in appropriate units, measured and specified as prescribed in paragraph
(e)(6) of this section;
(C) Appropriate controls of the hazardous waste firing system;
(D) Allowable variation in boiler and industrial furnace system design or operating
procedures;
(E) Minimum combustion gas temperature measured at a location indicative of
combustion chamber temperature, measured and specified as prescribed in paragraph (e)(6)
of this section;
(F) An appropriate indicator of combustion gas velocity, measured and specified as
prescribed in paragraph (e)(6) of this section, unless documentation is provided under
§270.66 of this chapter demonstrating adequate combustion gas residence time; and
(G) Such other operating requirements as are necessary to ensure that the DRE
performance standard of § 266.104(a) is met
(ii) Carbon monoxide and hydrocarbon standards. The permit must incorporate a
carbon monoxide (CO) limit and, as appropriate, a hydrocarbon (HC) limit as provided by
paragraphs (b), (c), (d), (e) and (f) of §266.104. The permit limits will be specified as
follows:
(A) When complying with the CO standard of §266.104(b)(l), the permit limit is
lOOppmv;
(B) When complying with the alternative CO standard under §266.104(c), the
permit limit for CO is based on the trial bum and is established as the average over all valid
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runs of the highest hourly rolling average CO level of each run, and the permit limit for HC
is 20 ppmv (as defined in 5266.104(c)(l)), except as provided in §266.104(0.
(C) When complying with the alternative HC limit for industrial furnaces under
§266.104(f), the permit limit for HC and CO is the baseline level when hazardous waste is
not burned as specified by that paragraph.
(tii) Start-up and shut-down. During start-up and shut-down of the boiler or
industrial furnace, hazardous waste (except waste fed solely as an ingredient under the Tier
I (or adjusted Tier I) feed rate screening limits for metals and chloride/chlorine, and except
low risk waste exempt from the trial burn requirements under §§266.104(a)(5), 266.105,
266.106, and 266.107) must not be fed into the device unless die device is operating within
the conditions of operation specified in me permit
(3) Requirements to ensure conformance with the paniculate standard, (i) Except as
provided in paragraphs (e)(3)(ii) and (iii) of this section, the permit shall specify the
following operating requirements to ensure conformance with the paniculate standard
specified in §266.105:
(A) Total ash feed rate to the device from hazardous waste, other fuels, and
industrial furnace feedstocks, measured and specified as prescribed in paragraph (e)(6) of
this section;
(B) Maximum device production rant when producing normal product expressed in
appropriate units, and measured and specified as prescribed in paragraph (e)(6) of this
section;
(C) Appropriate controls on operation and maintenance of the hazardous waste
firing system and any air pollution control system;
(D) Allowable variation in boiler and industrial furnace system design including any
air pollution control system or operating procedures; and
(E) Such other operating requirements as are necessary to ensure that the paniculate
standard in § 266.11 l(b) is met
(ii) Permit conditions to ensure conformance with the paniculate matter standard
shall not be provided for facilities exempt from the paniculate matter standard under
§266.105(b);
(iii) For cement loins and light-weight aggregate kilns, permit conditions to ensure
compliance with the paniculate standard shall not limit the ash content of hazardous waste
or other feed materials.
(4) Requirements to ensure conformance with the metals emissions standard, (i)
For conformance with the Tier I (or adjusted Tier I) metals feed rate screening limits of
paragraphs (b) or (e) of § 266.106, the permit shall specify the following operating
requirements:
(A) Total feed rate of each metal in hazardous waste, other fuels, and industrial
furnace feedstocks measured and specified under provisions of paragraph (e)(6) of this
section;
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(B) Total feed rate of hazardous waste measured and specified as prescribed in
paragraph (e)(6) of this section;
(Q A sampling and metals analysis program for the hazardous waste, other fuels,
and industrial furnace feedstocks;
(ii) For conformance with the Tier n metals emission rate screening limits under
§266.106(c) and the Tier ffl metals controls under § 266.106(d), the permit shall specify
the following operating requirements:
(A) Maximum emission rate for each metal specified as the average emission rate
during the trial bum;
(B) Feed rate of total hazardous waste and pumpable hazardous waste, each
measured and specified as prescribed in paragraph (e)(6)(i) of this section;
(C) Feed rate of each metal in the following feedstreams, measured and specified as
prescribed in paragraphs (e)(6) of this section:
(7) Total feed streams;
(2) Total hazardous waste feed; and
(5) Total pumpable hazardous waste feed;
(D) Total feed rate of chlorine and chloride in total feed streams measured and
specified as prescribed in paragraph (e)(6) of this section;
(£) Maximum combustion gas temperature measured at a location indicative of
combustion chamber temperature, and measured and specified as prescribed in paragraph
(e)(6) of this section;
(F) Maximum flue gas temperature at the inlet to the paniculate matter air pollution
control system measured and specified as prescribed in paragraph (e)(6) of this section;
(G) Maximum device production rate when producing normal product expressed in
appropriate units and measured and specified as prescribed in paragraph (e)(6) of this
section;
(H) Appropriate controls on operation and maintenance of the hazardous waste
firing system and any air pollution control system;
(I) Allowable variation in boiler and industrial furnace system design including any
air pollution control system or operating procedures; and
(J) Such other operating requirements as are necessary to ensure that the metals
standards under §§ 266.106(c) or 266.106(d) are met
(iii) For conformance with an alternative implementation approach approved by the
Director under §266.106(0, the permit will specify the following operating requirements:
(A) Maximum emission rate for each metal specified as the average emission rate
during the trial bum;
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(B) Feed rate of total hazardous waste and pumpablc hazardous waste, each
measured and specified as prescribed in paragraph (e)(6)(i) of this section;
(Q Feed rate of each metal in the following feedstreams, measured and specified as
prescribed in paragraph (e)(6) of this section:
(7) Total hazardous waste feed; and
(2) Total pumpable hazardous waste feed;
(D) Total feed rate of chlorine and chloride in total feed streams measured and
specified as prescribed in paragraph (e)(6) of this section;
(E) Maximum combustion gas temperature measured at a location indicative of
combustion chamber temperature, and measured and specified as prescribed in paragraph
(e)(6) of this section;
(F) Maximum flue gas temperature at the inlet to the paniculate matter air pollution
control system measured and specified as prescribed in paragraph (e)(6) of this section;
(G) Maximum device production rate when producing normal product expressed in
appropriate units and measured and specified as prescribed in paragraph (e)(6) of this
section;
(H) Appropriate controls on operation and maintenance of the hazardous waste
firing system arid any air pollution control system;
(I) Allowable variation in boiler and industrial furnace system design including any
air pollution control system or operating procedures; and
(J) Such other operating requirements as are necessary to ensure that the metals
standards under §§ 266.106(c) or 266.106(d) are met
(5) Requirements to ensure conformance with the hydrogen chloride and chlorine
gas standards, (i) For conformance with the Tier I total chloride and chlorine feed rate
screening limits of § 266.107(b)(l), the permit will specify the following operating
requirements:
(A) Feed rate of total chloride and chlorine in hazardous waste, other fuels, and
industrial furnace feedstocks measured and specified as prescribed in paragraph (e)(6) of
this section;
(B) Feed rate of total hazardous waste measured and specified as prescribed in
paragraph (e)(6) of this section;
(C) A sampling and analysis program for total chloride and chlorine for the
hazardous waste, other fuels, and industrial furnace feedstocks;
(ii) For conformance with the Tier n HQ and Cl2 emission rate screening limits
under §266.107(bX2) and the Tier m HQ and Cl2 controls under § 266.107(c), the permit
will specify the following operating requirements:
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(A) Maximum emission rate for HQ and for Cl2 specified as the average emission
rate during the trial bum;
(B) Feed rate of total hazardous waste measured and specified as prescribed in
paragraph (e)(6) of this section;
(C) Total feed rate of chlorine and chloride in total feed streams, measured and
specified as prescribed in paragraph (e)(6) of this section;
(D) Maximum device production rate when producing normal product expressed in
appropriate units, measured and specified as prescribed in paragraph (e)(6) of this section;
(E) Appropriate controls on operation and maintenance of the hazardous waste
firing system and any air pollution control system;
(F) Allowable variation in boiler and industrial furnace system design including any
air pollution control system or operating procedures; and
(G) Such other operating requirements as are necessary to ensure that the HQ and
Cl2 standards under §266.107(b)(2) or (c) are met
(6) Measuring parameters and establishing limits based on trial burn data, (i)
General requirements. As specified in paragraphs (e)(2) through (e)(5) of this section,
each operating parameter shall be measured, and permit limits on the parameter shall be
established, according to either of the following procedures:
(A) Instantaneous limits. A parameter may be measured and recorded on an
instantaneous basis (i.e., the value that occurs at any time) and the permit limit specified as
the time-weighted average during all valid runs of the trial burn; or
(B) Hourly rotting average. (7) The limit for a parameter may be established and
continuously monitored on an hourly rolling average basis defined as follows:
(0 A continuous monitor is one which continuously samples the regulated
parameter without interruption, and evaluates the detector response at least once each 15
seconds, and computes and records the average value at least every 60 seconds.
(it) An hourly rolling average is the arithmetic mean of the 60 most recent 1-minute
average values recorded by the continuous monitoring system.
(2) The permit limit for the parameter shall be established based on trial bum data as
the average over all valid test runs of the highest hourly rolling average value for each run.
(ii) Rolling average limits for carcinogenic metals and lead. Feed rate limits for the
carcinogenic metals (i.e., arsenic, beryllium, cadmium and chromium) and lead may be
established either on an hourly rolling average basis as prescribed by paragraph (e)(6)(i) of
this section or on (up to) a 24 hour rolling average basis. If the owner or operator elects to
use an averaging period of from 2 to 24 hours:
(A) The feed rate of each metal shall be limited at any time to ten times the feed rate
that would be allowed on a hourly rolling average basis;
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(B) The continuous monitor shall meet the following specifications:
CO A continuous monitor is one which continuously samples the regulated
parameter without interruption, and evaluates the detector response at least once each 15
seconds, and computes and records the average value at least every 60 seconds.
(2) The rolling average for the selected averaging period is defined as the arithmetic
mean of the most recent one hour block averages for the averaging period. A one hour
block average is the arithmetic mean of the one minute averages recorded during the 60-
minute period beginning at one minute after the beginning of preceding clock hour, and
(C) The permit limit for the feed rate of each metal shall be established based on trial
burn data as the average over all valid test runs of the highest hourly rolling average feed
rate for each run.
(iii) Feed rate limits for metals, total chloride and chlorine, and ash. Feed rate limits
for metals, total chlorine and chloride, and ash are established and monitored by knowing
the concentration of the substance (i.e., metals, chloride/chlorine, and ash) in each
feedstream and the flow rate of the feedstream. To monitor the feed rate of these
substances, the flow rate of each feedstream must be monitored under the continuous
monitoring requirements of paragraphs (e)(6)(i) and (ii) of this section.
(iv) Conduct of trial burn testing. (A) If compliance with all applicable emissions
standards of §§266.104 through 266.107 is not demonstrated simultaneously during a set
of test runs, the operating conditions of additional test runs required to demonstrate
compliance with remaining emissions standards must be as close as possible to the original
operating conditions.
(B) Prior to obtaining test data for purposes of demonstrating compliance with the
emissions standards of §§266.104 through 266.107 or establishing limits on operating
parameters under mis section, the facility must operate under trial bum conditions for a
sufficient period to reach steady-state operations. The Director may determine, however,
that industrial furnaces that recycle collected paniculate matter back into the furnace and that
comply with an alternative implementation approach for metals under §266.106(f), need
not reach steady state conditions with respect to the flow of metals in the system prior to
beginning compliance testing for metals emissions.
(C) Trial bum data on the level of an operating parameter for which a limit must be
established in the permit must be obtained during emissions sampling for the pollutant(s)
(i.e., metals, PM, HC1/C12. organic compounds) for which the parameter must be
established as specified by paragraph (e) of this section.
(7) General requirements, (i) Fugitive emissions. Fugitive emissions must be
controlled by:
(A) Keeping the combustion zone totally sealed against fugitive emissions; or
(B) Maintaining the combustion zone pressure lower than atmospheric pressure; or
(C) An alternate means of control demonstrated (with Part B of the permit
application) to provide fugitive emissions control equivalent to maintenance of combustion
zone pressure lower than atmospheric pressure.
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(ii) Automatic waste feed cutoff. A boiler or industrial furnace must be operated
with a functioning system that automatically cuts off the hazardous waste feed when
operating conditions deviate from those established under this section. The Director may
limit the number of cutoffs per an operating period on a case-by-case basis. In addition:
(A) The permit limit for (the indicator of) minimum combustion chamber
temperature must be maintained while hazardous waste or hazardous waste residues remain
in the combustion chamber,
(B) Exhaust gases must be ducted to the air pollution control system operated in
accordance with the permit requirements while hazardous waste or hazardous waste
residues remain in the combustion chamber, and
(Q Operating parameters for which permit limits are established must continue to
be monitored during the cutoff, and the hazardous waste feed shall not be restarted until the
levels of those parameters comply with the permit limits. For parameters that may be
monitored on an instantaneous basis, the Director will establish a minimum period of time
after a waste feed cutoff during which the parameter must not exceed the permit limit before
the hazardous waste feed may be restarted.
(iii) Changes. A boiler or industrial furnace must cease burning hazardous waste
when changes in combustion properties, or feed rates of the hazardous waste, other fuels,
or industrial furnace feedstocks, or changes in the boiler or industrial furnace design or
operating conditions deviate from the limits as specified in the permit
(8) Monitoring and Inspections, (i) The owner or operator must monitor and record
the following, at a minimum, while burning hazardous waste:
(A) If specified by the permit, feed rates and composition of hazardous waste, other
fuels, and industrial furnace feedstocks, and feed rates of ash, metals, and total chloride
and chlorine;
(B) If specified by the permit, carbon monoxide (CO), hydrocarbons (HC), and
oxygen on a continuous basis at a common point in the boiler or industrial furnace
downstream of the combustion zone and prior to release of stack gases to die atmosphere in
accordance with operating requirements specified in paragraph (e)(2)(ii) of this section.
CO, HC, and oxygen monitors must be installed, operated, and maintained in accordance
with methods specified in Methods Manual for Compliance with the BIF Regulations
(incorporated by reference, see § 260.11).
(C) Upon the request of the Director, sampling and analysis of the hazardous waste
(and other fuels and industrial furnace feedstocks as appropriate), residues, and exhaust
emissions must be conducted to verify that the operating requirements established in the
permit achieve the applicable standards of §§ 266.104,266.105,266.106, and 266.107.
(ii) All monitors shall record data in units corresponding to the permit limit unless
otherwise specified in toe permit
(iii) The boiler or industrial furnace and associated equipment (pumps, valves,
pipes, fuel storage tanks, etc.) must be subjected to thorough visual inspection when it
contains hazardous waste, at least daily for leaks, spills, fugitive emissions, and signs of
tampering.
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(iv) The automatic hazardous waste feed cutoff system and associated alarms must
be tested at least once every 7 days when hazardous waste is burned to verify operability,
unless uie applicant demonstrates to the Director that weekly inspections will unduly restrict
or upset operations and that less frequent inspections will be adequate. At a minimum,
operational testing must be conducted at least once every 30 days.
(v) These monitoring and inspection data must be recorded and the records must be
placed in the operating record required by §264.73 of this chapter.
(9) Direct transfer to the burner. If hazardous waste is directly transferred from a
transport vehicle to a boiler or industrial furnace without the use of a storage unit, the
owner and operator must comply with §266. 111.
(10) Recordkeeping. The owner or operator must keep in the operating record of
the facility all information and data required by this section for not less than three years.
(11) Closure. At closure, the owner or operator must remove all hazardous waste
and hazardous waste residues (including, but not limited to, ash, scrubber waters, and
scrubber sludges) from the boiler or industrial furnace.
(Approved by the Office of Management and Budget under control number )
§ 266.103 Interim status standards for owners and operators of facilities
that burn hazardous waste in a boiler or industrial furnace.
(a) Purpose, scope, applicability. (1) General, (i) The purpose of this section is to
establish minimum national standards for owners and operators of "existing" boilers and
industrial furnaces that burn hazardous waste where such standards define the acceptable
management of hazardous waste during the period of interim status. The standards of this
section apply to owners and operators of existing facilities until either a permit is issued
under § 266.102(d) or until closure responsibilities identified in this section are fulfilled.
(ii) Existing or in existence means a boiler or industrial furnace that on or before
[insert date 6 months after promulgation of this rule] is either in operation burning or
processing hazardous waste or for which construction (including the ancillary facilities to
burn or process the hazardous waste) has commenced. A facility has commenced
construction if the owner or operator has obtained the Federal, State, and local approvals or
permits necessary to begin physical construction; and either
(A) A continuous on-site, physical construction program has begun; or
(B) The owner or operator has entered into contractual obligations-which cannot be
canceled or modified without substantial loss-for physical construction of the facility to be
completed within a reasonable time.
(iii) If a boiler or industrial furnace is located at a f acility that already has a permit or
interim status, then the facility must comply with the applicable regulations dealing with
permit modifications in § 270.42 or changes in interim status in §270.72 of this chapter.
(2) Exemptions. The requirements of this section do not apply to hazardous waste
and facilities exempt under §§ 266.100(5), (c) or 266.108.
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(3) Prohibition on burning dioxin-listed wastes. Hazardous waste listed for dioxin
or derived from any of the following dioxin-listed wastes may not be burned in a boiler or
industrial furnace operating under interim status: EPA Hazardous Waste Numbers F020,
F021, F022, F023, F026, or F027.
(4) Applicability of Pan 265 standards. Owners and operators of boilers and
industrial furnaces that bum hazardous waste and are operating under interim status are
subject to the following provisions of Part 265 of this chapter, except as provided
otherwise by this section:
(i) In Subpart A (General), §265.4;
(ii) In Subpart B (General facility standards), §§265.11-265.17;
(iii) In Subpart C (Preparedness and prevention), §§265.31-265.37;
(iv) In Subpart D (Contingency plan and emergency procedures), §§265.51-
265.56;
(v) In Subpart E (Manifest system, recordkeeping, and reporting), §§265.71-
265.77, except that §§265.71, 265.72, and 265.76 do not apply to owners and operators
of on-site facilities that do not receive any hazardous waste from off-site sources;
(vi) In Subpart G (Closure and post-closure), §§ 265.111-265.115;
(vii) In Subpart H (Financial requirements),§§ 265.141, 265.142, 265.143, and
265.147-265.151, except that States and the Federal government are exempt from the
requirements of Subpart H; and
(viii) Subpart BB (Air emission standards for equipment leaks), except
§265.1050(a).
(5) Special requirements for furnaces. The following controls apply during interim
status to industrial furnaces (e.g., kilns, cupolas) that feed hazardous waste for a purpose
other than solely as an ingredient (see paragraph (a)(5)(ii) of this section) at any location
other than the hot end where products are normally discharged and where fuels are
normally fired:
(i) Controls. (A) The hazardous waste shall be fed at a location where combustion
gas temperatures are at least 1800°F;
(B) The owner or operator must determine that adequate oxygen is present in
combustion gases to combust organic constituents in the waste and retain documentation of
such determination in the facility record;
(Q For cement kiln systems, the hazardous waste shall be fed into the kiln; and
(D) The hydrocarbon controls of §266.104
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(A) The hazardous waste has a total concentration of nonmetal compounds listed in
Part 261, Appendix Vm, of this chapter exceeding 500 ppm by weight as-generated (and,
so, is considered to be burned for destruction); or
(B) The hazardous waste has a heating value of 5,000 Btu/lb or more, as-generated
or as-fired (and, so, is considered to be burned as fuel).
(6) Restrictions on burning hazardous waste that is not a fuel. Prior to certification
of compliance under paragraph (c) of this section, owners and operators shall not feed
hazardous waste (other than hazardous waste burned solely as an ingredient) in a boiler or
industrial furnace that has a heating value less than 5,000 Btu/lb, as-generated, except for
purposes of compliance testing (or testing prior to compliance testing) for a total period of
time not to exceed 720 hours.
(7) Direct transfer to the burner. If hazardous waste is directly transferred from a
transport vehicle to a boiler or industrial furnace without the use of a storage unit, the
owner and operator must comply with §266.111.
(b) Certification of precompliance. (1) General. The owner or operator must
provide complete and accurate information specified in paragraph (b)(2) of this section to
the Director on or before [the effective date of this rule], and must establish limits for the
operating parameters specified in paragraph (b)(3) of this section. Such information is
termed a "certification of precompliance" and constitutes a certification that the owner or
operator has determined that, when the facility is operated within the limits specified in
paragraph (b)(3) of this section, the owner or operator believes that, using best engineering
judgment, emissions of paniculate matter, metals, and HQ and Cl2 are not likely to exceed
the limits provided by §§266.105, 266.106, and 266.107. The facility may burn
hazardous waste only under the operating conditions that the owner or operator establishes
under paragraph (b)(3) of this section until the owner or operator submits a revised
certification of precompliance under paragraph (b)(8) of this section or a certification of
compliance under paragraph (c) of this section, or until a permit is issued.
(2) Information required. The following information must be submitted with the
certification of precompliance to support the determination that the limits established for the
operating parameters identified in paragraph (b)(3) are not likely to result in an exceedance
of the allowable emission rates for paniculate matter, metals, and HC1 and Cl2:
(i) General facility information:
(A) EPA facility ID number,
(B) Facility name, contact person, telephone number, and address;
(C) Description of boilers and industrial furnaces burning hazardous waste,
including type and capacity of device;
(D) A scaled plot plan showing the entire facility and location of the boilers and
industrial furnaces burning hazardous waste; and
(E) A description of the air pollution control system on each device burning
hazardous waste, including the temperature of the flue gas at the inlet to the paniculate
matter control system.
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(ii) Except for facilities complying with the Her I feed rate screening limits for
metals or total chlorine and chloride provided by §§266.106(b) or (e) and 266.107(b)(l) or
(e) respectively, die estimated uncontrolled (at the inlet to the air pollution control system)
emissions of paniculate matter, each metal controlled by §266.106, and hydrogen chloride
and chlorine, and the following information to support such determinations:
(A) The feed rate Qb/hr) of ash, chlorine, antimony, arsenic, barium, beryllium,
cadmium, chromium, lead, mercury, silver, thallium in each feedstream (hazardous waste,
other fuels, industrial furnace feedstocks);
(B) The estimated partitioning factor to the combustion gas for the materials
identified in paragraph (b)(ii)(A) of this section and the basis for the estimate and an
estimate of the partitioning to HC1 and Cl2 of total chloride and chlorine in feed materials.
To estimate the partitioning factor, the owner or operator must use either best engineering
judgment or the procedures specified in Methods Manual for Compliance with the BIF
Regulations (incorporated by reference, see §260.11).
