EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
                     CONDITIONAL TEST METHOD

Prepared by Emission Measurement Branch       EMTIC CTM-012.WPF
Technical Support Division, OAQPS, EPA            June 30, 1992

    Determination of Metals Emissions from Stationary Sources

Note:  This conditional method (CTM-012.WPF) replaces the EMTIC
"Interim" test method for metals emissions from stationary
sources (ITM-001).  The current version of the method reflects
the slated-to-be proposed "Method 29 - Determinarion of Metals
Emissions from Stationary Sources" which will be proposed in
conjunction with additional standards regulating municipal waste
combustors.  A copy of Method 29 (dated 6/30/93) is contained in
Docket A-90-45, item II-B-12.

1.   Applicability and Principle

     1.1  Applicability.   This method is  applicable  to  the

determination of total chromium (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 (Hg)

emissions from stationary sources.  This method may also be used

for determining particulate emissions when the prescribed

procedures and precautions are followed.   Changes in the

procedures to further facilitate particulate determination may

affect the front-half mercury determination.

     1.2  Principle.   A stack sample  is withdrawn  isokinetically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

solutions of acidic hydrogen peroxide and acidic potassium

permanganate.  The recovered samples are digested, and

-------
appropriate fractions are analyzed for mercury by cold vapor



atomic absorption spectroscopy (CVAAS) and for Cr, Cd, Ni, Mn,



Be, Cu, Zn, Pb, Se, P, Tl, Ag, Sb, Ba, and As by inductively



coupled argon plasma emission spectroscopy (ICAP) or atomic



absorption spectroscopy (AAS).  Graphite furnace atomic



absorption spectroscopy (GFAAS) is used for analysis of Sb, As,



DC, Pb, Se, and Tl if these elements require greater analytical



sensitivity than can be obtained by ICAP.  Additionally, if



desired, the tester may use AAS for analysis of all metals if the



resulting in-stack method detection limits meet the goal of the



testing program.



2.  Range, Sensitivity, Precision, and Interferences



     2.1  Range.   For  the  analysis described  and  for  similar



analyses, the ICAP response is linear over several orders of



magnitude.  Samples containing metal concentrations in the



nanograms per ml (ng/ml) to micrograms per ml (//g/ml) range in



the final analytical solution can be analyzed using this method.



Samples containing greater than approximately 50 jug/ml Cr, Pb, or



As should be diluted to that level or lower for final analysis.



Samples containing greater than approximately 20 //g/ml of Cd



should be diluted to that level before analysis.



     2.2  Analytical Sensitivity.   ICAP  analytical  detection



limits for the sample solutions (based on SW-846, Method 6010)



are approximately as follows: Sb (32 ng/ml),  As (53 ng/ml),



Ba (2 ng/ml), Be (0.3 ng/ml), Cd (4 ng/ml), Cr (7 ng/ml),



Cu (6 ng/ml), Pb (42 ng/ml), Mn (2 ng/ml), Ni (15 ng/ml),

-------
P (75 ng/ml), Se (75 ng/ml), Ag (7 ng/ml), Tl (40 ng/ml), and



Zn (2 ng/ml).  The actual method detection limits are sample



dependent and may vary as the sample matrix may affect the



limits.  The analytical detection limits for analysis by direct



aspiration AAS (based on SW-846, Method 7000 series) are



approximately as follows: Sb (200 ng/ml), As (2 ng/ml), Ba



(100 ng/ml), Be (5 ng/ml), Cd (5 ng/ml), Cr (50 ng/ml), Cu



(20 ng/ml), Pb (100 ng/ml), Mn (10 ng/ml), Ni (40 ng/ml),



Se (2 ng/ml), Ag (10 ng/ml), Tl (100 ng/ml), and Zn (5 ng/ml).



The detection limit for mercury by CVAAS is approximately



0.2 ng/ml.   The use of GFAAS can give added sensitivity compared



to direct aspiration AAS for the following metals:  Sb (3 ng/ml),



As (1 ng/ml), Be (0.2 ng/ml), Cd (0.1 ng/ml), Cr (1 ng/ml), Pb



(1 ng/ml),  Se (2 ng/ml), and Tl (1 ng/ml).



     2.3  In-stack  Detection  Limit.



     2.3.1   Using  (1)  the procedures  described  in  this  method,



(2) the analytical detection limits described in the previous



paragraph,  (3) a volume of 300 ml (Fraction 1)  for the front-half



and 150 ml  (Fraction 2A) for the back-half samples, and (4) a



stack gas sample volume of 1.25 m3, the  corresponding  in-stack



method detection limits are presented in Table 29-1 and



calculated using Eq. 29-1.





                    A x B/C = D                   Eq.  29-1

-------
     where:



             A = Analytical detection limit, //g/ml.



             B = Volume of sample prior to aliquotting for



                 analysis, ml.



             C = Stack sample volume, dsm3.



             D = In-stack detection limit, jug/m3.



Values in Table 29-1 are calculated for the front- and back-half



and/or the total train.



     2.3.2   To  ensure  optimum  sensitivity  in the measurements,



the concentrations of target metals in the solutions are



suggested to be at least ten times the analytical detection



limits.  Under certain conditions, and with greater care in the



analytical procedure,  this concentration can be as low as



approximately three times the analytical detection limit.  In all



cases, on at least one sample (run) in the source test and for



each metal analyzed, repetitive analyses,  method of standard



additions (MSA), serial dilution, or matrix spike addition, etc.,



shall be used to establish the quality of the data.



     2.3.3  Actual in-stack method detection limits will be



determined based on actual source sampling parameters and



analytical results as described above.  If required, the method



in-stack detection limits can be made more sensitive than those



shown in Table 29-1 for a specific test by using one or more of



the following options:



     2.3.4  A 1-hour sampling run may collect a stack gas



sampling volume of about 1.25 m3.   If the  sampling time  is

-------
                Table 29-1.   In-stack method detection limits.
 Front-half
 Metal
    Back-half
  Fraction 1
Probe and Filter
    Back-half
  Fraction 2
Impingers 1-3
Fractions
"Hg, only"
Impincters 4-6
                                                   Total Train
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
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)*
0.6**
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 (0.1)*
0.7
5.0 (0.1)*
0.2 (0.1)*
3.0** 2.0**
1.8
9
9 (0.3)*
0.9
4.8 (0.1)*
0.3
11.5 (1.1)*
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)*
5.6**
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,  estimated for back-Half and
     total Train.
     Note: Actual  method in-stack detection limits will be determined based
     on actual source sampling parameters  and analytical results  as  described
     earlier in this section.

-------
increased and 5 m3 are collected,  the in-stack method detection



limits would be one fourth the values shown in Table 29-1 (with



this change, the method is four times more sensitive than a



1-hour run.  Larger sample volumes (longer runs) would make it



even more sensitive.



