-------
Chapter I—Environmental Protection Agency
\
FILTER (CLASS WOOD
P». 60, App. A, Meth. 3
SQUfE2f IUII
3 I G'lO
1-2. inteqwM gM-M«n»iin«
423
3-3
-------
». 60, App. A, M*th. 3
Ti»!e 40— Protection of Environment
2:2 Csrse-ser. An ».r cooled ar water-
cco.ei csr.ier.ser. or other condenser tAat
•*ii: not remove O,. COi. CO. arc; .V,. may bt
•.ised :o remove exeess moisture »mcA
would interfere witA ;ftt operation of the
pump and flow meter.
2.2.3 Valve. A needle valve la used to
adjust sample gas How rait.
2.2.4 Pump. A leak-free, diaphragm-type
pump, or equivalent, is used to transport
sample (u to the flexible bag. Install a
small surf* tank between the pump and
ratt meter :o ehmir.au tat pulsation effect
of the diaphragm pump on (At rotaat(«r.
2.2.3 Rat* Meter. The rotameur. or
equivalent rite meter, used should bt cap*-
31* of measuring raw rate to witAin s 1 per-
cent of tn* Ml«c:*d f.o* rat*. A flow ratt
rant* of 300 co 1000 erav mm u suggested.
2.2.9 flexible Sag. Any leak-free plutte
(e.g.. T»dlar. Mylar. Teflon) or plastic-
coated aluminum (e.r.. alusunoed Mylar)
bag. ar equivalent, having a opacity eon-
sistent witft th* Ml*cttitr maint«n«net and operation proct-
durcs. follow tAt innructloM neommtndtd
Sy tnt manufaetur»r. unltst otAtrvtM ip«e-
.fled Atrttn.
2.3.1 Dry MoItcuJsr WtifAt Oturalna-
tion. An Omt aaalyttr or r>-ntt tjrp* com-
bvuuon CM aaalmr auy B* u»«d.
J4.3 Cminlan lUu Correction Factor or
Xxcw Air Dturainauon. An Oraat anaiyt-
•r mu>t &• UMC for low GOt <)«• tA«n 4.0
») or tUfft O« (fTMttr tAat 13.0 p«r-
c) eenetntnuioni. tAt mttiurinc burtttt
of Uit Oraat must Aav* at Itut o.l ptretnt
MMtrttioni.
3. Orf MoUttl&r Vrtgfit Dtttrminttio*
Any of tAt tArtt tamplint and anaJytteaJ
proccdurtt dtscn&td below may bt oi«d for
determining tAt dry molecular wen At.
3 1 Sincie-Point. Crab Sampling and
Analytical Proctdurt.
3.: I The sampl..-.g point m '.he duet
sAall either 5e at the centraid of the e.-su
section or at a point no closer to the waia
than 1.00 m (3.3 fj) unlesi athen-ue speci-
fied By tne Admmatrator.
3.1.2 Set up the equipment vi sno*-n in
Figure 3-1. maxing sure all connection*
»h*ad of the anal^ier are tight and leak-
fret. I-f and Orwt analyzer U u*ed. it 4 ree-
ommtPded tAat the inal>-wr be leaked-
eAeeked ay following trse procedure in Sec-
tion 3: Aowevtr. the leak-cheek U optional.
3.1.3 Plact tAt probe m the stack. »ith
the tip of the probe positioned at the sam-
pling point, purge the sampling line. Dra* a
sarapl* into the analyzer and immediately
ar.ajyzt it for percent CO, and percent O,.
Determine tA* percentage of the ru that u
N, and CO by subtracting tn* sum ef the
percent CO, and percent O, from 100 per-
cent. Calculate tAt dry molecular weigAt u
indicated ia Section «.3.
3.1.4 Repeat tA* sampling, analyst*, and
calculation procedure*, until tAt dry molec-
ular weignt* of any tArtt gno samples
differ from tneir mean by no more than 0.3
g/g-moit <0.3 Ib/lb-molt). Average tAtM
tArtt molecular vetghta, and report tAt re-
sol u M tnt atann a.i g/g-mol* ub/Io»
molt).
3.: Slngle-Mnt. Integrated Sampling
and Analytical Procedure.
3.2.1 TAt sampling point in tAt duct
stall oe located a* specified in Section 3.1.1.
3.2.2 L«ak-eh*ek (optional) tAt ftesible
bag at la Section 2.2.C. Set up the equip-
ment u sAovn ut figure. 3-2. Ju*t prior to
sampling. leak-cAeek (optional) tAt tram by
placing a vacuum caugt at tAt eondtnser
inlet, pulling a vacuum of at least 290 mm
Hg (10 in. Kg), plugging tAt outltt at tAt
quick disconnect, and then turning off tn*
pump. Th* vacuum should remain jtaai* for
at Itut 0.9 minute. Cvacuau tA* flexible
bag. Connect th* probe and place it in tne
stack, wtth tAt tip of Utt probe positioned
at tAe sampling point: purgt tAt sampling
tin*. Xtxt. connect the ba« and make sure
tnat all connections art tight and leak fret.
3.2.3 Sample at a constant ratt. TA* sam-
pling run should bt simultaneous vttA. and
for tAt same total length of time as. tn* pol-
lutant emission rat* determination. Collec-
tion of at least 30 liters (1.00 ft1) of sample
CM ts recommended; ho»e»er. smaller vol-
umes may bt collected. If desired.
3.2.4 Obtain ant integrated flue gas
sample during each pollutant emission ratt
determination. WitAin I hours after tAt
sample Is taken, analyst it for percent COi
and ptretnt Ot using tttAer aa Orsu analyz-
er or a fymt-typt combustion gas analyzer.
If an Orsat analyzer is used. It ts recom-
mended that tne Onat Itak-cAtck descnbed
in Section $ bt ptrformtd before this deter-
mination: however. tAe cheek is optional.
424
B-4
-------
Chapter I—Environmental Projection Agency
P». 60, App. A, Meth. 3
O«-.errr.:.-i« -.he serrenuje of the ;as '.hat :s
V, ird CO Sy sustracting the sum of '.he
percent COt *nd percent d .'rcm 100 3«r-
cent. Ci.cu.ii* the dry molecular weight u
indicated m Section 6.3.
3.2.S Repeat the analysis and calculation
procedures until the individual dry molecu-
lar weighu for any three analyse* differ
from their mean by no more than O.I g/g-
mole (0.3 ib/lb-mole). Average these three
molecular weights, and rteon the results to
the nearest 0.1 g/g-mole <0.1 Ib/lb'-mole).
3.3 Multi-Point. Integrated Sampling and
Analytical Procedure.
3.3.1 Cnlest otherwise specified by the
Administrator, a minimum of «i|ht traverse
poinu shall be used for circular sucu
having diameters lea than 0.61 m i24 in.), a
minimum of nine shall be used for rectangu-
lar staciu having equivalent diameters lest
than 0.61 m (54 in.), and a minimum of
:»-e!ve traverse poinu shall be used for all
other cases. The traverse poinu shall be lo-
cated according to Method 1. The use ot
fewer poinu is subject to approval of the
Administrator.
3.3.2 Follow the procedures outlined in
sections 3.2.2 :hroufht 3.2.5. except for the
following: traverse all sampling points and
sample at each point for an ec.ua! length of
'.me. Record sampling data as shown in
Figure 3-3.
4. Cmitnen Xcu Correction Fteior or
frees* xtr Oetcmtneiion
Sore A Fynte-iype combustion cas ana-
lyzer -4 not acceptable for excess air or emis-
sion rate correction factor determination.
unless approved by the Administrator. If
both percent CO, and percent Ot are meas-
ured, the analytical result! of any of the
three procedures even below may also be
used for calculating the dry molecular
«-eight.
Each of the three procedures below shall
Se used only when specified in an applicable
subcan of the standards. The use of these
procedures for other purposes must have
specific prior approval of the Administrator.
4.1 Single-Poinu Orab Sampling and
Analytical Procedure.
4.1.1 The sampling; point In the duct
shall either be at the ccntroid at the cross-
section or at a point no closer to the walls
than l.M ra (3.3 ft), unless; otherwise speci-
fied by the Administrator.
4.1.2 Set up the equipment as shown in
Figure 3-1. making sure all connections
ahead of the analyser art tight and leak-
free. Leak-check the Orsat analyzer accord-
ins to the procedure described in Section 9.
This leak-cheek is mandatory
3-3—
•s 3e» •iC-0«J<0_ « '00
4.1.3 PJace the probe in the stack, nth
:ht tip of the probe positioned at the sam-
pling point: purge the sampling line. Draw a
sample into the analyzer. For emission rate
correction .'actor determination, immediate-
ly analyze the sample, u outlined :n Sec-
tions 4.1.4 and 4.1.5. for percent CO, or per-
cent O» If excess air is desired, proceed as
follows: d) iomediauly analyze the sample.
as in Sections 4.1.4 and 4.1.5. for percent
CO,. 0,. and CO: <2> determine the percent-
are of the cas that is N, by subtracting -.he
sum of the percent CO,, ptretnt O,. and per-
cent CO from 100 percent: and (3) calculate
percent excess air u outlined in Section 4.2.
4.1.4 To insure complete absorption of
the CO,. 0^ or if applicable. CO. make re-
peated passes :hrough each absorbing solu-
tion until two consecutive readings are the
same. Several passes (three or four) should
be made between readings.
-------
Pr, 60, App. A, Meth. 3
Title 40—Protection of Environment
-.!•. ;•..:.-i a -. ieii-.m of i .east :SO .r..~. K»
.: .-. -!j' 3..gg;r.j :.-.« au;:e'. it •..".* suic*
: jeer.-;•:•.. i.-.d '..-ler! •.urn:-t off :he pump.
Tvs .»e^-.T. sr.ail remain icaoi* .'or it least
S 5 rr-.nuce. Evacuate :he f'«x:S.« sag. Con-
r.eet ;.-.r pros* and place >c in the S:ICK.
*;:h :he tip of :he probe positioned it the
sampling pome: purge the jampti.-.g line.
Xext. connect the bag and make sure that
ail connections are '.;f.H.t ar.d leatt frtt.
4.2.3 Sample at a constant race, or u
specified by :he Administrator, The sam-
pling run must 3t jimuiuneous with, and
for the same caul ler.gh of t.me as. tht pol-
'.utant emission rate Seterm;.-.at:on. Collect
it least 30 liten a.00 ft') of sample ru.
Smaller volumes .r.ay be eoi:«c:ed. iu8ject
to approval of the Adrainacrator.
4.2.4 Obtain one mtetnced flut »«
sample dunn» cteA pollutant «.naiion rate
determinatjon. Tor esusaion ntte correction
factor determination, analyze tfte sample
wttRui 4 noun alter it K taken for percent
CO, or ptretnt C, ier
must be leak-chert (set Section J) before
tht analysts. IX exceu air u desired, proceed
u fotlovK (U vtthtn 4 hours alter the
sample u taken, analyst it tai in Section*
4.J.S throutn 4.1?) for ptreent CO,. O,. and
CO: (2) dttermlnt the ptreentact of the fa*
that i* X, by lubtnetutf the sua of tht per-
ctr.t CO* ptretnt O.. and ptreent CO from
100 percent: (3) calculate percent escesa air.
u outlined in Section 1.2.
4.2.) To Injure complete absorption at
the CO,. 0,. or U applicable. CO. make re-
peated passes throutA each absorautf solu-
tion until t«o eoRseeuuve readv.o art tAt
samt. Several passes <:hret of four) should
be make between rtadinsa. (If constant
readings cannot at obtained alter three eon-
secuuve rtadints. replace tht absorbing so*
lution.)
4.2.8 Repeat tht analysis ur.ul tht fol-
io»nr.f ertterta art met:
4.2.6.1 for ptretnt CO«. reseat the ana-
lytical procedure until tAt results of any
three analysts dUftr by no mort that (a) 0.3
percent by veiuat «hen CO, ts crtater than
4.0 ptretnt or 0.3 ptretnt by volume
when CO, is less than or to.ua! to 4.0 per-
cent. Averact tht tbrtt seetptablt \-alues of
percent CO* and report tnt results to the
mfrat 0.1 percent.
4.2.1.2 for ptreent O.. repeat the analyt-
ical procedure until tAt results of any thrtt
analysts dilftr by no mart than 0.3 ptr-
etat by volumt «Atn O, ts less than 13.0
peretflt or (b) 0.2 ptretnt by voiumt *htn
O, is treater than or equal to 13.0 ptretnt.
Avtract tht three acceptable values of per-
cent Oi and report tAt results to the nearest
0.1 ptretnt.
4.2.1.1 For ptretnt CO. repeat the ana-
lytical procedure until tht results of any
three analysts dltter by no more than 0.3
sercerv. Ave.-ife c-.e trtre* »ce«3i»3le
ia!ues of percent CO and report the resui'-s
10 :ne nearest 0 1 percent.
4.2.7 Af:er the analysis is completed
leak-check (mandatory) tne Onat aralxter
once acam. as described m Section S. For
che results of the analysis to b« valid, the
Orsat analyzer must pass this leak test
before an a/cer the analysis.
NOTE Although in most instances only
CO, or O, is required, it is recommended
chat both CO, and O, bt measured, and that
Citation S in the Bibliography bt used :o
validate the analytical data.
4.3 Multi-Point. Integrated Sampling and
Analytical Procedure.
4.3.1 Both the minimum number of sam-
pling points and cht sampling point location
shall be as specified in Section 3.3.1 of this
method. The use of fewer points than speci-
fied is subject to tne approval of the Admin-
istrator.
4.3.2 Follow the procedures outlined in
Sections 4.2.2 through 4.2.7. escspt for tht
following: Traverse all sampling poinu and
sample at each point for aa equal length of
ttsit. Record sampling data as shown in
Figure 3-J.
S. £*c*-C7Ue* *TQCs4»rt for Orttt Aiiatvsen
Movinsj an Onat analyser frequently
causes It to teak. Therefore, an Onat ana-
l>zcr should be -.hroughly leak-checked on
sit* btfart tht flut gas sample is introduced
into it. Tht procedure for leak-cheeking aa
Orsat analyzer UK
3.1.1 Bring tht liquid level in each pi-
petit up to tAt referene* mark on the capil-
lary tubisg and then close the pipette stop-
cock.
3.1.2 Raise tAt leveling bulb sufficiently
to bring tAt eoatiaing liquid meniscus onto
the graduated portion of tAt burnt* and
then close the manifold stopcock.
3.1.3 Record tne meniscus position.
3.1.4 Observe tAt mtmcus in the burette
and tht liquid level ia tAt pipette for move-
ment over tAt ntkt 4 minutes,
3.1.3 For tAt Onat analyzer to pass the
leak-check, two conditions must bt met.
3.1.3.1 Tht liquid Itvtl IB each pipette
must not fall below tnt bottom of tht capil-
lary tubing during this 4-m«uu inurval.
3.1.3.2 Tht mtniacus in the burette must
net change by mort than 0.2 ml durtn* this
4-aunut* interval.
3.1.8 If tAt analyatr fail* tht leak-check
procedure, all rubber connection* and stop-
cocks should bt checked until tAt cause of
tht leak is identified. Leaking stopcocks
must bt disassemble*, cleaned, ant) rt-
grtattd. Uaking rubber connections must
bt replaced. After the analyzer ts reassem-
bled, th* Itak-cAtek proetdurt must be re-
peated.
426
B-6
-------
I—Environmental Protection Agency
ft. 60, App. A, M«th. 4
S.I Somencliture.
.v£,«3ry woiecuiar weight, g/g-mole Ub/lb-
melt).
»i£A« Percent excess air.
«VCOt» Percent CO, by volume (dry basis).
%Oi" Percent O. by volume (dry but*).
•VCO-Percent CO by volume (dry basis).
?,M,-Percent M, by volume (dry basis).
0.284 -Ratio of Ot to Nt in tir. »/v.
0.2M-Molecular weight of H. or CO. divid-
ed by 100.
0.320-Molecular weight of O, divided by
100.
0.440•Molecular weight «f CO. divided by
100.
8.2 Percent Excess Air. Calculate the per-
cent excess air (if applicable), by subsutut-
int the appropriate values of percent O,.
CO. and N, (obuined from Section 4.1.3 or
4.2.4) into Equation 3-1.
"«O,-O.S% CO
0.2*4%
-O.S % CO)
x 100
Equation 1-1
Xorr The equation above assumes that
ambient air is used as the source of 0, and
that the fuel dots not conum appreciable
amounts of Vi *
Cauation 3-2
Norr The above equation does not consid-
er artoa in air (about O.S percent, molecu-
lan weight of Jt.7). A negative error of
about 0.4 percent is Introduced. The tester
may opt i« include anon in the analysis
i subject to approval of the
7. JtMtegvuAy
1. Altshuller. A. P. Storage of Oases and
Vapors In Plastic Bags. International Jour-
nal of Air and Water Pollution, 1/79-41.
1M3.
2. Conner. William O. and J. S. Nader. Air
Sampling with Plastice Bags. Journal of the
American Industrial Hygiene Association.
212<1-217.1M4.
3. Burrell Manual for Gu Analysts. Sev-
enth edition. Burrell Corporation. :::3
fifth Avenue. Pittsburih. Pv IS219. 1951.
4. Mluhsll. W J. and M. R. Midgett. Pfeld
Reliability of the Orsat Anal)-zer. Journal
of Air Pollution Control Association 21491-
499. May 1976.
3. Shigehan, R. T, R. M. Neullcht. and
W. S. South. Validating Onat Analysis Data
from FoatU Fuel-Fired Units. Suck Sam-
pling News. «2):21-2f. August. 197«.