(C) For industrial furnaces that recycle collected paniculate matter (PM) back into
the furnace, the estimated enrichment factor for each metal. To estimate the enrichment
factor, the owner or operator must use either best engineering judgment or the procedures
specified in "Alternative Methodology for Implementing Metals Controls" in Methods
Msnusl f°r Compliance with the BIF Regulations (incorporated by reference in §266.11).
(D) If best engineering judgment is used to estimate partitioning factors or
enrichment factors under paragraphs (b)(ii)(B) or (b)(ii)(C) respectively, the basis for the
judgment. When best engineering judgment is used to develop or evaluate data or
information and make determinations under this section, the determinations must be made
by a qualified, registered professional engineer and a certification of his/her determinations
in accordance with §270.11(d) of this chapter must be provided in the certification of
precompliance.
(iii) For facilities complying with the Tier I feed rate screening limits for metals or
total chlorine and chloride provided by §§266.106(b) or (e) and 266.107(b)(l) or (e), the
feed rate (Ib/hr) of total chloride and chlorine, antimony, arsenic, barium, beryllium,
cadmium, chromium, lead, mercury, silver, and thallium in each feedstream (hazardous
waste, other fuels, industrial furnace feedstocks).
(iv) For facilities complying with the Tier n or Tier in emission limits for metals or
HC1 and Cfe (under §§266.106(c) or (d) or 266.107(b)(2) or (c)), the estimated controlled
(outlet of the air pollution control system) emissions rates of paniculate matter, each metal
controlled by §266.106, and Hd and Cl2, and the following information to support such
determinations:
(A) The estimated air pollution control system (APCS) removal efficiency for
paniculate matter, HC1, Cl2, antimony, arsenic, barium, beryllium, cadmium, chromium,
lead, mercury, silver, and thallium.
(B) To estimate APCS removal efficiency, the owner or operator must use either
best engineering judgment or the procedures prescribed in Methods Manual for Compliance
with the BIF Regulations (incorporated by reference, see §260.11).
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(C) If best engineering judgment is used to estimate APCS removal efficiency, the
basis for the judgment Use of best engineering judgment must be in conformance with
provisions of paragraph (bX2Xu'XD) of this section.
(v) Determination of allowable emissions rates for HC1, Cl2, antimony, arsenic,
barium, beryllium, cadmium, chromium, lead, mercury, silver, and thallium, and the
following information to support such determinations:
(A) For all facilities:
(7) Physical stack height;
(2) Good engineering practice stack height as defined by 40 CFR 51.100(ii);
(3) Maximum flue gas flow rate;
(4) Maximum flue gas temperature;
(5) Attach a US Geological Service topographic map (or equivalent) showing the
facility location and surrounding land within 5 km of the facility.
(6) Identify terrain type: complex or noncomplex; and
(7) Identify land use: urban or rural.;
(B) For owners and operators using Tier ffl site specific dispersion modeling to
determine allowable levels under §266.106(d) or §266. 107 (c), or adjusted Tier I feed rate
screening limits under §§266.106(e) or 266. 107 (c):
(7) Dispersion model and version used;
(2) Source of meteorological data;
(3) The dilution factor in micrograms per cubic meter per gram per second of
emissions for the maximum annual average off-site (unless on-site is required) ground level
concentration (MEI location); and
(4) Indicate the MEI location on the map required under paragraph (b)(2)(v)(A)(5);
(vi) For facilities complying with the Tier n or m emissions rate controls for metals
or HC1 and Cl2. a comparison of the estimated controlled emissions rates determined under
paragraph (b)(2)(iv) with the allowable emission rates determined under paragraph
(vii) For facilities complying with the Tier I (or adjusted Tier I) feed rate screening
limits for metals or total chloride and chlorine, a comparison of actual feed rates of each
metal and total chlorine and chloride determined under paragraph (b)(2)(iii) to the Tier I
allowable feed rates; and
(viii) For industrial furnaces that feed hazardous waste for any purpose other than
solely as an ingredient (as defined by paragraph (a)(5)(ii) of this section) at any location
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other than the product discharge end of the device, documentation of compliance with the
requirements of paragraphs (aX5Xi)(A), (B), and (C) of this section.
(ix) For industrial furnaces that recycle collected paniculate matter (PM) back into
the furnace and that will certify compliance with the metals emissions standards under
paragraph (c)(3)(ii)(A) of this section:
(A) The applicable paniculate matter standard in Ib/hr, and
(B) The precompliance limit on the concentration of each metal in collected PM
(3) Limits on operating conditions. The owner and operator shall establish limits
on the following parameters consistent with the determinations made under paragraph
(b)(2) of this section and certify (under provisions of paragraph (b)(9) of this section) to
the Director that the facility will operate within the limits during interim status when there is
hazardous waste in the unit until revised certification of precompliance under paragraph
(b)(8) of this section or certification of compliance under paragraph (c) of this section:
(i) Feed rate of total hazardous waste and (unless complying with the Tier I or
adjusted Tier I metals feed rate screening limits under §266.106(b) or (e)) pumpable
hazardous waste;
(ii) Feed rate of each metal in the following feed streams:
(A) Total feed streams, except that industrial furnaces that must comply with the
alternative metals implementation approach under paragraph (b)(4) of this section must
specify limits on the concentration of each metal in collected paniculate matter in lieu of
feed rate limits for total feedstreams;
(B) Total hazardous waste feed; and
(C) Total pumpable hazardous waste feed, unless complying with the Tier I or
adjusted Tier I metals feed rate screening limits under §266.106(b) or (e);
(iii) Total feed rate of chlorine and chloride in total feed streams;
(iy) Total feed rate of ash in total feed streams, except that the ash feed rate for
cement kilns and light-weight aggregate kilns is not limited; and
(v) Maximum production rate of the device in appropriate units when producing
normal product
(4) Operating requirements for furnaces that recycle PM. Owners and operators of
furnaces that recycle collected paniculate matter (PM) back into the furnace and that will
certify compliance with the metals emissions controls under paragraph (c)(3)(ii)(A) of this
section must comply with the special operating requirements provided in "Alternative
Methodology for Implementing Metals Controls" in Methods Manual for Compliance with
the BIF Regulations (incorporated by reference in §260.11).
(5) Measurement of feed rates and production rate, (i) General requirements.
Limits on each of the parameters specified in paragraph (b)(3) of this section (except for
limits on metals concentrations in collected paniculate matter (PM) for industrial furnaces
that recycle collected PM) shall be established and continuously monitored under either of
the following methods:
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(A) Instantaneous limits. A limit for a parameter may be established and
continuously monitored on an instantaneous basis (i.e., the value that occurs at any time)
not to be exceeded at any time; or
(B) Hourly rolling average limits. A limit for a parameter may be established and
continuously monitored on an hourly rolling average basis defined as follows:
(/) A continuous monitor is one which continuously samples the regulated
parameter without interruption, and evaluates the detector response at least once each 15
seconds, and computes and records the average value at least every 60 seconds.
(2) An hourly rolling average is the arithmetic mean of the 60 most recent 1-minute
average values recorded by the continuous monitoring system.
(ii) Rolling average limits for carcinogenic metals and lead. Feed rate limits for the
carcinogenic metals (arsenic, beryllium, cadmium, and chromium) and lead may be
established either on an hourly rolling average basis as prescribed by paragraph (e)(5)(i)(B)
or on (up to) a 24 hour rolling average basis. If the owner or operator elects to use an
averaging period from 2 to 24 hours:
(A) The feed rate of each metal shall be limited at any time to ten times the feed rate
that would be allowed on a hourly rolling average basis;
(B) The continuous monitor shall meet the following specifications:
(7) A continuous monitor is one which continuously samples the regulated
parameter without interruption, and evaluates the detector response at least once each 15
seconds, and computes and records the average value at least every 60 seconds.
(2) The rolling average for the selected averaging period is defined as the arithmetic
mean of the most recent one hour block averages for the averaging period. A one hour
block average is the arithmetic mean of the one minute averages recorded during the 60-
minute period beginning at one minute after the beginning of preceding clock hour.
(iii) Feed rate limits for metals, total chloride and chlorine, and ash. Feed rate limits
for metals, total chlorine and chloride, and ash are established and monitored by knowing
the concentration of the substance (i.e., metals, chloride/chlorine, and ash) in each
feedstream and the flow rate of the feedstream. To monitor the feed rate of these
substances, the flow rate of each feedstream must be monitored under the continuous
monitoring requirements of paragraphs (b)(5)(i) and (ii) of this section.
(6) Public notice requirements at precompUance. On or before [the effective date of
this rule] the owner or operator must submit a notice with the following information for
publication in a major local newspaper of general circulation and send a copy of the notice
to the appropriate units of State and local government. The owner and operator must
provide to the Director with the certification of precompUance evidence of submitting the
notice for publication . The notice, which shall be entitled "Notice of Certification of
Precompliance with Hazardous Waste Burning Requirements of 40 CFR 266.103(b)",
must include:
(i) Name and address of the owner and operator of the facility as well as the
location of the device burning hazardous waste;
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(ii) Date that die certification of precompliance is submitted to the Director;
(iii) Brief description of the regulatory process required to comply with the interim
status requirements of this section including required emissions testing to demonstrate
conformance with emissions standards for organic compounds, paniculate matter, metals,
and HC1 and Cl2;
(iv) Types and quantities of hazardous waste burned including, but not limited to,
source, whether solids or liquids, as well as an appropriate description of the waste;
(v) Type of device(s) in which the hazardous waste is burned including a physical
description and maximum production rate of each device;
(vi) Types and quantities of other fuels and industrial furnace feedstocks fed to each
unit;
(vii) Brief description of the basis for this certification of precompliance as specified
in paragraph (b)(2) of this section;
(viii) Locations where the operating record for the facility can be viewed and copied
by interested parties. These locations shall at a minimum include:
(A) The Agency office where the supporting documentation was submitted or
another location designated by the Director, and
(B) The facility site where the device is located;
(ix) Notification of the establishment of a facility mailing list whereby interested
parties shall notify the Agency that they wish to be placed on the mailing list to receive
future information and notices about this facility, and
(x) Location (mailing address) of the applicable EPA Regional Office, Hazardous
Waste Division, where further information can be obtained on EPA regulation of hazardous
waste burning.
(7) Monitoring other operating parameters. When the monitoring systems for the
operating parameters listed in paragraphs (c)(l)(v through xiii) of this section are installed
and operating in conformance with vendor specifications or (for CO, HC, and oxygen)
specifications provided by the Methods Manual for Compliance with the BIF Regulations
(incorporated by reference, see §260.11), as appropriate, the parameters shall be
continuously monitored and records shall be maintained in the operating record.
(8) Revised certification of precompliance. The owner or operator may revise at
any time the information and operating conditions documented under paragraphs (b)(2) and
(b)(3) of this section in the certification of precompliance by submitting a revised
certification of precompliance under procedures provided by those paragraphs.
(i) The public notice requirements of paragraph (b)(6) of this section do not apply to
recertifications.
(ii) The owner and operator must operate the facility within the limits established for
the operating parameters under paragraph (b)(3) of mis section until a revised certification
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is submitted under this paragraph or a certification of compliance is submitted under
paragraph (c) of this section.
(9) Certification of precompliance statement. The owner or operator must include
the following signed statement with the certification of precompliance submitted to the
Director
" I certify under penalty of law that this information was prepared under my
direction or supervision in accordance with a system designed to ensure that qualified
personnel properly gathered and evaluated the information and supporting documentation.
Copies of all emissions tests, dispersion modeling results and other information used to
determine conformance with the requirements of §266.103(b) are available at the facility
and can be obtained from the facility contact person listed above. Based on my inquiry of
the person or persons who manages the facility, or those persons directly responsible for
gathering the information, the information submitted is, to the best of my knowledge and
belief, true, accurate, and complete. I am aware that there are significant penalties for
submitting false information, including the possibility of fine and imprisonment for
knowing violations.
I also acknowledge that the operating limits established in this certification pursuant
to §266.103(b)(3) and (4) are enforceable limits at which the facility can legally operate
during interim status until: (1) a revised certification of precompliance is submitted, (2) a
certification of compliance is submitted, or (3) an operating permit is issued."
(c) Certification of compliance. On or before [date 18 months after promulgation of
the rule], the owner or operator shall conduct emissions testing to document compliance
with the emissions standards of §§266.104(5) through (e), 266.105, 266.106, 266.107,
and paragraph (a)(5)(i)(D) of this section, under the procedures prescribed by this
paragraph, except under extensions of time provided by paragraph (c)(7). Based on the
compliance test, the owner or operator shall submit to die Director a complete and accurate
"certification of compliance" (under paragraph (c)(4) of this section) with those emission
standards establishing limits on the operating parameters specified in paragraph (c)(l).
(1) Limits on operating conditions. The owner or operator shall establish limits on
the following parameters based on operations during the compliance test (under procedures
prescribed in paragraph (c)(4)(iv) of this section) and include these limits with the
certification of compliance. The boiler or industrial furnace must be operated in accordance
with these operating limits at all times when there is hazardous waste in the unit until an
operating permit is issued.
(i) Feed rate of total hazardous waste and (unless complying with the Tier I or
adjusted Tier I metals feed rate screening limits under §266.106(b) or (e)), pumpable
hazardous waste;
(ii) Feed rate of each metal in die following feedstreams:
(A) Total feedstreams, except that industrial furnaces that must comply with the
alternative metals implementation approach under paragraph (c)(3)(ii) of this section must
specify limits on the concentration of each metal in collected paniculate matter in lieu of
feed rale limits for total feedstreams;
(B) Total hazardous waste feed (unless complying with the Tier I or adjusted Tier I
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(Q Total pumpable hazardous waste feed;
(iii) Total feed rate of chlorine and chloride in total feed streams;
(iv) Total feed rate of ash in total feed streams, except that the ash feed rate for
cement kilns and light-weight aggregate kilns is not limited;
(v) Carbon monoxide concentration, and where required, hydrocarbon
concentration in stack gas. When complying with the CO controls of §266.104(b), the CO
limit is 100 ppmv, and when complying with the HC controls of §266.104(c), the HC limit
is 20 ppmv. When complying with the CO controls of §266.104(c), the CO limit is
established based on the compliance test;
(vi) Maximum production rate of the device in appropriate units when producing
normal product;
(vii) Maximum combustion chamber temperature where the temperature
measurement is as close to the combustion zone as possible and is upstream of any quench
water injection, except for boilers and industrial furnaces that have only pumpable liquid or
gaseous feed streams (unless complying with the Tier I or adjusted Tier I metals feed rate
screening limits under §266.106(5) or (e));
(viii) Maximum flue gas temperature entering a paniculate matter control device
(unless complying with Tier I or adjusted Tier I metals feed rate screening limits under
§266.106(b)or(e));
(ix) For systems using wet scrubbers, including wet ionizing scrubbers (unless
complying with the Tier I or adjusted Tier I metals feed rate screening limits under
§266.106(5) or (e) and the total chlorine and chloride feed rate screening limits under
§266.107(b)(l)or(e)):
(A) Minimum liquid to flue gas ratio;
(6) Minimum scrubber blowdown from the system or maximum suspended solids
content of the scrubber water; and
(Q Minimum pH level of the scrubber water,
(x) For systems using venturi scrubbers, the minimum differential gas pressure
across the venturi (unless complying with the Tier I or adjusted Tier I metals feed rate
screening limits under §266.106(b) or (e) and the total chlorine and chloride feed rate
screening limits under §266.107(b)(l) or (e));
(xi) For systems using dry scrubbers (unless complying with the Tier I or adjusted
Tier I metals feed rate screening limits under §266.106(b) or (e) and the total chlorine and
chloride feed rate screening limits under §266.107(b)(l) or (e)):
(A) Minimum caustic feed rate; and
(B) Maximum flue gas flow rate;
(xii) For systems using wet ionizing scrubbers or electrostatic precipitators (unless
complying with the Tier I or adjusted Tier I metals feed rate screening limits under
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§266.106(5) or (e) and the total chlorine and chloride feed rate screening limits under
§266.107(b)(l)or(e)):
(A) Minimum electrical power in Itilovolt amperes (kVA) to the precipitator plates;
and
(B) Maximum flue gas flow rate;
(xiii) For systems using fabric filters (baghouses), the minimum pressure drop
(unless complying with the Her I or adjusted Her I metals feed rate screening limits under
§266.106(b) or (e) and the total chlorine and chloride feed rate screening limits under
§266.107(b)(l) or (e».
(2) Prior notice of compliance testing. At least 30 days prior to the compliance
testing required by paragraph (c)(3) of this section, the owner or operator shall notify the
Director and submit the following information:
(i) General facility information including:
(A) EPA facility ID number,
(B) Facility name, contact person, telephone number, and address;
(C) Person responsible for conducting compliance test, including company name,
address, and telephone number, and a statement of qualifications;
(D) Planned date of the compliance test;
(ii) Specific information on each device to be tested including:
(A) Description of boiler or industrial furnace;
(B) A scaled plot plan showing the entire facility and location of the boiler or
industrial furnace;
(C) A description of the air pollution control system;
(D) Identification of the continuous emission monitors that are installed, including:
(7) Carbon monoxide monitor,
(2) Oxygen monitor,
(3) Hydrocarbon monitor, specifying the minimum temperature of the system and,
if the temperature is less than 150*0, an explanation of why a heated system is not used
(see paragraph (cX5) of this section) and a brief description of die sample gas conditioning
system;
(E) Indication of whether the stack is shared with another device that will be in
operation during the compliance test;
(F) Other information useful to an understanding of the system design or operation.
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(iii) Information on the testing planned, including a complete copy of the test
protocol and Quality Assurance/Quality Control (QA/QQ plan, and a summary description
for each test providing the following information at a minimum:
(A) Purpose of the test (e.g., demonstrate compliance with emissions of paniculate
matter); and
(B) Planned operating conditions, including levels for each pertinent parameter
specified in paragraph (c)(l) of this section.
(3) Compliance testing, (i) General. Compliance testing must be conducted under
conditions for which the owner or operator has submitted a certification of precompliance
under paragraph (b) of this section and under conditions established in the notification of
compliance testing required by paragraph (c)(2) of this section.
(ii) Special requirements for industrial furnaces that recycle collected PM. Owners
and operators of industrial furnaces that recycle back into the furnace paniculate matter
(PM) from the air pollution control system must comply with one of the following
procedures for testing to determine compliance with the metals standards of §266.106(c) or
(d):
(A) The special testing requirements prescribed in "Alternative Method for
Implementing Metals Controls" in Methods Manual for Compliance with the BIF
Regulations (incorporated by reference in §260.11); or
(B) Stack emissions testing for a minimum of 6 hours each day while hazardous
waste is burned during interim status. The testing must be conducted when burning normal
hazardous waste for that day at normal feed rates for that day and when the air pollution
control system is operated under normal conditions. During interim status, hazardous
waste analysis for metals content must be sufficient for the owner or operator to determine
if changes in metals content may affect the ability of the facility to meet the metals
emissions standards established under §266.106(c) or (d). Under this option, operating
limits (under paragraph (c)(l)) must be established during compliance testing under
paragraph (c)(3) only on the following parameters:
(7) Feed rate of total hazardous waste;
(2) Total feed rate of chlorine and chloride in total feed streams;
(3) Total feed rate of ash in total feed streams, except that the ash feed rate for
cement kilns and light-weight aggregate kilns is not limited;
(4) Carbon monoxide concentration, and where required, hydrocarbon
concentration in stack gas;
(5) Maximum production rate of the device in appropriate units when producing
normal product; or
(C) Conduct compliance testing to determine compliance with the metals standards
to establish limits on the operating parameters of paragraph (c)( 1) only after the kiln system
has been conditioned to enable it to reach equilibrium with respect to metals fed into the
system and metals emissions. During conditioning, hazardous waste and raw materials
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having the same metals content as will be fed during the compliance test must be fed at the
feed rates that will be fed during the compliance test
(iii) Conduct of compliance testing. (A) If compliance with all applicable emissions
standards of §§266.104 through 266.107 is not demonstrated simultaneously during a set
of test runs, the operating conditions of additional test runs required to demonstrate
compliance with remaining emissions standards must be as close as possible to the original
operating conditions.
(B) Prior to obtaining test data for purposes of demonstrating compliance with the
applicable emissions standards of §§266.104 through 266.107 or establishing limits on
operating parameters under this section, the facility must operate under compliance test
conditions for a sufficient period to reach steady-state operations. Industrial furnaces that
recycle collected paniculate matter back into the furnace and that comply with paragraphs
(c)(3)(ii)(A) or (B) or this section, however, need not reach steady state conditions with
respect to the flow of metals in the system prior to beginning compliance testing for metals.
(C) Compliance test data on the level of an operating parameter for which a limit
must be established in the certification of compliance must be obtained during emissions
sampling for the pollutant(s) (i.e., metals, PM, HC1/C12. organic compounds) for which
the parameter must be established as specified by paragraph (c)(l) of this section.
(4) Certification of compliance. Within 90 days of completing compliance testing,
the owner or operator must certify to the Director compliance with the emissions standards
of §§266.104(b), (c), and (e), 266.105, 266.106, 266.107, and paragraph (a)(5)(i)(D) of
this section. The certification of compliance must include the following information:
(i) General facility and testing information including:
(A) EPA facility ID number,
(B) Facility name, contact person, telephone number, and address;
(C) Person responsible for conducting compliance test, including company name,
address, and telephone number, and a statement of qualifications;
(D) Date(s) of each compliance test;
(E) Description of boiler or industrial furnace tested;
(F) Person responsible for quality assurance/quality control (QA/QC), title, and
telephone number, and statement that procedures prescribed in the QA/QC plan submitted
under §266.103(c)(2)(iii) have been followed, or a description of any changes and an
explanation of why changes were necessary.
(G) Description of any changes in the unit configuration prior to or during testing
that would alter any of the information submitted in the prior notice of compliance testing
under paragraph (c)(2) of this section, and an explanation of why the changes were
necessary;
(H) Description of any changes in the planned test conditions prior to or during the
testing that alter any of the information submitted in the prior notice of compliance testing
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under paragraph (c)(2) of this section, and an explanation of why the changes were
necessary; and
(I) The complete report on results of emissions testing.
(ii) Specific information on each test including:
(A) Purpose(s) of test (e.g., demonstrate conformance with the emissions limits for
paniculate matter, metals, HC1, Cl2, and CO)
(B) Summary of test results for each run and for each test including the following
information:
(7) Date of run;
(2) Duration of run;
(3) Time-weighted average and highest hourly rolling average CO level for each run
and for the test;
(4) Highest hourly rolling average HC level, if HC monitoring is required for each
run and for the test;
(5) If dioxin and furan testing is required under §266.104(e), time-weighted
average emissions for each run and for the test of chlorinated dioxin and furan emissions,
and the predicted maximum annual average ground level concentration of the toxicity
equivalency factor;
(6) Time-weighted average paniculate matter emissions for each run and for the test;
(7) Time-weighted average HC1 and Cl2 emissions for each run and for the test;
(8) Time-weighted average emissions of the metals subject to regulation under
§266.107 for each run and for the test; and
(9) QA/QC results.