     2.3.5   The  in-stack detection limits assume that all of the



sample is digested  (except the aliquot for mercury) and the final



liquid volumes for analysis are 300 ml (Fraction l) for the



front-half and 150 ml  (Fraction 2A) for the back-half sample.  If



the front-half volume  is reduced from 300 to 30 ml, the front-



half in-stack detection limits would be one tenth the values



shown above (ten times more sensitive).  If the back-half volume



is reduced from 150 to 25 ml, the in-stack detection limits would



be one sixth the above values.  Matrix effect checks are



necessary on sample analyses and typically are of greater



significance for samples that have been concentrated to less than



the normal original sample volume.  Reduction to a volume of less



than 25 ml may not allow redissolving of the residue and may



increase interference by other compounds.



     2.3.6   When both  of the  above modifications are  used



simultaneously on one sample, the resultant improvements are



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 reduced by a factor of six,



the in-stack method detection limit is reduced by a factor of



thirty (the method is thirty times more sensitive).  Conversely,

-------
reducing stack sample volume and increasing sample liquid volume



will increase in-stack detection limits (the method would then be



less sensitive).  The front-half and back-half samples (Fractions



1A and 2A) can be combined proportionally (see Section 1.2) prior



to analysis.  The resultant liquid volume (excluding the mercury



fractions, which must be analyzed separately) is recorded.



Combining the sample in this manner does not allow the point of



capture in the train to be determined.  The in-stack method



detection limit then becomes a single value for all metals except



mercury (due to exclusion of the mercury fraction).  This



discussion assumes no blank correction.  Blank corrections are



discussed later in this method.



     2.4   Precision.   The  precision  (relative  standard  deviation)



for each metal detected in a method development test at a sewage



sludge incinerator are as follows: Sb (12.7 percent), As



(13.5 percent), Ba (20.6 percent), Cd (11.5 percent), Cr



(11.2 percent), Cu (11.5 percent), Pb (11.6 percent), P



(14.6 percent), Se (15.3 percent), Tl (12.3 percent), and Zn



(11.8 percent).  The precision for Ni was 7.7 percent for another



test conducted at a source simulator.  Beryllium, Mn, and Ag were



not detected in the tests; however,  based on the analytical



sensitivity of the ICAP for these metals,  it is assumed that



their precisions should be similar to those for the other metals



when detected at similar levels.



     2.5   Interferences.   Iron  can be  a spectral  interference



during the analysis of As, Cr,  and Cd by ICAP.  Al can be a

-------
spectral interference during the analysis of As and Pb by ICAP.



Generally, these interferences can be reduced by diluting the



sample, but this increases the method detection limit (in-stack



detection limit).  Refer to Method 6010 of Citation 1 of the



Bibliography or the other analytical methods used for details on



potential interferences to this method.  The analyst must



eliminate or reduce interferences to acceptable levels.  For all



GFAAS analyses, matrix modifiers should be used to limit



interferences, and standards should be matrix matched.



3.  Apparatus



     3.1   Sampling  Train.   A schematic  of  the sampling train is



shown in Figure 29-1.  It is similar to the Method 5 train and



consists of the following components.



     3.1.1   Probe Nozzle  (Probe  Tip)  and Borosilicate  or  Quartz



Glass Probe Liner.   Same as Method 5, Sections 2.1.1 and 2.1.2,



except that glass nozzles are required unless alternate tips are



constructed of materials that are free from contamination and



will not interfere with the sample.  If a probe tip other than



glass is used, no correction to the sample test results may be



made to compensate for its effect on the sample.  Probe fittings



of plastic such as Teflon, polypropylene,  etc. are recommended



over metal fittings to prevent contamination; further, if



desired,  a single glass piece consisting of a combined probe tip



and probe liner may be used, but such a single glass piece is not



a requirement of this methodology)

-------
Theriraeter
     (T)         Glass Filter Holder
                                                               Thermometer
    Glass Probe Liner

Glass Probe Tip
                       Empty (Optional)     I /      Enpty

                              5'0 H03/105B H2Q2
           Pi tot tenoteter
                                                            Air-tight
                                                   Dry Gas    pMp
                                                    Heter
                 Figure  29-1,    Sampling  train

-------
     3.1.2   Pitot Tube and Differential Pressure Gauge.   Same as



Method 2, Sections 2.1 and 2.2, respectively.



     3.1.3   Filter Holder.  Glass,  same as Method 5,



Section 2.1.5, except a Teflon filter  support or other non-



metallic, non-contaminating support must be used in place of the



glass frit.



     3.1.4   Filter Heating System.   Same as Method 5,



Section 2.1.6.



     3.1.5   Condenser.   The following system shall be  used for



condensing and collecting gaseous metals and determining the



moisture content of the stack gas.  The condensing system should



consist of four to seven  impingers connected in series with leak-



free ground glass fittings or other leak-free, non-contaminating



fittings.  The first impinger is optional and is recommended as a



moisture trap.  The second impinger (or the first HNO3/H2O2



impinger) shall be as described for the first impinger in



Method 5.  The third impinger (or second HNO3/H2O2 impinger) shall



be the Greenburg Smith impinger with the standard tip described



as the second impinger in Method 5, Section 2.1.7.  All other



impingers are the same as the first HNO3/H2O2 impinger previously



described.   A thermometer capable of measuring to within 1°C



(2°F)  shall be placed at the outlet of the last impinger.   If



mercury analysis is not to be performed, the potassium
                                10

-------
permanganate impingers and the empty impinger preceding them are



removed.



     3.1.6   Metering  System,  Barometer,  and  Gas  Density



Determination Equipment.  Same as Method 5,  Sections 2.1.8



through 2.1.10, respectively.



     3.1.7   Teflon  Tape.   For capping openings and sealing



connections, if necessary, on the sampling train.



     3.2  Sample  Recovery.   Same  as  Method 5, Sections  2.2.1



through 2.2.8 (Probe-Liner and Probe-Nozzle Brushes or Swabs,



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   Non-metallic  Probe-Liner and Probe-Nozzle Brushes or



Swabs.  For quantitative recovery of materials collected in the



front-half of the sampling train.  A description of acceptable



all-Teflon component brushes or swabs are to be included in EPA's



Emission Measurement Technical Information Center (EMTIC) files.



     3.2.2   Sample  Storage Containers.   Glass bottles with



Teflon-lined caps which are non-reactive to the oxidizing



solutions,  with capacities of 1000- and 500-ml shall be used for



KMnO4-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  identifying samples.





                               11

-------
     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 dilutions.



     3.3.2   Graduated Cylinders.  For preparation  of reagents.



     3.3.3   ParrE Bombs or Microwave Pressure Relief Vessels with



Capping Station (CEM Corporation model or equivalent).