MtTHOB 4—OCTtHMIXATIOIt Of MOISTTU
CoxTtn a STACK GASCS
1. fnnnpl* and Ayyliettrdiit
1.1 Principle. A cat sample u extracted
at a constant rate from the source: moisture
is removed from the sample stream and de-
termined either voluaetncally or grarime-
irtcally.
1.2 Applicability. This method is applica-
ble for determining the mout.ure content of
suck gas,
Two procedures are given. The first Is a
reference method, for accurate determina-
tions of moisture content (such as are
needed te calculate emission dau). The
second Is an approximation method, wruch
provides estimates of percent moisture to
aid in setting isokinetlc sampling rates prior
to a pollutant emission measurement run.
The approximation method described
herein a only a suggested approach; alter-
native means for approximating the mois-
ture content, e.g.. drying: tubes, wet bulb-dry
bulb techniques, condensation techniques.
stoichlometrtc calculations, previous experi-
ence. et&. are also acceptable.
The reference method is often conducted
simultaneously with a pollutant emission
measurement run: when it is. calculation of
percent isokineiie. pollutant emission rate.
ete« for the run shall be based upon the re-
sults of the reference method or its equiva-
lent: these calculations shall not be based
upon the results of the approximation
method, unless the approximation method
is shown, to the satisfaction of the Adminis-
trator. U.S. Environmental Protection
Agency, to be capable of yielding results
within 1 percent HiO of the reference
method.
XOTC The reference method may yield
questionable results when applied to satu-
rated gas streams or to streams that contain
water droplet*. Therefore, when these con-
ditions exist or are suspected, a second de-
termination of the moisture content shall
be made simultaneously with the reference
method, as follows: Assume that the fas
stream is saturated. Attach a temperature
sensor (capable of measuring to al' C
-------
Pf. 60, A pp. A. M.fh. 4 Till. 40— ^rgf.ctian of Env,,Onm.nf
:.H.e stacK cu temperature »t eacrt ;.-ai«rse .•.»;« rr.etr.ads. sus.'t
soint tee Section 2.2. D during trie refer- Aam:-.s;r»'.or sr.».,
e.-.ee rr.ethod cravers«: calculate tr.e average , ».,,._„
"e'e enc* •
.
r.acx gu terr.pfrature. Next, determine trie
.T.outure percentage, either by U) U4:ng a 4"* Procedure deicr-.Sed .n Metftod J .'or
asychrometnc ch»r: and makmg appropn- deterrr.;r.:ng moisture content a acceptaaie
ate correctionj if suck pressure d deferent ** * reference method.
from :n« a( the chart, or (2) using wturt- 2-1 Apparatus. A schematic of the sa.-n-
uon vaaor pressure tables. In cases where B'in* t'"*"5 'J*«* 'n ihu reference method :s
th« Byseftromeu'ic ciiart or tfte saturation »no*t» in Figure 4-1. AJJ compcnents shall
vapor preswre tables are not applicable *• maintained and calibrated according 10
(based on evaluation of the process), alter- th* procedure outlined in Method S.
423
8-3
-------
•*
£
•
a
a.
-o
9
<
C
a.
a
O>
I
to
X3VIS
•JVIS M VHtllJl
NUV*
-------
Pt. 60, App. A. Mefh. 4
Till* 40— Protection of Environment
:onsirue:ed of
r.i.-.esi steel sr t.ua tjbir.g. sufficiently
r:«a:ed :a srevent *»ter cor.der.*ac:on. and
.j equipped »-.tn a .'slier, either in-stac*
. co remove partic-
ular mat:er.
When stack conditions permit, other
metals or plastic tubine may be used for tne
probe. subject to che approval of tne Admin-
istrator.
2.1.2 Condenser. The condenser consuls
of .'our iir.pir.cen connected in series with
eround class, leak-free fittings or any simi-
larly leak-free rion-contasunating fittings.
The firs:, third, ar.d fourth impingers shall
se of the Greenourg-Smith desv«n. modified
by replacinc the tip with a 1.3 centimeter
< '-, inch) ID class tube extending to about
1.3 cm (>-. in.) from the bottom of the flask.
The second impinger shall be of the Green-
Surf-Smith design with the standard tip.
Modifications passing the sample gu
stream through a tared silica gel < or equiva-
lent dea .cant) trap, with exit cues kept
below 20* C (M* F). and determining the
weight gain.
It means other than silica gel are used to
determine the amount of moisture leaving
the condenser, it is recommended that silica
gel (or equivalent) sull Se used between the
condenser system and pump, to prevent
moisture condensation in the pump and me-
certr.g devices and to avoid the need to make
corrections for moisture in the metered
volume.
: 1 3 Cooi.r.j S>S:«TI A.-, ce satr. c:-
•.4;"fr ir.d sr-.sr.ed ice or ••:-.•• ».«•: ire
used '.a us in sorser.sir.g moisture
314 M«:«r:r.« 5>s:ern. TT.:s S>SI«T. ..-.
eludes a tacuu.-n »i.j« :«»x free ?U.T:.
thermometers eaoaoie of measuring tem-
perature co *-tinm 3' C iJ4" F) dry ru
meter capable of rr.eijur.r.c volume :a
within 2 percent. »nd related equipment u
$rto»n in F-.jur* 4-1. Other metertr.c sys-
tems, capable at .-namtaininc a fonsunc
samplmc rate and decermminc sample ru
\olume. may be used, subject co che approv-
al of the Administrator
2 IJ Barometer. Mercury ar.eroid. or
ocr.er Sarometer capasie of T.easur-.r.c at-
mospheric prsssure ta »-icr.;n 2.3 mm He
10.1 in. Kg) rr.ay 9e used. In many cases, tne
barometric reading may be obta.ned from a
nearby national 'feather service station, in
which case tne station value < *hxn is trie
absolute barometric pressure) shall be re-
quested and an adjustment for elevation dif-
ferences bctwten tne weather station and
the sampling point shall be applied at a rate
of minus 2.) mm Kg <0.1 in. He) per 30 m
COO ft) elevation increase or vice versa for
elevation decrease.
2.1.8 Graduated Cylinder and/or Bal-
ance. These items are used co measure con-
densed water and moisture caught in the
silica eel to within 1 ml or 0.3 e Graduated
cylinden shall have subdivisions no greater
than 2 ml. Mast .iSoriccry balances are ca-
pable of wc.ghir.g to the nearest 0.3 g or
less. These balances are suitable for use
here.
2.J Procedure. The following procedure
is written for a condenser system (such as
the impinger system described m Section
2.1.H incorporating volumetric analysis to
measure the condensed moisture, and silica
gel and gravimetric analysis to measure the
moisture leaving the condenser.
2.11 Unless otherwise speci/led by the
Administrator, a minimum of eieht traverse
points shall be used for circular stacks
having diameten-less than O.«l m (24 m.). a
minimum of nine points shall be used for
rectangular stacks having equivalent diame-
ters less than O.J1 m n the
flnt two impmgers. Weigh and record tne
430
3-10
-------
Chopter I — Environmental Protection Ag«n«y
Pt. 60, App. A. Meth.
Me-grit of -.rie silica, gel to the nearest 0 5 g.
ind '.nr.s.'er -.r>e s:iica gel to '..".« fourth :m-
;:rger alternatively, the silica gel may .'irst
se '.ra.-.sferred to the impinger. and the
» eight o.' the'silica gel plus imsmger record-
ed.
2.2.2 Select a tout sampling time such
that a minimum total gas volume of 0.60
sera (21 sef) will be collected, at a ratt no
greater than 0.021 raVmm (0 7S cfm). When
both moisture content and pollutant emis-
sion rate arc to b« determined, the moisture
determination shall be simultaneous witn.
and for ihe sane total length of tune u. ihe
pollutant emission rat* run. unless other-
wist specified in an applicable subpart of
the standards.
2.2.3 Set up the sampling train u shown
in Figure 4-1. Turn on the probe heater and
uf applicable) the filter heating sysura to
temperatures of about 120' C <24»' n. to
prevent water condensation ahead of the
condenser allow time for the temperatures
to stabilize. Place crushed ice m the ic* bath
container. It is recommended, but not re-
quired, that a leak check be dene, u follows:
Disconnect the probe from the flrn im-
pinger or (if applicable) from the filter
holder. Plug the inlet to the first impinger
ior filter holder) and pull a 310 mm US in.)
Hg vacuum: a lower vacuum may be used.
provided that it is not exceeded during the
test. A leakage rate in excess of 4 percent of
the average sampling rate or 0.00097 mV
rr.in (0.02 efm). whichever is less, is unacees-
table. Following the leak check, reconnect
the probe vo the sampling train.
2.2.4 Ounng the sampling run. maintain
a sampling rate within 10 percent of con-
stint rate, or u ssec:f;ed Sy :.*•.« Adrr.ir.is-
•-.-aior. Far eacn run. record :?.t saia -e-
cuired on ;Se exajraie data sneet snoar. n
F:r-re 4-2. 3e sure to record ;r:e i.-y »aj
meter reading at the Seg'.r.nir.g and end of
each sampling ::me increment and a.*.*--
-ever sampling 4 halted. Take other appro-
priate readincs at each sample point, at
leut once during each time increment.
2.2.9 To begin sampling, position the
probe up at the first traverse point. Imme-
diately start the pump and adjust the How
to the desired rite. Traverse the cross sec-
tion, sampling at each traverse point for an
equal length of time. Add more ice and. :f
necessary, salt to maintain a temperature of
less :o* C <6»' Tl at the silica gel outlet.
:.:.« After collecting the sample, discon-
nect the probe from the filter holder
-------
FKUME 4-2-ficioMoisiuME DCICHMINAIIOM ntf(HENCE METMOO
MM MB
c o» SIMM CMM*
llMWU yaM I
UJ
I
fS> C*
tout
••.TO
*' "**>
•'!*•>
•*•• M *y g»>
11-0 X fft
••** ul |)At
n»««m uxniMiuN w
o
a
o
3
-------
Chapter I — Environmentol Protection Agency
CATA—n£r£3ENCS
S-ei «•>
9
•-*
Pt. 60, App. A, Meth. 4
j.-2erj.:> of uater. 0 9982 g, ml 0 OC::Ol
3 nl)
: 3 : Volume of 4-»:er •. isor condensed.
23.1 Nomenclature.
3 „ m Proportion of water vapor, ay volumt.
.n -.he gas stream.
M.*Molecular weight of water. 18.0 g/t-
mole i '.I 0 lb/!b-mole).
p.mAbsolute pressure (for this method.
same as barometric pressure) at ine dry
gas meter, mm Hg (tn. Hg).
£,_. Standard absolute pressure. TSO mm
Hg (29.92 in. H«>.
*«Ideal cu consult. 0.09239 .
r..Dry gas volume meuuied ay dry gu
meter dcm' «:-:t:al volume, if any. of condenser
i ater. ml.
'•v »F:.-.»J weight of silica gel or silica gel
;lus .rr.amger. g.
'•v »:.-.it:al weight of silica gel or silica gsl
?!us i.-r.ointer, f.
Y m Dry gu meter calibration factor.
Equation 4-1
where:
K, -0.001333 mVml for metric uniu
• 0.04707 ft'/ral for English units
2.3.3 Volume of water vapor collected
silica (el.
:n
Equation 4-2
wnere:
X1,.0.001333 m"g for metric units
• 0.04715 ft"| for English uniu
2.3.4 Sample cu volume.
Ecuation 4-3
where:
X,-0.3IS8 •K/mm Hf for metric uniu
• 17 64 R.'in. He for English uniu
Norr If :he post-iest lead rate (Section
2.2.S) exceed! the allowable rate, correct the
value of V. m Equation 4-3. u described in
Section 9.3 of Method i.
2.3.3 Moisture Content.
^M,
Equation 4-4
Vorr In saturated or moisture droplet-
:*den gsj streams, two calculations of the
•noisture content of the suck gu shall be
made, one ujmg a value based upon the
saturated conditions (set Section 1.2). and
another based upon '..1e resuiu of trie I.-B-
singer analysis. The lower of these two
values of J~ shall be considered correct.
2.3« Venficanon of constant sampling
rate, for each time increment, determine
ihe iVm. Calculate the average. If the value
433
B-13
-------
Pt. 60, App. A, M«th. 4
.'or ir.y -...-Be increment differs from the
*.«nje oy more than 10 percent, reject the
result* and repeat the run.
3 /»9?rarimczton AfetAod
The approximation method described
below is presented only u a luccested
method (see Section 1.2).
3.1 Apparatus.
3.1.1 Probe. -Stainless itetl flu* tubinc.
sufficiently neated to prevent water conden-
sation and equipped vtth a filter (either in-
stack or heated out-stack) to remove partic-
alate matter. A pluc of class wool, inserted
into the end of the probe, is a satisfactory
filter.
3.1.2 Impmcen. Two midcet impmcen.
each win 30 mi capacity, or equivalent.
3.1.3 Ice Bath. Container and ice. to aid
in condensint Moisture in mpincen.
3.1.4 Oryinc TuBe. Tube packed wuh
nev or retencrated «• to H-aiesh indtcatuif-
cype silin rel (or equivalent desiccant). to
try the uaple cat and to protect the meter
and punp.
3.1.5 Valve. Needle vaive. to reculate the
sample rat flow rate.
3.1.J Puna. Leak-free. dla?hr*«m t>-pe.
or equivalent. M pull the c« sample
throuf A the tram.
3.1.7 Volume Meter. Orr «as meter, suffl-
c-.ently accurate to measure the sample
Title 40—Profeetian of Environment
volume *ithm 2",. and caliS.-»:ed o\«r the
range of Ho* rates and condit.ons »c:.»i:>
encountered dur.r.f san«pl:n«.
3.1 1 Rate Meter. Rouneter. to measure
the no* rante from 0 to 3 !sm (0 to 0 ii
c.'m).
3.1.9 Graduated Cylinder 25 mi.
3.1.10 Barometer. Mercury, aneroid, or
other barometer, as descri&ed in Section
2.1.5 above.
3.1.11 Vacuum Gauge. At least TSO mm
Hi <30 m. Hf) fauce. to be used for the sam-
pimf leswt cheek.
3.2 Procedure.
3.2.1 P'.ace exactly 5 ml distilled *ater .n
each impincer.
Leak check the samplinf train as follows:
Temporarily insert a vacuum fauce at or
near the probe inlec then, pluc the probe
inlet and pull a vacuum of at least 250 mm
Hf dO in. H»). Mote, the time rate of
chance of the dry ru meter dial: alterna-
tively, a roumeter *0-*0 cc/min) may be
temporarily attached to the dry fas meter
outlet to determine the leakage rate. A leak
rate not ui excess of 2 percent of the aver-
a«e samptof rate U acceptable.
NOTC Carefully release the prod* imet
pluc before turnmc off the pump.
434
3-U
-------
j:
•
f.
o.
a
•pmjiouj uoneujtxojdde • UIPJI 6ui|duips
SM99NI.INI iioam
c
o
o
^
E
c
o
ITOO* SSV19I
M111H
«o •—
ro i
3 AIV A
' H111H 11VH
a
o
.
o
-------
Ft. 60, App. A, M«th. 4
TitU 40—Pro««ction at 6nvif«nm«nt
,Mat-en
"«i
Cut
Oo^tior . . .
l«r«>*«tnc am*ur«
ATIO* MtTMOB
Co"""*"™
*«t*
Ooei now
CC«)
*, »Ory its volume mtaaurtd sy dry tu
meter, dem idef).
V.»,,«Ory tu volume meaiurtd Sy ar> cu
meter, corrected :o *t*nd*ra conditions.
d*cm (iic'v
V^VM,* Volume of »ater vaoor condensed.
corrected to standard conditions, scrn
>scf).
Ar*Otiuity of water. O.M«2 f/ml (0.002:ai
.
Y«Dry cu meter calibration factor.
3.3.3 Volumt of water vapor collected.
*htrt:
3 2.2 Conatet tht probe, insert it into :ht
stack, and samplt at 4 constant rate of :
1pm (0.071 cfau. Conunut sampllnt ur.til
tht dry r*» nttttr refiaters about 30 llur*
C.: ftn or until vutolt lidujd droplets art
earned ovtr .'rom tht first unpirntr to tht
second. Record temptraturt. proaurt. &r.d
dry cu ffltttr rttdino u rt^uirtd by
F!»urt 4-5.
3.2.3 A/ttr colltcunc tnt lamolt. core-
bint tht conttnu of tnt two impmctn u>d
tntuurt tht volumt to tht ntirttt O.S nl.
3.3 Calculation*. Tht calculation ottthod
artstnttd tj dtitfntd to ntimatt tht rnou-
turt m iht itack taa: thtrtfort. ochtr data.
w!*.:ch art only ntetaaary for accurate mou-
curt dtttrmiRAtioRt. art not collteud, T>.t
foilo*un Muauotu adtquaitly Mtunatt tht
rr.outurt cent tnt. for tht auraoM of dtttr-
mir.inc isokmttic samplint ratt ittunxa.
3.3.1 XomtneUturt.
J,.-Aspr«xlfflait proportion, by volumt.
of *a;«r vapor In tht cu stream Itavini
tht attend UBptnctr. 0.025.
J«.w»t»r vapor in tht »a* itrtaa. propor-
tion Sy volumt.
Af,«Mol*ojiar wtl^ht of vaur. 11.0 », f •
mott (11.0 16/ Ib-molt).
•^••Abtolutt prtuurt ifor this ntt.tod.
aaat at oaromttrlc prtaiurtt at iht dry
iu mtur.
A» •Standard abaolutt prtaurt. "M nun
Ht<».t3tn.H«>.
ff-ldtal iu coratant. 0 MJ3J (mm H|)
/(rmolt) CK) for metric umu and
21.89 (in. Mfl AOMlutt ump«r&iurt at meter. *K <'R).
r«. «Standard abtotutt ttmptraturt. 293* K
^™^« . **- *
I *tT' «i.,,ll
r.