(iii) Comparison of the actual emissions during each test with the emissions limits
prescribed by §§266.104(b), (c), and (e), 266.105, 266.106, and 266.107 and established
for the facility in the certification of precompliance under paragraph (b) of this section.
(iv) Determination of operating limits based on all valid runs of the compliance test
for each applicable parameter listed in paragraph (c)(l) of this section using either of the
following procedures:
(A) Instantaneous limits. A parameter may be measured and recorded on an
instantaneous basis (Le., the value that occurs at any time) and the operating limit specified
as the time-weighted average during all runs of die compliance test; or
(B) Hourly rolling average basis. (/) The limit for a parameter may be established
and continuously monitored on an hourly rolling average basis defined as follows:
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(0 A continuous monitor is one which continuously samples the regulated
parameter without interruption, and evaluates the detector response at least once each 15
seconds, and computes and records the average value at least every 60 seconds.
(it) An hourly rolling average is the arithmetic mean of the 60 most recent 1-minute
average values recorded by the continuous monitoring system.
(2) The operating limit for the parameter shall be established based on compliance
test data as the average over all test runs of the highest hourly rolling average value for each
run.
(Q Rolling average limits for carcinogenic metals and lead. Feed rate limits for the
carcinogenic metals (i.e., arsenic, beryllium, cadmium and chromium) and lead may be
established either on an hourly rolling average basis as prescribed by paragraph
(c)(4)(iv)(B) of this section or on (up to) a 24 hour rolling average basis. If the owner or
operator elects to use an averaging period of from 2 to 24 hours:
(1) The feed rate of each metal shall be limited at any time to ten times the feed rate
that would be allowed on a hourly rolling average basis;
(2) The continuous monitor shall meet the following specifications:
(/) A continuous monitor is one which continuously samples the regulated
parameter without interruption, and evaluates the detector response at least once each IS
seconds, and computes and records the average value at least every 60 seconds.
(«) The rolling average for the selected averaging period is defined as the arithmetic
mean of the most recent one hour block averages for the averaging period. A one hour
block average is die arithmetic mean of the one minute averages recorded during the 60-
minute period beginning at one minute after the beginning of preceding clock hour, and
(3) The operating limit for the feed rate of each metal shall be established based on
compliance test data as the average over all test runs of the highest hourly rolling average
feed rate for each run.
(D) Feed rate limits for metals, total chloride and chlorine, and ash. Feed rate limits
for metals, total chlorine and chloride, and ash are established and monitored by knowing
the concentration of the substance (i.e., metals, chloride/chlorine, and ash) in each
feedstream and the flow rate of the feedstream. To monitor the feed rate of these
substances, the flow rate of each feedstream must be monitored under the continuous
monitoring requirements of paragraphs (cK4Xrv)(A) through (Q of this section.
(v) Certification of compliance statement. The following statement shall accompany
the certification of compliance:
"I certify under penalty of law that this information was prepared under my
direction or supervision in accordance with a system designed to ensure that qualified
personnel properly gathered and evaluated the information and supporting documentation.
Copies of all emissions tests, dispersion modeling results and other information used to
determine confonnance with the requirements of §266.103(c) are available at the facility
and can be obtained from the facility contact person listed above. Based on my inquiry of
the person or persons who manages the facility, or those persons directly responsible for
gathering the information, the information submitted is, to the best of my knowledge and
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belief, true, accurate, and complete. I am aware that there are significant penalties for
submitting false information, including the possibility of fine and imprisonment for
knowing violations.
I also acknowledge that the operating conditions established in this certification
pursuant to §266.103(c)(4)(iv) are enforceable limits at which the facility can legally
operate during interim status until a revised certification of compliance is submitted."
(5) Special requirement for HC monitoring systems. When an owner or operator
is required to comply with the hydrocarbon (HC) controls provided by §§266.104(c) or
paragraph (a)(5)(i)(D) of this section, a conditioned gas monitoring system may be used in
conformance with specifications provided in Methods M^nqaj for Compliance with the BIF
Regulations (incorporated by reference, see §260.11) provided that the owner or operator
submits a certification of compliance without using extensions of time provided by
paragraph (c)(7) of this section.
(6) Special operating requirements for industrial furnaces that recycle collected PM.
Owners and operators of industrial furnaces that recycle back into the furnace particulate
matter (PM) from the air pollution control system must*
(i) When complying with the requirements of paragraph (c)(3)(ii)(A) of this section,
the operating requirements prescribed in "Alternative Method to Implement the Metals
Controls" in Methods Manual for Compliance with the BIF Regulations (incorporated by
reference in §260.11); and
(ii) When complying with the requirements of paragraph (c)(3)(ii)(B) of this
section, the operating requirements prescribed by that paragraph.
(7) Extensions of time, (i) If the owner or operator does not submit a complete
certification of compliance for all of the applicable emissions standards of §§266.104,
266.105, 266.106, and 266.107 by [insert date 18 months from promulgation], he/she
must either
(A) Stop burning hazardous waste and begin closure activities under paragraph (1)
of this section for the hazardous waste portion of the facility; or
(B) Limit hazardous waste burning to a total period of 720 hours for the period of
time beginning [insert date 18 months from promulgation], submit a notification to the
Director by [insert date 18 months from promulgation] stating that the facility is operating
under restricted interim status and intends to resume burning hazardous waste, and submit
a complete certification of compliance by [insert date 30 months from promulgation]; or
(C) Obtain a case-by-case extension of time under paragraph (c)(7)(ii) of this
section.
(ii) The owner or operator may request a case-by-case extension of time to extend
any time limit provided by paragraph (c) of this section if compliance with the time limit is
not practicable for reasons beyond the control of the owner or operator.
(A) In granting an extension, die Director may apply conditions as the facts warrant
to ensure timely compliance with the requirements of this section and that the facility
operates in a manner that does not pose a hazard to human health and the environment;
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(B) When an owner and operator request an extension of time to enable diem to
obtain a RCRA operating permit because the facility cannot meet the HC limit of
§266.104(0 of this chapter
(7) The Director shall, in considering whether to grant the extension:
(0 Determine whether die owner and operator have submitted in a timely manner a
complete Part B permit application that includes information required under §270.22(b) of
this chapter, and
(if) Consider whether the owner and operator have made a good faith effort to
certify compliance with all other emission controls, including the controls on dioxins and
furans of §266.104(e) and the controls on PM, metals, and HC1/CI2.
(2) If an extension is granted, the Director shall, as a condition of the extension,
require the facility to operate under flue gas concentration limits on CO and HC that, based
on available information, including information in the Pan B permit application, are
baseline CO and HC levels as defined by §266.104(0(1).
(8) Revised certification of compliance. The owner or operator may submit at any
time a revised certification of compliance (recertification of compliance) under the following
procedures:
(i) Prior to submittal of a revised certification of compliance, hazardous waste may
not be burned for more than a total of 720 hours under operating conditions that exceed
those established under a current certification of compliance, and such burning may be
conducted only for purposes of determining whether the facility can operate under revised
conditions and continue to meet the applicable emissions standards of §§266.104,
266.105, 266.106, and 266.107;
(ii) At least 30 days prior to first burning hazardous waste under operating
conditions that exceed those established under a current certification of compliance, the
owner or operator shall notify the Director and submit the following information:
(A) EPA facility ID number, and facility name, contact person, telephone number,
and address;
(B) Operating conditions that tile owner or operator is seeking to revise and
description of the changes in facility design or operation that prompted the need to seek to
revise the operating conditions;
(Q A determination that when operating under the revised operating conditions, the
applicable emissions standards of §§266.104, 266.105, 266.106, and 266.107 are not
likely to be exceeded. To document this determination, the owner or operator shall submit
the applicable information required under paragraph (bX2) of this section; and
(D) Complete emissions testing protocol for any pretesting and for a new
compliance test to determine compliance with the applicable emissions standards of
§§266.104, 266.105, 266.106, and 266.107 when operating under revised operating
conditions. The protocol shall include a schedule of pie-testing and compliance testing. If
the owner and operator revises the scheduled date for the compliance test, he/she shall
notify the Director in writing at least 30 days prior to the revised date of the compliance test;,
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(iii) Conduct a compliance test under the revised operating conditions and the
protocol submitted to the Director to determine compliance with the applicable emissions
standards of §§266.104, 266.105,266.106, and 266.107; and
(iv) Submit a revised certification of compliance under paragraph (c)(4) of this
section.
(d) Periodic Recertifications. The owner or operator must conduct compliance
testing and submit to the Director a recertification of compliance under provisions of
paragraph (c) of this section within three years from submitting the previous certification or
recertification. If the owner or operator seeks to recertify compliance under new operating
conditions, he/she must comply with the requirements of paragraph (c)(8) of this section.
(e) Noncompliance with certification schedule. If the owner or operator does not
comply with the interim status compliance schedule provided by paragraphs (b), (c), and
(d) of this section, hazardous waste burning must terminate on the date that the deadline is
missed, closure activities must begin under paragraph (1) of this section, and hazardous
waste burning may not resume except under an operating permit issued under §270.66 of
this chapter.
(0 Start-up and shut-down. Hazardous waste (except waste fed solely as an
ingredient under the Tier I (or adjusted Tier I) feed rate limits for metals and
chloride/chlorine) must not be fed into the device during start-up and shut-down of the
boiler or industrial furnace, unless the device is operating within the conditions of operation
specified in the certification of compliance.
(g) Automatic waste feed cutoff. During the compliance test required by paragraph
(c)(3) of this section, and upon certification of compliance under paragraph (c) of this
section, a boiler or industrial furnace must be operated with a functioning system that
automatically cuts off the hazardous waste feed when the applicable operating conditions
specified in paragraphs (c)(l)(i) and (v through xiii) of this section deviate from those
established in the certification of compliance. In addition:
(1) To minimize emissions or organic compounds, the minimum combustion
chamber temperature (or the indicator of combustion chamber temperature) mat occurred
during the compliance test must be maintained while hazardous waste or hazardous waste
residues remain in the combustion chamber, with the minimum temperature during the
compliance test defined as either
(i) If compliance with the combustion chamber temperature limit is based on a
hourly rolling average, the minimum temperature during the compliance test is considered
to be the average over all runs of the lowest hourly rolling average for each run; or
(ii) If compliance with the combustion chamber temperature limit is based on an
instantaneous temperature measurement, the ipininmrn temperature during the compliance
test is considered to be the time-weighted average temperature during all runs of the test;
and
(2) Operating parameters limited by the certification of compliance must continue to
be monitored during the cutoff, and the hazardous waste feed shall not be restarted until the
levels of those parameters comply with the limits established in the certification of
compliance.
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(h) Fugitive emissions. Fugitive emissions must be controlled by:
(1) Keeping the combustion zone totally sealed against fugitive emissions; or
(2) Maintaining the combustion zone pressure lower than atmospheric pressure; or
(3) An alternate means of control that the owner or operator can demonstrate
provide fugitive emissions control equivalent to maintenance of combustion zone pressure
lower than atmospheric pressure. Support for such demonstration shall be included in the
operating record.
(i) Changes. A boiler or industrial furnace must cease burning hazardous waste
when changes in combustion properties, or feed rates of the hazardous waste, other fuels,
or industrial furnace feedstocks, or changes in the boiler or industrial furnace design or
operating conditions deviate from the limits specified in the certification of compliance.
(j) Monitoring and Inspections. (1) The owner or operator must monitor and record
the following, at a minimum, while burning hazardous waste:
(i) Feed rates and composition of hazardous waste, other fuels, and industrial
furnace feed stocks, and feed rates of ash, metals, and total chloride and chlorine as
necessary to ensure conformance with the certification of precompliance or certification of
compliance;
(ii) Carbon monoxide (CO), oxygen, and if applicable, hydrocarbons (HC), on a
continuous basis at a common point in the boiler or industrial furnace downstream of the
combustion zone and prior to release of stack gases to the atmosphere in accordance with
the operating limits specified in the certification of compliance. CO, HC, and oxygen
monitors must be installed, operated, and maintained in accordance with methods specified
in Methods Manual for Compliance with the BIF Regulations (incorporated by reference,
see §260.11).
(iii) Upon the request of the Director, sampling and analysis of the hazardous waste
(and other fuels and industrial furnace feed stocks as appropriate) and the stack gas
emissions must be conducted to verify that the operating conditions established in the
certification of precompliance or certification of compliance achieve the applicable standards
of §§266.104, 266.105, 266.106, and 266.107.
(2) The boiler or industrial furnace and associated equipment (pumps, valves,
pipes, fuel storage tanks, etc.) must be subjected to thorough visual inspection when they
contain hazardous waste, at least daily for leaks, spills, fugitive emissions, and signs of
tampering.
(3) The automatic hazardous waste feed cutoff system and associated alarms must
be tested at least once every 7 days when hazardous waste is burned to verify operability,
unless the owner or operator can demonstrate that weekly inspections will unduly restrict or
upset operations and that less frequent inspections wUl be adequate. Support for such
demonstration shall be included in the operating record. At a minimum, operational testing
must be conducted at least once every 30 days.
(4) These monitoring and inspection data must be recorded and the records must be
placed in the operating log.
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(k) Recordkeeping. The owner or operator must keep in the operating record of the
facility all information and data required by this section for a period of three years.
0) Closure. At closure, the owner or operator must remove all hazardous waste
and hazardous waste residues (including, but not limited to, ash, scrubber waters, and
scrubber sludges) from the boiler or industrial furnace and must comply with §§265.1 1 1-
265. 1 IS of this chapter.
(Approved by the Office of Management and Budget under control number _ )
§ 266.104 - Standards to control organic emissions.
(a) DRE standard. (1) General. Except as provided in paragraph (a)(3) of this
section, a boiler or industrial furnace burning hazardous waste must achieve a destruction
and removal efficiency (DRE) of 99.99% for all organic hazardous constituents in the
waste feed. To demonstrate conformance with this requirement, 99.99% DRE must be
demonstrated during a trial burn for each principal organic hazardous constituent (POHC)
designated (under paragraph (a)(2) of this section) in its permit for each waste feed. DRE
is determined for each POHC from the following equation:
DRE=[ l-.SJjjui ] X 100
Win
where:
W^ SB Mass feed rate of one principal organic hazardous constituent (POHC) in the
hazardous waste fired to the boiler or industrial furnace; and
Wout = Mass emission rate of the same POHC present in stack gas prior to release
to the atmosphere.
(2) Designation of POHCs. Principal organic hazardous constituents (POHCs) are
those compounds for which compliance with the DRE requirements of this section shall be
demonstrated in a trial burn in conformance with procedures prescribed in §270.66 of this
chapter. One or more POHCs shall be designated by the Director for each waste feed to be
burned. POHCs shall be designated based on the degree of difficulty of destruction of the
organic constituents in the waste and on their concentrations or mass in the waste feed
considering the results of waste analyses submitted with Part B of the permit application.
POHCs are most likely to be selected from among those compounds listed in Part 261,
Appendix Vm of this chapter that are also present in the normal waste feed However, if
the applicant demonstrates to the Regional Administrator's satisfaction mat a compound not
listed in Appendix Vm or not present in the normal waste feed is a suitable indicator of
compliance with the DRE requirements of this section, that compound may be designated
as a POHC Such POHCs need not be toxic or organic compounds.
(3) Dioxin-listed waste. A boiler or industrial furnace burning hazardous waste
containing (or derived from) EPA Hazardous Wastes Nos. F020, F021, F022, F023,
F026, or F027 must achieve a destruction and removal efficiency (DRE) of 99.9999% for
each POHC designated (under paragraph (a)(2) of this section) in its permit This
performance must be demonstrated on POHCs that are more difficult to burn than tetra-,
penta-, and hexachlorodibenzo-p-dioxins and dibenzofurans. DRE is determined for each
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POHC from the equation in paragraph (a) of this section. In addition, the owner or
operator of the boiler or industrial furnace must notify the Director of intent to burn EPA
Hazardous Waste Nos. F020, F021, F022, F023, F026, or F027.
(4) Automatic waiver of ORE trial burn. Owners and operators of boilers operated
under the special operating requirements provided by § 266.110 are considered to be in
compliance with the DRE standard of paragraph (a)(l) of this section and are exempt from
the DRE trial burn.
(5) Low risk waste. Owners and operators of boilers or industrial furnaces that
bum hazardous waste in compliance with the requirements of §266.109(a) are considered
to be in compliance with the DRE standard of paragraph (a)(l) of this section and are
exempt from the DRE trial burn.
(b) Carbon monoxide standard. (1) Except as provided in paragraph (c) of this
section, the stack gas concentration of carbon monoxide (CO) from a boiler or industrial
furnace burning hazardous waste cannot exceed 100 ppmv on an hourly rolling average
basis (i.e., over any 60 minute period), continuously corrected to 7 percent oxygen, dry
gas basis.
(2) CO and oxygen shall be continuously monitored in conformance with
"Performance Specifications for Continuous Emission Monitoring of Carbon Monoxide
and Oxygen in Hazardous Waste Incinerators, Boilers, and Industrial Furnaces" in
Methods Manual for Compliance wfoh the BIF Regulations (incorporated by reference in
§260.11 of this chapter).
(3) Compliance with the 100 ppmv CO limit must be demonstrated during the trial
burn (for new facilities or an interim status facility applying for a permit) or the compliance
test (for interim status facilities). To demonstrate compliance, the highest hourly rolling
average CO level during any valid run of the trial burn or compliance test must not exceed
100 ppmv.
(c) Alternative carbon monoxide standard. (1) The stack gas concentration of
carbon monoxide (CO) from a boiler or industrial furnace burning hazardous waste may
exceed the 100 ppmv limit provided mat stack gas concentrations of hydrocarbons (HC) do
not exceed 20 ppmv, except as provided by paragraph (f) of this section for certain
industrial furnaces.
(2) HC limits must be established under this section on an hourly rolling average
basis (i.e., over any 60 minute period), reported as propane, and continuously corrected to
7 percent oxygen, dry gas basis.
(3) HC shall be continuously monitored in conformance with "Measurement of
Total Hydrocarbons in Stack Gases from Hazardous Waste Incinerators, Boilers, and
Industrial Furnaces" in Methods Manual for Compliance with the BIF Regulations
(incorporated by reference in §260.11 of this chapter). CO and oxygen shall be
continuously monitored in conformance with paragraph (b)(2) of this section.
(4) The alternative CO standard is established based on CO data during the trial
burn (for a new facility) and the compliance test (for an interim status facility). The
alternative CO standard is the average over all valid runs of the highest hourly average CO
level for each run. The CO limit is implemented on an hourly rolling average basis, and
continuously corrected to 7 percent oxygen, dry gas basis.
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(d) Special requirements for furnaces. Owners and operators of industrial furnaces
(e.g., kilns, cupolas) that feed hazardous waste for a purpose other than solely as an
ingredient (see §266.103(a)(5)(ii)) at any location other than the end where products are
normally discharged and where fuels are normally fired must comply with the hydrocarbon
limits provided by paragraphs (c) or (f) of this section irrespective of whether stack gas CO
concentrations meet the 100 ppmv limit of paragraph (b) of this section.
(e) Controls for dioxins andfurans. Owners and operators of boilers and industrial
furnaces mat are equipped with a dry paniculate matter control device that operates within
the temperature range of 450-750°F, and industrial furnaces operating under an alternative
hydrocarbon limit established under paragraph (0 of this section must conduct a site-
specific risk assessment as follows to demonstrate that emissions of chlorinated dibenzo-p-
dioxins and dibenzofurans do not result in an increased lifetime cancer risk to the
hypothetical maximum exposed individual (MET) exceeding 1 in 100,000:
(1) During the trial burn (for new facilities or an interim status facility applying for a
permit) or compliance test (for interim status facilities), determine emission rates of the
tetra-octa congeners of chlorinated dibenzo-p-dioxins and dibenzofurans (CDDs/CDFs)
using Method 23, "Determination of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans (PCDFs) from Stationary Sources" in Methods Manual for
Compliance with the BIF Regulations (incorporated by reference in §260.11).
(2) Estimate the 2,3,7,8-TCDD toxicity equivalence of the tetra-octa CDDs/CDFs
congeners using "Procedures for Estimating the Toxicity Equivalence of Chlorinated
Dibenzo-p-Dioxin and Dibenzofuran Congeners" in Methods Manual for Compliance with
the BIF Regulations (incorporated by reference in §260.11). Multiply the emission rates of
CDD/CDF congeners with a toxicity equivalence greater than zero (see the procedure) by
the calculated toxicity equivalence factor to estimate the equivalent emission rate of 2,3,7,8-
TCDD.
(3) Conduct dispersion modeling using methods recommended in Guideline on Air
Quality Models, the "Hazardous Waste Combustion Air Quality Screening Procedure"
described in Methods Manual for Compliance with the BIF Regulations, or "EPA
SCREEN Screening Procedure" as described in Screening Procedures for Estimating Air
Quality Tmpact of Stationary Sources (all three documents are incorporated by reference in
§260.11) to predict the maximum annual average off-site ground level concentration of
2,3,7,8-TCDD equivalents determined under paragraph (e)(2) of this section. The
maximum annual average on-site concentration must be used when a person resides on-site;
and
(4) The ratio of the predicted maximum annual average ground level concentration
of 2,3,7,8-TCDD equivalents to the risk-specific dose for 2,3,7,8-TCDD provided in
Appendix V of this part (2.2 X 10~7) shall not exceed 1.0.
(f) Alternative HC limit for furnaces with organic matter in raw material. For
industrial furnaces that cannot meet the 20 ppmv HC limit because of organic matter in
normal raw material, the Director may establish an alternative HC limit on a case-by-case
basis (under a Pan B permit proceeding) at a level that ensures that flue gas HC (and CO)
concentrations when burning hazardous waste are not greater than when not burning
hazardous waste (the baseline HC level) provided that the owner or operator complies with
the following requirements. However, cement loins equipped with a by-pass duct meeting
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the requirements of paragraph (g) of this section, are not eligible for an alternative HC
limit.