     3.3.4   Beakers  and Watch Glasses.   250-ml beakers for  sample




digestion with watch glasses 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   Disposable  Pasteur Pipets and  Bulbs.



     3.3.8   Volumetric  Pipets.



     3.3.9   Analytical  Balance.  Accurate  to within  0.1 mg.



     3.3.10   Microwave  or  Conventional  Oven.   For  heating samples



at fixed power levels or temperatures.



     3.3.11   Hot  Plates.



     3.3.12   Atomic  Absorption Spectrometer  (AAS).   Equipped with



a background corrector.



     3.3.12.1  Graphite Furnace Attachment.  With  Sb,  As, Cd, Pb,



Se, and Tl  hollow cathode lamps (HCLs)  or electrodeless discharge



lamps (EDLs).  Same as Bibliography Citation 1 Methods 7041 (Sb),



7060 (As),  7131 (Cd),  7421 (Pb),  7740  (Se),  and 7841 (Tl).






                               12

-------
     3.3.12.2   Cold Vapor Mercury Attachment.   With a mercury HCL



or EDL.  The equipment needed for the cold vapor mercury



attachment includes an air recirculation pump, a quartz cell, an



aerator apparatus, and a heat lamp or desiccator tube.  The heat



lamp should be capable of raisinq the ambient temperature at the



quartz cell by 10°C such that no condensation  forms on the wall




of the quartz cell.  Same as Method 7470 in Citation 2 of the



Biblioqraphy.



     3.3.13   Inductively Coupled Argon  Plasma  Spectrometer.   With



either a direct or sequential reader and an alumina torch.  Same



as EPA Method 6010 in Citation 1 of the Biblioqraphy.



4.  Reagents



     4.1   Unless  otherwise indicated, it is  intended that  all



reaqents conform to the specifications established by the



Committee on Analytical Reagents of the American Chemical



Society, where such specifications are available; otherwise, use



the best available grade.



     4.2   Sampling.   The reagents used  in sampling  are as



follows:



     4.2.1  Filters.   The filters shall contain less than



1.3 /xg/in.2  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



analyzed for each target metal prior to emission testing.   Quartz



or glass fiber filters without organic binders shall be used.



The filters should,^ exhibit at least 99.95 percent efficiency





                                13

-------
(<0.05 percent penetration) on 0.3-/U dioctyl phthalate smoke



particles.  The filter efficiency test shall be conducted in



accordance with ASTM Standard Method D2986-71  (incorporated by




reference).  For particulate determination in  sources containing




sulfur dioxide (SO2)  or sulfur trioxide (S03),  the  filter




material must be of a type that is unreactive  to S02 or S03/ as




described in Method 5.  Quartz fiber filters meeting these




requirements are recommended.



     4.2.2   Water.  To conform to  ASTM Specification D1193-77,



Type II (incorporated by reference).  If necessary, analyze the



water for all target metals prior to field use.  All target



metals should be less than 1 ng/ml.



     4.2.3   Nitric  Acid.   Concentrated.   Baker Instra-analyzed or



equivalent.



     4.2.4   Hydrochloric  Acid.   Concentrated.   Baker Instra-



analyzed or equivalent.



     4.2.5   Hydrogen  Peroxide,  30  Percent (V/V).



     4.2.6   Potassium Permanganate.



     4.2.7   Sulfuric  Acid.   Concentrated.



     4.2.8   Silica  Gel and Crushed Ice.   Same  as  Method 5,



Sections 3.1.2 and 3.1.4, respectively.



     4.3  Pretest Preparation of Sampling Reagents.



     4.3.1   Nitric  Acid (HNO3)/Hydrogen Peroxide  (H2O2) Absorbing



Solution, 5 Percent HNO3/10 Percent  H2O2.   Add carefully with



stirring 50 ml of concentrated HNO3  to a  1000-ml  volumetric  flask



containing approximately 500 ml of water, and3  then add carefully






                                14

-------
with stirring 333 ml of 30 percent H2O2.  Dilute to volume with



water.  Mix well.  The reagent shall contain less than 2 ng/ml of



each target metal.



     4.3.2   Acidic  Potassium Permanganate (KMn04) Absorbing



Solution, 4 Percent KMn04  (W/V),  10 Percent H2S04 (V/V).   Prepare



fresh daily.  Mix carefully, with stirring, 100 ml of



concentrated H2S04 into approximately 800 ml of water, and add




water with stirring to make a volume of 1 liter:  this solution



is 10 percent H2SO4  (V/V).  Dissolve, with stirring,  40 g of KMn04



into 10 percent H2S04 (V/V) and add 10 percent H2SO4  (V/V) with



stirring to make a volume of 1 liter:  this is the acidic



potassium permanganate absorbing solution.  Prepare and store in



glass bottles to prevent degradation.  The reagent shall contain



less than 2 ng/ml of Hg.



     Precaution:  To prevent autocatalytic  decomposition  of  the



permanganate solution,  filter the solution through Whatman 541



filter paper.  Also, due to the potential reaction of the



potassium permanganate with the acid, there may be pressure



buildup in the sample storage bottle; these bottles shall not be



fully filled and shall be vented to relieve excess pressure and



prevent explosion potentials.  Venting is reguired, but should



not allow contamination of the sample; a No. 70-72 hole drilled



in the container cap and Teflon liner has been used.



     4.3.3   Nitric  Acid, 0.1  N.   Add  with stirring  6.3 ml of



concentrated HNO3 (70 percent)  to a flask containing



approximately 900 ml of water.  Dilute to 1000 ml with water.





                                15

-------
Mix well.  The reagent shall contain less than 2 ng/ml of each



target metal.



     4.3.4   Hydrochloric  Acid  (HC1),  8  N.  Make  the  desired



volume of 8N HCl in the following proportions.  Carefully add



with stirring 690 ml of concentrated HCl to a flask containing



250 ml of water.  Dilute to 1000 ml with water.   Mix well.  The



reagent shall contain less than 2 ng/ml of Hg.



     4.4  Glassware  Cleaning Reagents.



     4.4.1   Nitric Acid,  Concentrated.   Fisher ACS grade  or



equivalent.



     4.4.2   Water.   To  conform to  ASTM  Specifications  D1193-77,



Type II.



     4.4.3   Nitric Acid,  10  Percent  (V/V).   Add  with stirring



500 ml of concentrated HNO3  to a flask  containing approximately



4000 ml of water.  Dilute to 5000 ml with water.  Mix well.



Reagent shall contain less than 2 ng/ml of each target metal.



     4.5  Sample Digestion and Analysis Reagents.



     4.5.1   Hydrochloric  Acid,  Concentrated.



     4.5.2   Hydrofluoric  Acid,  Concentrated.



     4.5.3   Nitric Acid,  Concentrated.   Baker  Instra-analyzed or



equivalent.