--(002V,
Eqtarion 4-T
4. C«/.S
4.1 For tht rtftrtnct mtthod, esUibratt
equipment M «p*etfiefl .n the followinc stc-
uont of Method S: Stetion S.3 (mtttnnc
lystem): Section S.3 (ttmptrmturt cau«ts>:
and Section S.7 (barometer). Tht recom-
mended lea* chock of the mettnnc system
(Section 9.1 of Method 9) alao applies to tht
reference method. For tht approximation
method, ust tht procedures outlined m Sec-
tion 9.1.1 of Method • to calibrate tnt me-
436
-------
CJiapter I — Environmental Protection Agency
Pt. 60, App. A, M«'h. 5
•j.r ~S s;s:fm. ar.d -.:•« ;roceiure at S'e'.nod
5 Sec' rr J 7 :o ca..Sr»:e :.'.e si.-ome'.er
5 5 i •:?•:?*.;•
; A.r ?o.!u;;er. i.-.gi.-ie«r:.-.g Manual
Second Edition) Oanieison. J. A. ted.). C S.
r.n .ron.T.enuU Protection Agency. Office of
v.r Quality Planning ind Standards. Re-
i«arch Triangle Pirn. N.C. Publiciuon No.
.\f-4Q. 19T3.
:. OevorKin. Howird. et *J. Air Pollution
Source Tcsunf M«nu»J Air Pollution Con-
;rol Outnci. L&J Anteles. Cil:f. Sovember.
:9«3.
3. MethodJ for Oetermjn»tion of Velocity.
volume Dust »nd MUt Content of Cues.
Western Precaution Oiv.non of Joy M*n-
u.'ic'.ur.nf Co.. lxj» .Utgeles. Cilii. Bulletin
•AT-50. 1»6I.
MtTMOS S—OtTrHMISATIOK Of
E*:snoxs rnoM STAnoMAjiY Socxcx*
V ?-mcipJ« and vtppiicaWUv
t.l Principle. ?\nicui».u RUUCT J *nth-
dravn isokineuuUy from tAc aoure* wd
collected on i ilui fiber filter m*ifli*in«d
it a icmptmure in tne ranee nt IMsl*' C
-:«*. = 25' F) or tuch oiher ump«r»tur« M
specified Br ta »pplic*ale lubptrt of tnt
stind&rdi or approved by AdmlniJtntor.
" S. Sr.\ .re- — e.".il Protection Agency .'or
i 3U"..c-..ir i33v.ci:.on. Tne ;ir-..c-..a;e
m«j. *"ic*. :nc:»des ».-.y .r.ateni '..".at con-
denses it jf aboxe '..".e .'iltratior. -.err.pera-
lure. ;s de'.errr.ined rri'.-imetricaily a/;er .-e-
niovaJ of uncomomed »aier.
1.2 Applicability. T^is method :i aosltca-
ble for :.ne determination of saniculaie
emissions from stationary sources.
2. xpparatuj
2.1 Sampling Trun. A scnernatie of '.^e
larapling train us«4 in this method is shovn
in Flrure S-l. Complete construction details
are pven in APTO-0581 (Ctution 2 in Sec-
tion T): commercial model* of this tninare
also available. For charges from .VPTD-
0581 and for allowable modifications of the
train shovn m f.rure 5-1. sec the lolloping
subMcuou.
Die operating and maintenance proce-
dures for the sampling train are described in
APTO-OSTS (Ciiauon 3 .n Section 'i. Since
correct usage is important in oouirur.r valid
rtsulu. all users should read AfTO-Oi'S
and adopt the operaung and maintenance
procedures) outlined in it. unless othtrv.se
specified herein. The sampling train con-
sists of the following componenu:
437
8-17
-------
TEMPERATURE SENSOR
d~
c-i:
-------
I —Environmental Protection Agency
Pt. 60. App. A. Meth. 5
: '. '. ?-cse Senile 5n.r..ess SIM! 3'.6;
;.- i.us *.;.*. srarp. -.ijered lesdir.g ?S«e.
?"•.« irs.e ;f -»3er sr.all be 30* i.nd the
•.i;er s.-.a.i be or> the outside :o ;resene a
constant .nterr.al e-.vrtti.er, The probe
nozzle shall Se of the button-hook or elbow
design- unless otherwise specified by the Ad-
ministrator. If made of stainless steel, the
node shall be constructed from seamless
tubinr. other materials of construction may
be 'ised. subject to the approval of tht Ad-
ministrator.
A rar.fe of nozzle sizes suitable for isokin-
et;c sair.plmg should b« available. e.g.. 0-32
io 1.27 cm <"i to '•» m.)-or larger tf higher
volume sampling trains are used—inside di-
ameter ilO> nozzles in increments of 0.:« cm
i"n m.>. Each nozzle shall be calibrated ae-
cord:n( to the procedures outlined ;n Sec-
tor. S.
2.1.2 Probe Uner. 3orosilica;e or quartz
glass tubing with a heating system capable
of mainuining a gas temperature at the exu
end dur.ni sampling of :20sl4' C HixZi'
?•>. or sucn other temperature u specified
by an applicable subpart of the standards or
approved by the Administrator for a partic-
ular application. (The tester may opt to op-
erate the equipment at a tempera fire lover
than that specif ltd.) Since the actual tem-
perature at the outlet of the prob« is not
usually monitored dunni sampling. ;rcb*s
constructed according to APTD-0381 and
^::lu^-.« tilt calibration curves of A?TD-
QSTS . Both type* of
Uners may M used at hi»her temperatures
:han specified for shon ptnod* of time, sub-
ject to tht approval of tnt Administrator.
Tht sofuninc temperature for borosillcaie
:s 820* C (1.30T n. and for quanz it x 1.300*
c i :.'32' rt.
'.vy.enever practical, every effort should
be —.»d« to use borosilicate or quanx (lass
;robe iinen. AltemaUvely. metal liners
•«.f.. 314 sta;r.lesa steel. Incoloy «J3.! or
other corrosion resistant metals) madt of
stamltn tubinc may bt used, subject to the
approval of tht Administrator.
2.14 Pltot Tub*. Type S. as described in
Section 2.1 of Method 2. or other device ap-
proved by tnt Administrator. The pitot tube
shall bt attached u tht probt •
;:ar.e isee Method :. ~:rure 2-«b) aur..-(
sarapl:r.«. The Type S sitot tube aasembly
shall have a Known co«.'ric:er.t. 2«',errr.;ned
as outlined :n Section 4 of Method 2.
2.1.4 Differentia Pressure Oau»e. In-
clined manometer or equivalent device
(two), as described in Section 2.: of Method
2. One manometer shall be used or velocity
head (M) readings, and the other, for or.'ice
differentia pressure readings.
2.1.3 niter Holder. Borosilicatc class.
with a fiaas frit filter support and a silicon*
rubber gasket. Other materials of construc-
tion (e.g.. stainless steel. Teflon, vuoni may
be used, subject to approval of the Adminis-
trator. Tht holotr design shall provide a
positive seal against icakagt from the out-
side or around tht filter, the holder shall
bt attached immediately at the outlet of the
probt (or cyclone, it used).
2.1.8 Filter Heating System. Any heating
system capable of maintaining a tempera-
ture around :he filter holder during sam-
pling of ::osi4' c <:48s:s* n. or such
other temperature u specified br an appli-
cable subpan of tht standards or approved
by tht Administrator for a parv.cular appli-
cation. Alternatively, the tester may opt :o
operate tht equipment at a temperature
lover than that specified. A temperature
gauge capable of measuring temperature to
within 3* C (3.4* Pi shall bt installed so that
the temperature around tht filter holder
can bt regulated and monitored during sam-
pling. Heating systems other than the or.c
shown in APTD-0381 mar bt used.
2.1.7 Condenser. Tht following system
shall at used 10 deterrune the suck fas
raouture content: Pour impmgcrs connected
in series with leak-fret ground glass fittings
or any similar leak-fret non-contaminating
fittings. Tht first, third, and four.h ia-
Singers shall bt of tht Cretnburt-Smith
design, modified by replacing tht up with
1.3 en c* in.) ID glass tubt extending to
about 1.3 cm (H in.) froa the bottom of the
flask. The second impsngtr shall bt of the
Grttnburg-Smith design with tht standard
tip. Modifications 'e.g.. using flexible con-
nections bttwetn tht impingers. using mate-
rials other than glass, or using flexible
vacuum lines to connect tht filter holder to
tht condenser) may bt used, subject M the
approval of tht Administrator. Tht first and
second unpingtrs shall eonuun known quan-
tities of water < Section 4.1.3). the third shall
bt empty, and tht fourth shall contain a
known weight of silica gel. or equivalent
desiccanr. A thermometer, capable of meas-
uring umptrturt to «iUun 1* C
-------
Pf. 60, Ape. A, Mtth. 5
Titlo 40—Protection of Environment
of the **ter condensed and moisture leav-
:.-.g the condenser, each :a within I ml at I «
may Se used, subject to the appro* al of the
Administrator. Acceptable means are to
measure the condensed water either (raw
metrically or volumemcally and to measure
the moisture leaving tht condenser by: (1)
monitoring tht temperature and pressure at
the exit of tht condtnMr and using Daiton's
law of partial pressure*: or (2) passing th*
sample ha* stream through a tared silica gel
-ztr. tf necessary, u
described in Method 3. The tewperature
setuor shall, preferably, be permanently »t-
tachtd to tht pitot tube or sampluic arobt
in a fixed eonfifuration. such that the tip of
the sensor extends beyond the leading «lce
of tnt probe sheath and doe* not touch any
metal. Alternatively, the sensor may be at-
tached just pr.or to use in tnt field. Note.
however, that if tht temperature sensor is
attached in tht field, tht sensor must s«
placed ia an interference-free arrantemcnt
with respect to the Type S pitot tube open-
inn
-------
Chapter !—Environmental Protection Agency
ft. 60, App. A, Meth. 5
::3 "..-.-•! Glass 3r pc
i.i .r s«r:;.e recovery
:: .»_-.i.js:s. "or missis, the folla*thg
#qu:;.Tert .J needed.
:.3 t Glass washing Dishes.
232 Desiccatsr.
:.3 3 Analytical Balance. Ta measure 10
wuh:n 0 1 rr.g.
2.3.4 Balance. To measure to within 0.3 g.
2.3.S Beakers. ISO .711.
13.8 Hygrometer. "To measure the reia-
::ve hu.-r.idi:y at the laboratory environ-
ment.
2.3.' Temperature Gaute. To measure
:he temperature of the laboratory environ-
ment.
3. A«cj«ni»
3.1 Sampling. The reagents used in sam-
pling are u follows:
31.1 Fillers. Glass fiber filters, without
orranic binder, exhibiting at least 99.J3 per-
cent efficiency <<0.03 percent penetration)
on 0.3-mieron dioc-.yl phthalate smoke parti-
cles. The filter efficiency test shall be con-
ducted :n accordance with ASTM standard
method D29««-n (Reapproved 19TI) SOi
cr SO:. Ctat-.cn '.0 :n Section T aibliocra-
phy. r.ay be used :o select the appropriate
filter.
3.1.: Silica Cel. Indieatinf t>-pe. « to 19
raesh. U previously used, dry at ITS' C (330*
F) .'cr 2 hours. .Ve« silica leJ may be us«d u
received, .\iterr.auvely. other types of desic-
canu -equivalent or better) may be used.
subject us :he approval of ihe Adcurostra-
:or.
3.1.3 '*aur. When analysis of tht maie-
r:al caucht in tht mpln«en is required, cis-
::Ued »ater shall be used. Run blanks pnor
-.0 field use to elirsuiate a huh blank on ten
samples.
3.1.4 Crashed Ice.
3.1.S Stopcock Grease. Acetone-insoluble.
heat-stable silicon* crease. This is not nec-
essary it screw-on connectors vnh Teflon
sleeves, or similar, are used. Alternatively.
otne> types of stopcock crease may be used.
subject to the approval of the Administra-
tor.
).l Sample Recovery. Acetone-rcaccnt
trade. < 0.001 percent residue, '.n flats bet-
Ues—u required. Acetone from metal con-
talners (cnerally has a hl«h residue blank
and should not be used. SomeUmes. suppli-
ers transfer acetone to (lass bottles from
.-neul containers: thus, acetone blanks shall
be run prior to field use and only acetone
with :o« blank values uo.OQi percent) shall
be csed. In no case shall a blank value of
creaur than 0.001 percent of the wettht of
acetone used be su5t.-»c'.ed .'.-cm ;he s«rr;.e
3 3 Analysis. T»o reagents ire required
for the analysis:
33.1 Acetone. Same u 3 2.
3.3 2 Oesiccam. Anhydrous calcium s^l-
fate, indicating type. Alternatively, other
types of desiccants may be used, subject '-o
the approval of the Administrator.
4. ?i-oeedtire
4.1 Saaipling. The complexity of •.his
method is such that, in order to obtain reli-
able results, testers should be trained and
experienced with the '.est procedures.
4.1.1 Pretest Preparation. All the compo-
nents shall be maintained and calibrated ac-
cording to the procedure described .n
AJTD-OSTj. unless othen~.se specified
herein.
'.Veigh several 200 to 300 g portions of
silica i el Ji air-tight containers to the near-
est O.S g. Record the total weight sf :.".»
sthca gel plus container, on each convi;-er.
As an altematnc. the silica gel need not :e
preveighed. but may be weighed directly .n
the inspinger or sampling holder just "-.or
to train assembly.
Check filters t-jually agautst light for .r-
refjlarities and flaws or pmhole leaks.
Label filters of the proper diameter on *.he
back side near the edge usir.g numbering
machine ink. AS an alternate e. label '.:-.«
shipping conts^ners (flats or plastic petri
dishes) and keep the filters in these contain-
ers at all '.:»es except dur.r.g sampling and
weighing.
Desiccate the filters at :o=3.8' C 'S«=:o-
Tl and ire a: en t pressure for at least :<
hours and weigh at mten-als of it least s
hours to a constant * eight, i.e.. 0.3 r.g
change from previous weighing: record re-
sults '.o the nearest 0.1 rag. Dunng each
weighing :he filter must not be exposed '.o
the laboratory atmosphere for a period
greater than 2 minutes and a relative hu-
midity abo*e SO percent. Alternatively
r unless otherwise specified by the Adminis-
trator), the filters raay be oven dried at IDS'
C (230* n for 2 to 3 hours, desiccated for 2
hours, and weighed. Procedures other than
those described, which account for relative
hucudlty effects, may be used. iu eject :o
the approval of the Administrator.
4.1.2 Preliminary Determinations. Select
the sampling site and the minimum number
of sampling points according to Method 1 or
as specified by the Administrator. Deter-
mine the stack pressure, temperature. ar.J
the range of velocity heads using Method 2:
It Is recommended that a leak-check of the
pttot lines (set Method 1 Section 3.1) be
performed. Determine the moisture content
using Approximation Method 4 or its alter-
native* for the purpose of making tsokmeuc
sampling rate settings. Determine the stack
441
B-21
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Pt. 60, App. A, Meth. 5
Title 40—Protection of Environment
the sample
volume taken (corrected to standard condi-
tions) will exceed tne required minimum
total gas sample volume. Tne latter u Based
on an approximate average sampling rate.
It is recommended tnat the number of
minute* sampled at each point be an integer
or an integer plus one-half minute, in order
to avoid timekeeping errors. The sampling
time at tun point snail be tne same.
In some cirumstanees. e.g.. batch cycles, it
rr.ay be necessary to sample for shorter
•,:-.« at the traverse points and to obtain
smaller gas samslt volumes. In tnese cases.
tht Administrator's approval must first be
obtained.
4.1.3 Preparation of Collection Train.
During preparation and assembly of tne
sampling tram, keep all openings where con-
tamination can occur covered until just
pnor to assembly or until sampling is about
to begin.
Place 100 ml of water in each of the first
two imptngen. leave tne third impingar
tmpty. and transfer approximately 200 to
100 g of prrwetgned' silica gel from its con-
tainer to tn* founa impinger. More silica
gel mar be used, out care should be taken to
ensure that it is not entrained and earned
out from tn« tmptngtr during sampling.
Race the container tn a clean place for later
use in the sample recovery. Alternatively.
tht weight of the silica gel plus impingtr
may be determined to the nearest 0.3 g and
recorded.
Using a tweeter or clean disposable surgt-
cal gloves, place a labeled (identified) and
weifhed filter tn the filter holder. Be sure
:.*m the filter is property centered and the
fasKtt properly placed so as to prevent the
sample gas stream from circumventing tnt
Mter CnecK the .'.::«• far tears i::er userr.
tly is completed.
When class linen are used, install the se-
lected noale using a Viton A 0-rmg *nen
stack temperatures art less than 240' C
(500* F) and an asbestos string casket wr.en
temperatures are higher. See AJTD-OST4
for details. Other connecting systems using
either 11< stauutss steel or Teflon rerruies
may be used. When metal linen are used.
install the nosie as abovt or by s leak -free
direct mechanical connection. Mark t.H.e
probe with htat resistant us* or ay some
other method to denote the prooer distance
into the stack or duct for eacn sampling
point.
Set up tht cram as in Figure J-l. using (if
necessary) a very light coat of silicone
grease, on all ground glass joints, grtaitng
only tht outer portion (see APTO-05'S) to
avoid possibility of contamination sy the
silicone- grease. Subject to the approval of
the Administrator, a glass cyclone may se
used between tne probe and filter holder
wntn tnt total paniculate catch j expected
to exceed 100 mg or when water dropleu are
present m tht stacx gas.
Place crushed ice around the impingen.
4.1.4 Leak-Check procedures.
4.1.4.1 Pretest Leak-Check. A pretest
leak-check is recommended, but not re-
quired. If the tester opu to conduct :he pre-
test leak-check, the following procedure
shall be used.