(1) The owner or operator must demonstrate that the facility is designed and
operated to minimize hydrocarbon emissions from fuels and raw materials when the
baseline HC (and CO) level is determined. The baseline HC (and CO) level is defined as
the average over all valid test runs of the highest hourly rolling average value for each run
when the facility does not burn hazardous waste, and produces normal products under
normal operating conditions feeding normal feedstocks and fuels. More than one baseline
level may be determined if the facility operates under different modes that may generate
significantly different HC (and CO) levels;
(2) The owner or operator must develop an approach to monitor over time changes
in the operation of the facility that could reduce die baseline HC level;
(3) The owner or operator must conduct emissions testing during the trial burn to:
(i) Determine the baseline HC (and CO) level;
(ii) Demonstrate that, when hazardous waste is burned, HC (and CO) levels do not
exceed the baseline level; and
(iii) Identify the types and concentrations of organic compounds listed in Appendix
Vm, Part 261 of this chapter, that are emitted and conducts dispersion modeling to predict
the maximum annual average ground level concentration of each organic compound. On-
site ground level concentrations must be considered for this evaluation if a person resides
on site.
(A) Sampling and analysis of organic emissions shall be conducted using
procedures prescribed by the Director.
(B) Dispersion modeling shall be conducted according to procedures provided by
paragraph (e)(2) of this section; and
(iv) Demonstrate that maximum annual average ground level concentrations of the
organic compounds identified in paragraph (f)(2)(iii) of this section do not exceed the
following levels:
(A) For the noncarcinogenic compounds listed in Appendix IV of this part, the
levels established in Appendix IV;
(B) For the carcinogenic compounds listed in Appendix V of this part, the sum for
all compounds of die ratios of the actual ground level concentration to die level established
in Appendix V cannot exceed 1.0. To estimate the health risk from chlorinated dibenzo-p-
dipxins and dibenzofuran congeners, use the procedures prescribed by paragraph (e)(3) of
this section to estimate the 23,7,8-TCDD toxicity equivalence of the congeners.
(C) For compounds not listed in Appendix IV or V, 0.09 micrograms per cubic
meter.
(4) All hydrocarbon levels specified under this paragraph are to be monitored and
reported as specified in paragraphs (cXl) and (cX2) of this section.
40
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(g) Monitoring CO and HC in the by-pass duct of a cement kiln. Cement loins may
comply with the carbon monoxide and hydrocarbon limits provided by paragraphs (b), (c),
and (d) of this section by monitoring in the by-pass duct provided that:
(1) Hazardous waste is fired only into the kiln and not at any location downstream
from the kiln exit relative to the direction of gas flow, and
(2) The by-pass duct diverts a minimum of 10% of kiln off-gas into the duct(g)
Use of emissions test data to demonstrate conformance and establish operating limits:
Conformance with the requirements of this section must be demonstrated simultaneously
by emissions testing or during separate runs under identical operating conditions. Further,
data to demonstrate compliance with the CO and HC limits provided by this section or to
establish alternative CO or HC limits provided by this section must be obtained during the
time that DRE testing, and where applicable, CDD/CDF testing is being conducted.
(h) Use of emissions test data to demonstrate compliance and establish operating
limits. Compliance with the requirements of this section must be demonstrated
simultaneously by emissions testing or during separate runs under identical operating
conditions. Further, data to demonstrate compliance with the CO and HC limits of this
section or to establish alternative CO or HC limits under this section must be obtained
during the time that DRE testing, and where applicable, CDD/CDF testing under paragraph
(e) and comprehensive organic emissions testing under paragraph (f) is conducted.
(i) Enforcement. For the purposes of permit enforcement, compliance with the
operating requirements specified in the permit (under § 266.102) will be regarded as
compliance with this section. However, evidence that compliance with those permit
conditions is insufficient to ensure compliance with the requirements of this section may be
"information" justifying modification or revocation and re-issuance of a permit under
§270.41 of this chapter.
§ 266.105 Standards to control particulate matter.
(a) A boiler or industrial furnace burning hazardous waste may not emit particulate
matter in excess of 180 milligrams per dry standard cubic meter (0.08 grains per dry
standard cubic foot) after correction to a stack gas concentration of 7% oxygen, using
>rocedures prescribed in 40 CFR Pan 60, Appendix A, Methods 1 through 5, and Methods
vianual for Compliance with the BIF Regulations (incorporated by reference, see
§260.11).
(b) An owner or operator meeting the requirements of §266.109(b) for the low risk
waste exemption is exempt from the particulate matter standard.
(c) For the purposes of permit enforcement, compliance with the operating
requirements specified in the permit (under § 266.102) will be regarded as compliance with
this section. However, evidence mat compliance with those permit conditions is insufficient
to ensure compliance with the requirements of this section may be "information" justifying
modification or revocation and re-issuance of a permit under § 270.41 of this chapter.
§ 266.106 Standards to control metals emissions.
(a) General. The owner or operator must comply with the metals standards
provided by paragraphs (b), (c), (d), (e), or (f) of this section for each metal listed in
paragraph (b) of this section that is present in the hazardous waste at detectable levels using
41
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analytical procedures specified in Test Methods for Evaluation Solid Waste.
Physical/Chemical Methods (SW-846V incorporated by reference in §260.11 of this
chapter.
(b) Tier I feed rate screening limits. Feed rate screening limits for metals are
specified in Appendix I of this part as a function of terrain-adjusted effective stack height
and terrain and land use in the vicinity of the facility. Criteria for facilities that are not
eligible to comply with die screening limits are provided in paragraph (b)(7) of this section.
(1) Noncarcinogenic metals. The feed rates of antimony, barium, lead, mercury,
thallium, and silver in all feed streams, including hazardous waste, fuels, and industrial
furnace feed stocks shall not exceed the screening limits specified in Appendix I of this
part
(i) The feed rate screening limits for antimony, barium, mercury, thallium, and
silver are based on either
(A) An hourly rolling average as defined in §266.102(e)(6)(i)(B); or
(B) An instantaneous limit not to be exceeded at any time.
(ii) The feed rate screening limit for lead is based on one of the following:
(A) An hourly rolling average as defined in §266.102(e)(6)(i)(B);
(B) An averaging period of 2 to 24 hours as defined in §266.102(e)(6)(ii) with an
instantaneous feed rate limit not to exceed 10 times the feed rate that would be allowed on
an hourly rolling average basis; or
(C) An instantaneous limit not to be exceeded at any time.
(2) Carcinogenic metals, (i) The feed rates of arsenic, cadmium, beryllium, and
chromium in all feed streams, including hazardous waste, fuels, and industrial furnace feed
stocks shall not exceed values derived from the screening limits specified in Appendix I of
this part The feed rate of each of these metals is limited to a level such mat the sum of the
ratios of the actual feed rate to the feed rate screening limit specified in Appendix I shall not
exceed 1.0, as provided by the following equation:
n
i=l FRSL(i)
where:
n = number of carcinogenic metals
APR = actual feed rate to the device for metal "i"
FRSL = feed rate screening limit provided by Appendix I of this pan for metal "i".
(ii) The feed rate screening limits for the carcinogenic metals are based on either
(A) An hourly rolling average; or
42
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(B) An averaging period of 2 to 24 hours with an instantaneous feed rate limit not to
exceed 10 times the feed rate that would be allowed on an hourly rolling average basis.
(3) TESH. (i) The terrain-adjusted effective stack height is determined according to
the following equation:
TESH = Ha + HI -Tr
where:
Ha = Actual physical stack height
HI = Plume rise as determined from Appendix VI of this part as a function of stack
flow rate and stack gas exhaust temperature.
Tr = Terrain rise within five kilometers of the stack.
(ii) The stack height (Ha) may not exceed good engineering practice as specified in
40CFRPart51.100(ii).
(iii) If the TESH for a particular facility is not listed in the table in the appendices,
the nearest lower TESH listed in the table shall be used. If the TESH is four meters or
less, a value of four meters shall be used.
(4) Terrain type. The screening limits are a function of whether the facility is
located in noncomplex or complex terrain. A device located where any part of the
surrounding terrain within 5 kilometers of the stack equals or exceeds the elevation of the
physical stack height (Ha) is considered to be in complex terrain and the screening limits
for complex terrain apply. Terrain measurements are to be made from U.S. Geological
Survey 7.5-minute topographic maps of the area surrounding the facility.
(5) Land use. The screening limits are a function of whether the facility is located
in an area wher he land use is urban or rural. To determine whether land use in the
vicinity of the facility is urban or rural, procedures provided in Methods Manual for
Compliance with the BIF Regulations (incorporated by reference, see § 260.11) or
Guideline on Air Quality Models (incorporated by reference, see § 260.11) shall be used.
(6) Multiple stacks. Owners and operators of facilities with more than one on-site
stack from a boiler, industrial furnace, incinerator, or other thermal treatment unit subject to
controls of metals emissions under a RCRA operating permit or interim status controls
must comply with the screening limits for all such units assuming all hazardous waste is
fed into the device with the worst-case stack based on dispersion characteristics. The
worst-case stack is determined from the following equation as applied to each stack:
K = HVT
where:
K = a parameter accounting for relative influence of stack height and plume rise;
H = physical stack height (meters);
V = stack gas flow rate (m^/second); and
T = exhaust temperature (°K).
The stack with the lowest value of K is the worst-case stack.
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(7) Criteria for facilities not eligible for screening limits. If any criteria below are
met, the Tier I (and Tier n) screening limits do not apply. Owners and operators of such
facilities must comply with the Tier ffl standards provided by paragraph (d) of this section.
(i) The device is located in a narrow valley less than one kilometer wide;
(U) The device has a stack taller than 20 meters and is located such that the terrain
rises to the physical height within one kilometer of the facility;
(iii) The device has a stack taller than 20 meters and is located within five kilometers
of a shoreline of a large body of water such as an ocean or large lake;
(iv) The physical stack height of any stack is less than 2.5 times the height of any
building within five building heights or five projected building widths of the stack and the
distance from the stack to the closest boundary is within five building heights or five
projected building widths of the associated building; or
(v) The Director determines that standards based on site-specific dispersion
modeling are required.
(8) Implementation. The feed rate of metals in each feedstream must be monitored
to ensure that the feed rate screening limits are not exceeded
(c) Tier II emission rate screening limits. Emission rate screening limits are
specified in Appendix I as a function of terrain-adjusted effective stack height and terrain
and land use in the vicinity of the facility. Criteria for facilities that are not eligible to
comply with the screening limits are provided in paragraph (b)(7) of this section.
(1) Noncarcinogenic metals. The emission rates of antimony, barium, lead,
mercury, thallium, and silver shall not exceed the screening limits specified in Appendix I
of this part
(2) Carcinogenic metals. The emission rates of arsenic, cadmium, beryllium, and
chromium shall not exceed values derived from the screening limits specified in Appendix I
of this part The emission rate of each of these metals is limited to a level such that the sum
of the ratios of the actual emission rate to the emission rate screening limit specified in
Appendix I shall not exceed 1.0, as provided by the following equation:
i=l ERSL(i)
where:
n = number of carcinogenic metals
AER = actual emission rate for mftid "i"
ERSL = emission rate screening limit provided by Appendix I of this part for metal
II-H
1 •
(3) Implementation. The emission rate limits must be implemented by limiting feed
rates of the individual metals to levels during the trial bum (for new facilities or an interim
status facility applying for a permit) or the compliance test (for interim status facilities).
44
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The feed rate averaging periods are the same as provided by paragraphs (b)(lXi and ii) and
(b)(2)(ii) of this section. The feed rate of metals in each feedstream must be monitored to
ensure that the feed rate limits for the feedstreams specified under §§266.102 or 266.103
are not exceeded.
(4) Definitions and limitations. The definitions and limitations provided by
paragraph (b) of this section for the following terms also apply to the Tier n emission rate
screening limits provided by paragraph (c) of this section: terrain-adjusted effective stack
height, good engineering practice stack height, terrain type, land use, and criteria for
facilities not eligible to use the screening limits.
(5) Multiple stacks, (i) Owners and operators of facilities with more than one on-
site stack from a boiler, industrial furnace, incinerator, or other thermal treatment unit
subject to controls on metals emissions under a RCRA operating permit or interim status
controls must comply with the emissions screening limits for any such stacks assuming all
hazardous waste is fed into the device with the worst-case stack based on dispersion
characteristics.
(ii) The worst-case stack is determined by procedures provided in paragraph (b)(6)
of this section.
(iii) For each metal, the total emissions of the metal from those stacks shall not
exceed the screening limit for the worst-case stack.
(d) Tier III site-specific risk assessment. (1) General. Conformance with the Tier
m metals controls must be demonstrated by emissions testing to determine the emission
rate for each metal, air dispersion modeling to predict the maximum annual average off-site
ground level concentration for each metal, and a demonstration that acceptable ambient
levels are not exceeded.
(2) Acceptable ambient levels. Appendices IV and V of this part list the acceptable
ambient levels for purposes of this rule. Reference air concentrations (RACs) are listed for
the noncarcinogenic metals and 10~5 risk-specific doses (RSDs) are listed for the
carcinogenic metals. The RSD for a metal is the acceptable ambient level for that metal
provided that only one of the four carcinogenic metals is emitted. If more than one
carcinogenic metal is emitted, the acceptable ambient level for the carcinogenic metals is a
fraction of the RSD as described in paragraph (d)(3).
(3) Carcinogenic metals. For the carcinogenic metals, arsenic, cadmium,
beryllium, and chromium, the sum of the ratios of the predicted maximum annual average
off-site ground level concentrations (except that on-site concentrations must be considered
if a person resides on site) to the risk-specific dose (RSD) for all carcinogenic metals
emitted shall not exceed 1.0 as determined by the following equation:
Predicted Ambient Concentration fl) ^ J.Q
Risk-Specific Dose (i)
i=l
where: n = number of carcinogenic metals
(4) Noncarcinogenic metals. For the noncarcinogenic metals, the predicted
maximum annual average off-site ground level concentration for each metal shall not exceed
the reference air concentration (RAQ.
45
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(5) Multiple stacks. Owners and operators of facilities with more than one on-site
stack from a boiler, industrial furnace, incinerator, or other thermal treatment unit subject to
controls on metals emissions under a RCRA operating permit or interim status controls
must conduct emissions testing and dispersion modeling to demonstrate that the aggregate
emissions from all such on-site stacks do not result in an exceedance of the acceptable
ambient levels.
(6) Implementation. Under Tier m, the metals controls must be implemented by
limiting feed rates of die individual metals to levels during the trial bum (for new facilities
or an interim status facility applying for a permit) or the compliance test (for interim status
facilities). The feed rate averaging periods are the same as provided by paragraphs (b)( 1 )(i
and ii) and (b)(2)(ii) of this section. The feed rate of metals in each feedstream must be
monitored to ensure mat the feed rate limits for the feedstreams specified under §§266.102
or 266.103 are not exceeded.
(e) Adjusted Tier I feed rate screening limits. The owner or operator may adjust the
feed rate screening limits provided by Appendix I of this part to account for site-specific
dispersion modeling. Under this approach, the adjusted feed rate screening limit for each
metal is determined by back-calculating from the acceptable ambient levels provided by
Appendices IV and V of this part using dispersion modeling to determine the maximum
allowable emission rate. This emission rate becomes the adjusted Tier I feed rate screening
limit The feed rate screening limits for carcinogenic metals are implemented as prescribed
in paragraph (b)(2) of this section.
(f) Alternative implementation approaches. (1) The Director may approve on a
case-by-case basis approaches to implement the Tier n or Tier m metals emission limits
provided by paragraphs (c) or (d) of this section alternative to monitoring the feed rate of
metals in each feedstream.
(2) The emission limits provided by paragraph (d) of this section must be
determined as follows:
(i) For each noncarcinogenic metal, by back-calculating from the RAG provided in
Appendix IV of this part to determine the allowable emission rate for each metal using the
dilution factor for the rna»jnwip annual average ground level concentration predicted by
dispersion modeling in conformance with paragraph (h) of this section; and
(ii) For each carcinogenic metal, by:
(A) Back-calculating from the RSD provided in Appendix V of this part to
determine the allowable emission rate for each metal if that metal were the only carcinogenic
metal emitted using the dilution factor for the maximum annual average ground level
concentration predicted by dispersion modeling in conformance with paragraph (h) of this
section; and
(B) If more than one carcinogenic metal is emitted, selecting an emission limit for
each carcinogenic metal not to exceed the emission rate determined by paragraph
(f)(2Xii)(A) of this section such that the sum for all carcinogenic metals of the ratio of the
selected emission limit to the emission rate determined by that paragraph does not exceed
1.0.
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(g) Emissions testing. (1) General. Emissions testing for metals shall be
conducted using the Multiple Metals Train as described in Methods Manual for Compliance
with the BTJF Regulations (incorporated by reference, see § 260.11).
(2) Hexavalent chromium. Emissions of chromium are assumed to be hexavalent
chromium unless die owner or operator conducts emissions testing to determine hexavalent
chromium emissions using procedures prescribed in Methods Manual for Compliance with
the BIF Regulations (incorporated by reference, see § 260.11).
(h) Dispersion modeling. Dispersion modeling required under this section shall be
conducted according to methods recommended in Guideline on Air Quality Models
(Revised), the "Hazardous Waste Combustion Air Quality Screening Procedure" described
in Methods Manual for Compliance with the BIF Regulations, or "EPA SCREEN
Screening Procedure" as described in Screening Procedures for Estimating Air Quality
Impact of Stationary Sources (all three documents are incorporated by reference, see
§260.11) to predict the maximum annual average off-site ground level concentration.
However, on-site concentrations must be considered when a person resides on-site.
(i) Enforcement. For the purposes of permit enforcement, compliance with the
operating requirements specified in the permit (under § 266.102) will be regarded as
compliance with this section. However, evidence that compliance with those permit
conditions is insufficient to ensure compliance with the requirements of this section may be
"information" justifying modification or revocation and re-issuance of a permit under §
270.41 of this chapter.
§266.107 Standards to control hydrogen chloride (HCI) and chlorine (CI2)
emissions.
(a) General. The owner or operator must comply with the hydrogen chloride (HCI)
and chlorine (Cl2) controls provided by paragraphs (b), (c), or (d) of this section.
(b) Screening limits. (1) Tier I feed rate screening limits. Feed rate screening limits
are specified for total chlorine in Appendix n of this part as a function of terrain-adjusted
effective stack height and terrain and land use in the vicinity of the facility. The feed rate of
total chlorine and chloride, both organic and inorganic, in all feed streams, including
hazardous waste, fuels, and industrial furnace feed stocks shall not exceed the levels
specified.
(2) Tier II emission rate screening limits. Emission rate screening limits for HCI
and Cl2 are specified in Appendix m of this part as a function of terrain-adjusted effective
stack height and terrain and land use in the vicinity of the facility. The stack emission rates
of HQ and Cl2 shall not exceed the levels specified.
(3) Definitions and limitations. The definitions and limitations provided by
§266.106(b) for the following terms also apply to the screening limits provided by this
paragraph: terrain-adjusted effective stack height, good engineering practice stack height,
terrain type, land use, and criteria for facilities not eligible to use the screening limits.
(4) Multiple stacks. Owners and operators of facilities with more than one on-site
stack from a boiler, industrial furnace, incinerator, or other thermal treatment unit subject to
controls on HCI or C\2 emissions under a RCRA operating permit or interim status controls
must comply with the Tier I and Tier n screening limits for those stacks assuming all
47
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hazardous waste is fed into the device with the worst-case stack based on dispersion
characteristics.
(i) The worst-case stack is determined by'procedures provided in §266.106(b)(6).
(ii) Under Tier I, the total feed rate of chlorine and chloride to all subject devices
shall not exceed the screening limit for the worst-case stack.
(iii) Under Tier n, the total emissions of HQ and Q2 from all subject stacks shall
not exceed the screening limit for the worst-case stack.
(c) Tier HI site-specific risk assessment. (1) General. Conformance with the Tier
IQ controls must be demonstrated by emissions testing to determine the emission rate for
HQ and Cl2, air dispersion modeling to predict the ma^imym annual average off-site
ground level concentration for each compound, and a demonstration that acceptable ambient
levels are not exceeded.
(2) Acceptable ambient levels. Appendix IV of this part lists the reference air
concentrations (RACs) for HQ (7 micrograms per cubic meter) and Q2 (0.4 micrograms
per cubic meter).
(3) Multiple stacks. Owners and operators of facilities with more than one on-site
stack from a boiler, industrial furnace, incinerator, or other thermal treatment unit subject to
controls on HQ or Q2 emissions under a RQIA operating permit or interim status controls
must conduct emissions testing and dispersion modeling to demonstrate that the aggregate
emissions from all such on-site stacks do not result in an exceedance of the acceptable
ambient levels for HQ and Q2-
(d) Averaging periods. The HQ and Q2 controls are implemented by limiting the
feed rate of total chlorine and chloride in all feedstreams, including hazardous waste, fuels,
and industrial furnace feed stocks. Under Tier I, the feed rate of total chloride and chlorine
is limited to the Tier I Screening Limits. Under Tier n and Tier HI, the feed rate of total
chloride and chlorine is limited to the feed rates during the trial bum (for new facilities or an
interim status facility applying for a permit) or the compliance test (for interim status
facilities). The feed rate limits are based on either
(i) An hourly rolling average as defined in §266.102(e)(6); or
(ii) An instantaneous basis not to be exceeded at any time.
(e) Adjusted Tier I feed rate screening limits. The owner or operator may adjust the
feed rate screening limits provided by Appendix I of this pan to account for site-specific
dispersion modeling. Under this approach, the adjusted feed rate screening limit is
determined by back-calculating from the acceptable ambient level for Cl2 provided by
Appendix IV of this part using dispersion modeling to determine the maximum allowable
emission rate. This emission rate becomes the adjusted Tier I feed rate screening limit
(f) Emissions testing. Emissions testing for HQ and Q2 shall be conducted using
the procedures described in Methods Manual for Compliance with the BIF Regulations
(incorporated by reference, see § 260.11).
(g) Dispersion modeling. Dispersion modeling shall be conducted according to the
provisions of §266.106(h).
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(h) Enforcement. For the purposes of permit enforcement, compliance with the
operating requirements specified in the permit (under § 266.102) will be regarded as
compliance with this section. However, evidence that compliance with those permit
conditions is insufficient to ensure compliance with the requirements of this section may be
"information" justifying modification or revocation and re-issuance of a permit under §
270.41 of this chapter.
§ 266.108 Small quantity on-site burner exemption.
(a) Exempt quantities. Owners and operators of facilities that burn hazardous waste
in an on-site boiler or industrial furnace are exempt from the requirements of this section
provided that:
(1) The quantity of hazardous waste burned in a device for a calendar month does
not exceed the limits provided in the following table based on the terrain-adjusted effective
stack height as defined in § 266.106(b)(3):
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Exempt Quantities for Small Quantity Burner Exemption
Terrain-Adjusted
Effective Stack
Height of Device
(Meters)
Allowable
Hazardous
Waste Burning
Rate
Terrain-Adjusted
Effective Stack
Height of Device
(Meters)
Allowable
Hazardous
Waste Burning
Rate
••••MMMMMMM
0 to 3.9
4.0 to 5.9
6.0 to 7.9
8.0 to 9.9
10.0 to 11.9
12.0 to 13.9
14 .0 to 15.9
16.0 to 17.9
18.0 to 19.9
20.0 to 21.9
22.0 to 23.9
24.0 to 25.9
26.0 to 27.9
28.0 to 29.9
30.0 to 34.9
35.0 to 39.9
(Gallons/Mo.)