     4.5.4   Nitric Acid,  50  Percent  (V/V).   Add  with stirring



125 ml of concentrated HNO3  to 100 ml of $/ater.   Dilute to 250 ml



with water.  Mix well.   Reagent shall contain less than 2 ng/ml



of each target metal.

-------
     4.5.5   Nitric Acid,  5 Percent (V/V).   Add with stirring 50



ml of concentrated HN03 to 800 ml of water.  Dilute to 1000 ml



with water.  Mix well.  Reagent shall contain less than 2 ng/ml



of each target metal.



     4.5.6   Water.   To conform to ASTM Specifications D1193-77,




Type II.




     4.5.7   Hydroxylamine Hydrochloride and Sodium Chloride




Solution.  See Citation 2 of the Bibliography for preparation.




     4.5.8   Stannous Chloride.   See Citation 2 of the



Bibliography for preparation.



     4.5.9   Potassium Permanganate, 5 Percent (W/V).   See



Citation 2 of the Bibliography for preparation.



     4.5.10  Sulfuric Acid,  Concentrated.



     4.5.11  Nitric Acid,  50 Percent (V/V).



     4.5.12  Potassium Persulfate,  5 Percent (W/V).   See



Citation 2 of the Bibliography for preparation.



     4.5.13  Nickel Nitrate, Ni(N03)2-6H20.



     4.5.14  Lanthanum Oxide,  La203.



     4.5.15  Hg Standard (AAS Grade), 1000 /zg/ml.



     4.5.16  Pb Standard (AAS Grade), 1000 //g/ml.



     4.5.17  As Standard (AAS Grade), 1000 jug/ml.



     4.5.18  Cd Standard (AAS Grade), 1000 //g/ml.



     4.5.19  Cr Standard (AAS Grade), 1000 ng/ml.



     4.5.20  Sb Standard (AAS Grade), 1000 //g/ml.



     4.5.21  Ba Standard (AAS Grade), 1000 /xg/ml.



     4.5,^2  Be Standard (AAS Grade), 1000






                                17

-------
     4.5.23   Cu Standard (AAS Grade),  1000 /Ltg/ml.



     4.5.24   Mn Standard (AAS Grade),  1000 jug/ml.



     4.5.25   Ni Standard (AAS Grade),  1000 /Ltg/ml.



     4.5.26   P  Standard (AAS Grade),  1000 /Ltg/ml.



     4.5.27   Se Standard (AAS Grade),  1000



     4.5.28   Ag Standard (AAS Grade),  1000



     4.5.29   Tl Standard (AAS Grade),  1000 jug/ml.



     4.5.30   Zn Standard (AAS Grade),  1000 /Ltg/ml.



     4.5.31   Al Standard (AAS Grade),  1000 jug/ml.



     4.5.32   Fe Standard (AAS Grade),  1000 /Ltg/ml.



     4.5.33   The metals standards may  also be made from solid



chemicals as described in Citation 3 of the Bibliography.



Citations 1, 2, or 4 of the Bibliography  should be referred to



for additional information on mercury standards.



     4.5.34   Mercury Standards and Quality Control Samples.



Prepare fresh weekly a 10 /Ltg/ml  intermediate mercury standard by



adding 5 ml of 1000 /ig/ml mercury stock solution to a  500-ml



volumetric flask; dilute with stirring to 500 ml by first



carefully adding 20 ml of 15 percent HNO3 and then adding water



to the 500-ml volume.  Mix well.  Prepare a 200 ng/ml  working



mercury standard solution fresh  daily:  add 5 ml of the  10 /ig/ml



intermediate standard to a 250-ml volumetric flask, and  dilute to



250 ml with 5 ml of 4 percent KMnO4,  5 ml of 15 percent HNO3, and



then water.   Mix well.  At least six separate aliquots of the



working mercury standard solution should  be used to prepare the



standard curve.  These aliquots  should contain 0.0, 1.0, 2.0,





                                18

-------
3.0, 4.0, and 5.0 ml of the working standard solution containing

0, 200, 400, 600, 800, and 1000 ng mercury, respectively.

Quality control samples should be prepared by making a separate

10 pig/ml standard and diluting until in the range of the

calibration.

     4.5.35   ICAP Standards and Quality Control  Samples.

Calibration standards for ICAP analysis can be combined into four

different mixed standard solutions as shown below.

            MIXED STANDARD SOLUTIONS  FOR ICAP ANALYSIS

          Solution                   Elements
            I                As,  Be,  Cd,  Mn,  Pb,  Se,  Zn
            II               Ba, Cu, Fe
          III              Al, Cr, Ni
            IV               Ag, P, Sb, Tl

Prepare these standards by combining and diluting the appropriate

volumes of the 1000 //g/ml solutions with 5 percent HNO3.   A

minimum of one standard and a blank can be used to form each

calibration curve.  However, a separate quality control sample

spiked with known amounts of the target metals in quantities in

the mid-range of the calibration curve should be prepared.

Suggested standard levels are 25 /ig/ml for AL, Cr and Pb,

15 jug/ml for Fe, and 10 /Ltg/ml for the remaining elements.

Prepare any standards containing less than 1 /Ltg/ml of metal on a

daily basis.  Standards containing greater than 1 /Ltg/ml of metal

should be stable for a minimum of 1 to 2 weeks.

     4.5.36   Graphite  Furnace AAS Standards.   Sb,  As,  Cd,  Pb,  Se,

and Tl.  Prepare a 10 /jg/ml standard by adding 1 ml of 1000 /Ltg/ml

standard to a 100-ml volumetric flask.  Dilute with stirring to


                                19

-------
100 ml with 10 percent HNO3.   For graphite furnace AAS,  the



standards must be matrix matched.  Prepare a 100 ng/ml standard



by adding 1 ml of the 10 jug/ml standard to a 100-ml volumetric



flask, and dilute to 100 ml with the appropriate matrix solution.



Other standards should be prepared by diluting 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 /Lig/ml standard and diluting until it is in the



range of the samples.  Any standards containing less than 1 /^g/ml



of metal should be prepared on a daily basis.  Standards



containing greater than 1 /ng/ml of metal should be stable for a



minimum of 1 to 2 weeks.



     4.5.37  Matrix  Modifiers.



     4.5.37.1   Nickel  Nitrate,  1  Percent (V/V).   Dissolve  4.956  g



of Ni(N03)2• 6H20 in approximately 50 ml of water in a 100-ml



volumetric flask.  Dilute to 100 ml with water.



     4.5.37.2   Nickel  Nitrate,  0.1  Percent (V/V).   Dilute  10  ml



of the 1 percent nickel nitrate solution from Section 4.5.37.1



above to 100 ml with water.  Inject an egual amount of sample and



this modifier into the graphite furnace during AAS analysis for



As.