After the sampling :ram has seen assem-
bled, turn on and set the ftlur and proce
heating systems at the desired operating
temperatures. Allow time .'ar the terr.sera-
tures to stabilize. If a Viton A O-rt.-.c or
other leak-free connection is used in assem-
bling the probe noslt to the probe liner.
leak-check the train at the sair.altng s:t* sy
plugging the noalt and pulling a 380 mm
Kg i IS la. Hg) vacuum.
Nore A lowtr vacuum say bt used, pro-
vided that It is not exceeded during ;he :est.
If an asbestos suing is used, dp not con-
nect the probe to tne tram durtSt tne leax-
cheek. Instead, leak-check tne tram by Mrst
plugging the inlet to tne filter holder
icycone. if applicable) and pulling a JsO mm
Hg (IS in. Kg) vacuum (see Note immediate-
ly above). Then connect the probe co the
train and leak-check at about 25 ma Hg < i
in. Kg) vacuum: alternatively, use probe
may IM leak-cheeked with the rest of the
sampling train, in one step, at 1«Q mm Hg
(13 in. Kg> vacuum. Uakagt rHei in excess
of 4 percent of tht average sampling rate ar
0.00047 m'/min (0.01 cfm>. whichtvtr is itss.
are unacceptable.
The following leak-cheek instructions for
the sampling train described in A*TO-OS.«
and AJTO-04*! may be helpfuL Start tne
puma with bypass valve fully open and
442
B-22
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APPENDIX C
MEASUREMENT OF TOTAL HYDRpCARBONS_ IH STACK GASES FROM
HAZARDOUS WASTE INCINERATORS, BOILERS. AND
INDUSTRIAL FURNACES
C-l
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APPENDIX C
MEASUREMENT OF TOTAL HYDROCARBONS IN STACK GASES FROM
HAZARDOUS WASTE INCINERATORS. BOILERS. ANQ
INDUSTRIAL FUR
NACl
C-i
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APPENDIX C~ICASUROCMT OF TOTAL HYDROCARBONS in SJACX SASES ROM
HAZARDOUS WASTE INCINERATORS, BOILERS, AMD INDUSTRIAL RJRJWCES
1.0 Applicability and Principle
1.1 Applicability.
This method applies to the measurement of total hydrocarbons as a surrogate
measure for total gaseous organic concentration in the combustion gas
streaii. The concentration 1s expressed 1n terms of propane by volume (ppmv).
1.2 Principle.
A gas sample 1s extracted from the source through a sample line, and gas
conditioning system to a ft we 1on1zat1on detector (FIO). Results are
reported as volume concentration equivalents of the propane.
2.0 Definitions
2.1 Continuous Emission Monitoring System (COC).
The CEMS 1s comprised of all the equipment used to generate data and includes
the sample extraction and transport hardware, sample conditioning system, the
FIO analyzer(s), and the data recording/processing hardware (and software).
A continuous monitor 1s one 1n which the sample to be analyzed passes the
metsureMfit fiction of the analyzer without interruption and which evaluates
the detector response to the sample at least once etch IS s and records the
average of these observations each and every minute.
C-2
-------
The hourly rolling average 1s the arithmetic mean of sixty (60) most recent
l-m1n average values recorded by the continuous monitoring system.
2.3 Soan Value.
The upper limit of the gas concentration measurement range. For most incine-
rators a 50-ppm propane span 1s appropriate. Higher span values may be
necessary If the THC emission spikes are several and higher. In such cases a
100-ppm propant span should be adequate. For convenience, the span value
should correspond to 100 percent of the recorder scale.
2.4 Calibration Sas.
A known concentration of a gas 1n an appropriate diluent gas.
2.5 Zero Drift.
The difference 1n the measurement system response to a zero level calibration
gas before and after a stated period of operation during which no unscheduled
maintenance, repair, or adjustment took place.
2.6 Calibration Drift.
The difference 1n the measurement system response to a mid-level calibration
gas before and after a stated period of operation during which no unscheduled
maintenance, repair, or adjustMnt took place.
2.7
The time Intmrval from) a step change 1n pollutant concentration at the inlet
to the emission measurement system to the time at which 95 percent of the
corresponding final value Is reached as displayed on the recorder.
C-3
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2.8 Calibration
The difference between the gas concentration indicated by the measurement sys-
tem and the known concentration of the calibration gas.
3.0 Monitoring System Types
Thert art two acceptable types of THC monitoring systems: heated and
unheated. Heated systems maintain the temperature of the sample gas between
ISO* to 17S*C throughout the system. This requires all system components like
probe, calibration valve, filters, sample lines, pump, and the FIO analyzer to
be kept heated at all times such that no moisture 1s condensed out of the
system. Unheated system remove excess moisture from the system and pass it
through a gas conditioning system kept at temperatures between 5* to 18*C (40*
to 64*F) so that the moisture of the sample gas entering the FIO does not
exceed 2 percent.
3.1 CDC Components.
The essential components of the measurement system are described below.
3.1.1 FID Analyzer.
That portion of the system that senses organic concentration and generates an
output proportional to the gas concentration.
3.1.2
That portion of the system that computes the hourly rolling averages, displays
and records a permanent record of the measurement values. Combinations of
gauges, strip chart recorders, data loggers, and computers are examples. The
nimnum data recording requirement 1s one measurement value per mm.
C-4
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3.1.3 Staple Probe.
Stainless steel, OP equivalent, three-hole rake type. Sample holes sna" ;e
4 mm in diameter or smaller and located at 16.7, 50, and 83.3 percent of tr-e
eauivalent stack diameter. Alternatively, a single opening probe may Be used
so that a gas sample 1s collected fro* the centrally located 10 percent area
of the stack cross section.
3.1.4 Saaple Una.
Stainless steel or Teflon* tubing to transport the saaple gas to the analyzer.
3.1.5 Calibration Ve1v« Assembly.
A three-way valve assembly to direct the zero and calibration gases to the
analyzers 1s recommended. Other methods, such as quick-connect lines, to
route calibration gas to the analyzers are applicable.
3.2 Sample Conditioning System for Unheated Analyzer.
A sample conditioning systea consisting of parti oil ate fHter(s), chHler(s),
and condenser(s) shall be provided to remove partlculates and excess nolsture
froa the saaple gas before 1t reaches the FID. Partlculates removal prevents
damage to the pump and the sampling valves and avoids full or partial blockage
of sampling lines which could result 1n decreased flow to the FID. The
part leulate filters Bay be of 1n-stack or out-of-stac* type and should be
heated to prevent condensation.
The moisture} content of the sample gas entering the FIO should not exceed 2
percent. Chillers or condensers should be provided 1n the system to take out
the excess aolsture. A temperature between 40* to 64*F should be maintained
in the saaple conditioning systea, since the saturated moisture content of air
* Mention of trade neaes or specific products dots not constitute endorsement
by the Environmental Protection Agency.
C-5
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at those teaptratures would be 0.8 to 2 percent. The chiller/condenser s/stt
snould not allow the sample gas to bubble through the candensate to
ng of soluble organic* out of the gas streaa.
4.0 Calibration and Other Casts
Gases used for calibration, fuel, and coabustlon air (1f required) are con-
talned 1n compressed gas cyllndtrs. Preparation of calibration gases shall be
done according to tht procedure 1n Protocol No. 1 (listed 1n Reference 2,
Section 10.0). Additionally, tht manufacturer of tht cylinder should provide
a recommended shtlf Hfe for each calibration gas cylinder over which the
concentration dots not change acre than ±2 ptrctnt fron tht certified valut.
4.1 Futl.
A 40 ptrctnt H,/60 ptrctnt Ht or 40 ptrctnt H,/60 ptrctnt N, gas alxturt 1s
rtcoaatndtd to avoid an oxygen syn«rg1sa effect that reportedly occurs wntn
oxygtn conctntratlon varlts significantly fro* a Man value.
4.2 Zero Gts.
High purity air with Itss than 0.1 parts ptr Million by volume (ppav) of
organic aattHal atthant or carbon equivalent or Itss than 0.1 ptrctnt of the
span valut, whichever 1s greater.
4.3 Lo»-ltvtl Calibration 6as.
Propant catprttlon gas (1n air or nitrogen) with a concentration equivalent
to 20 to 30 ptrctnt of tht applicable span valut.
4.4 Wd^tvtl Calibration Oat.
Propant calibration gas (1n air or nltrogtn) with a conctntratlon toiilvaltnt
to 45 to 55 ptrctnt of tht applicable span valut.
-------
4.5 High-level Calibration 6as.
Propane calibration gas (in air or nitrogen) *Uh a concentration
to 80 to 90 percent of the applicable span value.
5.0 Measurement Systea Performance Specifications
5.1 Zero Drift.
Less than ±3 percent of the span value.
5.2 Calibration Drift.
Less than ±3 percent of the span value.
5.3 Calibration Error.
Less than ±5 percent of the calibration gas value.
6.0 Pretest Preparations
••* Selection of Sailing Site.
The location of the sampling site 1s generally specified by the applicable
regulation or purpose of the test. I.e., exhaust stack, Inlet line, etc. The
sample port shall be located at least 1.5 • or 2 equivalent dlaMters upstream
of the gas discharge to the ataosphere.
Install the sample probe so that the probe Is centrally located 1n the stack,
pipe, or duct and Is sealed tightly at the stack port connection.
C-7
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6.3 Measurement Systaa Preparation.
Prior to the emission test, assemble the measurement system following :-e
manufacturer's written Instructions In preparing the sample interface and -re
organic analyzer. Make the system operable.
6.4 Calibration Error Test.
Immediately prior to the test strlts (within 2 h of the start of the test)
introduce zero gas and high-level calibration gas at the calibration valve
assembly. Adjust the analyzer output to the appropriate levels, if neces-
sary. Calculate the predicted response for tht low-level and itld-level gases
based on a linear response line between the zero and high-level responses.
Then introduce low-level and mid-level calibration gases successively to the
measurement systea. Record the analyzer responses for low-level and aid-level
calibration gases and determine the differences between the measurement systea
responses and the predicted responses. These differences must be less than
5 percent of the respective calibration gas value. If not, the measurement
systea 1s not acceptable and aust be replaced or repaired prior to testing.
No adjustments to the measurement system shall be conducted after the calibra-
tion and before the drift check (Section 7.3). If adjustments are necessary
before the completion of the test series, perform the drift checks prior to
the required adjustments and repeat the calibration following the adjust-
ments. If multiple electronic ranges are to be used, each additional range
must be checked with a aid-level calibration gas to verify the multiplication
factor.
0*5 HmMtPOiUMI __J|IJBml
x
Introduce zero gas Into the measurement system at the calibration valve assem-
bly. Wntn tUt system output has stabilized, switch quickly to the high-level
calibration gas. Record tht time from tht concentration change to the mea-
surement system responst equivalent to 98 percent of tht step change. Repeat
the test three times and average tht results.
c-a
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7.0 Emissions *M«urement Test Procedure
7.1 Organic He«surgment.
Begin sampling at the start of the test period, recording the time and any re-
quired process information as appropriate. In particular, note on the record-
Ing chart periods of process Interruption or cyclic operation.
7.2 Drift Determination.
[immediately following tht completion of tht test period and hourly during the
test period, reIntroduce tht zero and did-level calibration gases, one at a
tint, to tht mtasureMnt system at tht calibration valve assembly. (Make no
adjustments to tht Measurement system until afttr both tht zero and calibra-
tion drift checks art made.) Record tht analyzer response. If tht drift
values exceed the specified Units, invalidate the test results preceding the
check and repeat the test following corrections to tht measurement system.
Alternatively, recalibrate tht ttst measurement system as 1n Section 6.4 and
report the results using both sets of calibration data (I.e., data determined
prior to the test period and data determined following tht ttst period).
8.0 Organic Conctntrttlon Calculations
determine tht avtragt organic concentration 1n terms of ppmv propane. Tht
average shall be determined by tht Integration of tht output recording over
the period specifltd 1n tht applicable regulation.
Levels
THC levels from tht trial burn will bt reported as ppmv propane and need to be
converted to tht mg/s units used for tht dmmfrtbnfe THC valuts. This
conversion Is accomplished with tht following equation:
C-9
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ag/s • (THC ppew propane) x (Stack gas flow) x 2.8 x 10'2
where:
THC » concentration as measured by the THC Method, :o«r
propane.
Stack gas flow • 1n dry standard cubic meters ptr nilnutt
measured by EPA Reference Method S (or Modified £PA Method §)
during the ORE trial burn, and
The constant factor 2.8 x 10"2 1s derived fro* the following
equation: f6.9 x 10"4) U».M
(0.75) (1.5)
where:
6.9 x 1
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10.0 Bibliography
1. Measurement of Volatile Organic Compounds—Guide tin* S«n«, j.S
Environmental Protection Agency, Research Triangle Park, North Carolina
Publication No. EPA-450/2-78-041. pp. 46-54 (June 1973).
2. Traceobiltty Protocol for Establishing True Concentrations of Cases C/sed foi
Calibration and Audits of Continuous Source Emissions Monitors (Protocol So. I),
U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Research Triangle Park, North Carolina (June 1978).
3. Gasoline Vapor Emission Laboratory Evaluation—Part 2, U.S. Environmental
Protection Agency, Office of A1r Quality Planning and Standards, Research
Triangle Park, North Carolina, EM Report No. 7S-SAS-6 (August 1975).
C-ll
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APPENDIX 0
DRAFT METHODS FOR THE DETERMINATIONI OF_ HC1 _EMI_SSIONS FROM
MUNICIPAL AND HAZARDOUS WASTE INCINERATORS
0-1
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METHOD
MIDGET IMPINGES HC1/C1, EMISSION SAMPLING TRAIN
.DRAFV
This eathod has been drmfted based on the result* of laboratory and field
studies carried out under contract to the Source Branch of the Quality
Assurance Division. Ataespheric Research and Exposure Assessaent Laboratory
(QAD/AREAL). United States Environaental Protection Agency (U.S. EPA). The
method is still under investigation and is subject to revision.
D-2
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METHOD
MIDGET IMPINGE? HCI -ci, EMISSION SAMPLING TRAIN
1.3 SCOPS AND APPLICATION
1.1 This method describes the collection of hydrogen chloride ,(HC1, CAS
Registry Nuaber 7647-01-0) and chlorine (C12, CAS Registry Number 7782-50-5)
in stack gas emission samples froa hazardous waste incinerators and municipal
waste combustors. The collected saaples are analyzed using Method XXXX. This
method is designed to collect HC1/C1, in their gaseous forms. Sources, such as
those controlled by wet scrubbers, that emit acid particulata natter (e.g.. HCI
dissolved in water droplets) must be sampled using an isokinetic HC1/C1.
sampling train (see Method XXXX).
2.0 SUMMARY OF METHOD
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 solu-
tions. In the acidified water absorbing solution, the HCI 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 aeasured
by ion chromatography (Method XXXX).
3.0 INTERFERENCES
3.1 Volatile materials which produce chloride ions upon dissolution
during sampling are obvious interferences in the measurement of HCI. One
ir.terferent for HCI is diatomic chlorine (Cla) gas which disproportionates to
HCI and hypochlorous acid (HOC1) upon dissolution in water. Cl, gas exhibits a
low solubility in water, however, and the us* 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 HCI gas stream
containing 50 ppm Cl- with this method does not cause a significant bias.
Sampling a 220 ppm HCI gas stream containing 180 ppm Cl, results in a positive
bias of 3.^5 in the HCI measurement.
4.0 APPARATUS AND MATERIALS
4.1 Sampling Train. The sampling train is shown in Figure 1 and
component parts are discussed below.
4.1.1 Probe. Borosilicate glass, approximately 3/8-ir.. (9-=!
inside diameter, with a halting system to prevent condensation. When the
concentration of alkaline particulate matter in the emissions is high, a
3/8-in. (9-am) inside diameter Teflon elbow should be attached to the
inlet of the probe: a 1-in. (25-mm) length of Teflon tubing with a 3'3-ir..
XXXX - 1 Revision
Draft August 1989*** Date
0-3
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/o-aa) inside diaaeter should be attached at the open end of the elbow -
perait the opening of the probe to be turned away from tr.e gzs stream.
thus reducing the amount of particulate entering the train. When r.i?n
conoentrations of particuiate aatter are not present, the Teflon elbow •__
r.ct r.ecessary, and the probe inlet can be perpendicular to the gas 3—3.=:
When sampling at locations where gas temperatures are greater than
approximately 400"F. such as wet scrubber inlets, glass or quartz elbows -
aust be used. In no case should a glass wool 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 4.1.5.
4.1.2 Three-way stopcock. A bore-silicate, three-way glass stopcock
with a heating systea to prevent condensation. The heated stopcock
should connect directly to the outlet of the probe and filter assembly and
the inlet of the first iapinger. The heating systea should be capable of
preventing condensation up to the inlet of the first iapinger. Silicone
grease may be used, if necessary, to prevent leakage.
4.1.3 lapingers. 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
tiaes greater than one hour, a midget iapinger with a shortened stem (such
that the gas sample does not bubble through the collected condensate)
should be used in front of the first iapinger.
4.1.4 Mae West iapinger 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.
4.1.5 Saaple line. Leak-free, with compatible fittings to connect
the last iapinger to the needle valve.
4.1.6 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure within 2.5 aa Hg (0.1 in. Hg). In many
cases, the barometric reading may be obtained froa a nearby National
Weather Service station, in which case the station value (which is the
absolute barometric pressure) shall be requested and an adjustaent for the
elevation differences between the weather station and sampling point shall
be applied at rate of ainus 2.5 aa Hg (0.1 in. Hg) per 30 m (100 ft)
elevation increase or vice versa for elevation decrease.
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 puap. and a rate
meter, 0 to 5 liters/min.