0
13
18
27
40
48
59
69
76
84
93
100
110
130
140
170
40.0 to 44.9
45.0 to 49.9
50.0 to 54.9
55.0 to 59.9
60.0 to 64.9
65.0 to 69.9
70.0 to 74.9
75.0 to 79.9
80.0 to 84.9
85.0 to 89.9
90.0 to 94.9
95.0 to 99.9
100.0 to 104.9
105.0 to 109.9
110.0 to 114.9
115.0 or greater
(Gallons/Mo.)
210
260
330
400
490
610
680
760
850
960
1,100
1,200
1,300
1,500
1,700
1,900
50
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(2) The maximum hazardous waste firing rate does not exceed at any time 1 percent
of the total fuel requirements for the device (hazardous waste plus other fuel) on a volume
basis;
(3) The hazardous waste has a minimum heating value of 5,000 Btu/lb, as
generated; and
(4) The hazardous waste fuel does not contain (and is not derived from) EPA
Hazardous Waste Nos. F020, F021, F022, F023, F026, or F027.
(b) Mixing with nonhazardous fuels. If hazardous waste fuel is mixed with a
nonhazardous fuel, the quantity of hazardous waste before such mixing is used to comply
with paragraph (a).
(c) Multiple stacks. If an owner or operator burns hazardous waste in more than
one pn-site boiler or industrial furnace exempt under this section, the quantity limits
provided by paragraph (a)(l) of this section are implemented according to the following
equation:
n Actual Quantity Burnedfl}
£ Allowable Quantity Burned(i) < 1.0
i= 1
where:
n means the number of stacks;
Actual Quantity Burned means the waste quantity burned per month in device "i";
Allowable Quantity Burned, means the maximum allowable exempt quantity for
stack "i" from the table in (a)(l) above.
Note: Hazardous wastes that are subject to the special requirements for small
quantity generators under § 261.5 of this chapter may be burned in an off-site device under
the exemption provided by § 266.108, but must be included in the quantity determination
for the exemption.
(d) Notification Requirements. The owner or operator of facilities qualifying for
the small quantity burner exemption under this section must provide a one-time signed,
written notice to EPA indicating the following:
and
(1) The combustion unit is operating as a small quantity burner of hazardous waste;
(2) The owner and operator are in compliance with the requirements of this section;
(3) The maximum quantity of hazardous waste that the facility may burn per month
as provided by §266.108(a)(l).
(e) Recordkeeping requirements. The owner or operator must maintain at the
facility for at least three years sufficient records documenting compliance with the
hazardous waste quantity, firing rate, and heating value limits of this section. At a
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minimum, these records must indicate the quantity of hazardous waste and other fuel
burned in each unit per calendar month, and the heating value of the hazardous waste.
(Approved by the Office of Management and Budget under control number )
§266.109 Low risk waste exemption.
(a) Waiver of ORE standard. The DRE standard of §266.104(a) does not apply if
the boiler or industrial furnace is operated in conformance with (a)(l) of this section and the
owner or operator demonstrates by procedures prescribed in (a)(2) of this section that the
burning will not result in unacceptable adverse health effects.
(1) The device shall be operated as follows:
(i) A rnininmm of SO percent of fuel fired to the device shall be fossil fuel, fuels
derived from fossil fuel, tall oil, or, if approved by the Director on a case-by-case basis,
other nonhazardous fuel with combustion characteristics comparable to fossil fuel. Such
fuels are termed "primary fuel" for purposes of this section. (Tall oil is a fuel derived from
vegetable and rosin fatty acids.) The SO percent primary fuel firing rate shall be determined
on a total heat or volume input basis, whichever results in the larger volume of primary fuel
fired;
(ii) Primary fuels and hazardous waste fuels shall have a minimum as-fired heating
value of 8,000 Btu/lb;
(iii) The hazardous waste is fired directly into the primary fuel flame zone of the
combustion chamber, and
(iv) The device operates in conformance with the carbon monoxide controls
provided by §266.104(b)(l). Devices subject to the exemption provided by this section are
not eligible for the alternative carbon monoxide controls provided by §266.104(c).
(2) Procedures to demonstrate that the hazardous waste burning will not pose
unacceptable adverse public health effects are as follows:
(i) Identify and quantify those nonmetal compounds listed in Appendix Vm, Part
261 of this chapter that could reasonably be expected to be present in the hazardous waste.
The constituents excluded from analysis must be identified and the basis for their exclusion
explained;
(ii) Calculate reasonable, worst case emission rates for each constituent identified in
paragraph (aX2)(i) of this section by assuming the device achieves 99.9 percent destruction
and removal efficiency. That is, assume that 0.1 percent of the mass weight of each
constituent fed to the device is emitted.
(iii) For each constituent identified in paragraph (a)(2)(i) of this section, use
emissions dispersion modeling to predict the maximum annual average ground level
concentration of die constituent
(A) Dispersion modeling shall be conducted using methods specified in
§266.106(h).
(B) Owners and operators of facilities with more than one on-site stack from a
boiler or industrial furnace that is exempt under this section must conduct dispersion
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modeling of emissions from all stacks exempt under this section to predict ambient levels
prescribed by mis paragraph.
(iv) Ground level concentrations of constituents predicted under paragraph (a)(iii)
of this section must not exceed the following levels:
(A) For the noncarcinogenic compounds listed in Appendix IV of this part, the
levels established in Appendix IV;
(B) For the carcinogenic compounds listed in Appendix V of this part, the sum for
all constituents of the ratios of the actual ground level concentration to the level established
in Appendix V cannot exceed 1.0; and
(C) For constituents not listed in Appendix IV or V, 0.002 micrograms per cubic
meter.
(b) Waiver of paniculate matter standard. The paniculate matter standard of
§266.105 does not apply if:
(1) The DRE standard is waived under paragraph (a) of this section; and
(2) The owner or operator complies with the Tier I metals feed rate screening limits
provided by §266.106(b).
§266.110 Waiver of DRE trial burn for boilers.
Boilers that operate under the special operating requirements of this section, and
that do not bum hazardous waste containing (or derived from) EPA Hazardous Waste Nos.
F020, F021, F022, F023, FO26, or F027, are considered to be in conformance with the
DRE standard of §266.104(a), and a trial burn to demonstrate DRE is waived. When
burning hazardous waste:
(a) A minimum of 50 percent of fuel fired to the boiler shall be fossil fuel, fuels
derived from fossil fuel, tall oil, or, if approved by the Director on a case-by-case basis,
other nonhazardous fuel with combustion characteristics comparable to fossil fuel. Such
fuels are termed "primary fuel" for purposes of this section. (Tall oil is a fuel derived from
vegetable and rosin fatty acids.) The 50 percent primary fuel firing rate shall be determined
on a total heat or volume input basis, whichever results in the larger volume of primary fuel
fired;
(b) Boiler load shall not be less than 40 percent Boiler load is the ratio at any time
of the total heat input to the mgrimuni design heat input;
(c) Primary fuels and hazardous waste fuels shall have a minimum as-fired heating
value of 8,000 Btu/lb, and each material fired in a burner where hazardous waste is fired
must have a heating value of at least 8,000 Btu/lb, as-fired;
(d) The device shall operate in conformance with the carbon monoxide standard
provided by §266.104(b)(l). Boilers subject to the waiver of the DRE trial burn provided
by this section are not eligible for the alternative carbon monoxide standard provided by
§266.104(c);
(e) The boiler must be a watertube type boiler that does not feed fuel using a stoker
or stoker type mechanism; and
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(0 The hazardous waste shall be fired directly into the primary fuel flame zone of
the combustion chamber with an air or steam atomizarion firing system, mechanical
atomization system, or a rotary cup atomization system under the following conditions:
(1) Viscosity. The viscosity of the hazardous waste fuel as-fired shall not exceed
300 SSU;
(2) Particle size. When a high pressure air or steam atomizer, low pressure
atomizer, or mechanical atomizer is used, 70% of the hazardous waste fuel must pass
through a 200 mesh (74 micron) screen, and when a rotary cup atomizer is used, 70% of
the hazardous waste must pass through a 100 mesh (ISO micron) screen;
(3) Mechanical atomization systems. Fuel pressure within a mechanical atomization
system and fuel flow rate shall be maintained within the design range taking into account
the viscosity and volatility of the fuel;
(4) Rotary cup atomization systems. Fuel flow rate through a rotary cup
atomization system must be maintained within the design range taking into account the
viscosity and volatility of me fuel.
§ 266.111 Standards for direct transfer.
(a) Applicability. The regulations in this section apply to owners and operators of
boilers and industrial furnaces subject to §§266.102 or 266.103 if hazardous waste is
directly transferred from a transport vehicle to a boiler or industrial furnace without the use
of a storage unit
(b) Definitions. (1) When used in this section, the following terms have the
meanings given below:
Direct transfer equipment means any device (including but not limited to, such
devices as piping, fittings, flanges, valves, and pumps) that is used to distribute, meter, or
control the flow of hazardous waste between a container (i.e., transport vehicle) and a
boiler or industrial furnace.
Container means any portable device in which hazardous waste is transported,
stored, treated, or otherwise handled, and includes transport vehicles that are containers
themselves (e.g., tank trucks, tanker-trailers, and rail tank cars), and containers placed on
or in a transport vehicle.
(2) This section references several requirements provided in Subparts I and J of
Parts 264 and 265. For purposes of this section, the term "tank systems" in those
referenced requirements means direct transfer equipment as defined in paragraph (b)(l) of
this section.
(c) General operating requirements. (1) No direct transfer of a pumpable hazardous
waste shall be conducted from an open-top container to a boiler or industrial furnace.
(2) Direct transfer equipment used for pumpable hazardous waste shall always be
closed, except when necessary to add or remove the waste, and shall not be opened,
handled, or stored in a manner that may cause any rupture or leak.
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(3) The direct transfer of hazardous waste to a boiler or industrial furnace shall be
conducted so that it does not:
(i) Generate extreme heat or pressure, fire, explosion, or violent reaction;
(ii) Produce uncontrolled toxic mists, fumes, dusts, or gases in sufficient quantities
to threaten human health;
(iii) Produce uncontrolled flammable fumes or gases in sufficient quantities to pose
a risk of fire or explosions;
(iv) Damage the structural integrity of the container or direct transfer equipment
containing the waste;
(v) Adversely affect the capability of the boiler or industrial furnace to meet the
standards provided by §§266.104 through 266.107; or
(vi) Threaten human health or the environment
(4) Hazardous waste shall not be placed in direct transfer equipment if it could
cause the equipment or its secondary containment system to rupture, leak, corrode, or
otherwise fail.
(5) The owner or operator of the facility shall use appropriate controls and practices
to prevent spills and overflows from the direct transfer equipment or its secondary
containment systems. These include at a minimum:
(i) Spill prevention controls (e.g., check valves, dry discount couplings); and
(ii) Automatic waste feed cutoff to use if a leak or spill occurs from the direct
transfer equipment.
(d) Areas where direct transfer vehicles (containers) are located. Applying the
definition of container under this section, owners and operators must comply with the
following requirements:
(1) The containment requirements of §264.175 of this chapter;
(2) The use and management requirements of Subpart I, Part 265 of this chapter,
except for §§ 265.170 and 265.174; and
(3) The closure requirements of §264.178 of this chapter.
(e) Direct transfer equipment. Direct transfer equipment must meet the following
requirements:
(1) Secondary containment. Owners and operators shall comply with the secondary
containment requirements of §265.193 of this chapter, except for paragraphs 265.193(a),
(d), (e), and (i) as follows:
(i) For all new direct transfer equipment, prior to their being put into service; and
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(ii) For existing direct transfer equipment within 2 years after [the effective date of
the rule].
(2) Requirements prior to meeting secondary containment requirements, (i) For
existing direct transfer equipment that does not have secondary containment, the owner or
operator shall determine whether the equipment is leaking or is unfit for use. The owner or
operator shall obtain and keep on file at the facility a written assessment reviewed and
certified by a qualified, registered professional engineer in accordance with §270.1 l(d) of
this chapter that attests to the equipment's integrity by [12 months after the effective date of
this rule.]
(ii) This assessment shall determine whether the direct transfer equipment is
adequately designed and has sufficient structural strength and compatibility with the
waste(s) to be transferred to ensure that it will not collapse, rupture, or fail. At a minimum,
this assessment shall consider the following:
(A) Design standard(s), if available, according to which the direct transfer
equipment was constructed;
(B) Hazardous characteristics of the waste(s) that have been or will be handled;
(C) Existing corrosion protection measures;
(D) Documented age of the equipment, if available, (otherwise, an estimate of the
age); and
(E) Results of a leak test or other integrity examination such that the effects of
temperature variations, vapor pockets, cracks, leaks, corrosion, and erosion are accounted
for.
(iii) If, as a result of the assessment specified above, the direct transfer equipment is
found to be leaking or unfit for use, the owner or operator shall comply with the
requirements of §§265.196(a) and (b) of this chapter.
(3) Inspections and recordkeeping. (i) The owner or operator must inspect at least
once each operating hour when hazardous waste is being transferred from the transport
vehicle (container) to the boiler or industrial furnace:
(A) Overfill/spill control equipment (e.g., waste-feed cutoff systems, bypass
systems, and drainage systems) to ensure that it is in good working order;
(B) The above ground portions of the direct transfer equipment to detect corrosion,
erosion, or releases of waste (e.g., wet spots, dead vegetation); and
(C) Data gathered from monitoring equipment and leak-detection equipment, (e.g.,
pressure and temperature gauges) to ensure that the direct transfer equipment is being
operated according to its design.
(ii) The owner or operator must inspect cathodic protection systems, if used, to
ensure that they are functioning properly according to the schedule provided by
§265.195(b) of this chapter
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(iii) Records of inspections made under this paragraph shall be maintained in the
operating record at the facility, and available for inspection for at least 3 years from the date
of the inspection.
(4) Design and installation of new ancillary equipment. Owners and operators must
comply with the requirements of §265.192 of this chapter.
(5) Response to leaks or spills. Owners and operators must comply with the
requirements of §265.1% of this chapter.
(6) Closure. Owners and operators must comply with the requirements of
§265.197 of this chapter, except for § 265.197(c)(2) through (c)(4).
(Approved by the Office of Management and Budget under control number )
§ 266.112 Regulation of residues.
A residue derived from the burning or processing of hazardous waste in a boiler or
industrial furnace is not excluded from the definition of a hazardous waste under
§261.4(b)(4), (7), or (8) unless the device and the owner or operator meet the following
requirements:
(a) The device meets the following criteria:
(1) Boilers. Boilers must burn coal and at least 50% of the heat input to the boiler
must be provided by the coal;
(2) Ore or mineral furnaces. Industrial furnaces subject to §261.4(b)(7) must
process at least 50% by weight normal, nonhazardous raw materials;
(3) Cement kilns. Cement kilns must process at least 50% by weight normal
cement-production raw materials;
(b) The owner or operator demonstrates that the hazardous waste does not
significantly affect the residue by demonstrating conformance with either of the following
criteria:
(1) Comparison of waste-derived residue with normal residue. The waste-derived
residue must not contain Appendix Vm, Pan 261 constituents (toxic constituents) that
could reasonably be attributable to the hazardous waste at concentrations significantly
higher than in residue generated without burning or processing of hazardous waste, using
the following procedure. Toxic compounds mat could reasonably be attributable to burning
or processing the hazardous waste (constituents of concern) include toxic constituents in
the hazardous waste, and the 31 organic compounds listed in Appendix VD1 of this part
that may be generated as products of incomplete combustion. Sampling and analyses shall
be in conformance with procedures prescribed in Test Methods for Evaluating Solid Waste.
Physical/Chemical Methods, incorporated by reference in §260.11 (a) of this chapter.
(i) Normal residue. Concentrations of toxic constituents of concern in normal
residue shall be determined based on analyses of a minimum of 10 composite samples.
The upper 95% confidence level about the mean of the concentration in the normal residue
shall be considered the statistically-derived concentration in the normal residue. If changes
in raw materials or fuels reduce the statistically-derived concentrations of the toxic
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constituents of concern in the normal residue, the statistically-derived concentrations must
be revised or statistically-derived concentrations of toxic constituents in normal residue
must be established for a new mode of operation with the new raw material or fuel. To
determine the upper 95% confidence level about the mean of die concentration in the normal
residue, the owner or operator shall use statistical procedures prescribed in "Statistical
Methodology for Bevill Residue Determinations" in Methods Manual far Compliance with
the BIF Regulations, incorporated by reference in §260.11 (a) of this chapter.
(ii) Waste-derived residue. Concentrations of toxic constituents of concern in
waste-derived residue shall be determined based on analysis of samples composited over a
period of not more than 24 hours. The concentration of a toxic constituent in the waste-
derived residue is not considered to be significantly higher than in the normal residue if the
concentration in the waste-derived residue does not exceed the concentration established for
the normal residue under paragraph (b)(l)(i) of this section; or
(2) Comparison of waste-derived residue concentrations with health-based limits.
(i) Nonmetal constituents. The concentrations of nonmetal toxic constituents of concern
(specified in paragraph (b)(l) of this section) in the waste-derived residue must not exceed
the health-based levels specified in Appendix VII of this part If a health-based limit for a
constituent of concern is not listed in Appendix VII of this pan, then a limit of 0.002
micrograms per kilogram or die level of detection (using analytical procedures prescribed in
SW-846), whichever is higher, shall be used; and
(ii) Metal constituents. The concentration of metals in an extract obtained using the
Toxicity Characteristic Leaching Procedure of §261.24 of this chapter must not exceed the
levels specified in Appendix VII of this part; and
(c) Records sufficient to document compliance with the provisions of this section
must be retained for a period of three years. At a minimum, the following shall be
recorded:
(1) Levels of constituents in Appendix Vm, Part 261, that are present in waste-
derived residues;
(2) If the waste-derived residue is compared with normal residue under paragraph
(b)(l) of this section:
(i) The levels of constituents in Appendix Vm, Pan 261, that are present in normal
residues; and
(ii) Data and information, including analyses of samples as necessary, obtained to
determine if changes in raw materials or fuels would reduce the concentration of toxic
constituents of concern in the normal residue.
PART 270--EPA ADMINISTERED PERMIT PROGRAMS: THE
HAZARDOUS WASTE PERMIT PROGRAM.
VI. In Part 270:
1. The authority citation for Pan 270 continues to read as follows:
Authority: Sees. 1006,2002,3005,3007, and 7004 of the Solid Waste Disposal
Act, as amended by the Resource Conservation and Recovery Act of 1976, as amended (42
U.S.C. 6905, 6912, 6925, 6927, and 6974.
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2. Pan 270 is amended by adding §270.22 to read as follows:
§270.22 Specific Part B information requirements for boilers and
industrial furnaces burning hazardous waste.
(a) Trial bums. (1) General. Except as provided below, owners and operators that
are subject to the standards to control organic emissions provided by §266.104 of this
chapter, standards to control paniculate matter provided by §266.105 of this chapter,
standards to control metals emissions provided by §266.106 of this chapter, or standards to
control hydrogen chloride or chlorine gas emissions provided by §266.107 of this chapter
must conduct a trial burn to demonstrate conformance with those standards and must
submit a trial burn plan or the results of a trial burn, including all required determinations,
in accordance with §270.66.
(i) A trial burn to demonstrate conformance with a particular emission standard may
be waived under provisions of §§266.104 through 266.107 of this chapter and paragraphs
(a)(2) through (a)(5) of this section; and
(ii) The owner or operator may submit data in lieu of a trial burn, as prescribed in
paragraph (a)(6) of this section.
(2) Waiver of trial burn for ORE. (i) Boilers operated under special operating
requirements. When seeking to be permitted under §§266.104(a)(4) and 266.110 of this
chapter that automatically waive the DRE trial bum, the owner or operator of a boiler must
submit documentation that the boiler operates under the special operating requirements
provided by §266.110 of this chapter.
(ii) Boilers and industrial furnaces burning low risk waste. When seeking to be
permitted under the provisions for low risk waste provided by §§266.104(a)(5) and
266.109(a) of this chapter that waive the DRE trial bum, the owner or operator must
submit:
(A) Documentation that the device is operated in conformance with the requirements
of §266.109(a)(l) of this chapter;
(B) Results of analyses of each waste to be burned, documenting the concentrations
of nonmetal compounds listed in Appendix VHI of Pan 261 of this chapter, except for
those constituents that would reasonably not be expected to be in the waste. The
constituents excluded from analysis must be identified and the basis for their exclusion
explained The analysis must rely on analytical techniques specified in Test Methods for
the Evaluation of Solid Waste. Physical/ Chemical Methods (incorporated by reference, see
§260.11).
(Q Documentation of hazardous waste firing rates and calculations of reasonable,
worst-case emission rates of each constituent identified in paragraph (a)(l)(U)(B) of this
section using procedures provided by §266.109(a)(2)(ii) of this chapter,
(D) Results of emissions dispersion modeling for emissions identified in
paragraphs (a)(2)(ii)(C) of this section using modeling procedures prescribed by
§266.106(h) of mis chapter. The Director will review the emission modeling conducted by
the applicant to determine conformance with these procedures. The Director will either
approve the modeling or determine that alternate or supplementary modeling is appropriate.
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(E) Documentation that the mammum a^pimi average ground level concentration of
each constituent identified in paragraph (a)£2)(ii)(B) of this section quantified in
conformance with paragraph (a)(2)(ii))D) of this section does not exceed the allowable
ambient level established in Appendices IV of V of Pan 266. The acceptable ambient
concentration for emitted constituents for which a specific Reference Air Concentration has
not been established in Appendix IV or Risk-Specific Dose has not been established in
Appendix V is 0.09 micrograms per cubic meter, as noted in the footnote to Appendix IV.
(3) Waiver of trial burn for metals. When seeking to be permitted under the Tier I
(or adjusted Tier I) metals feed rate screening limits provided by §266.106(b) and (e) of
mis chapter that control metals emissions without requiring a trial burn, the owner or
operator must submit:
(i) Documentation of the feed rate of hazardous waste, other fuels, and industrial
furnace feed stocks;
(ii) Documentation of the concentration of each metal controlled by §266.106(b) or
(e) of this chapter in the hazardous waste, other fuels, and industrial furnace feedstocks,
and calculations of the total feed rate of each metal;
(iii) Documentation of how the applicant will ensure that the Tier I feed rate
screening limits provided by §266.106(b) or (e) of this chapter will not be exceeded during
the averaging period provided by that paragraph;
(iv) Documentation to support the determination of the terrain-adjusted effective
stack height, good engineering practice stack height, terrain type, and land use as provided
by §266.106(b)(3) through (b)(5) of this chapter,
(v) Documentation of compliance with the provisions of §266.106(b)(6), if
applicable, for facilities with multiple stacks;
(vi) Documentation that the facility does not fail the criteria provided by
§266.106(b)(7) for eligibility to comply with the screening limits; and
(vii) Proposed sampling and metals analysis plan for the hazardous waste, other
fuels, and industrial furnace feed stocks.