     4.5.37.3   Lanthanum.   Carefully dissolve 0.5864  g  of  La203 in



10 ml of concentrated HN03,  and dilute the solution by  adding it



with stirring to approximately 50 ml of water.  Dilute to 100 ml



with water,  and mix well.  Inject an equal amount of sample and





                                20

-------
this modifier into the graphite furnace during AAS analysis for



Pb.



     4.5.38   Whatman  541  Filter  Paper  (or  equivalent).   For



filtration of digested samples.



5.   Procedure



     5.1   Sampling.   The  complexity  of this  method is  such that,



to obtain reliable results, testers and analysts should be



trained and experienced with the test procedures, including



source sampling, reagent preparation and handling, sample



handling, safety equipment, analytical calculations, reporting,



and specific descriptions throughout this method.



     5.1.1  Pretest Preparation.   Follow the same general



procedure given in Method 5, Section 4.1.1,  except that, unless



particulate emissions are to be determined,  the filter need not



be desiccated or weighed.  All sampling train glassware should



first be rinsed with hot tap water and then washed in hot soapy



water.  Next, glassware should be rinsed three times with tap



water, followed by three additional rinses with water.  All



glassware should then be soaked in a 10 percent (V/V) nitric acid



solution for a minimum of 4 hours, rinsed three times with



water, rinsed a final time with acetone, and allowed to air dry.



All glassware openings where contamination can occur should be



covered until the sampling train is assembled for sampling.



     5.1.2  Preliminary Determinations.  Same as  Method  5,



Section 4.1.2.
                                21

-------
     5.1.3   Preparation of Sampling Train.



     5.1.3.1  Follow the same general procedures given in



Method 5, Section 4.1.3, except place 100 ml of the HN03/H2O2



solution (Section 4.2.1) in each of the two impingers as shown in



Figure 29-1 (normally the second and third impingers).  Place



100 ml of the acidic KMn04 absorbing solution (Section 4.2.2)  in



each of the two impingers as shown in Figure 29-1, and transfer



approximately 200 to 300 g of preweighed silica gel from its



container to the last impinger.  Alternatively, the silica gel



may be weighed directly in the impinger just prior to train



assembly.



     5.1.3.2  Several options are  available  to  the tester based



on the sampling reguirements and conditions.  The use of an empty



first impinger can be eliminated if the moisture to be collected



in the impingers will be less than approximately 100 ml.  If



necessary,  use as applicable to this methodology the procedure



described in Section 7.1.1 of Method 101A, 40 CFR Part 61,



Appendix B, to maintain the desired color in the last



permanganate impinger.



     5.1.3.3  Retain for reagent blanks  volumes of the HNO3/H202



solution per Section 5.2.16 of this method and of the acidic



KMnO4 solution per  Section 5.2.17.   These  reagent blanks should



be labeled and analyzed as described in Section 7.  Set up the



sampling train as shown in Figure 29-1.   If mercury analysis is



not desired, delete the empty impinger and the two permanganate



impingers following the HNO3/H2O2 impingers.   If necessary to





                               22

-------
ensure leak-free sampling train connections, Teflon tape or other



non-contaminating material should be used instead of silicone



grease to prevent contamination.  Precaution:  Extreme care



should be taken to prevent contamination within the train.



Prevent the mercury collection reagent (acidic KMn04)  from



contacting any glassware of the train which is washed and



analyzed for Mn.  Prevent H202 from mixing with the acidic KMnO,.



     5.1.3.4   Mercury  emissions  can  be  measured,  alternatively,



in a separate train using EPA Method 101A with the modifications



for processing the permanganate containers as described in the



precaution in Section 4.3.2 and the note in Section 5.2.11 of



this method).  This alternative method is applicable for



measurement of mercury emissions, and it may be of special



interest to sources which must measure both mercury and manganese



emissions.



     5.1.4  Leak-Check Procedures.   Follow the  leak-check



procedures given in Method 5, Section 4.1.4.1 (Pretest Leak-



Check), Section 4.1.4.2 (Leak-Checks During the Sample Run), and



Section 4.1.4.3 (Post-Test Leak-Checks).



     5.1.5  Sampling Train  Operation.   Follow the procedures



given in Method 5, Section 4.1.5.  For each run, record the data



required on a data sheet such as the one shown in Figure 5-2 of



Method 5.



     5.1.6  Calculation of  Percent Isokinetic.   Same as  Method  5,



Section 4.1.6.
                                23

-------
     5.2   Sample  Recovery.



     5.2.1  Begin cleanup procedures  as  soon  as  the  probe  is



removed from the stack at the end of a sampling period.  The



probe should be allowed to cool prior to sample recovery.   When




it can be safely handled,  wipe off all external particulate



matter near the tip of the probe nozzle and place a rinsed, non-



contaminating cap over the probe nozzle to prevent losing or



gaining particulate matter.  Do not cap the probe tip tightly



while the sampling train is cooling; a vacuum may form in the



filter holder with the undesired result of drawing liquid from



the impingers onto the filter.



     5.2.2  Before moving the  sampling train  to  the  cleanup site,



remove the probe from the sampling train and cap the open outlet.



Be careful not to lose any condensate that might be present.   Cap



the filter inlet where the probe was fastened.  Remove the



umbilical cord from the last impinger and cap the impinger.  Cap



off the filter holder outlet and impinger inlet.  Use non-



contaminating caps, whether ground-glass stoppers, plastic caps,



serum caps, or Teflon tape to close these openings.



     5.2.3  Alternatively,  the train  can be disassembled before



the probe and filter holder/oven are completely cooled if this



procedure is followed:  Initially disconnect the filter holder



outlet/impinger inlet and loosely cap the open ends.  Then



disconnect the probe from the filter holder or cyclone inlet and



loosely cap the open ends.   Cap the probe tip and remove the



umbilical cord as previously described.





                                24

-------
     5.2.4   Transfer  the  probe  and  filter-impinger  assembly  to  a



cleanup area that is clean and protected from the wind and other



potential causes of contamination or loss of sample.  Inspect the



train before and during disassembly and note any abnormal



conditions.  The sample is recovered and treated as follows (see



schematic in Figures 29-2a and 29-2b).   Assure that all items



necessary for recovery of the sample do not contaminate it.



     5.2.5   Container No.  1  (Filter).   Carefully  remove  the



filter from the filter holder and place it in its identified



petri dish container.  Acid-washed polypropylene or Teflon coated



tweezers or clean, disposable surgical  gloves rinsed with water



and dried should be used to handle the  filters.  If it is



necessary to fold the filter, make certain the particulate cake



is inside the fold.  Carefully transfer the filter and any



particulate matter or filter fibers that adhere to the filter



holder gasket to the petri dish by using a dry (acid-cleaned)



nylon bristle brush.   Do not use any metal-containing materials



when recovering this train.   Seal the labeled petri dish.