4.1.8 Metering systea. The following iteas coaprise the metering
system which is identical to that used for EPA Method 6 (see Reference 5)•
4.1.8.1 Valve. Needle valve, to regulate saaple gas flow rate.
XXXX - 2 Revision
•**0raft August 1989*** Date
0-4
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4.1/3.2 Puap. Leak-free diaphragm puap, or equivalent.' ~z . ..
gas through trair.. Install a snail surge tank between the puss =.-.-
the rate aeter to eliainace the pulsation effect of. the diapr.ra?=
pump on the rotaaecer.
4.1.8.3 Rate meter. Rotameter, or equivalent, capable cf
measuring flow rate to within 2 percent of selected flow rate of 2
liters/min.
4.1.8.4 Voluae meter. Dry gas aeter, sufficiently accurate to
measure the sample voluae within 2 percent, calibrated at the
selected flow rate and conditions encountered during sampling, and
equipped with a temperature gauge (dial thermometer or equivalent)
capable of measuring temperature to within 3°C (5.4°F).
U.I.8.5 Vacuum gauge. At least 760 ma Hg (30 in. Kg) gauge to
be used for leak check of the sampling train.
4.2 Sample Recovery.
4.2.1 Wash bottles. Polyethylene or glass, 500 ml or larger, two.
4.2.2 Storage bottles. Glass, with Teflon-lined lids. ICO ml. to
store impinger samples (two per sampling run).
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications arm available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 ASTM Type II Water (ASTM D1193-77 (1963))- All references 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 XXXX).
5.3 Sulfuric add (0.1 N). H,SO». Used as the HC1 absorbing reagent. To
prepare 100. mL, slowly add 0.28 mL of concentrated H,SOk 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 XXXX).
5.4 Sodium hydroxide (0.1 M), NaOH. Used as the Cl, absorbing reagent.
To prepare 100 mL. dissolve 0.40~g of solid MaOH in about 90 mL of water and
adjust the final volume to 100 mL using additional water. Shake well to mix
XXXX - 3 Revision
•"Draft August 1989*** D*tm
0-3
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the solution. It is advisable to analyze a blank saaple of this reager.t pr.cr
to sanplir.?, since the reagent blank value obtained during the field sa==-e
analysis aust be less than 10 percent of the saaple values (see Metr.od 'O'JCX .
25-sa Teflon mat Pallflex* TXUCKIT5 or equivalent.
Locate in a glass or quartz filter holder in a filter -box heated to 250° F.
5-6 Stopcock grease. Acetone-insoluble, heat-stable silicone grease say
be used, if necessary.
5.7 Silica gel. Indicating type, 6- to 16-mesh. If the silica gel has
been used previously, dry ac 175° C (350°F) for 2 hours. New silica gel nay be
used as received. Alternatively, other types of desiccants (equivalent or
better) nay be used.
6.0 SAMPLE. COLLECTION, PRESERVATION. AND HANDLING
6.1 Saaple collection is described in this method. The analytical
procedures are described in Method XXXX.
6.2 Samples should be stored in clearly labeled, tightly sealed
containers between saaple recovery and analysis. They «ay be analyzed up to
four weeks after collection.
7-0 PROCEDURE
7.1 Calibration. Section 3- 5-2 of EPA 'a Quality Assurance Handbook.
Voluae III (Reference 4) may be used as a guide for these operations.
7.1.1 Dry Gas Metering Systea.
7.1.1.1 Initial calibration. Before its initial use in the
field, first leak check the metering system (saaple 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 aa (10 in.) Hf. plus; 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, the system by slowly
removing the plug froa the saaple line inlet. Remove the sampling
line (and drying tube, if applicable) . and connect the dry gas
metering systea to a appropriately sized wet test meter (e.g. . l
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
voluae divided by the dry gas aeter voluae, with both volumes
adjusted to the saae reference temperature and pressure) . for each
run, and average the results. If any Y value deviates by more than 2
percent froa the average, the metering systea is unacceptable for
use. Otherwise, use the average as the calibration factor for
subsequent test runs.
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7.1.1.2 Post-test calibration check. After each field :sst
series, conduct a calibration check as in Section 7.1.1.1 accve.
except for the following variations: (a) the Leak check is r.ct tr z*
conducted, (b) three or more revolutions of the dry gas aeter say z=
used, (c) only two independent runs need to be made. If tne
calibration factor does not deviate by more than 5 percent froa tr.e
initial calibration factor (determined in Section 7.1.1.1). the dry
gas meter voluaes obtained during the test series are acceptable. If
the calibration factor deviates by more than 5 percent, recalibrate
the metering systea as Section 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.
7.1.2 Thermometer(s). Prior to each field test, calibrate against
mercury-in-glass thermometers at ambient temperature. If the thermometer
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.
7.1.3 R»te meter. The rate meter need not be calibrated, but should
be cleaned and maintained according to the manufacturer's instructions.
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 the mercury barometer. If it does not, the field barometer should be
adjusted.
7.2 Sampling.
7.2.1 Preparation of collection train. Prepare the sampling train
as fallows: 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 iapingers should each be filled with 15 mL of 0.1 N H,S04. and the
fourth and fifth iapingers should each be filled with 15 ml of 0.1 N NaCH.
Place a fresh charge of silica gel, or equivalent, in the Mae West
iapinger (or the drying tube). Connect the impingers in series with the
knockout iapinger first, followed by the two impingers containing the
acidified reagent and two impingers containing the alkaline reagent, and
the Mae West impinger containing the silica gel. If the moisture will be
determined, welch the impinger assembly to the nearest ^ 0.5 g and record
the weight. "
7-2.2 Leak check procedures. Leek 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. Pluf 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 protu 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 iapinger to the stopcock, and connect the sample line to
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•••Draft August 1989***
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the last ispinger and the needle valve. Upon completion of a saapli~?
run. reaove the prooe from the stack and leak check as described az-cve
If a leak has occurred, the sampling run must be voided. Alternatively.
the portion of the train behind the prooe aay be leak checked between
aultiple runs at the same sice as follows: Close the stopcock to tne
first iapinger (see Figure 1A). and turn on the sample puap. Pull a
vacuua of at least 250 am Hg (10 in. Hg), turn off the needle valve, and
note the vacuua gauge reading. The vacuua should remain stable for at
least 30 seconds. Release the vacuua on the impinger train by turning the
stopcock to the vent position to permit ambient air to enter (see Figure
IB). 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.
7.2.3 Pure* procedure. Immediately prior to sampling, connect the
purge line to the stopcock and turn the stopcock to permit the purge puap
to purge the probe (see Figure 1A). Turn on the purge pump, and adjust
the purge rate to 2 liters/ain. Purge for at least 5 minutes prior to
sampling.
7.2.4 Sample collection. Turn on sample puap, pull a slight vacuum
of approximately 25 ma 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 1C). 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
temperature, rate meter, and vacuum gauge at least once every five minutes
during tne run. A sampling time of two hours 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 aay be
used or (2) two sequential one-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 7.2.2.
7.3 Sample recovery. Following sampling, disconnect the impinger train
from the remaining sampling equipment at the inlet to the knockout iapinger and
the outlet to the last iapinger. If performing a moisture determination, wipe
off any moisture on the outside of the* train and any excess silicon* grease at
the inlet and outlet openings; weigh the train to the nearest 0.5 ff and record
this weight. Then disconnect the iapingers from each other. Quantitatively
transfer the contents of the first three impingers (the knockout iapinger and
the two 0.1 N HjS04 impingers) to a leak-free storage bottle. Add the water
rinses of each of them* iapingers and connecting glassware to the storage
bottle. Tae contents of the iapingers and connecting glassware from the second
set of impinfmrs (containing the 0.1 N NaOH) should be recovered in a similar
manner if a Cl, analysis is desired. "The sample bottle should be sealed.
shaken to mix. and labeled; the fluid level should bm 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 H,SOt and 0.1 N NaOH used as
impinger reagents as reagent blanks. Takm~50 «1 of each and place in separate
leak-free storage bottles. Label and mark the fluid levels as previously
described.
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7.4 Calculations. Retain at least one extra deciaal figure beyor.d t.-.cse
contained in the available data in intermediate calculations, and rcur.d cff
only the final answer appropriately.
7-4.1 Noaenciature.
9-t » Water vapor in the gas stream , proportion by volume.
M » 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, ma Hg (in. Hg) .
Pit4 « Standard absolute pressure, 760 mm Hg (29.92 in. Hg) .
R • Ideal gas constant, 0.06236 mm Hg-aV°K-g-mole
(21.85 in. Hg-ftV'R-lb-mole) .
TM » Average dry gas meter absolute temperature, °K (°R).
Ttt4 • Standard absolute temperature, 293* K (528cR).
Vle » Total volume of liquid collected in impingers and silica
gel, mL (equivalent to the difference in weight of the
iapinger train before and after sampling. 1 ag • 1 mL) .
V * Dry gas volume as measured by the dry gas meter, dca
(dcf ) .
V«<«t4) * Bry gas volume measured by the. dry gas meter, corrected
to standard conditions, dscm (dscf ) .
V¥ ( • 1 4 j * Volume of water vapor in the gas sample . corrected to
standard conditions, scm (scf).
Y » Dry gas meter calibration factor.
pv • Density of water. 0.9962 g/mL (0.002201 Ib/mL) .
7.4.2 Sample volume, dry basis, corrected to standard conditions.
Calculate as described below:
kar
T P
«MiHMBl
u*.
where:
K. • 0.3858°K/«m Hg for metric units.
« 17.64°R/in. Hg for English units.
P,
ktr
(i;
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•**Draft August 1989*** D*te
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T.4.3 Voluae of water vapor.
J^_ ^
*• i § ; 4 ) " 1 c —— ———
M- P,
where:
^ » 0.0013333 mVnL for metric units.
« 0.04707 ftVnL for English units.
I Moisture content.
B
"w < • t 4 )
wt ^ J /
V * V
*•(•<«) ¥w(«t«)
8.0 QUALITY CONTROL
8.1 At the present tiae, a validated audit material doee not exist for
this method. Analytical quality control procedures are detailed in Method XXXX.
9-0 METHOD PERFORMANCE
9.1 The in-stacle detection limit for the method is approximately 0.04 ug
of HC1 per liter of stack fas for a 2-hour saaple.
9.2 The precision and bias for measurestent of HC1 usinc this sampling
protocol combined with the analytical protocol of Method XXXX have been
determined. The within laboratory relative standard deviation is 6.2% and 3.2S
at HC1 concentrations of 3.9 and 15.3 PP*. respectively. The method does not
exhibit any bias for HC1 when sampling at Cl, concentrations less than 50 ppo.
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
Protection Agency, Office of Research and Development. Report No. .
, 1989.
2. State of California. Air Resources Board, Method 421. "Determination of
Hydrochloric Acid Emissions from Stationary Sources." March Id. 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.
Vorth 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 19T7-
XXXX - 8 Revision
***Draft August 1969*** Date
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5. U. S. Environmental Protection Agency. ^0 CFR Part 60. Appendix A, ye-
6.
XXXX - 9 Revision
•••Draft August 19$9***
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jj.i fill iff
Hi I-H js|
i
i
XXXX - 10
•**Drmft August 1989***
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Revision
Date
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METHOD
PROTOCOL FOR ANALYSIS OF SAMPLES
FROM HC1/CI, EMISSION SAMPLING TRAINS
D
|ij
J\ru i
This aethod has been drafted based on the results of laboratory and field
studias catriad out under contract to tha Sourca Branch of tha Quality
Assurance Division, Atmospheric Research and Exposure Assessment Laboratory
(QAD/AREAL), United States Environmental Protection Afency (U.S. EPA). The
aethod is still under investigation and is subject to revision.
0-13
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METHOD
PP.QTCCCL rC?.. . ANALYSIS 3? .SAMPLES
F?CM HCl Cl- EMI5SICN SA.MFLI.NG TRAINS
1.0 SCOPE. AND .APPLICATION
1.1 This method describes the analtyical protocol for determination of
hydrogen chloride (HCl. CAS Registry Number 7647-01-0) and chloride (C12, CAS
Registry Nuaber 7782-50-5) iA stack gas emission samples collected from
hazardous waste and municipal waste incinerators using the midget impinger
HCl/Clj sampling train (Method XXXX) or the isokinetic HC1/C1, sampling train
(Method XXXX).
1.2 The lower detection limit is 0.1 ug of chloride (Cl~) per mi. of
sample solution. Samples with concentrations which exceed the linear range of
the analytical instrumentation may be diluted.
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.
2.0 SUMMARY OF METHOD
2.1 The KC1 and C17 collected in the sampling train are solubilized to
chloride ions (Cl*) in the acid and alkaline absorbing solutions, respectively.
Non-suppressed or suppressed ion chromatography (1C) is used for analysis of
cr.
3.0 INTERFERENCES
3-1 Volatile materials which produce chloride ions upon dissolution
during sampling are obvious interferences in the measurement of HCl. One
likely interferent is diatomic chlorine (C17) gas which disproportionates to
HCl 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 HCl gas stream
containing 50 ppm Cl~ with this method does not cause a significant bias.
Sampling a 220 ppm HCl gas stream containing 180 ppm Cl, results in a positive
bias of 3-4X in the KC1 measurement. Other interferents have not been
encountered.
4.0 APPARATUS AND MATERIALS
4.1 Volumetric Flasks. Class A. various sizes.
4.2 Volumetric Pipettes. Class A. assortment, to dilute samples to
calibration range of the 1C.
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•**Draft August 1989*** D«t«
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4.3 Ion Chromatograph. Suppressed or non-suppressed, with a conduct:.•.-•_v/
detector and electronic Integrator operating in the peak area aode. Cther
detectors, a strip chart recorder, and peak heights may be used provided t.-.s
5 percent repeatability criteria for sample analysis and the linearity enter:.!
for the calibration curve can be met.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tescs. Unless otherwise
indicated, it is intended that all reagents shall conform to the specif icaticr.s
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 ASTM Type II Water (ASTM 01193-77 (1983)). All references to water
in the method refer to ASTM Type II unless otherwise specified.
5.3 Sulfuric acid (0.1 N), K,SOk. To prepare 100 mL. slowly add 0.28 ml
of concentrated H,SOU 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.
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.
5.5 Reagent blank solutions. A separate blank solution of each sampling
train reagent used and collected in the field (0.1 N H,S04 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.
5.6 Sodium chloride. NaCl. stock standard solution. Solutions containing
a nominal certified concentration of 1000 ag/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 been dried at 110*C for two or
more hours and then cooled to roo» temperature in a desiccator immediately
before weighing. Accurately weigh 1.6 to 1.7 ff of the dried NaCl to within 0.1
mg. dissolve in water, and dilute to 1 liter. The exact Cl~ concentration can
be calculated usinc the equation:
uf Cl-/mL « g of NaCl x 10* x 35-^53/53.44
Refrigerate the stock standard solutions and store no longer than one month.
5.7 Chromatographic effluent. Effective eluents for non-suppressed ion
chromatography using a resin- or silica-based week 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-dydroxy benzoata solution.
XXXX - 2 Revision
Draft August 1989*** Date
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adjusted to a pH of 8.6 using 1 N sodiua hydroxide. An effective el-er.t :~T
suppressed ion chrooatcgraphy is~a solution containing 3 aM sodiua =icar = cr.a-.=
and 2.4 aM sodiua carbonate. Other dilute solutions buffered to a siailar --.
-hat contain no ions interfering with the chromatographic analysis zay ce _s=;.
If. -sing suppressed ion chrsaatography. the "water dip" resulting froa sa^p.e
injection is interfering with the chlorine peak, use a 2 aM sodiua hydroxide
2.4 -M sodiua bicarbonate eluent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Sample collection using the midget iapinger HC1/C1, train or the
isokinetic HC1/C1, train is described in Method XXXX or XXXX. respectively.
6.2 Samples should be stored in clearly labeled, tightly sealed
containers between sample recovery and analysis. They say be analyzed up to
four weeks after collection.
7.0 PROCEDURE
7.1 Saaple preparation for analysis. Check the liquid level in each
saaple, and determine if any sample was lost during shipment. If a 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 iapinger 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.
7.2 Calibration of Ion Chromatograph.
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. An example chromatogram from a system using non-
suppressed ion chromatography with a 150 mm Hamilton PRP-X100 anaon
column, a 2 mL/min flow rate of a 4 mL 4-hydroxy benzoate solution
adjusted to a pH of 8.6 using 1 N sodium hydroxide, a 50 ul sample loop.
and a conductivity detector set on 1.0 uS full scale is shown in Figure 1.
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.
712.2 To prepare the calibration standards, dilute given amounts
(1.0 mL or greater) of the stock standard solution to convenient voluaes.
usinf 0.1 N H,S04 or 0.1 N NaOH. as appropriate. Prepare at least four
standards that are within'the linear ranee 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 saap.e.
reagent blank, and field samples. This allows compensation for any
instrument drift occurring during sample analysis.
XXXX - 3 Revision .
•"Draft August 1989
0-16
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"•2-3 After injecting the standards the first tiae. determine :.-e
?eax area or height for each standard. Using linear re greasier. . .e-arr-.r
the equation for the calibration curve. Coapare the known concentrati:.-.
cf each standard to its concentration predicted by the calibraticr.
equation; the percent error as calculated below should be less -.-.an :r
equal to 7 percent.
; Error » Predic-ed Conc- " toown Cone- x 10C5 i
Known Conc.
7.2.4 Following analysis of the quality control sample, the reagent
blanks, and the field sasples. the calibration standards are injected a
second tiae.
7.2.5 Using: the average of the initial and final injections of the
standards and linear regression, determine the formulas for the
calibration curve to be used to calculate the field sample concentrations.
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. Each response (peak height or
area) for a duplicate injection should be within 5 percent of the average
response. Use the average 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 shall not exceed 10 percent of the
corresponding value for a field sample.