(4) Waiver of trial burn for paniculate matter. When seeking to be permitted under
the low risk waste provisions of §266.109(b) which waives the paniculate standard (and
trial burn to demonstrate conformance with the paniculate standard), applicants must
submit documentation supporting conformance with paragraphs (a)(2Xii) and (aX3) of this
section.
(5) Waiver of trial burn for HCl and C/2. When seeking to be permitted under the
Tier I (or adjusted Tier I) feed rate screening limits for total chloride and chlorine provided
by §266.107(b)(l) and (e) of this chapter that control emissions of hydrogen chloride
(HCl) and chlorine gas (Q2) without requiring a trial bum, the owner or operator must
submit:
(i) Documentation of the feed rate of hazardous waste, other fuels, and industrial
furnace feed stocks;
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(ii) Documentation of the levels of total chloride and chlorine in the hazardous
waste, other fuels, and industrial furnace feedstocks, and calculations of the total feed rate
of total chloride and chlorine;
(iii) Documentation of how the applicant will ensure that the Tier I (or adjusted Tier
I) feed rate screening limits provided by §266.107(b)(l) or (e) of this chapter will not be
exceeded during the averaging period provided by that paragraph;
(iv) Documentation to support the determination of the terrain-adjusted effective
stack height, good engineering practice stack height, terrain type, and land use as provided
by §266.107(b)(3) of this chapter;
(v) Documentation of compliance with the provisions of §266.107(b)(4), if
applicable, for facilities with multiple stacks;
(vi) Documentation that the facility does not fail the criteria provided by
§266.107(b)(3) for eligibility to comply with the screening limits; and
(vii) Proposed sampling and analysis plan for total chloride and chlorine for the
hazardous waste, other fuels, and industrial furnace feedstocks.
(6) Data in lieu of a trial burn. The owner or operator may seek an exemption from
the trial bum requirements to demonstrate conformance with §§266.104 through 266.107
of this chapter and §270.66 by providing the information required by §270.66 from
previous compliance testing of the device in conformance with §266.103 of this chapter, or
from compliance testing or trial or operational bums of similar boilers or industrial furnaces
burning similar hazardous wastes under similar conditions. If data from a similar device is
used to support a trial burn waiver, the design and operating information required by
§270.66 must be provided for both the similar device and the device to which the data is to
be applied, and a comparison of the design and operating information must be provided.
The Director shall approve a permit application without a trial burn if he finds that the
hazardous wastes are sufficiently similar, the devices are sufficiently similar, the operating
conditions are sufficiently similar, and the data from other compliance tests, trial burns, or
operational burns are adequate to specify (under §266.102 of this chapter) operating
conditions that will ensure conformance with §266.102(c) of this chapter. In addition, the
following information shall be submitted:
(i) For a waiver from any trial burn:
(A) A description and analysis of the hazardous waste to be burned compared with
the hazardous waste for which data from compliance testing, or operational or trial burns
are provided to support the contention that a trial burn is not needed;
(B) The design and operating conditions of the boiler or industrial furnace to be
used, compared with that for which comparative burn data are available; and
(Q Such supplemental information as the Director finds necessary to achieve the
purposes of this paragraph.
(ii) For a waiver of the DRE trial bum, the basis for selection of POHCs used in the
other trial or operational bums which demonstrate compliance with the DRE performance
standard in §266.104(a) of this chapter. This analysis should specify the constituents in
Appendix VIE, Part 261 of this chapter, that the applicant has identified in die hazardous
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waste for which a permit is sought, and any differences from the POHCs in the hazardous
waste for which bum data are provided.
(b) Alternative HC limit for industrial furnaces with organic matter in raw materials.
Owners and operators of industrial furnaces requesting an alternative HC limit under
§266.104(f) of mis chapter shall submit the following information at a minimum;
(1) Documentation that the furnace is designed and operated to minimize HC
emissions from fuels and raw materials;
(2) Documentation of the proposed baseline flue gas HC (and CO) concentration,
including data on HC (and CO) levels during tests when the facility produced normal
products under normal operating conditions from normal raw materials while burning
normal fuels and when not burning hazardous waste;
(3) Test burn protocol to confirm the baseline HC (and CO) level including
information on the type and flow rate of all feedstreams, point of introduction of all
feedstreams, total organic carbon content (or other appropriate measure of organic content)
of all nonfuel feedstreams, and operating conditions that affect combustion of fuel(s) and
destruction of hydrocarbon emissions from nonfuel sources;
(4) Trial burn plan to:
(i) Demonstrate that flue gas HC (and CO) concentrations when burning hazardous
waste do not exceed the baseline HC (and CO) level; and
(ii) Identify the types and concentrations of organic compounds listed in Appendix
Vin, Part 261 of this chapter, that are emitted when burning hazardous waste in
confonnance with procedures prescribed by the Director,
(5) Implementation plan to monitor over time changes in the operation of the facility
that could reduce the baseline HC level and procedures to periodically confirm the baseline
HC level; and
(6) Such other information as the Director finds necessary to achieve the purposes
of this paragraph.
(c) Alternative metals implementation approach. When seeking to be permitted
under an alternative metals implementation approach under §266.106(f) of mis chapter, the
owner or operator must submit documentation specifying how the approach ensures
compliance with the metals emissions standards of §266.106(c) or (d) and how the
approach can be effectively implemented and monitored. Further, the owner or operator
shall provide such other information that the Director finds necessary to achieve the
purposes of mis paragraph.
(d) Automatic waste feed cutoff system. Owners and operators shall submit
information describing the automatic waste feed cutoff system, including any pre-alarm
systems that may be used.
(e) Direct transfer. Owners and operators that use direct transfer operations to feed
hazardous waste from transport vehicles (containers, as defined in §266.111 of this
chapter) directly to the boiler or industrial furnace shall submit information supporting
confonnance with the standards for direct transfer provided by $266.111 of this chapter.
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(f) Residues. Owners and operators that claim that their residues are excluded from
regulation under the provisions of §266.112 of this chapter must submit information
adequate to demonstrate conformance with those provisions.
(Approved by the Office of Management and Budget under control number )
3. In §270.42, paragraph (g) is revised to read as follows:
§270.42 Permit modifications at the request of the permittee.
(g) Newly regulated wastes and units. (1) The permittee is authorized to continue
to manage wastes listed or identified as hazardous under Pan 261 of this chapter, or to
continue to manage hazardous waste in units newly regulated as hazardous waste
management units, if:
(i) The unit was in existence as a hazardous waste facility with respect to the newly
listed or characterized waste or newly regulated waste management unit on the effective
date of the final rule listing or identifying the waste, or regulating the unit;
(ii) The permittee submits a Class 1 modification request on or before the date on
which the waste or unit becomes subject to the new requirements;
(iii) The permittee is in compliance with the applicable standards of 40 CFR Parts
265 and 266 of this chapter,
(iv) In the case of Classes 2 and 3 modifications, the permittee also submits a
complete modification request within 180 days of the effective date of the rule listing or
identifying the waste, or subjecting the unit to RCRA Subtitle C management standards;
(v) In die case of land disposal units, the permittee certifies that each such unit is in
compliance with all applicable requirements of Part 265 of this chapter for groundwater
monitoring and financial responsibility on the date 12 months after the effective date of the
rule identifying or listing the waste as hazardous, or regulating the unit as a hazardous
waste management unit If the owner or operator fails to certify compliance with all these
requirements, he or she will lose authority to operate under this section.
(2) New wastes or units added to a facility's permit under this subsection do not
constitute expansions for the purpose of the 25 percent capacity expansion limit for Class 2
modifications.
4. In §270.42, Appendix I is amended by revising Title L, "Incinerators", items 1
through 7 to read as follows:
APPENDIX I TO SECTION 270.42 •- CLASSIFICATION OF PERMIT
MODIFICATIONS
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flags
L. Incinerators, Boilers, and Industrial Furnaces
1. Changes to increase by more man 25% any of the following limits authorized in the
permit: A thermal feed cue *'m*T, a feedstream feed rate limit, a chlorine/chloride feed
rate limit, a metal feed rale limit, or an ash feed rale limit Hie Director will require a
new trial bum to substantiate compliance with the regulatory performance standards
unless this demonstration can be made through other means. — ................................
2. Changes to increase by up to 25% any of the following limits authorized in the permit:
A thermal feed rate limit, a feedstream feed rale limit, a chlorine/chloride feed rate limit,
a metal feed rate limit, or an ash feed rate timit. The Director will require a new trial
burn to substantiate compliance with the regulatory performance «t«nrianflg unless this
demonstration can be made through other means [[[
3. Modification of an incinerator, boiler, or industrial furnace unit by changing the internal
size or geometry of the primary or secondary combustion units, by adding a primary or
secondary combustion unit, by substantially changing the design of any component used
to remove HC1/C12, metals, or paniculate from the combustion gases, or by changing
other features of the incinerator, boiler, or industrial furnace that could affect its
capability to meet the regulatory performance standards. The Director will require a new
trial bum to substantiate compliance with the regulatory performance standards unless
this demonstration can be made through other means.
4. Modification of an incinerator, boikr, or industrial furnace unit in a manner that would
not likely affect the capability of the unit to meet the regulatory performance standards
but which would change the operating conditions or monitoring requirements specified in
the permit The Director may require a new trial burn to demonstrate compliance with
the regulatory performance standards [[[
5. Operating requirements:
a. Modification of the limits specified in the permit for minimum or maximum
combustion gas temperature, minimum combustion gas residence time, oxygen
concentration in the secondary combustion chamber, flue gas carbon monoxide and
hydrocarbon concentration, maximum temperature at the inlet to the paniculate matter
emission control system, or operating parameters for the air pollution control system.
The Director will require a new trial burn to substantiate compliance with the
regulatory performance standards unless this deinonstration can be inaoe through other
means [[[
* * *
6. Burning different wastes:
a. If the waste contains a POHC that is more difficult to bum than authorised by the
permit or if burning of the waste requires compliance with different regulatory
performance standards than specified in the permit The Director will require a new trial
bum to substantiate compliance with the regulatory performance standards unless mis
demonstration can be made through other means ----------------- ..... -----------------------------
b. If the waste does not contain a POHC that is more difficult to burn than authorized by
the permit and if burning of the waste does not require compliance with different
regulatory performance standards ftmn specified in the permit...................................
Note: See §270.42(g) for modification procedures to be used for the management of newly
listed or identified wastes.
7. Shakedown and trial burn:
* * *
b. Authorization of up to an additional 720 hours of waste burning during the shakedown
period for determining operational readiness after amstruction, with the prior approval
of the Director ................ .. [[[
• • •
-------
S. Part 270 is amended by adding §270.66 to read as follows:
§270.66 Permits for boilers and industrial furnaces burning hazardous
waste.
(a) General. Owners and operators of new boilers and industrial furnaces (those
not operating under the interim status standards of §266.103 of this chapter) are subject to
paragraphs (b) through (f) of this section. Boilers and industrial furnaces operating under
the interim status standards of §266.103 of this chapter are subject to paragraph (g) of this
section.
(b) Permit operating periods for new boilers and industrial furnaces. A permit for a
new boiler or industrial furnace shall specify appropriate conditions for the following
operating periods:
(1) Pretrial burn period. For the period beginning with initial introduction of
hazardous waste and ending with initiation of the trial bum, and only for the minimum time
required to bring the boiler or industrial furnace to a point of operation readiness to conduct
a trial burn, not to exceed 720 hours operating time when burning hazardous waste, the
Director must establish in the Pretrial Burn Period of the permit conditions, including but
not limited to, allowable hazardous waste feed rates and operating conditions. The Director
may extend the duration of this operational period once, for up to 720 additional hours, at
the request of the applicant when good cause is shown. The permit may be modified to
reflect the extension according to §270.42.
(i) Applicants must submit a statement, with Part B of the permit application, that
suggests the conditions necessary to operate in compliance with the standards of
§§266.104 through 266.107 of this chapter during this period. This statement should
include, at a minimum, restrictions on the applicable operating requirements identified in
§266.102(e) of this chapter.
(ii) The Director will review this statement and any other relevant information
submitted with Part B of the permit application and specify requirements for this period
sufficient to meet the performance standards of §§266.104 through 266.107 of this chapter
based on his/her engineering judgment
(2) Trial burn period. For the duration of the trial bum, the Director must establish
conditions in the permit for the purposes of determining feasibility of compliance with the
performance standards of §§266.104 through 266.107 of this chapter and determining
adequate operating conditions under §266.102(e) of this chapter. Applicants must propose
a trial bum plan, prepared under paragraph (c) of this section, to be submitted with Part B
of the permit application.
(3) Post-trial burn period, (i) For the period immediately following completion of
the trial burn, and only for the minimum period sufficient to allow sample analysis, data
computation, and submission of the trial burn results by the applicant, and review of the
trial bum results and modification of the facility permit by the Director to reflect the trial
burn results, die Director will establish the operating requirements most likely to ensure
compliance with the performance standards of §§266.104 through 266.107 of this chapter
based on his engineering judgment
(ii) Applicants must submit a statement, with Part B of the application, that
identifies the conditions necessary to operate during this period in compliance with the
65
-------
performance standards of §§266.104 through 266.107 of this chapter. This statement
should include, at a minimum, restrictions on the operating requirements provided by
§266.102(c) of this chapter.
(iii) The Director will review this statement and any other relevant information
submitted with Part B of the permit application and specify requirements for this period
sufficient to meet the performance standards of §§266.104 through 266.107 of this chapter
based on his/her engineering judgment
(4) Final permit period. For die final period of operation, die Director will develop
operating requirements in conformance with §266.102(e) of this chapter that reflect
conditions in die trial bum plan and are likely to ensure compliance with die performance
standards of §§266.104 through 107 of this chapter. Based on die trial bum results, die
Director shall make any necessary modifications to die operating requirements to ensure
compliance with die performance standards. The permit modification shall proceed
according to §270.42.
(c) Requirements for trial burn plans. The trial burn plan must include die
following information. The Director, in reviewing die trial bum plan, shall evaluate die
sufficiency of die information provided and may require die applicant to supplement this
information, if necessary, to achieve die purposes of this paragraph:
(1) An analysis of each feed stream, including hazardous waste, other fuels, and
industrial furnace feed stocks, as fired, that includes:
(i) Heating value, levels of antimony, arsenic, barium, beryllium, cadmium,
chromium, lead, mercury, silver, thallium, total chlorine/chloride, and ash;
(ii) Viscosity or description of die physical form of die feed stream;
(2) An analysis of each hazardous waste, as fired, including:
(i) An identification of any hazardous organic constituents listed in Appendix Vffi,
Part 261, of tiiis chapter diat are present in die feed stream, except diat die applicant need
not analyze for constituents listed in Appendix VEtt diat would reasonably not be expected
to be found in die hazardous waste. The constituents excluded from analysis must be
identified and die basis for dieir exclusion explained. The analysis must be conducted in
accordance witii analytical techniques specified in Test Methods for the F|V8lUfltion °f Solid
Waste. Physical/ Chemical Methods (incorporated by reference, see §270.6), or their
equivalent
(ii) An approximate quantification of die hazardous constituents identified in die
hazardous waste, witiiin the precision produced by die analytical mediods specified in Test
Methods for thq Evaluation of Solid Waste. Physical/Chemical Methods (incorporated by
reference, see §270.6), or odier equivalent
(iii) A description of blending procedures, if applicable, prior to firing die
hazardous waste, including a detailed analysis of die hazardous waste prior to blending, an
analysis of die material widi which die hazardous waste is blended, and blending ratios.
(3) A detailed engineering description of die boiler or industrial furnace, including:
(i) Manufacturer's name and model number of die boiler or industrial furnace;
66
-------
(ii) Type of boiler or industrial furnace;
(iii) Maximum design capacity in appropriate units;
(iv) Description of the feed system for the hazardous waste, and, as appropriate,
other fuels and industrial furnace feedstocks;
(v) Capacity of hazardous waste feed system;
(vi) Description of automatic hazardous waste feed cutoff system(s); and
(vii) Description of any air pollution control system; and
(vii) Description of stack gas monitoring and any pollution control monitoring
systems.
(4) A detailed description of sampling and monitoring procedures including
sampling and monitoring locations in the system, the equipment to be used, sampling and
monitoring frequency, and planned analytical procedures for sample analysis.
(5) A detailed test schedule for each hazardous waste for which the trial bum is
planned, including date(s), duration, quantity of hazardous waste to be burned, and other
factors relevant to the Director's decision under paragraph (b)(2) of this section.
(6) A detailed test protocol, including, for each hazardous waste identified, the
ranges of hazardous waste feed rate, and, as appropriate, the feed rates of other fuels and
industrial furnace feedstocks, and any other relevant parameters that may affect the ability
of the boiler or industrial furnace to meet the performance standards in §§266.104 through
266.107 of this chapter.
(7) A description of, and planned operating conditions for, any emission control
equipment that will be used
(8) Procedures for rapidly stopping the hazardous waste feed and controlling
emissions in the event of an equipment malfunction.
(9) Such other information as the Director reasonably finds necessary to determine
whether to approve the trial burn plan in light of the purposes of this paragraph and the
criteria in paragraph (b)(2) of this section.
(d) Trial burn procedures. (1) A trial bum must be conducted to demonstrate
conformance with the standards of §§266.104 through 266.107 of this chapter under an
approved trial bum plan.
(2) The Director shall approve a trial bum plan if he/she finds that:
(i) The trial burn is likely to determine whether the boiler or industrial furnace can
meet the performance standards of §§266.104 through 266.107 of this chapter,
(ii) The trial bum itself will not present an imminent hazard to human health and the
environment;
67
-------
(iii) The trial burn will help the Director to determine operating requirements to be
specified under $266.102(e) of this chapter, and
(iv) The information sought in the trial burn cannot reasonably be developed
through other means.
(3) The applicant must submit to the Director a certification that the trial burn has
been carried out in accordance with the approved trial bum plan, and must submit the
results of all the determinations required in paragraph (c) of this section. This submission
shall be made within 90 days of completion of the trial burn, or later if approved by the
Director.
(4) All data collected during any trial burn must be submitted to the Director
following completion of the trial burn.
(5) All submissions required by this paragraph must be certified on behalf of the
applicant by the signature of a person authorized to sign a permit application or a report
under §270.11.
(e) Special procedures for ORE trial burns. When a DRE trial burn is required
under §266.104(a) of this chapter, the Director will specify (based on .the hazardous waste
analysis data and other information in the trial burn plan) as trial Principal Organic
Hazardous Constituents (POHCs) those compounds for which destruction and removal
efficiencies must be calculated during the trial burn. These trial POHCs will be specified
by the Director based on information including his/her estimate of the difficulty of
destroying the constituents identified in the hazardous waste analysis, their concentrations
or mass in the hazardous waste feed, and, for hazardous waste containing or derived from
wastes listed in Part 261, Subpart D of this chapter, the hazardous waste organic
constituem(s) identified in Appendix VII of that pan as die basis for listing.
(f) Determinations based on trial burn. During each approved trial bum (or as soon
after the bum as is practicable), the applicant must make the following determinations:
(1) A quantitative analysis of the levels of antimony, arsenic, barium, beryllium,
cadmium, chromium, lead, mercury, thallium, silver, and chlorine/chloride, in the feed
streams (hazardous waste, other fuels, and industrial furnace feedstocks);
(2) When a DRE trial bum is required under §266.104(a) of mis chapter:
(i) A quantitative analysis of the trial POHCs in the hazardous waste feed;
(ii) A quantitative analysis of the stack gas for the concentration and mass emissions
of the trial POHCs; and
(iii) A computation of destruction and removal efficiency (DRE), in accordance with
die DRE formula specified in §266.104(a) of this chapter,
(3) When a trial burn for chlorinated dioxins and furans is required under
§266.104(e) of tiiis chapter, a quantitative analysis of die stack gas for die concentration
and mass emission rate of die 2,3,7,8-chlorinated tetra-octa congeners of chlorinated
dibenzo-p-dioxins and furans, and a computation showing conformance widi the emission
standard.
68
-------
(4) When a trial burn for particulate matter, metals, or HC1/C12 is required under
§§266.105, 266.106(c) or (d), or 266.107(b)(2.) or (c) of this chapter, a quantitative
analysis of the stack gas for the concentrations and mass emissions of particulate matter,
metals, or hydrogen chloride (HC1) and chlorine (Cl2), and computations showing
conformance with the applicable emission performance standards;
(5) When a trial bum for DRE, metals, or HC1/C12 is required under §§266.104(a),
266.106(c) or (d), or 266.107(b)(2) or (c) of this chapter, a quantitative analysis of the
scrubber water (if any), ash residues, other residues, and products for the purpose of
estimating the fate of the trial POHCs, metals, and chlorine/chloride;
(6) An identification of sources of fugitive emissions and their means of control;
(7) A continuous measurement of carbon monoxide (CO), oxygen, and where
required, hydrocarbons (HC), in the stack gas; and
(8) Such other information as the Director may specify as necessary to ensure that
the trial burn will determine compliance with the performance standards in §§266.104
through 266.107 of this chapter and to establish the operating conditions required by
§266.102(e) of this chapter as necessary to meet those performance standards.
(g) Interim status boilers and industrial furnaces. For the purpose of determining
feasibility of compliance with the performance standards of §§266.104 through 266.107 of
this chapter and of determining adequate operating conditions under §266.103 of this
chapter, applicants owning or operating existing boilers or industrial furnaces operated
under the interim status standards of §266.103 must either prepare and submit a trial burn
plan and perform a trial bum in accordance with the requirements of this section or submit
other information as specified in §270.22(a)(6). Applicants who submit a trial burn plan
and receive approval before submission of die Pan B permit application must complete the
trial bum and submit the results specified in paragraph (f) of this section with the Part B
permit application. If completion of this process conflicts with the date set for submission
of the Part B application, the applicant must contact the Director to establish a later date for
submission of the Part B application or the trial burn results. If the applicant submits a trial
burn plan with Pan B of the permit application, the trial bum must be conducted and the
results submitted within a time period prior to permit issuance to be specified by the
Director.
(Approved by the Office of Management and Budget under control number )
6. §270.72 is amended by adding paragraphs (a)(6) and (b)(7) to read as follows:
§270.72 Changes during interim status.
(a) * * *
(6) Addition of newly regulated units for the treatment, storage, or disposal of
hazardous waste if the owner or operator submits a revised Pan A permit application on or
before the date on which the unit becomes subject to the new requirements.