     5.2.6   Container No.  2  (Acetone  Rinse).   NOTE:  Perform  this



section only if determination of particulate emissions are



desired in addition to metals emissions.  Ensuring that dust on



the outside of the probe or other exterior surfaces does not get



into the sample, guantitatively recover particulate matter and
                                25

-------
Probe Liner Front Half of Filter Filter Support 1st Impinger 2nd A 3rd
and Nozzle Filter Housing


Einae with Brush


and Back Half £Effl.JPty at ImpLflgBrs
of Filter Housing beginning I^H]J03/H2O2^

with Gar ef ully RinsE
of test ^
three ueac
Tire Heosure
acetone nonmetallic brush rCfflOVC filter times with impinger impinger
and rinse with from support ° • tN HNQ3 contents contents
acetone with TeflOfl-

Bruch liner
brush ft rinse
with acetone



Check liner to see
if parciculate
rcoiDvedi if not !
repeat step above

coated tweezers
and place in
petri dish




Brush loose
p articulate
onto filter




Seal petrd. dish
with tajie

Einse three
muse cnrea Rinse three
times witli
times with
0.1M HH03
0 . IN
HNOQ
FE AR I




Empty the Empty the
cnntainer container






Hinse three Rinse three
times with times with
0.1H HN03 0.1N HH03







BI







I
(3)* C23 CO W
Hiunher in psreatheses indicates container number
                  Figure 29-Za.   Sample recovery scheme,
                                   26

-------
             4th  Impinger
                     & 5th
                             Last  Impinger
            and 6th impingers
            C Acidified KMn04)
                Measure
                Impinger
                contents
      I
  Empty  the
impinger No.  4
 contents  into
  container
  Rinse witii
   100 ml
 0.IN HN03
 0.IN HN03
           I
      Empty the
      impingers
      Nos. 5 & 6
      contents into
       container
      Rinse three
      times -with
     permanganate
      reagent,  then
       with water
                          Remove any
                          residue with
                           25 ml 8N
                           HC1 solution
                               Weigh for
                               moisture
            Discard
KMn04
 C5EO
8N HG1
 (SO)
            Figure  29-2b.   Sample  recovery  scheme
                                 28b
                             27

-------
any condensate from the probe nozzle, probe fitting, probe liner,



and front half of the filter holder by washing these components



with 100 ml of acetone and placing the wash in a glass container.



NOTE;  The use of exactly 100 ml is necessary for the subsequent



blank correction procedures.  Distilled water may be used instead



of acetone when approved by the Administrator and shall be used



when specified by the Administrator; in these cases, save a water




blank and follow the Administrator's directions on analysis.



Perform the acetone rinse as follows:  Carefully remove the probe



nozzle and clean the inside surface by rinsing with acetone from



a wash bottle and brushing with a non-metallic brush.  Brush



until the acetone rinse shows no visible particles, after which



make a final rinse of the inside surface with acetone.



     5.2.7   Brush and rinse  the  sample  exposed inside parts  of



the fitting with acetone in a similar way until no visible



particles remain.  Rinse the probe liner with acetone by tilting



and rotating the probe while squirting acetone into its upper end



so that all inside surfaces will be wetted with acetone.  Allow



the acetone to drain from the lower end into the sample



container.  A funnel may be used to aid in transferring liquid



washings to the container.  Follow the acetone rinse with a non-



metallic probe brush.  Hold the probe in an inclined position,



squirt acetone into the upper end as the probe brush is being



pushed with a twisting action through the probe.  Hold a sample



container underneath the lower end of the probe, and catch any



acetone and particulate matter which is brushed through the probe





                                28

-------
three times or more until no visible particulate matter is



carried out with the acetone or until none remains in the probe



liner on visual inspection.  Rinse the brush with acetone, and



quantitatively collect these washings in the sample container.



After the brushing, make a final acetone rinse of the probe as



described above.



     5.2.8   It is  recommended that  two  people  clean the  probe  to



minimize sample losses.  Between sampling runs, keep brushes



clean and protected from contamination.  Clean the inside of the



front-half of the filter holder by rubbing the surfaces with a



non-metallic nylon bristle brush and rinsing with acetone.  Rinse



each surface three times or more if needed to remove visible



particulate.  Make a final rinse of the brush and filter holder.



After all acetone washings and particulate matter have been



collected in the sample container,  tighten the lid so that



acetone will not leak out when shipped to the laboratory.  Mark



the height of the fluid level to determine whether or not leakage



occurred during transport.  Label the container clearly to



identify its contents.



     5.2.9   Container  No.  3  (Probe  Rinse).  Keep  the  probe



assembly clean and free from contamination during the probe



rinse.  Rinse the probe nozzle and fitting, probe liner, and



front-half of the filter holder thoroughly with 100 ml of



0.1 N HNO3,  and place  the  wash into a sample storage  container.



NOTE: The use of exactly 100 ml is necessary for the subsequent



blank correction procedures.  Perform the rinses as applicable





                                29

-------
and generally as described in Method 12, Section 5.2.2.  Record



the volume of the combined rinse.  Mark the height of the fluid



level on the outside of the storage container and use this mark



to determine if leakage occurs during transport.  Seal the



container, and clearly label the contents.  Finally, rinse the



nozzle, probe liner, and front-half of the filter holder with



water followed by acetone, and discard these rinses.



     5.2.10   Container  No.  4  (Impingers  1  through 3,  HN03/H202



Impingers and Moisture Knockout Impinger, when used, Contents and



Rinses). Due to the potentially large quantity of liquid



involved, the tester may place the impinger solutions from



impingers 1 through 3 in more than one container.  Measure the



liquid in the first three impingers to within 0.5 ml using a



graduated cylinder.  Record the volume.   This information is



required to calculate the moisture content of the sampled flue



gas.  Clean each of the first three impingers, the filter



support, the back half of the filter housing, and connecting



glassware by thoroughly rinsing with 100 ml of 0.1 N HNO3 using



the procedure as applicable in Method 12, Section 5.2.4.  NOTE:



The use of exactly 100 ml of 0.1 N HNO3  rinse is necessary for



the subsequent blank correction procedures.  Combine the rinses



and impinger solutions, measure and record the volume.  Mark the



height of the fluid level, seal the container, and clearly label



the contents.



     5.2.11   Container  Nos. 5A  (0.1 N HNO3) , 5B  (KMnO4/H2SO4



absorbing solution), and 5C (8 N HC1 rinse and dilution).  Pour





                                30

-------
all the liquid, if any, from the impinger which was empty at the



start of the run and which immediately precedes the two



permanganate impingers (normally impinger No. 4) into a graduated



cylinder and measure the volume to within 0.5 ml.  This



information is required to calculate the moisture content of the



sampled flue gas.  Place the liquid in Sample Container No. 5A.



Rinse the impinger (No. 4) with 100 ml of 0.1 N HN03 and place



this into Container No. 5A.