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.
7.4.1 Total ug HC1 per sample. Calculate as described below:
«HC1 - (S-B) x V. x 36.46/35.453 (2)
where: oucl * Mass of HC1 in sample, ug.
S • Analysis of sample, ug Cl'/mL,
B • Analysis of reagent blank, ug Cl'/aL.
V, * Volume of filtered and diluted sample. oL.
36.46 « Molecular weight of HC1, ug/ug-aole. and
35 '453 • Atomic weight of Cl. ug/ug-mole.
7 '4. 2 Total ug Cl, per sample. Calculate as described below:
Mcl . (S-B) x V. x 70.90/35.45 (3)
XXXX - 4 Revision
•**Draft August 1989*** Date
0-17
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where: vi , Mass of C12 in sample, ug,
70.90 » Molecular weight of C12 , ug/ug-moie, and
35.45 * Atcaic weight of Cl, ug/ug-aole.
7.^.3 Concentration of HC1 in the flue gas. Calculate as descr-.ze.
below:
where: C » Concentration of HC1 or C12 , dry basis, ng/dsca.
K » 10" 3 ag/ug,
a • Mass of HC1 or Cl, in saople, ug, and
v. dm) * Drv *** volume measured by the dry gas meter.
corrected to standard conditions, dsca (from Method
XXXX or Method XXXX).
8.0 QUALITY CONTROL
3.1 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.
8.1.1 Quality control check saaple. 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 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.
3.1.2 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
saaple in duplicate along with the field samples. Based on the matrix
spike results, determine the recovery for the spiked material. This
should be within 15 percent of the known spike value.
9.0 METHOD PERFORMANCE
9.1 The, lower detection limit of the analytical method is 0.1 ug of Cl*
per oL of sample solution. Samples with concentrations which exceed the linear
range of the 1C may be diluted.
9.2 The precision and bias for analysis of HC1 using this analytical
protocol have been measured in combination with the midget iapinger HC1/C1,
train (Method XXXX) for sample collection. The within laboratory relative
standard deviation is 6.25 and 3-25 at HC1 concentrations of 3-9 and 15-3 PP»-
XXXX - 5 Revision
***Draft August 1989*** Date
0-13
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respectively. The aethod does not exhibit any bias far HC1 when saspli-? at
Cl, ;3r.cer.r:raticns less than 50 ppm.
1. Steinsberger. S. C. and J. H. Margeson, "Laboratory and Field Evaluatic-
of a Methodology for Determination of Hydrogen Chloride Eaissions frsa
Municipal and Hazardous Waste Incinerators," U. S. Environmental
Protection Agency, Office of Research and Development, Report No. .
. 1989.
2. State of California. Air Resources Board, Method 421, "Determination of
Hydrochloric Acid Emissions froa Stationary Sources," March 18, 1987-
3. Entropy Environmentalists, Inc., "Laboratory Evaluation of a Sampling: and
Analysis Method for Hydrogen Chloride Emissions froa Stationary Sources:
Interim Report," EPA Contract No. 68-02-4442, Research Triangle Park,
North Carolina, January 22, 1988.
XXXX - 6 Revision
Draft August 1989*** D*t«
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r 5
•3
•r » — r
•r -5 r
H
Ii
•ft r.
•s
•: t
* _ • -f.
••» • £ »• •>
.A .7-. .v
• • u'*
3 .'.
-U X
•a •.<•
ui Z
o
w 3
u» x
X
•Jj
S t <±
5 wu .x
s o -.-••
s -S^
:?55 53E
u* U f •
i.i Z k_ »"• -• •" 4 r •
Figure 1. Exaapl* ion chromatograph.
XXXX - 7
AuffUSt 1969
Revision
Date
D-20
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APPENDIX 6
DRAFT METALS PROTOCOL
E-l
-------
a; :r t
ct
its
DRAFT 3 2; :"r
VETHCSCLOGY FOR THE DETERMINATION OF METALS EMISSIONS IN EXHAUST GASES
FROM HAZARDOUS WASTE INCINERATION AND SIMILAR COMBUSTION PROCESSES
1. Applicability and Principle
1.1 Applicability. This method is applicable for the determination of
total chromiua (Cr). cadmium (Cd). arsenic (As), nickel (Ni), manganese (Mn),
beryllium (Be), copper (Cu), zinc (Zn), lead (Pb), selenium (Se). phosphorus
(P), thallium (Tl), silver (Ag). antimony (Sb), barium (Ba). and mercury (Kg)
emissions from hazardous waste incinerators and similar combustion processes.
This method may also be used for the determination of particulate emissions
following the additional procedures described. Modifications to the sample
recovery and analysis procedures described in this protocol for the purpose of
determining particulate emissions may potentially impact the front half mercury
determination.*
1.2 Principle. The stack sample is withdrawn isokinetically from the
source, with particulate emissions collected in the probe and on a heated
filter and gaseous emissions collected in a series of chilled impingers
containing a solution of dilute nitric acid in hydrogen peroxide in two
impingers. and acidic potassium permanganate solution in two (or one)
ittpingers. Sampling train components are recovered and digested in separate
front and back half fractions. Materials collected in the sampling train are
digested with acid solutions to dissolve inorganics and to remove organic
constituents that may create- analytical interferences. Acid digestion is
performed using conventional Parr* Bomb or microwave digestion techniques. The
nitric acid and hydrogen peroxide impinger solution, the acidic potassium
permanganate impinger solution, and the probe rinse and digested filter
solutions arm analyzed for mercury by cold vapor atomic absorption spectroscopy
(CVAAS). Exempt for the permanganate solution, the remainder of the sampling
•Field tests, to date have shown that of the total amount of mercury measured
by the method, only 0 to <2% was measured in the front half. Therefore, it is
tentatively concluded, based on the above data, that particulate emissions may
be measured by this train, without significantly altering the mercury results.
c*** is a srtimiiwfy era*
««t MM fermatly rtl«t*es *
et M tft<* «*;• M
E-2
f-r.
c»re..witc mr comment M j*
i«cn
-------
train catches are analyzed for Cr, Cd. Hi, Mn, Be. Cu. Zn. Pb, Se, P. 71. AS.
Sb. Sa. and AJ by inductively coupled argon plasma emission spectroscopy CCA?1
or atcoic absorption spectroscopy (AAS). Graphite furnace atomic absorption
spectroscopy (GFAAS) is used for analysis of antimony, arsenic, cadaiua. lead,
seleniua. and thallium, if these elements require greater analytical
sensitivity than can b« obtained by ICAP. Additionally, if desired, the tester
may use AAS for analyses of all metals if the resulting in- stack method
detection liaits aa«t the goal of the tasting program. For convenience,
aliquots of each digested sample fraction can be combined proportionally for a
single analytical determination. The efficiency of the analytical procedure is
quantified by the analysis of spiked quality control samples containing each of
the target metals including actual sample aatrix effects checks.
2. Range, Sensitivity. Precision, and Interferences
2.1 Range. For the analyses described in this methodology and for similar
analyses, the ICAP response is linear over several orders of magnitude. Sam-
ples containing metal concentrations in the nanograms per ailliliter (ng/ml) to
micrograms per ailliliter (ug/ml) range in the) analytical finish solution can
be analyzed using this technique. Samples containing greater than
approximately 50 ug/ml of chromium, lead, or arsenic should be diluted to that
level or lower for final analysis. Samples containing greater than
approximately 20 ug/ml of cadmium should be diluted to that level before
analysis.
2.2 Analytical Sensitivity. ICAP analytical detection limits for the
sample solutions (based oa SW-846. Method 6010) are approximately as follows:
Sb (32 ng/ml), As (53 nc/«l). Be (2 ng/ml). Be (0.3 ng/«l). Cd (4 ng/ml), Cr (7
ng/ml). Cu (6 ng/ml). Pb (42 ng/ml). MA (2 ng/ml). Mi (15 ng/ml), P (75 ng/al) .
Se (75 ng/ml). Ag (7 ng/al). Ti (40 ng/ml). and Zn (2 ng/ml). The actual
method detection limits; are. sample dependent and may vary am the sample aatrix
may affect the limits. The analytical detection limits for analysis by direct
aspiration AAS (based oa SW-846. Method 7000) are approximately as follows: Sb
(200 ng/ml). As (2 ng/ml). Be (100 ng/ml). Be (5 ng/ml). Cd (5 ng/ml). Cr (50
ng/ml). Cu (20 ng/ml). Pb (100 ng/ml). MB (10 ng/ml). Ni (40 ng/ml). Se (2
ng/ml). Ag (10 ng/ml). Tl (100 ng/al). and Zn (5 ng/ml). The) detection limit
for mercury by CVAAS is approximately 0.2 ng/ml. The use of GPAAS can give
added sensitivity compared to the use of direct aspiration AAS for the
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-------
following setals: Sb (3 ng/ml). A* (1 ng/al), Be (0.2 ng/ml). C4 (0.1 ng/eli.
Cr (1 nc/al). Pb (1 nf/al). S« (2 nf/al). and Tl (1 nf/al).
- Using (1) the procedures described in this aethod, (2) the analytical
detection liaits described in the previous paragraph, (3) a voluae of 300 al
for the front half and 150 al for tha back half aaaplaa. and (<») a stack gas
sample volume of 1.25 a3, tha corresponding in-stack aethod dataetion liaits
are presented in Table A-l and calculated as shown:
A x B
• 0
where): A • analytical detection limit, ug/al.
B * voluae of saaple prior to aliquot for analysis, al.
C • stack saaple voluae, dsca (dsa3).
0 • in-stack detection lijait, ug/a3 .
Values in Table A-l are calculated for the front and back half and/or the total
train.
To ensure optiaua sensitivity ia obtaining the aeasureaants . the
concentrations of target aetals in the solutions are suggested to be at least
tan tiaes the analytical detection liaits. Under certain conditions, and with
greater care in the analytical procedure, this concentration can be as low as
approximately three tiaes the analytical detection limit. In all cases,
repetitive analyses, aethod of standard additions (MSA), serial dilution, or
aatrix spike addition should be used to establish the quality of the data.
, Actual in-stack aethod detection limits will be determined based on actual
source sampling parameters and analytical results as described above. If
required, the aethod la-stack detection limits can be aade more sensitive than
those shown in Table A-l for a specific test by using one or more of the
following options:
o A normal 1-hour sampling run collects a stack gas sampling volume of
about l>25 a*. Zf the sampling time ia increased and 3 ** are
collected, the la-stack method detection limits would be com fourth of
the values shown la Table A-l (this means that with this change, the
method is four times more sensitive than normal).
o The in-stack detection liaits assume that all of the sample is digested
(with exception of the aliquot for mercury) and the final liquid
volumes for analysis are 300 al for the front half and 150 ml for the
* * '
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-------
TABLE A-l. IN-STACX METHOD DETECTION LIMITS (ug/to3)
FOR TRAIN FRACTIONS USING ICAP AND AAS
Front Half Back Haif1 Back Half,
Fraction 1 Fraction 2 Fraction 3 Total Train
Metal Prob« and Filter Impingers 1-3 lapingers 4-5
Antimony
Arsenic
Bariua
Beryl liua
Cadmium
Chromium
Copp«r
Lead
Manganese
Mercury
Nickel
Phosphorus
Selenium
Silver
Thallium
Zinc
7.7 (0.7)*
12.7 (0.3)*
0.5
0.07 (0.05)*
1.0 (0.02)*
1.7 (0.2)*
1.4
10.1 (0.2)*
0.5 (0.2>*
0.05**
3.6
18
18 (0.5)*
1.7
9.6 (0.2)*
0.5
3-8 (0.4)*
6.4 (0.1)*
0.3
0.04 (0.03)*
0.5 (0.01)*
0.8 (Q.I)*
0.7
5-0 (0.1)*
0.2 (0.1)*
0.03** 0.03**
1.8
9
9 (0.3)*
0.9
4.8 (0.1)*
0.3
11.5 u.i)*
19.1 (0.4)*
0.8
0.11 (0.08)*
1.5 (0.03)*
2.5 (0-3)*
2.1
15.1 (0.3)*
0.7 (0.3)*
0.11**
5.4
27
27 (0.8)*
2.6
14.4 (0.3)*
0.8
( )* Detection limit when analyzed by GFAAS.
** Detection limit when analyzed by CVAAS.
Actual method in-stack detection liaits will be determined based
on actual source sampling parameters and analytical result* as
described earlier in this section.
back half sample. If the front half volume is reduced from 300 ml to
30 ml. the front half in-stack detection limits would be one tenth of
the values shown above (tan times morm sensitive). If the back half
volume is reduced from 150 ml to 25 ml, tha> in-stack detection limits
would be one sixth of the above values. Matrix effects checks are
necessary on analyses of samples and typically arm of greater signifi-
cance for samples that have been concentrated to less than the normal
sample volume. A volume less than 25 ml may not allow resolublllza-
tlon of the residue and may Increase interference by other compounds.
When both of the above two Improvements arm usmd on one sample at the
same time, the resultant improvements arm multiplicative. For example,
where stack gas volume is increased by a factor of five and the total
liquid sample digested volume) of both the) front and back halves is
reducsd by factor of six. thm in-stack method detection limit is
reduced by a factor of thirty (the method is thirty times morm
sensitive) .
r.c '•• ««dMie"« • a sreftmiflerr en*
=• 3 • ^M net OMA fermelly
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-------
o Conversely, reducing stack gas staple voluae and increasing saaple
liquid volume win increase limit*. The front half and back half,
caaples (Fractions 1 «nd 2) can be combined prior to analysis. The"
resultant liquid volume (excluding Fraction 3. which must be analyzed
separately) is recorded. Combining the saaple as described does not
allow determination (whether front or back half) of where in the train
the saaple was captured. The in-stack aethod detection liait then
becomes a single value for all aetals except mercury, for which the
contribution of Fraction 3 *u*t be considered.
o The above discussion assuaes no blank correction. Blank corrections
are discussed later in this aethod.
2.3 Precision. The precisions (relative standard deviation) for each
metal detected In a aethod development test at a sewage sludge Incinerator, are
as follows: Sb (12.7*). As (13-5*). Ba (20.6*), Cd (11-5*). Cr (11.22). Cu
(11.5*). Pb (11.6%), P (14.6*). Se (15-3*). Tl (12.3*). and Zn (11.8*). The
precision for nickel was 7.7* for another teat conducted at a source simulator.
Beryllium, manganese and silver were not detected In the tests; however, based
on the analytical sensitivity of the ICAP for these aetals. It Is assumed that
their precisions should be similar to those for the other metals, when detected
at similar levels.
2.4 Interferences. Iron can be a spectral interference during the
analysis of arsenic, chromium, and cadalua by ICAP. Aluminum) can be a spectral
interference during the analysis of arsenic and lead by ICAP. Generally, these
interferences can be reduced by diluting the saaple. but this Increases the
aethod detection limit. Refer to IPA Method 6010 (SM-SM61 for details on
potential interferences for this method. Per all OPAAS analyses, matrix
modifiers should be used to limit Interference*, and standards should be aatrix
matched.
3. Apparatus)
3.1 Sasjpll&c Train* A schematic of the sampling train is shown in Figure
A-l. It is similar to the Method 5 train. The sampling train consists of the
following components.
3.1.1 Probe Nossle (Probe Tip) and Borosilicate or Quarts Glass Probe
Liner. Saae as Method 5. Sections 2.1.1 and 2.1.2. Glass nessles are required
unless an alternate probe tip prevents the possibility of contamination or
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interference of the saaple with it* materials of construction. If a probe tip
other than glass is used, no correction of the stack saaple test results can be
Bade because of the effect on the results by the probe tip.
3.1.2 Pitot Tube and Differential Pressure Gauge. Saae as Method 2,
Sections 2.1 and 2.2. respectively.
3.1.3 Filter Holder. Glass, sane as Method 5. Section 2.1-5. except that
a Teflon filter support eust be used to replace the class frit.
3.1.4 Filter Heating Systee. Saae as Method 5, Section 2.1.6.
3.1.5 Condenser. The following systesi shell be used for the condensation
and collection of gaseous Betels end for determining the moisture content of
the stack gas. The condensing system should consist of four to six iapingers
connected in series with leak-free ground glass fittings or other leak-free.
non-contaainating fittings. The first iapinger is optional and is recommended
as a water knockout trap for use during test conditions which require such a
trap. The iapingers to be used in the aetals train are now described. When
the first iapinger is used as a water knockout, it shall be appropriately-sized
for an expected large aoisture catch and constructed generally as described for
the first iapinger in Method 5, Paragraph 2.1.7* The second iapinger (or the
first HNOj/HjO, iapinger) shall also be as described for the first iapinger in
Method 5> The third iapinger (or the iapinger used as the second HH03/H,0,
iapinger) shall be the saae as the Greenburg Saith iapinger with the standard
tip described as the second iapinger in Method 5. Paragraph 2.1.7. All other
Uapingers used in the aetals train are the saae as the second iapinger (the
first HNOj/HjOj iapinger) previously described in this paragraph. In summary.
the first Iapinger should be eapty, the second and third shall contain known
quantities of a nitric acid/hydrogen peroxide solution (Section 4.2.1). the
fourth (and fifth, if required) shall contain a known quantity of acidic
potassiua peraanganate solution (Section 4.2.2), and the last iapinger shall
contain a known quantity of silica gel or equivalent desiccant. A thermometer
capable of aaesnirfng to within 1*C (2*F) shall be placed at the outlet of the
last iapinger. When the water knockout iapinger is not needed, it is removed
froa the train and the other iapingers remain the saae. If mercury analysis is
not needed, the potassium permanganate iapingers arm removed.
3.1.6 Metering System, Baroaeter, and Gas Density Determination
Equipment. Saae as Method 5, Sections 2.1.8 through 2.1.10; respectively.