(b) * * *
(7) Addition of newly regulated units under paragraph (a)(6) of this section.
69
-------
7. §270.73 is anx».n
-------
Appendix I. - Tier I and Tier II Feed Rate and Emissions
Screening Limits for Metals
Table I-A. TIER I AND TIER II FEED RATE AND EMISSIONS SCREENING LIMITS
FOR NONCARCINOGENIC METALS FOR FACILITIES IN NONCOMPLEX TERRAIN
Values for Urb«p Ar»«t
Terrain Adjusted
lit. Stack Rt. (m)
4
6
e
10
12
1*
16
18
20
22
2*
26
26
30
33
to
45
50
55
60
65
70
75
60
65
90
95
100
105
110
115
120
Antimony
(c/hr)
6.0C+01
6.8E+01
7.61*01
8.6E+01
9.6E+01
1.1E-HJ2
1.31+02
1 . 4E+02
1.6E+02
1.8E*02
2.0E+02
2.3E*02
2.6E+02
3.0E+02
4.0E-M32
4 . 6E+02
6.0E+02
7.6E+02
9.6E+02
1.2E*03
1.5E-M)3
1.7E*03
1.9E+03
2.2E-MJ3
2.SK+03
2.8E*03
3.2B-M)3
3.6E*03
». OE+03
4 . 6E+03
3.4E+03
6.0E-H33
Barium
(t/hr) •
1 . OE+04
1 . 1E*04
1.3E+04
1.4E*04
1.7E+04
1.8E*04
2.1E*04
2.4E+0*
2.7E*04
3 . OE+04
3.4E*04
3.9E*04
4 . 3E*04
5 . OE+04
6.6E+04
7 . 8E-H34
1.0E*05
1.3E+05
1.7E*05
2.0E+03
2.5E+05
2.8E+05
3.2E-M55
3.6E+05
4.0E+05
4.8E+OS
5.4E*03
6.0E+OS
6.8E-H)5
7.8E+05
8.6E+05
l.OE+06
Lead
d/hr)
1.8E+01
2.0E+01
2.3E+01
2.8E+01
3.0E+01
3.4E+01
3.6E*01
4.3E+01
4.6E+01
5.4E-H)!
6.0E+01
8.8E+01
7.8E'M>1
9.0E+01
1.1E+02
1.4E+02
1.8E+02
2.3E+02
3.0E*02
3.6E-HJ2
4.3E-MJ2
5.0E+02
S.6E+02
8.4E+02
7.6E+02
8.2E+02
9.6E+02
1.1Z+03
1.2E-MJ3
1.4E-MJ3
1.8E+03
1.8E*03
Mercury
(c/hr)
6.0E+01
6.8E+01
7.6E*01
8.8E+01
9.6E+01
1.1E+02
1.3E+02
1.4E+02
1.8E+02
1.8E+02
2.0E+02
2.3E+02
2.6E+02
3.0E+02
4.0E+02
4.8E+02
8.0E+02
7.8E+02
9.6E+02
1.2E+03
1.5E+03
1.71*03
1.9E*03
2.2E+03
2.SE+03
2.8E*03
3 2E*03
3.8E*03
4.0E*«3
4.6E-MJ3
5.4E*03
6.0E*03
Silver
(«/hr)
6.0E+02
6 . 8E*02
7.6E+02
6.6E*02
9 . 6E*02
1 . 1E*03
1 . 3E*03
1.4E+03
1.6E+03
1.8E*03
2.0E*03
2.3E*03
2 . 6E+03
3.0E+03
4 . OE+03
4.8E*03
8.0E*03
7.8E*03
9.6E+03
1.2E*04
1.3E+04
1.7E+04
1.9E*04
2.22*04
2.JE-KJ4
2.8E-MJ4
3 2E*Q4
3.8E+04
4. OE+04
4.6E*04
S.4E*04
6.0E*04
Thallium
C«/hr)
6 OE+01
6.3E+01
7.6E+01
8.6E+01
9.6E+01
1 . 1E+02
1.3E+02
1.4E+02
1.6E+02
1.8E+02
2.0E+02 .
2.3E+02
2.6E+02
3.0E+02
4.0E+02
4 . 6E+02
6.0E+02
7 . 8E+02
9.6E+02
1.2E+03
1.5E+03
1.7E+03
1.9E+03
2.2E+03
2.5E+03
2.8E+03
3.2E+03
3.6E+03
4. OE+03
4.6E+03
3.4E+03
6.0E*03
-------
Appendix I. • Tier I and Tier II Feed Rate and Emissions
Screening Limits for Metals (Continued)
Table I-B. TIER I AND TIER II FEED'RATE AND EMISSIONS SCREENING LIMITS
FOR NONCARCINOGENIC METALS FOR FACILITIES IN NONCOMPLEX TERRAIN
V«Iu*i for Rural Ar««»
T»rr»in Adjusted
Cff. Stack Ht. (B)
4
6
8
10
12
14
16
18
20
22
24
26
28
30
35
40
45
SO
53
00
65
70
75
80
85
90
OS
100
105
110
113
120
Antiaony
(i/hr)
3.11+01
3.61+01
4.01+01
4.61+01
3.81+01
6.8E+01
8.6E+01
1.11+02
1.31+02
1.71+02
2.21+02
2.81+02
3 . 51+02
4.3E+02
7.21+02
1.11+03
1.51+03
2.01+03
2.61+03
3.41*03
4.61*03
5.41*03
6.41*03
7.61*03
9.41*03
1.11*04
1.3E+04
1.3X404
1. 61+04
2.21+04
2.6E-H>4
3.11+04
BtriUM
(>/hr)
5.2Z^3
6.0E+03
6.8E-HJ3
7.8E-W3
9.6E-HJ3
1.1E*04
1.4E*04
1.8E-H34
2.2Z+04
2.8E-H54
3.6E*04
4.6E*04
S.8E'H)4
7.K+04
1.2E*OS
1.8E-HJS
2.5E+OS
3.3E-HJ3
4.4Z+03
3.81*03
7.61*03
0.01+03
1.11*06
1.31*06
1.51*06
1.81*08
2.21*06
2.61*06
3.01*06
3.61*06
4.41*06
5.01*06
Lead
(t/hr)
9.41*00
1.11*01
1.21*01
1.41*01
1.71*01
2.11*01
2.61*01
3.21*01
4.0E+01
5.01*01
6.41*01
8.21*01
1.01*02
1.31*02
2.11*02
3.21*02
4.61*02
6.01*02
7.81*02
1.01*03
1.41*03
1.61*03
1.91*03
2.31*03
2.61*03
3.31*03
3.91*03
4.61*03
5.41*03
6.61*03
7.61*03
9.21*03
Mareury
(t/hr)
3.11*01
3.61*01
4.01*01
4.81*01
5.81*01
6.81*01
8.61+01
1.11*02
1.31*02
1.71*02
2.21*02
2.81*02
3.51*02
4.31*02
7 21*02
1.11*03
1.51*03
2.01*03
2.61*03
3.41*03
4.61*03
5.41*03
6.41*03
7.61*03
9.41*03
1 11*04
1.31*04
1.51*04
1.61*04
2.21*04
2.61*04
3.1Z*04
Silver
(c/hr>
3 . 11*02
3 . 61+02
4 . OE+02
4.6E+02
3 . 8E+02
6.8E+02
6.6E+02
1.11+03
1.31+03
1.71*03
2.21+03
2.61*03
3 . 51*03
4 . 31*03
7 21*03
1 . 11*04
1.51*04
2.01*04
2.61*04
3.41*04
4.61*04
5.41*04
6.41*04
7.61*04
9.41*04
1.11*05
1.31*05
1.51*05
1.61*05
2.21*03
2.61+05
3.11*05
ThaUiun
(g/hr)
3 . 1E+01
3.6E+01
*.OE+01
* . 6E+0 1
5.8E*01
6.8E+01
8.6E+01
1 . 1E+02
1 . 3E+02
1.7E+02
2.2E+02 -
2.8E+02
3 . 5E+02
4.3E+OZ
7.2E+02
1.1E+03
1.3E+03
2.0E+03
2.61+03
3.4E+03
4 . BE+03
5.4E+03
6.4E+03
7.61+03
9.4E+03
1.1E+04
1.31+04
1.51+04
1.81+04
2.21+04
2.61+04
3.11+04
-------
Appendix I. - Tier I and Tier II Feed Race and Emissions
Screening Limits for Metals (Continued) •'
Table I-C. TIER I AND TIER II FEED RATE AND EMISSIONS SCREENING LIMITS
FOR NONCARCINOGENIC METALS FOR FACILITIES IN COMPLEX TERRAIN
Values for Urban and Rural Areas
Terrain Adjusted
Eff. Stack Ht. (D)
4
8
8
10
12
1*
16
IS
20
22
2*
26
28
30
35
40
45
30
53
60
65
70
75
80
83
90
95
100
103
110
113
120
Antimony
(s/hr)
1.4E+01
2.12+01
3 OE+01
* . 3E+01
S.4E+01
6.8E+01
7.82+01
8.6E+01
9.62+01
1. OE+02
1.22+02
1.3E-MJ2
1 . *E+02
1.6E+02
2 . 02+02
2.4E+02
3 . OE+02
3 . 62+02
4.62+02
5.8E+02
6.62+02
7 . 82+02
8.62+02
9.62+02
1.12+03
1.22+03
1.4E+03
1.52+03
1.71*03
1.92+03
2.12+03
2.42+03
Barium
(c/hr)
2.4E+03
3 . 3E+03
5.0E+03
7 . 6E+03
9.0E+03
1.1E+04
1.3E+04
1 . 4E+04
1.8E+04
1 . 8E+0*
1.9E+04
2.2Z+0*
2.4E+04
2.7E+04
3 . 3E+04
4 . OE+04
5 . OE+04
6. OE+04
7.6E+04
9.4E+04
1.1Z+05
1.3E+03
1.4E+03
1.6E+05
1.8E+05
2.0E+03
2.3E+03
2.62+03
2.8E+05
3.2E+05
3.61+05
4.0E+05
L«ad
(K/hr)
4 . 3E+00
6 . 2E+00
9.2E+00
1.3E+01
1.7E+01
2.0E+01
2.4E+01
2.6E+01
2.9E+01
3.2E+01
3.5E+01
3.6E+01
4 . 3E+01
4.6E+01
5.8E+01
7.2E+01
9.0E+01
1 . 1E+02
1.4E+02
1.7E+02
2.1E+02
2.4E+02
2.6E+02
2.9E+02
3.3E+02
3.8E+02
4 . OE+02
4 . 6E+02
5. OE+02
S.8E+02
6.4E+02
7.2E+02
Mareury
(c/hr)
1.4E+01
2.1E+01
3.0E+01
4.3E+01
5.4E+01
6.6E+01
7.8E+01
8.6E+01
9.6E+01
1 . OE+02
1.2E+02
1 . 3E+02
1.4E+02
1 . 6E+02
2. OE+02
2.4E+02
3. OE+02
3.6E+02
4.6E+02
S.8E+02
6 . 8C+02
7 . 8E+02
8 . 6E+02
9.6E+02
1.1E+03
1.22+03
1 . 4E+03
1.52+03
1.72+03
1.92+03
2 . 12+03
2.42+03
Silver
(i/hr )
1 . 4E+02
2 . 1E+02
3 . OE+02
4 . 3E+02
5.4E+02
6.8E+02
7 . 8E+02
8 . 6E+02
9 . 6E+02
l.OE+03
1.2E+03
1 . 3E+03
1.4E+03
1.6E+03
2.0E+03
2.4E+03
3 . OE+03
3 . 6E+03
4.6E+03
5.82+03
6.82+03
7 . 82+03
8 . 62+03
9.62+03
1.12+04
1.22+4
1 . 4E+04
1. 52+04
1 . 72+04
1.92+04
2.12+04
2.42+04
ThaLUua
(s/hr)
1.4E+01
2 1E+-01
3 OE+01
4.3E+01
5 4E*01
6.8E+01
7 8E+01
8.5E+01
9.6E+01
1 OE+02
1.2E+02
1.3E+02
1 4E+02
1.6E+02
2. OE+02
2.4E+02
3. OE+02
3.6E+02 '
4.6E+02
S . 8E+02
6 . 8E+02
7 . 8E+02
8.6E+02
9 . 6E+02
1 . 1E+03
1.2E+03
1 4E+03
l.SE+03
1 7E+03
1 . 92+03
2 12+03
2.4E+03
-------
Appendix I. - Tier I and Tier II Feed Race and Emissions
Screening Limits for Metals (Continued)
Table I-D. TIER I AND TIER II FEED RATE AND EMISSIONS SCREENING LIMITS
FOR NONCARCINOGENIC METALS FOR FACILITIES IN NONCOMPLEX TERRAIN
Value* for Use In Or
Terrain
Adjusted
Eff.
Stack Bt.
120
Art mite
(«/hr)
4.6E-01
1.11*01
3.61*01
4 61*01
CadBiua
(8/hz)
1.11*00
1.31*00
1.41*00
1.61*00
1.81*00
2.11*00
2.31*00
2 . 61*00
3 . OE+00
3 . 41*00
3.41*00
I.*E+OI
2.21*01
3.11*01
3.6E*01
4.01*01
3.81*01
6.61*01
1 11*02
•n Areas
ChreaUuB
C«/hr)
1.71-0.1
1.91-01
2.2E-01
2.41-01
2.7E-01
3.1E-01
3.3E-01
4.01-01
4.41-01
S.OE-01
S.8E-01
8.4E-01
7.2E-01
8. 21-01
1.0E*00
1.3E*00
1.7E*00
2.2E-MW
2.7E+00
4.2E*00
5.4E-MJO
7.8E*00
9.0E+00
1.01*01
1.11*01
1.31*01
1 7E*01
Valuei t
BeryUiuB
(t/hx)
8.2E-01
9.4E-01
1.1E*00
1.2E*00
1 . *E*00
1.5E*00
1.7E*00
2.0E*00
2.2E+00
2.SE*00
2.8E*00
3.21*00
3.6E*00
4 . OE*00
S . 4E*00
6.8E*00
8.6E*00
1.1E*01
1.4E*01
1.7E*01
2.11*01
2.41*01
2.7E*01
3.0E*01
3.4E*01
3.9E*01
4.4E*01
S.OE*01
S.6E*01
6.4E*01
7.21*01
8.21*01
or U«« in
Arsenic
(l/hr)
2.4E-01
2.8E-01
3.2E-01
3.6E-01
4.3E-01
3.4E-01
8.8E-01
8.2E-01
1 . OE*00
1.3E*00
1.7E*00
2.1E*00
2.7E*00
3.51*00
S.4E*00
8.21*00
1.1E*01
1.3E*01
2.0E*01
2.7E*01
3.81*01
4.31*01
5.01*01
8.01*01
7.21*01
8.81*01
1.01*02
1.21*02
1.41*02
1.71*02
2.01*02
2.41*02
ral Areas
CadBiua
(C/hr)
5.81-01
8. 81-01
7.8E-01
8.81-01
1.1E*00
1.3E*00
}.6E*00
2.0E*00
2.5E*00
3 . 2E+00
4.0E*00
5.0E*00
6.4E*00
8.21*00
1.3E*01
2.01*01
2.81*01
3.71*01
5.01*01
8.41*01
8.61*01
1.01*02
1.21*02
1.41*02
1.71*02
2.01*02
2.41*02
291*02
3.41*02
4.01*02
4.11*02
3.81*02
ChroaUun
U/hr>
8.6E-02
l.OE-01
1.11-0!
1.3E-01
1.8E-01
2.0E-01
2.41-01
3.0E-01
3.71-01
4.81-01
6.01-01
7.61-01
9.81-01
1.21*00
1.91*00
3.01*00
4.21*00
3.41*00
7.21*00
9.61*00
1.31*01
1.31*01
1.61*01
2.21*01
2.61*01
3.01*01
3.61*01
4.31*01
5.01*01
6.01*01
7.21*01
8.61*01
Beryllium
(«/hr)
4.3E-01
5.0E-0!
3.6E-01
6.4E-01
7.8E-01
9.6E-01
1.2E+00
1 . 5E*00
1.9E+00
2.4E*00
3.0E*Ofl
3.9E*00
3.0E*00-
6.2E+00
9.6E*00
1.5E+01
2.1E*OL
2.8E*Ol
3.6E*01
4.8E*01 |
6.4E+01 I
7.6E*01 I
9.0E*01 |
1.1E*02
1.3E*02
1.5E*02
1.8E+02
2.2E*02
2.6E*02
3.01*02 j
3.61*02 1
4.3E*02 |
-------
Appendix I. - Tier I and Tier II Feed Race and Emissions
Screening Limits for Metals (Continued)
Table I-E. TIER I AND TIER II FEED RATE AND EMISSIONS SCREENING LIMITS
FOR CARCINOGENIC METALS FOR FACILITIES IN COMPLEX TERRAIN
V«lu«i lot U»« in Urban and Ru
T«rr«in Adju«t«d E«.
Stack Ht. (o)
4
6
6
10
12
14
16
18
20
22
2*
26
28
30
35
40
43
to
55
60
65
70
75
80
85
90
95
100
105
110
115
120
Ar»«Jie
<«/hr>
1.1E-01
1.6E-01
2.4E-01
3.5E-01
4.3-01
5.0E-01
6.0E-01
6.8E-01
7.6E-01
8.2E-01
9.0E-01
l.OE+00
1.1E+00
1.2E+00
1 . 5E*00
1.9E+00
2.4E+00
2.9E+00
3 . 5£*00
4 . 3E+00
5,4E*00
6.0E+00
6.8E*00
7.6E*00
8,21*00
9.4E-H30
1.0E-MJ1
l.2Z*01
1.3E*01
1.51*01
1.71*01
1.9E*01
Cadmium
(«/hr)
2.6E-01
3.9E-01
5.8E-01
8.2E-01
1.0E*00
1.3E+00
1 . 4E+00
1.6E+00
1.8E+00
1 . 9E+00
2.1EfOO
2.4E+00
2 . 7E*00
3 . OE+00
3 . 7E*00
4 . 6E+00
5.4E+00
6.8E*00
8.4E+00
1.0E*01
1.3E+01
l.*E*01
I.eE'H)!
1.8E+01
2.0E*01
2.3E*01
2.5E*01
2.81*01
3.2E+01
3 . 5E+01
*.OE*01
4 . 4E+01
Chromiun
(«/hr)
4.0E-02
5.8E-02
8.6E-02
1.3E-01
1.5E-01
1.9E-01
2.2E-01
2.4E-01
2.7E-01
3.0E-01
3.3E-01
3.6E-01
».OE-01
*.4E-01
5.4E-01
6.8E-01
8.4E-01
1.0E*00
1 . 3E+00
1 . 5E*00
1.9E+00
2.2E+00
2.4E+00
2.7E+00
3.0E*00
3.41*00
4 . OE*00
4.3E*00
4 . 8E+00
5 . 4+00
6.0E+00
6.41*00
B«ry Ilium
(*/hr)
2 OE-01
2 9E-01
4.3E-01
6.2E-01
7.6E-01
9.4E-01
1.1E+00
1.2E+00
1.3E+00
1 . 5E*00 .
1 . 6E+00
1.8E+00
2 . OE+00
2.2E*00
2 . 7E*00
3.4E+00
4 . 2E*00
5.0E*00
6.4E*00
7 . 8E+00
9.6E*00
1.1E+01
l.2E*01
1.3E*01
l.JE+01
1.7E*01
1.9E*01
2.1E*01
2.4E+01
2.7E*01
3.0E*01
3.3E*01
-------
Appendix II. - Tier I Feed Race Screening Limics for Total Chlorine and Chloride
TIER I FEED RATE SCREENING LIMITS FOR CHLORINE FOR FACILITIES IN
NONCOMPLEX AND COMPLEX TERRAIN
Terrain- adj u« c«d
•ff«cciv« seack
height (•)
4
6
8
10
12
14
16
18
20
22
24
26
28
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
None oap Lax
Urban
(Ib/hr)
1.8E-02
2.0E-02
2.2E-02
2.5E-02
2.9E-02
3.3E-02
3.7E-02
4.1E-02
4.7E-02
5.3E-02
6.0E-02
6.8E-02
7.6E-02
8.7E-02
1.2E-01
1.4E-01
1.8E-01
2.3E-01
2.9E-.01
3.6E-01
4.3E-01
.OE-01
.6E-01
.3E-01
.3E-01
.3E--1
.3E-01
1.1E-H)0
1.2E+00
1.4E+00
1.6E-MX)
1.8E+00
Rural
(Ib/hr)
9.2E-03
l.OE-02
1.2E-02
1.4E-02
1.7E-02
2.0E-02
2.5E-02
3.2E-02
3.9E-02
5.0E-02
6.3E-02
8.1E-02
1. OE-01
1.3E-01
2.1E-01
3.2E-01
4.4E-01
S.8E-01
7.7E-01
l.OE+00
1.4E+00
1.6E-M)0
1.9E-KOO
2.2E-M30
2.8E+00
3.2E-M)0
3.8E*00
4.6E-HX)
5.4E-M30
6.SE+00
7.7E+00
9.1E*00
Co«pl«x
(Ib/hr)
4.1E-03
6.1E-03
9.0E-03
1.3E-02
1.6E-02
2.0E-02
2.3E-02
2.5E-02
2.9E-02
3.1E-02
3.SE-02
3.8E-02
4.2E-02
4.7E-02
S.8E-02
7.2E-02
8.8E-02
1.1E-01
1.4E-01
1.7E-01
2. OE-01
2.3E-01
2.SE-01
2.9E-01
3.2E-01
3.6E-01
4. OE-01
4.4E-01
5. OE-01
5.6E-01
6.2E-01
7.1E-01
-------
Appendix III. . Tier II Emission Race Screening Limits for Free Chlorine and
Hydrogen Chloride
TIER II EMISSIONS SCREENING LIMITS FOR C12 AND HC1 IN NONCOMPLEX TERRAIN-
Te rrain - adj us ced
effective stack
height (a)
4
6
8
10
12
14
16
18
20
22
24
26
28
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
Values for us*
in urban areas
C12
(*/Sec)
2.3E-03
2.5E-03
2.8E-03
3.2E-03
3.6E-03
4.1E-03
4.7E-03
5.2E-03
5.9E-03
6.7E-03
7.6E-03
8.5E-03
9.6E-03
1.1E-02
1.5E-02
1.7E-02
2.3E-02
2.9E-02
3.6E-02
4.5E-02
5.5E-02
6.3E-02
7.1E-02
8.0E-02
9.2E-02
l.OE-01
1.2E-01
1.3E-01
1.5E-01
1.7E-01
2.0E-01
2.3E-01
HC1
(c/s«c)
4.0E-01
4.4E-01
4.9E-01
5.6E-01
6.3E-01
7.2E-01
8.2E-01
9.1E-01
l.OE+00
1.2E+00
1 . 3E+00
1.5E+00
1.7E+00
1.9E+00
2 . 6E+00
3.0E+00
4 . OE+00
5.1E+00
6.3E+00
7 . 9E+00
9 . 6E+00
1.1E+01
1.2E+01
1.4E-K)!