     5.2.12   Pour all  the  liquid from  the two permanganate



impingers into a graduated cylinder and measure the volume to



within 0.5 ml.  This information is required to calculate the



moisture content of the sampled flue gas.  Place this KMnO4



solution into Container No. 5B.  Using 100 ml total of fresh



acidified KMnO4 solution,  rinse the two permanganate impingers



and connecting glass a minimum of three times.  Pour the rinses



into Container No. 5B, carefully assuring transfer of all loose



precipitated materials from the two impingers.  Using



100 ml total of water, rinse the permanganate impingers and



connecting glass a minimum of three times, and pour the rinses



into Container 5B, carefully assuring transfer of all loose



precipitated material, if any.  Mark the height of the fluid



level, and clearly label the contents.  Note the precaution in



Section 4.3.2.  NOTE:   Due to the potential reaction of KMnO«



with acid, there may be pressure buildup in the sample storage



bottles.  These bottles shall not be filled completely and shall



be vented to relieve excess pressure.   A No. 70-72 hole drilled





                                31

-------
in the container cap and Teflon liner has been used successfully.



     5.2.13   If  no  visible  deposits  remain  after  the  above



described water rinse, no further rinse is necessary.  However,



if deposits do remain on the glassware, wash the impinger



surfaces with 25 ml of 8 N HC1, and place the wash in a separate



sample container labeled Container No. 5C containing 200 ml of



water as follows.  Place 200 ml of water in a sample container



labeled Container No. 5C.  Wash the impinger walls and stem with



the HC1 by turning the impinger on its side and rotating it so



that the HC1 contacts all inside surfaces.   Use a total of only



25 ml of 8 N HC1 for rinsing both permanganate impingers



combined.  Rinse the first impinger, then pour the actual rinse



used for the first impinger into the second impinger for its



rinse.  Finally, pour the 25 ml of 8 N HC1 rinse carefully into



Container No. 5C.  Mark the height of the fluid level on the



outside of the bottle to determine if leakage occurs during



transport.



     5.2.14   Container No.  6  (Silica Gel).   Note  the  color  of  the



indicating silica gel to determine whether it has been completely



spent and make a notation of its condition.  Transfer the silica



gel from its impinger to its original container and seal.  The



tester may use a funnel to pour the silica gel and a rubber



policeman to remove the silica gel from the impinger.  The small



amount of particles that may adhere to the impinger wall need not



be removed.  Do not use water or other liquids to transfer the



silica gel since weight gained in the silica gel impinger is used





                                32

-------
for moisture calculations.  Alternatively, if a balance is



available in the field, record the weight of the spent silica gel



(or silica gel plus impinger) to the nearest 0.5 g.



     5.2.15   Container No.  7 (Acetone Blank).   If  particulate



emissions are to be determined, at least once during each field



test, place a 100-ml portion of the acetone used in the sample



recovery process into a labeled container for use in the front-



half field reagent blank.  Seal the container.



     5.2.16   Container No.  8A (0.1  N  HNO3 Blank).  At least once



during each field test, place 300 ml of the 0.1 N HNO3  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.



     5.2.17   Container No.  8B (water  blank).   At least  once



during each field test, place 100 ml of the water used in the



sample recovery process into a labeled Container No. 8B.  Seal



the container.



     5.2.18   Container No.  9 (5  Percent HN03/10 Percent H2O2



Blank).  At least once during each field test, place 200 ml of



the 5 Percent HNO3/10  Percent H2O2 solution used as the  nitric



acid impinger reagent into a labeled container for use in the



back-half field reagent blank.  Seal the container.



     5.2.19   Container No.  10 (Acidified KMn04 Blank).  At least



once during each field test, place 100 ml of the acidified KMn04



solution used as the impinger solution and in the sample recovery



process into a labeled container for use in the back-half field





                                33

-------
reagent blank for mercury analysis.  Prepare the container as



described in Section 5.2.11.  See the note in Section 5.2.12.



     5.2.20   Container  No.  11  (8  N  HC1  Blank).   At  least  once



during each field test, perform both of the following.  Place



200 ml of water into a sample container.  Pour 25 ml of 8 N HC1



carefully with stirring into the container.  Mix well and seal



the container.




     5.2.21   Container  No.  12  (Filter Blank).  Once during each



field test,  place three unused blank filters from the same lot as



the sampling filters in a labeled petri dish.  Seal the petri



dish.  These will be used in the front-half field reagent blank.



     5.3   Sample  Preparation.   Note the level  of the liquid in



each of the containers and determine if any sample was lost



during shipment.   If a noticeable amount of leakage has occurred,



either void the sample or use methods,  subject to the approval of



the Administrator, to correct the final results.  A diagram



illustrating sample preparation and analysis procedures for each



of the sample train components is shown in Figure 29-3.



     5.3.1  Container No.  1  (Filter).   If  particulate emissions



are being determined,  desiccate the filter and filter catch



without added heat and weigh to a constant weight as described in



Section 4.3 of Method 5.  For analysis of metals, divide the



filter with its filter catch into portions containing



approximately 0.5 g each and place into the analyst's choice of



either individual microwave pressure relief vessels or Parr*



Bombs.  Add 6 ml of concentrated HNO3 and  4 ml of concentrated HF





                               34

-------
             Container 3
           Acid Probe Binsc
             CLdbelcd FH3
    Container  2
Acetone Probe  Einsc
   (Labeled AR}


Reduce to drynes:
in a tared be etc
I
Determine residm
weight in beaker
   Container 4
   HZOZ} Impiagcrs
   CLebeled SH)
Cinclude coadensate
         t  if used^
U)
Ul
                                                                                          Acidify

                                                                                       sample to pH 2
                                                                                      with cone. HMOS
                                                                                         Fraction 2A
                                                                                                   Containers 5A, SB,  & 5C
tion 1







Remove 70 to 100 mi
oliijTaot for Eg
a&ftlysia by CVAAS
Fraction IB




Direct witli acid aid
pBrnangaaate at BS C i


                                    ftetals by GFAAS'
                                       Fraction 3A
                                                                              Individually, ttu
                                                                            separate digeetiojii
                                                                               and snalyaea
                                                                              digest with acic
                                                                            and pernangfliiat
                                                                               at 95 C for 2 h
                                                                                and aaolyz.c
                                                                              fOP Hfl by CVAAS
                                                                                  Fractions
                                                                                  3A, 3B,  A 3C
     *Analysis by AA3 for metals found at less than 2 ug/nl in dlgestac*  solution,
      if desired,  Or analyze for each netal by AAS* if desired.
                             Figure  29-3.    Sample  preparation  and  analysis  scheme,
                                                            35

-------
to each vessel.  For microwave heating, microwave the sample



vessels for approximately 12-15 minutes in intervals of 1 to 2



minutes at 600 Watts.  For conventional heating, heat the ParrR



Bombs at 140°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;



     5.3.1.1   Suggested microwave  heating times  are  approximate



and are dependent upon the number of samples being digested.