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3.1.7 Teflon Tape. For capping openings and sealing connections on the
saapiing train.
3.2 Saaple Recovery. Saae as Method 5. Sections 2.2.1 through 2.2.8
(.Vonaetallic Probe-Liner and Probe-Nozzle Brushes, Wash Bottles. Sample
Storage Containers. Petri Dishes. Glass Graduated Cylinder. Plastic Storage
Containers. Funnel and Rubber Policeman, and Glass Funnel), respectively, with
the following exceptions and additions:
3.2.1 Nonaetallic Probe- Liner and Probe-Nozzle Brushes. For quantitative
recovery of aaterials collected in the front half of the sampling train.
Description of acceptable all-Teflon component brushes to be Included in EPA's
Eaission Measurement Technical Information Center (EMTXC) files.
3.2.2 Sample Storage Containers. Glass bottles with Teflon- lined caps.
1000- and 500-ml, shall be used for KMnOt -containing samples and blanks.
Polyethylene bottles may be used for other sample types.
3.2.3 Graduated Cylinder. Glass or equivalent.
3.2.4 Funnel. Glass or equivalent.
3.2.5 Labels. For identification of samples.
3.2.6 Polypropylene Tweezers and/or Plastic Gloves. For recovery of the
filter from the sampling train filter holder.
3.3 Sample Preparation and Analysis. For the analysis, the following
equipment is needed:
3.3.1 Volumetric Flasks. 100 ml. 250 ml, and 1000 ml. For preparation of
standards and sample dilution.
3.3.2 Graduated Cylinders. For preparation of reagents.
3.3.3 Parr" Bombs or Microwave Pressure Relief Vessels with Capping
Station (GEM Corpormtion model or equivalent).
3.3.4 Beakers and Watchf lasses. 250 ml beakers for sample digestion with
watchglasaes to cover the) tops.
3.3.5 Ring Stands and Clamps. For securing equipment such as filtration
apparatus.
3.3.6 Filter Funnels. For holding filter paper.
3.3.7 Whatman 541 Filter Paper (or equivalent). For filtration of
digested samples.
3.3.6 Disposable Pasteur Pipets and Bulbs.
3.3.9 Volumetric Pipets.
3.3.10 Analytical Balance. Accurate to within 0.1 mg.
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Amene* pettcy. it it
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-------
3.3.11 Microwave Or Conventional Oven. For betting staples at fixed -
power level* or teaperatures.
3.3.12 Hot Plates.
3.3.13 Atoeic Absorption Spectrometer (AAS). Equipped with a beckrround
corrector.
3.3.13-1 Graphite Furnace Attachment. With antiaony, arsenic, cadaiua,
lead, seleniua, thallium, and hollow cathode laaps (HCLi) or electrodeless
discharge laaps (EDU). Saae as EPA Methods 7041 (antimony). 7060 (arsenic),
7131 (cadaiua). 7421 (lead), 7740 (seleniua), and 7841 (thallium).
3.3.13.2 Cold Vapor Mercury Attachment. With a eercury HCL or EDL. The
equipment needed for the cold vapor mercury attachment includes an air
recirculatlon pump, a quarts cell, an aerator apparatus, and a heat laap or
desiccator tube. The heat laap should be capable of ralslnf the ambient
temperature at the quarts cell by 10*C such that no condensation forms on the
wall of the quarts cell. Saae as EPA Method 7470.
3-3.14 Inductively Coupled Argon Plasma Spectrometer. With either a
direct or sequential reader and an alumina torch. Same am EPA Method 6010.
4. Reagents
Unless otherwise indicated, it is intended that all reagents conform to
the specifications established by the Committee on Analytical Reagents of the
American Chemical Society, where such spec!fications are available; otherwise.
use the best available grade.
4
4.1 Sampling. The reagents used in sampling are aa follows:
4.1.1 Filters. The filters shall contain leaa than 1.3 ug/la.* of each of
the metals to be measured. Analytical results provided by filter manufacturers
are acceptable. However, if no such results are available, filter blanks must
be analysed for each target metal prior to emission testing. Quarts fiber or
glass fiber filters without organic binders shall be uaed. The filters should
exhibit at least 99*95 parcant efficiency (<0.05 percent penetration) on 0.3
micron dioctyl phthalate smoke partlclee. The filter efficiency test shall be
conducted la accordance with AST* Standard Method D2966-71 (Incorporated by
reference). For particulate determination in sourcea containing SO, or S03,
the filter material eust be of a type that is unreactive to SO, or SO,. aa
described la EPA Method 5. Quarts fiber filters meeting theme requirements are
recommended.
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•mac* ii is •*<«*
-------
4.1.2 Water. To conform to ASTM Specification 01193.77, 7yp« II
(incorporated by reference). Analyze the water for all target setals prior
field use. All target aetals should b« less than 1 ng/«l.
U.I. 3 Nitric Acid. Concentrated. 'Baker Ins tra- analyzed or equivalent.
4.1.4 Hydrochloric Acid. Concentrated. Baker Ins tra- analyzed or
i valent • :» -"•**« * • w™«.»
4.1.5 Hydrogen Peroxide, 30 Percent (V/V) . n« "»' «••« */m«n, >,,,«sto e,
'•
«oi ., -« .,...
4.1.6 Potassium Permanganate. -u r«o-«««m Af«ne>
4.1.7 Sulfuric Acid. Concentrated.
4.1.8 Silica Gel and Crushed Ice. Same as Method 5, Sections 3.1.2 and
3. 1.4, respectively.
4.2 Pretest Preparation for Sampling Reagents.
4.2.1 Nitric Acid {HN03) /Hydrogen Peroxide (H70a) Absorbing Solution.
5 Percent KNO^/10 Percent H,02. Add 50 el of concentrated HNO, and 333 al of
30 percent H,0, to a 1000-ml voluaetric flask or graduated cylinder containing
approxlaately 500 ad of water. Dilute to voluae with water. The reagent shall
contain less than 2 ng/al of each target aetal.
4.2.2 Acidic Potassiua Permanganate (KMn04 ) Absorbing Solution. 4 Percent
KMn04 (V/V) . Prepare fresh daily. Dissolve 40 g of KMnO, in sufficient 10
percent H,SO, to sake 1 liter. Prepare and store in glass bottles to prevent
degradation. The reagent shall contain lesa than 2 ng/al of Hg.
Precaution; To prevent autocatalytic decomposition of the permanganate
solution, filter the solution through Whatman 541 filter paper. Also, due to
reaction of the potassium permanganate with the acid, there may be pressure
buildup in the sample storage bottle; these bottles should not be fully filled
and should be vented both to relieve excess pressure and prevent explosion due
to pressure buildup. Venting is highly recommended, but should not allow
contamination of the sample; a No. 70-72 hole drilled in the container cap and
Teflon liner has been used.
4.2.3 Nitric Add. 0.1 N. Add 6.3 ml of concentrated RNO, (70 percent) to
a graduated cylinder containing approximately 900 ml of water. Dilute to 1000
ml with wmtmr. Nix well. The reagent shall contain less than 2 ng/al of each
target metal.
4.2.4 Hydrochloric Acid (HC1), 8 N. Add 690 ml of concentrated HC1 to a
graduated cylinder containing 250 ml of water. Dilute to 1000 ml with water.
Mix well. The reagent shall contain less than 2 ng/ml of Hg.
E-ll
-------
4.3 Glassware Cleaning Reagents.
4.3.1 Nitric Acid. Concentrated. Fisher ACS grade or equivalent.
4.3.2 Water. To conform to ASTM Specifications 01193-77. Typ* II.
4.3.3 Nitric Acid. 10 Percent (V/V). Add 500 ml of concentrated HN03 to a
graduated cylinder containing approximately 4000 ml of water. Dilute to 5000
ml with water.
4.4 Sample Digestion and Analysis Reagents.
4.4.1 Hydrochloric Acid, Concentrated.
4.4.2 Hydrofluoric Acid, Concentrated.
4.4.3 Nitric Acid, Concentrated. Baker Iftstra-anaiyzed or equivalent.
4.4.4 Nitric Acid, 10 Percent (V/V). Add 100 ml of concentrated HNO, to
800 el of water. Dilute to 1000 ml with water. Nix well. Reagent shall
contain lees than 2 ng/al of each target metal.
4.4.5 Nitric Acid, 5 Percent (V/V). Add 50 ml of concentrated KNO, to
800 el of weter. Dilute to 1000 ml with water. Reagent shall contain less
than 2 ng/ml of each target metal.
4.4.6 Water. To conform to ASTM Specifications 01193*77. Type II.
4.4.7 Hydroxylamine Rydrochloride end Sodium Chloride Solution. See EPA
Method 7470 for preparation.
4.4.8 Stannoue Chloride.
4.4.9 Potassium Permanganate. 5 Percent (V/V).
4.4.10 Sulfuric Acid. Concentrated.
4.4.11 Nitric Acid. 50 Percent (V/V). 1:" •*"-'* w •» »'* *"s* 9* e---
T> "••.•*e»vr A**: <«b po!'-*y. ft It s.
4.4.12 Potassium Persulfate. 5 Percent (W/V). "*»*'•£ ror ca-nmnv. o-i* .,-^
4.4.13 Nickel Nitrate. Mi(NOj),-6H,0. «*•-•-» »ne ,»«a>
4.4.14 Lanthanum Oxide. La,03.
4.4.15 AAS Grade Hg Standard. 1000 ug/ml.
4.4.16 AAS Grade Pb Standard. 1000 ug/ml.
4.4.17 AAS Grade As Standard, 1000 ug/ml.
4.4.18 AAS'Grade Cd Standard. 1000 ug/el.
4.4.19 AAS Grade Cr Standard. 1000 ug/al.
4.4.20 AAS Grade Sb Standard. 1000 ug/al.
4.4.21 AAS Grade Be Standard. 1000 ug/ml.
4.4.22 AAS Grade Be Standard. 1000 ug/al.
4.4.23 AAS Grade Cu Standard. 1000 ug/al.
4.4.24 AAS Grade Nn Standard. 1000 ug/ml.
£-12
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4.U.25 AAS Grade Ni Standard, 1000 ug/ml.
14.k.26 AAS Grade P Standard, 1000 ug/ml.
U.4.27 AAS Grade Se Standard, 1000 ug/ml. ^* «run«wit to •
U.4.28 AAS Grade Ag Standard. 1000 ug/ml. ne **Qi.,a net at wi'iw JITi**,.//,.1
4.U.29 AAS Grade Tl Standard, 1000 ug/ml. "-s^t^T'.^
4.4.30 AAS Grade Zn Standard. 1000 ug/ml. «•.••*•. •«•: • • »*v
4.4.31 AAS Grade Al Standard. 1000 ug/al.
4.4.32 AAS Grade Fe Standard. 1000 ug/ml.
4.4.33 The metals standards may also be made from solid chemicals as
described in EPA Method 200.7. EPA Method 7^70 or Standard Methods for the
Analysis of Water and Wastewater. 15th Edition. Method 303F should be referred
to for additional information on mercury standards.
4.4.34 Mercury Standards and Quality Control Samples. Prepare fresh
weekly a 10 ug/ml intermediate mercury standard by adding 5 ml of 1000 ug/ml
mercury stock solution to a 500 ml volumetric flask; dilute to 500 ml by first
adding 20 ml of 15 percent HN03 and then adding water. Prepare a working
mercury standard solution fresh daily: add 5 ml of the 10 ug/ml intermediate
standard to a 250 ml volumetric flask and dilute to 250 ml with 5 ml of
4 percent KMnO%. 5 ml of 15 percent HN03. and then water. At least six
separate allquots of the working mercury standard solution should be used to
prepare the standard curve. These allquots should contain 0.0. 1.0, 2.0, 3.0.
4.0, and 5.0 ml of the working standard solution. Quality control samples
should be prepared by making a separate 10 ug/ml standard and diluting until in
the range of the calibration.
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. Pe
III Al. Cr. Ni
IV Ag. P. Sb. n
Prepare these standards by combining and diluting the appropriate volumes of
the 1000 ug/ml solutions with 5 percent nitric acid. A minimum of one stan-
dard and a blank can be used to form each calibration curve. However, a
£-13
-------
separata quality control gample spiked with known amounts of the target sepals
in quantities in the midrange of the calibration curve should b« prepared.
Suggested standard levels are 50 ug/ml for Al. 25 ug/ml for Cr and Pb, 15 ug. il
for Fe. and 10 ug/ml for the remaining elements. Standards containing less
than 1 ug/ml of metal should b« prepared daily. Standards containing greater
than 1 ug/ml of metal should be stable for a minimus of 1 to 2 weeks.
4.4.36 Graphite Furnace AAS Standards for Antimony, Arsenic. Cadaiua,
Lead, Selenium, and Thalliua. Prepare a 10 uf/ml standard by adding 1 ml of
1000 ug/al standard to a 100 al volumetric flask. Dilute to 100 ml with 10
percent nitric acid. For graphite furnace AAS, the standards must be matrix
matched; e.g., if the samples contain 6 percent nitric acid and 4 percent
hydrofluoric acid, the standards should also be mad* up with 6 percent nitric
acid and 4 percent hydrofluoric acid. Prepare a 100 ng/ml standard by adding
1 al of the 10 ug/al standard to a 100 al volumetric flask and dilute to 100 al
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 ug/ml
•
standard and diluting until it is in the range of the samples. Standards
containing less than 1 ug/ml of metal should be prepared daily. Standards
containing greater than 1 ug/ml of metal should be stable for a minimum of 1 to
2 weeks.
4.4.37 Matrix Modifiers.
4.4.37.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of
Ni(N03)2 6HjO in approximately 50 ml of water la a 100 ml volumetric flask.
Dilute to 100 ml with water.
4.4.37.2 Nickel Nitrate. One-tenth Percent (V/V). Dilute 10 ml of 1 per-
cent nickel nitrate solution to 100 ml with water. Inject an equal amount of
sample and this modifier into the graphite furnace during AAS analysis for As.
4.4.37.3 -Lanthantsi. Dissolve 0.5864 g of Lrn^Oj la 10 ml of concentrated
HN03 and dilate to 100 ml with water. Inject an equal amount of sampls and
this modifier into the graphite furnace during AAS analysis for Pb.
5. Procedure
5.1 Sampling. The complexity of this method Is such that, to obtain reli-
able results, testers should be trained and experienced with the test procedures.
-------
5.1.1 Protest Preparation. Follow the same general procedure given in
Method 5. Section U.n, except that, unless particulate emissions are to be
detersined, the filter need not be desiccated or weighed. All saapling trair.
glassware should first be rinsed with hot tap water and then washed in hot
soapy water. Next, glassware should be rinsed three tiaes with tap water,
followed by three additional rinses with water. All glassware should then be
•oaked in a 10 percent (V/V) nitric acid solution for a ainiaua of 4 hours,
rinsed three tiaes with water, rinsed a final tiae with acetone, and allowed
to air dry. All glassware openings where contuinaeion can occur should be
covered until the saapllng train Is asse»bled. prior to sampling.
5.1.2 Preliminary Determinations. S«M am Method 5, Section 4.1.2.
5.1.3 Preparation of Sampling Train. Follow the same general procedures
given in Method 5. Section 4.1.3, «xc«pt placa 100 ml of the nitric
acid/hydrogen peroxide solution (Section 4.2.1) in the two HN03/H,0, impingers
(normally the second and third impingers). placm 100 ml of the acidic potassium
permanganate solution (Section 4.2.2) In the fourth and fifth Impinger, and
transfer approximately 200 to 300 f of preweighed silica g*l from its container
to the last impinger. Alternatively, the silica gel may be weighed directly in
thm imping*? just prior to train assembly.
Several options are available to thm tmstmr based on thm sampling
conditions. Thm use of an empty first impinfmr can be eliminated if the
•oisturm to be collected In thm implngmrs Is calculated or dmtmrmlnad to be
Itss than 150 ml. Thm tmstmr shall Include) two impingers containing thm
acidic potassium permanganate solution for thm first tmst run, unless past
tasting experience at thm samm or similar sources ham shown that only one is
necessary. Thm last permanganate Impinftr aay bm discarded if both
permanganate impingmrs havm retained thmlr original damp purpla permanganate
color. A aaxlmum of 200 ml la each permanganate implagmr (and a maximum of
three permanganate Impingmrs) may bm used, if amcmmsary. to maintain thm
desired color la thm last pmrmanganatm impingmr.
Retain for rmagmnt blanks. 100 ml of thm nitric acld/hydrogmn peroxide
solution and 100 •! of thm addle potassium pmrmancanatm solution. These
solutions should bm labeled and treated as dmmcrlbmd in Section 7. Set up the
sampling train as shown la Figure A-l. If nmcmssary to ansurm Imak-frms
saapling train connections, Teflon tap* should bm usad instead of silicon*
grmasm to prevent contamination.
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-------
Precaution L Extreme car* should b« taken to prevent contamination within
the train. Prevent the mercury collection reagent (acidic potassium
persanganate) from contacting any glassware of the train which is washed ar.d
analyzed for Mn*. Prevent hydrogen peroxide from mixing with the acidic
potassiua permanganate.
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 Staple Run), end Section 4.1.4.3 (Post-Test Leek-Checks).
5.1.5 Stapling Trein Operation. Follow the procedures given in Method 5,
Section 4.1.5. For ««ch run. record the data required on a data sheet such as
the one shown in Figure 5*2 of Method 5'
5.1.6 Calculation of Percent Isokinetie. Seme as Method 5. Section 4.1.6.
5.2 Saaple Recovery. Begin cleanup procedures as soon as the probe is
removed froe the stack at the end of a sampling period.