1.6E-K31
1.8E-MD1
2.1E+01
2.3E+01
2.6E*01
3.0E-M31
3 . 5E+01
4.0E-MD1
Values for use
in rural areas
C12
(«/sec)
1.2E-03
1.3E-03
1.5E-03
1.7E-03
2.1E-03
2.5E-03
3.2E-03
4.0E-03
4.9E-03
6.3E-03
8.0E-03
l.OE-02
1.3E-02
1.6E-02
2.7E-02
4.0E-02
5.6E-02
7.3E-02
9.7E-02
1.3E-01
1.7E-01
2.0E-01
2.4E-01
2.8E-01
3.5E-01
4.0E-01
4.8E-01
5.7E-01
6.8E-01
8.1E-01
9.7E-01
1.1E-»OO
HC1
(K/sec)
2.0E-01
2.3E-01
2.6E-01
3.0E-01
3.7E-01
4.4E-01
5.6E-01
7.0E-01
8.6E-01
1 . 1E+00
1.4E+00
1 . 8E+00
2.3E+00
2 . 8E+00
4.7E+00
7 . OE+00
9 . BE-t-00
I". 3E+01
1.7E+01
2.2E+01
3.0E+01
3.5E+01
4.2E+01
4.9Ef01
6.1Et-01
7.0E+01
8.4E+01
1.0E-K52
1 . 2E+02
1.4E+02
1.7E+02
2.0E+02
-------
Appendix III. (Continued)
TIER II EMISSIONS SCREENING LIMITS FOR Cl, AND HC1 IN COMPLEX TERRAIN
Terrain- adj us ted
effective stack
hcighc (a)
4
6
8
10
12
14
16
18
20
22
24
26
28
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
Values for use in urban
and rural areas
Cl,
(t/iec)
5.2E-04
7.7E-04
1.1E-03
1.6E-03
2.0E-03
2.SE-03
2.9E-03
3.2E-03
3.6E-03
3.9E-03
4.4E-03
4.8E-03
5.3E-03
5.9E-03
7,3E-03
9.1E-03
1.1E-02
1.3E-02
1.7E-02
2.1E-02
2.5E-02
2.9E-02
3.2E-02
3.6E-02
4.0E-02
4.5E-02
S.1E-02
5. 61-02
6.3E-02
7.11-02
7. 91-02
8.91-02
HC1
(e/sec)
9.1E-02
1.4E-01
2.0E-01
2.8E-01
3.5E-01
4.4E-01
5.1E-01
5.6E-01
6.3E-01
6.8E-01
7.7E-01
8.4E-01
9.3E-01
1.0E-M30
1.3E+00
1.6E-M)0
1 . 9E+00
2.3E-M50
3.0E-HDO
3 . 7E*00
4.4E+00
5.1E-M30
5.6E-MDO
6 . 3E+00
7,OE-K)0
7.9E-fOO
8.9E-HDO
9.8E+00
1.1E+01
1.2E-M31
1.4E-M31
1.6E+O1
-------
Appendix IV. - Reference Air Concentrations*
Constituent CAS No. RAC (ug/m3)
Acetaldehyde 75-07-0 10
Acetonitrile 75-05-8 10
Acetophenone 98-86-2 100
Acrolein 107-02-8 20
Aldicarb 116-06-3 1
Aluminum Phosphide 20859-73-8 0.3
Allyl Alcohol 107-18-6 5
Antimony 7440-36-0 0.3
Barium 7440-39-3 50
Barium Cyanide 542-62-1 50
Bromomethane 74-83-9 0.8
Calcium Cyanide 592-01-8 30
Carbon Disulfide 75-15-0 200
Chloral 75-87-6 2
Chlorine (free) 0.4
2-Chloro-l,3-butadiene... 126-99-8 3
Chromium III 16065-83-1 1000
Copper Cyanide 544-92-3 5
Cresols 1319-77-3 50-
Cumene 98-82-8 1
Cyanide (free) 57-12-15 20
Cyanogen 460-19-5 30
Cyanogen Bromide 506-68-3 80
Di-n-butyl Phthalate 84-74-2 100
o-Dichlorobenzene 95-50-1 10
p-Dichlorobenzene 106-46-7 10
Dichlorodifluoromethane.. 75-71-8 200
2,4-Dichlorophenol 120-83-2 3
Diethyl Phthalate 84-66-2 800
Dimethoate 60-51-5 0.8
2,4-Dinitrophenol 51.-28-5 2
Dinoseb 88-85-7 0.9
Diphenylanine 122-39-4 20
Endosulfan 115-29-7 0.05
Endrin 72-20-8 0.3
Fluorine 7782-41-4 50
Formic Acid 64-18-6 2000
Glycidyaldehyde 765-34-4 0.3
Hexachlorocyclopentadiene 77-47-4 5
Hexachlorophene 70-30-4 0.3
Hydrocyanic Acid 74-90-8 20
Hydrogen Chloride 7647-01-1 7
Hydrogen Sulfide 7783-06-4 3
Isobutyl Alcohol 78-83-1 300
Lead 7439-92-1 0.09
Maleic Anyhdride 108-31-6 100
Mercury 7439-97-6 0.3
Methacrylonitrile 126-98-7 0.1
-------
Appendix IV. (Continued)
Constituent CAS No. RAC '(ug/m3)
Methomyl 16752-77-5 20
Methoxychlor 72-43-5 50
Methyl Chlorocarbonate... 79-22-1 1000
Methyl Ethyl Ketone 78-93-3 80
Methyl Parathion 298-00-0 0.3
Nickel Cyanide 557-19-7 20
Nitric Oxide 10102-43-9 100
Nitrobenzene 98-95-3 0.8
Pentachlorobenzene 608 - 93 - 5 0.8
Pentachlorophenol 87-86-5 30
Phenol 108-95-2 30
M-Phenylenediamine 108-45-2 5
Phenylmercuric Acetate... 62-38-4 0.075
Phosphine 7803-51-2 0.3
Phthaiic Anhydride 85-44-9 2000
Potassium Cyanide 151-50-8 50
Potassium Silver Cyanide. 506-61-6 200
Pyridine 110-86-1 1
Selenious Acid 7783-60-8 3-
Selenourea 630-10-4 5
Silver 7440-22-4 3
Silver Cyanide 506-64-9 100
Sodium Cyanide 143-33-9 30
Strychnine 57-24-9 0.3
1,2,4,5-Tetrachlorobenzene 95-94-3 0.3
2,3,4,6-Tetrachlorophenol 58-90-2 30
Tetraethyl Lead 78-00-2 0.0001
Tetrahydrofuran 109-99-9 10
Thallic Oxide 1314-32-5 0.3
Thallium 7440-28-0 0.5
Thallium (I) Acetate 563-68-8 0.5
Thallium (I) Carbonate... 6533-73-9 0.3
Thallium (I) Chloride 7791-12-0 0.3
Thallium (I) Nitrate 10102-45-1 0.5
Thallium Selenite 12039-52-0 0.5
Thallium (I) Sulfat* 7446-18-6 0.075
Thiram 137-26-8 5
Toluene 108-88-3 300
1,2,4-Trichlorobenzene... 120-82-1 20
Trichloromonofluoromethane 75-69-4 300
2,4,5-Trichlorophenol 95-95-4 100
Vanadium Pentoxide 1314-62-1 20
Warfarin 81-81-2 0.3
Xylenes 1330-20-7 80
Zinc Cyanide 557-21-1 50
Zinc Phosphide 1314-84-7 0.3
* The RAC for other Appendix VIII Part 261 constituents not listed herein
or in Appendix 4. of this Part is 0.09 ug/m3.
-------
Appendix V. - Risk Specific Doses (10~5)
Constituent
Acrylonitrile
Aldrin
Anil ine
Arsenic
Benz (a) anthracene
Benxene
Benzidine .
Benzo(a)pyrene
Beryllium
Bis(2-chloroechyl)ether
Bis (chlorome thy 1) ether.
Bis(2-echylhexyl)-
phthalate
1,3- Butadiene
Cadmium
Carbon Tetrachloride . . .
Chlordane
Chloroform
Chlorome thane
Chromium VI
DDT
Dibenz (a, h) anthracene. .
l,2-Dibromo-3-
chloropropane
1 , 2-Dibromoehtane
1,1- Dichloroe thane
1 , 2 -Dichloroe chane
1 , 1-Dichloroethylene. . .
1 , 3 - Dichloropropene ....
Dieldrin
Diethylstilbestrol
Dimechylnicrosamine. . . .
2 ,4-Dinitrotoluene
1,2 -Diphenylhydrazine. .
1,4-Dioxane
Epichlorohydrin
Ethylene Oxide
Echylene Dibromide
Formaldehyde
Heptachlor
Heptachlor Eposide
Hexachlorobenzene
Hexachlorobutadiene. . . .
CAS No.
79-06-1
107-13-1
309-00-2
62-53-3
7440-38-2'
56-55-3
71-43-2
92-87-5
50-32-8
7440-41-7
111-44-4
542-88-1
117-81-7
106-99-0
7440-43-9
56-23-5
57-74-9
67-66-3
74-87-3
7440-47-3
50-29-3
53-70-3
96-12-8
106-93-4
75-34-3
107-06-2
75-35-4
542-75-6
60-57-1
56-53-1
62-75-9
121-14-2
122-66-7
123-91-1
106-89-8
75-21-8
106-93-4
50-00-0
76-44-8
1024-57-3
118-74-1
87-68-3
Unit risk
(m3/ug)
1 3E-03
6.8E-05
4.9E-03
7.4E-06
4.3E-03
8.9E-04
8.3E-06
6.7E-02
3.3E-03
2.4E-03
3.3E-04
6.2E-02
2.4E-07
2.8E-04
1.8E-03
1.5E-05
3.7E-04
2.3E-05
3.6E-06
1.2E-02
9.7E-05
1.4E-02
6.3E-03
2.2E-04
2.6E-05
2.6E-05
5.0E-05
3.5E-01
4 6E-03
1.4E-01
1.4E-02
8.8E-05
2.2E-04
1.4E-06
1.2E-06
l.OE-04
2.2E-04
1 3E-05
1.3E-03
2.6E-03
4.9E-04
2.0E-05
RsD
(ug/m3)
7 7E-03
1.5E-01
2.0E-03
1.4E+00
2.3E-03
1.1E-02
1 . 2E+00
1.5E-04
3.0E-03
4.2E-03
3.0E-02
1.6E-04
4.2E+01
3.6E-02
5.6E-03
6.7E-01
2.7E-02
4.3E-01
2 . 8E+00
8.3E-04
l.OE-01
7.1E-04
1.6E-03
4.5E-02
3.8E-01
3.8E-01
2.0E-01
2.9E-05
2.2E-03
7.1E-05
7.1E-04
1.1E-01
4.5E-02
7 . 1E+00
8 . 3E+00
l.OE-01
4.5E-02
7.7E-01
7.7E-03
3.8E-03
2.0E-02
5.0E-01
-------
Appendix V. (Continued)
Constituent
Alpha - hexachloro -
cyclohexane
Beta -hexachloro -
cyclohexane
Gamma -hexachloro -
cyclohexane
Hexachlorocyclo-
hexane, Technical.
Hexachlorodibenxo - p -
dioxin(l,2 Mixture)
Hexachloroethane
Hydraz ine
Hydrazine Sulfate. . . .
3-Methylcholanthrene. . .
Methyl Hydrazine
Methylene Chloride
4,4'-Methylene-bis-2-
chloroaniline
Nickel
Nickel Refinery Dust. . .
Nickel Subsulfide
2-Nitropropane
N-Nitroso-n-butylamine .
N-Nitroso-n-nethylurea.
N-Nitrosodiethylamine. .
N-Nttrosopyrrolidine. . .
Pentachloronitrobenzene
PCBs
Pronamide , ,
Reserpine
2,3,7 , 8-Tetrachloro-
dibenzo-p-dioxin. .
1,1,2, 2 -Tetrachloroe thane
Tetrachloroethylene. . . .
Thiourea
1,1, 2 -Trichloroethane . .
2,4,6-Trichlorophenol. .
Vinvl Chlorld*
CAS No.
319-84-6
319-85-7
58-89-9
67-72-1
302-01-2
302-01-2
56-49-5
60-34-4
75-09-2
101-14-4
7440-02-0
7440-02-0
12035-72-2
79-46-9
924-16-3
684-93-5
55-18-5
930-55-2
82-68-8
1336-36-3
23950-58-5
50-55-5
1746-01-6
79-34-5
127-18-4
62-56-6
79-00-5
79-01-6
88-06-2
8001-35-2
75-01-4
Unit risk
(m3/ug)
1 8E-03
5.3E-04
3.8E-04
5.1E-04
1.3E+00
4.0E-06
2.9E-03
2.9E-03
2.7E-03
3.1E-04
4.1E-06
4.7E-05
2.4E-04
2.4E-04
4.8E-04
2.7E-02
1.6E-03
8.6E-02
4.3E-02
6.1E-04
7.3E-05
1.2E-03
4.6E-06
3.0E-03
4.5E+01
5.8E-05
4.8E-07
5.5E-04
1.6E-05
1.3E-06
5.7E-06
3.2E-04
7.1E-06
RsD
(ug/m3)
5 fiF.m
1.9E-02
2 6E-02
2.0E-02
7.7E-06
2 . 5E+00
3.4E-03
3.4E-03
3.7E-03
3.2E-02
2 . 4E+00
2.1E-01
4.2E-02
4.2E-02
2 1E-02
3.7E-04
6.3E-03
1.2E-04
2.3E-04
1.6E-02
1.4E-01
8.3E-03
2 . 2E+00
3.3E-03
2.2E-07
1.7E-01
2.1E+01
1.8E-02
6.3E-01
7 . 7E+00
1.8E+00
3.1E-02
1.4E+00
-------
Appendix VI. - Stack Plum* Rise
u
s
H
W
H
H
M
3
(A
o
Cd
M
i
N*
Ol
l-l
u
i
W
I
3
00 9«
Si
§:
OO*
«»•*
wm
• ^inmr^o*
mmeeeeeiD
«ri *4 •*
-------
Appendix VII. - Health-Based Limits for Exclusion of Waste-Derived Residues*
Metals - TCLP Extract Concentration Limits
Conspjcuenc CAS No.
Antimony 7440-36-0
Arsenic 7440-38-2
Barium 7440-39-3
Beryllium 7440-41-7
Cadmium 7440-43-9
Chromium 7440-47-3
Lead 7439-92-1
Mercury 7439-97-6
Nickel 7440-02-0
Selenium 7782-49-2
Silver 7440-22-4
Nonmetals
Constituent
Acetonitrile
Acetophenone
Acrolein
Acrylamide
Acrylonitrile
Aldrin
Allyl alcohol
Aluminum phosphide
Aniline
Barium cyanide
Benz( a) anthracene
Benzene
Benzidine
Bis(2-chloroethyl) ether
Bis(chloromethyl) ether
B i s ( 2 - e thy Ihexyl ) phthalate
Bromofonn
Calcium cyanide
Carbon disulfide
Carbon tetrachloride
Chlordane
Chlorobenzene
Chloroform
Copper cyanide
Cresols (Cresylic acid)
Concentration
Limits (mg/Vcyl
IxE+OO
5xE+00
lxE+02
7xE-03
IxE+OO
5xE+00
5xE+00
2xE-01
7xE+01
IxE+OO
5xE+00
- Residue Concentration
CAS No.
75-05-8
98-86-2
107-02-8
79-06-1
107-13-1
309-00-2
107-18-6
20859-73-8
62-53-3
542-62-1
56-55-3
71-43-2
92-87-5
111-44-4
542-88-1
117-81-7
75-25-2
592-01-8
75-15-0
56-23-5
57-74-9
108-90-7
67-66-3
544-92-3
1319-77-3
Limits
Concentration
Limits for
Residues (me/kg)
2xE-01
4xE+00
5xE-01
2xE-04
7xE-04
2xE-05
2xE-01
lxE-02
6x£-02
IxE+OO
lxE-04
5xE-03
lxE-06
3xE-04
2xE-06
3xE+01
7xE-01
lxE-06
4xE+00
5xE-03
3xE-04
IxE+OO
6xE-02
2xE-01
2xE+00
-------
Appenldix VII.(Continued)
Nonmecals • Residue Concentration Limits
Constituent
Cyanogen
DDT
Dibenz( a, h) anthracene
1 , 2-Dibromo-3-chloropropane
p - Dichlorobenzene
Dichlorodifluorome thane
1 , 1-Dichloroethylene
2,4-Dichlorophenol
1 , 3 - Dichloropropene
Dieldrin
Diethyl phthalate
Diethylstilbesterol
Dimethoate
2 ,4-Dinitrotoluene
Diphenylamine
1, 2-Diphenylhydrazine
Endosulfan
Endrin
Epichlorohydrin
Ethylene dibromide
Ethylene oxide
Fluorine
Formic acid
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachlorodibenzo-p-dioxins
Hexachloroe thane
Hydrazine
Hydrogen cyanide
Hydrogen suifide
Isobutyl alcohol
Me thorny 1
Mechoxychlor
3 -Methylcholanthrene
4,4'-Methylenebls(2-chloro«nilln*)
Methylene chloride
Methyl ethyl keton* (MEK)
Methyl hydrazine
Methyl parathion
Naphthalene
Nickel cyanide
Nitric oxide
Nitrobenzene
CAS No.
460-19-5
50-29-3
53-70-3
96-12-8
106-46-7
75-71-8
75-35-4
120-83-2
542-75-6
60-57-1
84-66-2
56-53-1
60-51-5
121-14-2
122-39-4
122-66-7
115-29-7
72-20-8
106-89-8
106-93-4
75-21-8
7782-41-4
64-18-6
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
19408-74-3
67-72-1
302-01-1
74-90-8
7783-06-4
78-83-1
16752-77-5
72-43-5
56-49-5
101-14-4
75-09-2
78-93-3
60-34-4
298-00-0
91-20-3
557-19-7
10102-43-9
98-95-3
Concentration
Limits for
Residues (mg/kg)
IxE+OO
lxE-03
7xE-06
2xE-05
7.5xE-02
7xE+00
5xE-03
lxE-01
lxE-03
2xE-05
3xE+01
7xE-07
3xE-02
5xE-04
9xE-01
5xE-04
2xE-03
2xE-04
4xE-02
4xE-07
3xE-04
4xE+00
7xE+01
8xE-05
4xE-05
2xE-04
5xE-03
2xE-01
6xE-08
3xE-02
lxE-04
7xE-05
lxE-06
lxE+01
IxE+OO
lxE-01
4xE-05
2xE-03
5xE-02
2xE+00
3xE-04
2xE-02
lxE+01
7xE-01
4xE+00
2xE-02
-------
Appendix VII. (Continued)
Nonmecals - Residue Concentration Limits
Constituent
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitroso-N-raethylurea
N-Nitrosopyrrolidine
Pentachlorobenzene
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenol
Phenylmercury acetate
Phosphine
Polychlorinated biphenyls , N.O.S.
Potass iv- cyanide
Potassi silver cyanide
Pronami
Pyridin
Reserpi
Selenou. a
Silver cyanide
Sodium cyanide
Strychnine
1,2,4, 5-Tetrachlorobenzene
1,1,2,2- cetrachloroechane
Tetrachloroethylene
2,3,4, 6 -Tetrachlorophenol
Tetraethyl lead
Thallium
Thallic oxide
Thallium(I) acetate
Thai". Lum(I) carbonate
Thai um(I) chloride
Thai -ara(I) nitrate
Thal-iura selenite
Thallium(I) sulfate
Thiourea
Toluene
Toxaphene
1,1, 2 -Trichloroe thane
Trichloroethylene
CAS No.
924-16-3
55-18-5
684-93-5
930-55-2
608-93-5
82-68-8
87-86-5
108-95-2
62-38-4
7803-51-2
1336-36-3
151-50-8
506-61-6
23950-58-5
110-86-1
50-55-5
630-10-4
506-64-9
143-33-9
57-24-9
95-94-3
79-34-5
127-18-4
58-90-2
78-00-2
7440-28-0
1314-32-5
563-68-8
6533-73-9
7791-12-0
10102-45-1
12039-52-0
7446-18-6
62-56-6
108-88-3
8001-35-2
79-00-5
79-01-6
Concentration
Limits for
Residues (mg/ky)
6xE-05
2xE-06
lxE-07
2xE-04
3xE-02
lxE-01
IxE+OO
IxE-i-OO
3xE-03
lxE-02
5xE-05
2xE+00
7xE+00
3xE+00
4xE-02
3xE-05
2xE-01
4xE+00
IxE+OO
lxE-02
lxE-02
2xE-03
7xE-01
lxE-02
4xE-06
7xE+00
2xE-03
3xE-03
3xE-03
3xE-03
3xE-03
3xE-03
3xE-03
2xE-04
lxE-t-01
5xE-03
6xE-03
5xE-03
-------
Appendix VII. (Continued)
Nonraetals • Residue Concentration Limits
Constituent
Trichloromonofluoromethane
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Vanadium pentoxide
Vinyl chloride
CAS No.
75-69-4
95-95-4
88-06-2
1314-62-1
75-01-4
Concentration
Limits for
Residues (my/kg')
lxE+01
4xE+00
4xE+00
7xE-01
2xE-03
The health-based concentration limits for Appendix VIII Part 261
constituents for which a health-based concentration is not provided below
is 2xE-06 mg/kg.
-------
Appendix VIII. - Potential PICs for Determination of Exclusion of Waste-Derived
Residues
PICs FOUND IN STACK EFFLUENTS
Volatile* Semivolatiles
Benzene
Toluene
Carbon tetrachloride
Chloroform
Mechylene chloride
Trichloroethylene
Tetrachloroethylene
1,1,1-Trichloroethane
Chlorobenzene
cis-1,4-Dichloro-2-butene
Bromochloromethane
Bromodichloromethane
Bromofonn
Bromomethane
Mechylene bromide
Methyl ethyl ketone
Bis(2 -e thyIhexy1)phthalate
Naphthalene
Phenol
Diethy1 phthalate
Butyl benzyl phthalate
2,4-Dimethylphenol
o-Dichlorobenzene
m-Dichlorobenzene
p-Dichlorobenzene
Hexachlorobenzene
2,4,6-Trichlorophenol
Fluoranthene
o-Nitrophenol
1,2,4-Trichlorobenzene
o-Chlorophenol •
Pentachlorophenol
Pyrene
Dimethyl phthalate
Mononitrobenzene
2,6-Toluene diisocyanate
-------