The probe should be allowed to cool prior to saaple recovery. When it can
be safely handled, wipe off all external partieulate aatter near the tip of
the probe noszle and place a rinsed, non-contaminating cap over the probe
nozzle to prevent losing or gaining partieulate matter. Do not cap the probe
tip tightly while the sampling train ia cooling, this normally causes a 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 eight be present. Cap the filter inlet where the probe was
fastened. Remove the umbilical cord from the last impinger and cap the
iapinger. 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 arm completely cooled, if this procedure Is followed: Initially
disconnect the) filter bolder 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
E- 16 "•*«*«*** ft .
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-------
or loss of sample. Inspect the train before and during disassembly and note
any abnormal conditions. The sample is recovered and treated as follows ! see
schematic in Figure A-2). Assure that all items necessary for recovery of the
sasple do not contaainate it.
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 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 participate Batter 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. Seel the labeled petri dish.
5.2.2 Container No. 2 (Acetone Rinse). Taking care to see that dust on
the outside of the probe or other exterior surfaces does not get into the
sample, quantitatively recover particulata setter and any condensate free the
probe nozzle, probe fitting, probe liner, and front half of the filter holder
by washing these components with 100 al of acetone and placing the wash in a
glass container. Note; The use of exactly 100 al is necessary for the
subsequent blank correction procedures. Distilled water say 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 inside parts of the Swagelok 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 la 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
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Figure A-2. Saaple recovery ocheae.
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container underneath the lower «nd of the probe, and catch any acetone and
particuiate latter which is brushed through the probe three tiaes-or acr« until
no visible particuiate aatter is carried out with the acetone or until none
resains in the probe liner on visual inspection. Rinse the brush with acetone.
and quantitatively collect these washings in the saaple container. After the
brushing. Bake a final acetone rinse of the probe as described above.
It is recommended that two people clean the probe to minimize saaple
losses. Between sampling runs, keep brushes clean and protected from
contaaination.
Clean the inside of the front half of the filter holder by rubbing the
surfaces with a nonaetallic nylon bristle brush and rinsing with acetone.
Rinse each surface three tiaes or eore if needed to remove visible particuiate.
Make a final rinse of the brush and filter holder. After all acetone washings
and particuiate latter have been collected in the saaple container, tighten the
lid on the saaple container so that acetone will not leak out when it is
shipped to the laboratory. Nark the height of the fluid level to determine
whether or not leakage occurred during transport. Label the container clearly
to identify its contents.
5.2.3 Container No. 3 (Probe Rinse). Rinse the) probe) liner, probe nozzle.
and front half of the filter holder thoroughly with 100 al of 0.1 N nitric acid
and place the wash into a saaple storage container. Hote: The) use of exactly
100 al is necessary for the subsequent blank correction procedures. Perform
the rinses as described in Method 12. Section 5*2.2. Record the voluae of the
combined rinse. Mark the height of the fluid level on the outside of the
storage container and use this aark to determine if leakage occurs during
transport. Seal the container and clearly label the contents. Finally, rinse
the noMle. probe liner, tad front half of the filter holder with water
followed by acetone and discard these rinses.
5.2.4 Container No. * (Impinge** 1 through 3. Contents and Rinses). Due
to the large quantity of liquid Involved, the taster aay place the iapinger
solutions ia aore than on* container. Measure the liquid in the first three
iapingars voluaetrically to within 0.5 «1 using a graduated cylinder. Record
the voluae of liquid present. Ihis information is required to calculate the
moisture content of the saapled flue gas. Clean each of the first three
iapinger*, the filter support, the back half of the) filter houslnf. .and
connecting glassware by thoroufhly rinsing with 100 al of 0.1 V nitric acid as
femiaiiy
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-------
described in Method 12, Section 5.2.**. Note: The use of exactly 100 si of ;.:
S nitric »cid rinse is necessary for the subsequent blank correction
procedures. Coabine the rinses and iapir.ger solutions, aeaaure and record t.-.e
voluae. Calculate the 0.1 N nitric acid rinse volume by difference. 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.
$.2.5 Container No. 5 (Acidified Potassium Permanganate Solution and
Rinses. lapingers No. 4 4 5). Pour all the liquid from the permanganate
iapingers (fourth and fifth. If two permanganate iapingers are used) 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. Using
100 ml total of the acidified potassium permanganate solution, rinse the
permanganate iapinger(s) and connecting glass piece*) a minimum of three times.
Combine the rinses with the permanganate impinger solution. Finally, rinse the
permanganate impinger(s) and connectinf glassware with 50 ml of 8 M HC1 to
remove any residue. Note; The use of exactly 100 ml and 50 ml for the two
rinses is necessary for the subsequent blank correction procedures. Place the
combined rinses and iapinger contents la a labeled flams storage) bottle. 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 4.2.2 and properly seal the bottle end clearly label the contents.
Mote; Due to the potential reaction of the potassium permanganate with the
acid, there may be pressure buildup in the sample storage bottles. These
bottles should not be filled full and should be vented to relieve excess
pressure. Venting is highly recommended. A Ho. 70-72 hole drilled in the
container cap and Teflon liner has been found to allow adequate venting without
loss of sample.
5.2.6 Container Mo. 6 (Silica Gel). Note the color of the indicating
silica gel tb determine whether it has been completely spent and make a
notation of ita condition. Transfer the silica gel from its impinger to its
original container end semi. The teeter may use a funnel to pour the silica
gel and a rubber policeman to remove the silica gel from the impinger. The
small amount of particles) that may adhere to the iapinger 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.
£-20 ** •aneiVM k .
-------
Alternatively, if a balance i» available in the field, record the weigh- of
the spent silica gel (or silica gel plus iapinger) to the nearest 0.5 g.
5.2.7 Container No. 7 (Acetone Blank). Once during each field test, place
100 ml 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.
5.2.8 Container No. 8 {0.1 N Nitric Acid Blank). Once during each field
test, place 200 al 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.
5.2.9 Container No. 9 (5% Nitric Acid/10% Hydrogen Peroxide Blank). Once
during each field test, place 200 el of the 5JK 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.
5.2.10 Container No. 10 (Acidified Potassium Permanganate Blank). Once
during each field test, place 300 el 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. Seel the container.
Note; This container should be vented, am described in Section 5.2.4, to
relieve excess pressure.
5.2.11 Container No. 11 (8 N HC1 Blank). Once during each field test.
place 50 ml of the 8 N hydrochloric acid used to rinse the acidified potassium
permanganate impingers into a labeled container for use in the back half
reagent blank for mercury.
5.2.12 Container No. 12 (Filter Blank). Once during each field test.
place an unused filter from the same lot am the sampling filters in a labeled
petri dish. Seal the petri dish. This will be used in the front half field
reagent blank.
5*3 Sample Preparation. Note the level of the liquid in each of the
containers mad determine if any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
aethods. 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 A-3.
5.3.1 Container No. 1 (Filter). If particulatre emissions are being
determined, then desiccate the filter and filter cmtch without heat and weigh to
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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 k ml of concentrated hydrofluoric acid to each
vessel. For microwave heating, microwave the saaple vessels for approximately
12-15 minutes in intervals of 1 to 2 ainutes at 600 Watts. For conventional
heating, heat the Parr Bombs at 1^0°C (285°F) for 6 hours. Then cool the
samples to room temperature and combine with the acid digested probe rinse as
required in Section 5-3-3. below.
Notes; 1. Suggested aierowave 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 sample*. Sufficient 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.
5.3.2 Container No. 2 (Acetone Rinse). Note the level of liquid in the
container and confirm on the analysis sheet whether or not leakage occurred
during transport. If a noticeable amount of leakage ham occurred, either void
the sample or use methods, subject to the approval of the Administrator, to
correct the final results. Measure the liquid in this container either
volumetrlcally to ±1 ml or fravimetrically to +0.5 g. Transfer the contents to
an acid-cleaned tared 250-ml beaker and evaporate to dryneaa at ambient
temperature and pressure. If pmrticulate emissions are being determined.
desiccate for 24 hours without heat, weigh to a constant weight according to
the procedures deacrlbed la Section 4.3 of Method 5, and report the results to
the nearest 0.1 mg. fteeolubllize the residue with concentrated nitric acid and
combine the resultant aample includinc ell liquid and any pmrticulate aattar
with Container Mb. 3 prior to beginning the following Section 5.3.3.
5.3.3 Container No. 3 (Probe Rinse). The pH of this aample shall be 2 or
lower. If the pH is higher, the sample should be acidified with concentrated
nitric acid to pH 2. The) sample should be rinsed into a beaker with water and
the beaker should be covered with a ribbed watchglaaa. The aample volume should
be reduced to approximately 50 ml by heating on a hot plate at a temperature
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-------
just below boiling. Inspect the saaple for visible particulate matter, and
depending; on the results of the inspection, perform one of the following. If r.c
particulars satter is observed, combine the sample directly with the acid
digested portions of the filter prepared previously in Section 5.3 1. If
particular* natter is observed, digest the sample in microwave vessels or Parr'
3oabs following the procedures described in Section 5.3.!; then combine the
resultant sacple directly with the acid digested portions of the filter prepared
previously in Section 5.3 .1. The resultant combined saaple is referred to as
Fraction 1. Filter the combined solution of the acid digested filter and probe
rinse samples using Whataan $11 filter paper. Dilute to 300 mi (or the
appropriate volume for the expected metals concentration) with water. Measure
and record the combined 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 al portion as Fraction 1A. Fraction 1A is used for ICAP or AAS
analysis. Fraction IB is used for the determination of front half mercury.
5.3.4 Container No. 4 (Impingers 1-3) . Measure and record the total vol-
ume of this sample (Fraction 2) to within 0.5 «l. Remove a 50 ad aliquot for
mercury analysis and label as Fraction 2B. Label the regaining portion of
Container Ho. 4 as Fraction 2A. The Fraction 23 aliquot should be prepared and
analyzed as described la Section 5.4.3. Fraction 2A shall be pH 2 or lower.
If necessary, use concentrated nitric acid to lower Fraction 2A to pfl 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 al by heating on a hot plate at a temperature just below
boiling. Then follow either of the digestion procedures described in Sections
5.3-^-1 «nd 5-3-*-2, below.
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 10 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 al (or the appropriate volume) for the expected metals
concentration*) with water.
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 minute* 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 additional 5 minutes.
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Cool, filter the saaple. and dilute to 150 •! (or the appropriate voluae for --he
expected aetals concentrations) with water.
Note: All microwave heating times given are approximate and are dependent
upon the nuaber of samples being digested at a tiae. Heating times as giver.
above have b««n found acceptable for simultaneous digestion of up to 12
individual saaples. Sufficient heating is evidenced by solvent reflux within
the vessel.
5.3.5 Container No. 5 (Impingers 445). Measure and record the total
voluae of this saaple to within 0.5 el. This aasiple is referred to as Fraction
3. Follow the analysis procedures described in Section 5.4.3.
5.3.6 Container No. 6 (Silica Gel). Weigh the) spent silica gel (or silica
gel plus iapinger) to the; nearest 0.5 ff using a balance. (This step
may be conducted in the field.)
5.4 Saaple Analysis. For each sampling train, five individual saaples are
generated for analysis. A schematic identifying each sample and the prescribed
sample preparation and analysis scheme is shown in Figure A-3. The first two
saaples, labeled Fractions 1A and IB, consist of the digested saaples froa the
front half of the train. Fraction 1A is for ICAP or AAS analysis as described
in Sections 5.4.1 and/or 5.4.2. Fraction IB is for determination of front half
mercury as described la Section 5**»«3.
The back half of the train was used to prepare the third through fifth
samples. The third and fourth samples, labeled Fractions 2A and 28, contain
the digested samples from) the 8,0 and HNOj/H,0, lapingers 1 through 3. Fraction
2A is for ICAP or AAS analysis. Fraction 2B will be analysed for mercury.
The fifth sample, labeled Fraction 3. consists of the iapinger contents and
rinses from the permanganate lapingers 4 end 5« This sample is analyzed for
mercury as described la Section 5*^*3* The total back half mercury catch is
determined free) the SUB of Fraction 2B and Fraction 3.
5.4.1 XCAP Analysis. Fraction 1A and Fraction 2A are analysed by ICAP
using EPA Method 200.7 (*0 Cfft 136. Appendix C). Calibrate the ICAP. and set up
an analysis profram ss described in Method 200.7* The quality control proce-
dures described la Section 7*3.1 of this method shall be followed. Recommended
wavelengths for use la the analysis are listed below.
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Elea«nt Wavelength (na)
Aluainua
Antiaorxy
Arsenic
Barium
3«rylliua
Cadaium
Chromium
Copper
Iron
Lead
Manganese
Nickel
Selenium
Silver
Thallium
Zinc
303.215
206.333
193.696 ** oa
455 .^03 * *•» •
313.042 l?w th<=
226.502 ' "°"
267.716 ^™
324.754
259-940
220.353
257.610
231.604
196.026
328.068
190.864
213.356
It
pone/,
Th« «av*l«nffthj listed *r» r»co«a«nd«d b«eaus« of their sensitivity and overall
acceptance. Other wavelengths eay be substituted if they can provide the
needed sensitivity and are treated with the saoe corrective techniques for
spectral interference.
Initially, analyze all saaples for the target eetals plus iron and
aluBlnua. If iron and aluminum are present in the sample, the sample say have
to be diluted so that each of these elements is at a concentration of less than
50 PP« to reduce their spectral interferences on arsenic and lead.
Note; When analyzing samples la a hydrofluoric acid matrix, an alumina
torch should be used; since all front half samples will contain hydrofluoric
acid, use an alumina torch.
5.4.2 AAS by Direct Aspiration and/or Graphite Furnace. If analysis of
oetals In Fraction 1A and Fraction 2A using graphite furnace or direct
aspiration AAS is desired. Table A-2 should be used to determine which
techniques and methods should be applied for each target metal. Table A-2
should also be consulted to determine) possible interferences and techniques to
be followed for their minimization. Calibrate the Instrument according to
Section 6.3 and follow the quality control procedures specified in Section
7.3-2.
5.4.3 Cold Vapor AAS Mercury Analysis. Fraction IB. Fraction 2B. and
Fraction 3 should be analysed for mercury using cold vapor atomic absorption
spectroscopy following the method outlined in EPA Method 7*70 or in Standard
Methods for Water and tfastewater Analysis. 15th Edition. Method 303?*. Set up
E-26
-------
TABLE A-2. APPLICABLE TECHNIQUES, METHODS. AND MINIMIZATION OP INTEFEHKNCE I OH AAS ANALYSIS
Metal
Sb
Sb
As
Be
Be
Be
Cd
Cd
Cr
Cr "•
Technique
Aspiration
Furnace
Furnace
Aapiratlon
Aspiration
Furnace
Aspiration
Furnace
Aspiration
Furnace
Method
No.
70*0
70*1
7060
7080
7090
7091
7130
7131
7190
7191
Wavelength
(n.)
217.6
217.6
193-7
553.6
23*. 9
234.9
226.8
226.8
357-9
357-9
Interfei
Cause
1000 •«/•! Pb
Ni. Cu. or acid
High Pb
Arsenic volatl -
cation
Aluainiue
Calciue
BarliM ionizatlon
500pp. Al
High Mg 1 SI
Be in optical path
Absorption ft light
scattering
As above
Excess chloride
Pipet tips
Alkali atttal
Absorption ft scatt
200 eg/L calciue
ft phosphate
•ence
Minimization
Use secondary waveleiifcla <>f 2J1.1 it*.
Natch sample ft standards acid concentration
or use nitrous onide/ac.etylene flame
Secondary wavelength or Zceaan correction
Spiked saeples ft add nickel ni irate solution
to digeststes prior to analyses
Use Zeeean background correction
High hollow cathode current 1 narrow band set
2 eL of KC1 per 100 eL of saaple
Add 0. 1* fyi/ride
Use Method of standard additions
Optimize parameters to miminize effects
Background correction is required
As above
Aeaoniua phosphate used as a aatrix modifier
Use cadeiua-free tips
KC1 Ionizatlon suppressant in saaple I stand
Consult manufacturer's literature
All calcitui nitrate for a know constant effect
and to eliminate effect of phosphate
m
i
rv>
(continued)
*rurfr»ni l
• hrt not lM«a
t:+ ahould not «t UtU sUj* M con«iru««
v (•f>r*&«nt AgMMy policy. II to belnf
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TAIII.K A-2 (CONTINUKD)
Mutal
Cu
Fe
Pb
Pb
Nn
Mi
S-
i
0
St * \ * * Ag
? 3 ^ S •
ii''i
JlfHt-n
*i*5l-
{• _ z 2 «•
5i*fl Tl
i$*If
^ 4 S f
si » si
li.'jij
ill'8 z"
"fa
Technique
Aspi ratio*
Aspiration
Aspiration
Furnaca
Aspiration
Aspiration
Furnaca
Aspiration
Aspiration
Furnaca
Aspiration
MullttMl
No.
7210
7180
7420
7421
7460
7520
77*0
7760
7840
7841
7950
Wavelength
32'i . 7
248.1
281.1
281.1
279-5
212.0
196.0
}28.1
276.8
276.8
213 9
Interference
Cause
Absorpt ft scatter
Contamination
217.0 na alternat
Poor recoveries
401.1 na alternat
152.4 na alternat
Fa. Co. & Cr
Monlinear respons
Volitality
Adsorpt ft scatter
Absorpt i scatter
AgCl iasolubla
Viscosity
Hydrochloric acid
or chloride
High Si. Cu ft P
Contamination
Minimization
Consul I manufacturer's Miinu.il
Great care taken to iiviotl rmtlummul ion
Background correction required
Matrix modifier, add III id. of i>)n>s|.l.oni3 acid
to 1-ml. of prepared sample in uumplrr cu|»
Background correction required
Background correction required
Matrix matching or a nitrous-oMide/ucely flama
Sample dilution or use. 152. iiiH«li">t !<>it
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