Twelve to 15 minute heating times have been found to be



acceptable for simultaneous digestion of up to 12 individual



samples.  Sufficient heating is evidenced by sorbent reflux



within the vessel.



     5.3.1.2   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



liguid in the container and confirm on the analysis sheet whether



or not leakage occurred during transport.   If a noticeable amount



of leakage has occurred,  either void the sample or use methods,



subject to the approval of the Administrator, to correct the



final results.  Measure the liguid in this container either



volumetrically within 1 ml or gravimetrically within 0.5 g.



Transfer the contents to an acid-cleaned,  tared 250-ml beaker and



evaporate to dryness at ambient temperature and pressure.  If



particulate emissions are being determined,  desiccate for





                                36

-------
24 hours without added heat, weigh to a constant weight according



to the procedures described in Section 4.3 of Method 5, and



report the results to the nearest 0.1 mg.  Redissolve the residue



with 10 ml of concentrated HNO3.   Quantitatively combine the



resultant sample, including all liquid and any particulate



matter, with Container No. 3 before beginning Section 5.3.3.



     5.3.3   Container No.  3  (Probe Rinse).   The  pH of  this sample



shall be 2 or lower.  If the pH is higher, the sample should be



acidified by careful addition with stirring of concentrated HN03



to pH 2.  The sample should be rinsed into a beaker with water,



and the beaker should be covered with a ribbed watch glass.  The



sample volume should be reduced to approximately 20 ml by heating



on a hot plate at a temperature just below boiling.  Digest the



sample in microwave vessels or ParrE Bombs by quantitatively



transferring the sample to the vessel or bomb, carefully adding



the 6 ml of concentrated HNO3,  4  ml of concentrated HF,  and then



continuing to follow the procedures described in Section 5.3.1.



Then combine the resultant sample directly with the acid digested



portions of the filter prepared previously in Section 5.3.1.  The



resultant combined sample is referred to as Fraction 1 precursor.



Filter the combined solution of the acid digested filter and



probe rinse samples using Whatman 541 filter paper.  Dilute to



300 ml (or the appropriate volume for the expected metals



concentration) with water.  This dilution is Fraction 1.



Measure and record the volume of the Fraction 1 solution to



within 0.1 ml.  Quantitatively remove a 50-ml aliquot and label





                               37

-------
as Fraction IB.  Label the remaining 250-ml portion as



Fraction 1A.  Fraction 1A is used for ICAP or AAS analysis.



Fraction IB is used for the determination of front-half mercury.



     5.3.4   Container  No.  4  (Impingers  1-3).   Measure  and record



the total volume of this sample (Fraction 2) to within 0.5 ml.



Remove a 75- to 100-ml aliquot for mercury analysis and label as



Fraction 2B.  Label the remaining portion of Container No. 4 as



aliquot Fraction 2A.  Aliquot Fraction 2A defines the volume of



2A prior to digestion.  All of aliquot Fraction 2A is digested to



produce concentrated Fraction 2A.  Concentrated Fraction 2A



defines the volume of 2A after digestion and is normally 150 ml.



Only concentrated Fraction 2A is analyzed for metals  (except that



it is not analyzed for mercury).  The Fraction 2B aliquot should



be prepared and analyzed for mercury as described in



Section 5.4.3.  Aliquot Fraction 2A shall have a pH of 2 or



lower.  If necessary,  use concentrated HNO3  by careful addition



and stirring to lower aliquot Fraction 2A to pH 2.  The sample



should be rinsed into a beaker with water and the beaker covered



with a ribbed watchglass.  The sample volume should be reduced to



approximately 20 ml by heating on a hot plate at a temperature



just below boiling.  Then follow either of the digestion



procedures described in Sections 5.3.4.1 and 5.3.4.2,  below.



     5.3.4.1  Conventional Digestion  Procedure.   Add 30 ml  of



50 percent HNO3,  and heat  for  30  minutes  on  a  hot plate to just



below boiling.  Add 10 ml of 3 percent H2O2 and heat for 10 more



minutes.  Add 50 ml of hot water, and heat the sample for an





                                38

-------
additional 20 minutes.  Cool, filter the sample, and dilute to



150 ml (or the appropriate volume for the expected metals



concentrations) with water.  This dilution is concentrated



Fraction 2A.  Measure and record the volume of the Fraction 2A



solution to within 0.1 ml.



     5.3.4.2   Microwave  Digestion Procedure.   Add 10  ml  of




50 percent HN03 and heat for 6  minutes  in intervals of 1 to 2



minutes at 600 Watts.  Allow the sample to cool.  Add 10 ml of



3 percent H2O2  and heat  for  2 more minutes.  Add  50 ml of hot



water, and heat for an additional 5 minutes.  Cool, filter the



sample, and dilute to 150 ml (or the appropriate volume for the



expected metals concentrations) with water.  This dilution is



concentrated Fraction 2A.  Measure and record the volume of the



Fraction 2A solution to within 0.1 ml.   NOTE;  All microwave



heating times given are approximate and are dependent upon the



number of samples being digested at a time.  Heating times as



given above have been found acceptable for simultaneous digestion



of up to 12 individual samples.  Sufficient heating is evidenced



by solvent reflux within the vessel.



     5.3.5   Container Nos.  5A,  5B,  and  5C (Impingers  4,  5,



and 6).  Keep these samples separate from each other and measure



and record the volumes of 5A and 5B separately to within 0.5 ml.



Dilute sample 5C to 500 ml with water.   These samples 5A, 5B,  and



5C are referred to respectively as Fractions 3A, 3B,  and 3C.



Follow the analysis procedures described in Section 5.4.3.



Because the permanganate rinse and water rinse have the





                                39

-------
capability to recover a high percentage of the mercury from the



permanganate impingers, the amount of mercury in the HC1 rinse



(Fraction 3C) may be very small, possibly even insignificantly



small.  However, as instructed in this method, add the total of



any mercury measured in and calculated for the HC1 rinse



(Fraction 3C) to that for Fractions IB, 2B, 3A, and 3B for



calculation of the total sample mercury concentration.



     5.3.6   Container  No.  6  (Silica Gel).   Weigh  the  spent  silica



gel (or silica gel plus impinger) to the nearest 0.5 g using a



balance.  (This step may be conducted in the field.)



     5.4 Sample Analysis.   For each sampling  train,  seven



individual samples are generated for analysis.  A schematic



identifying each sample and the prescribed sample preparation and



analysis scheme is shown in Figure 29-3.  The first two samples,



labeled Fractions 1A and IB, consist of the digested samples from



the front-half of the train.  Fraction 1A is for ICAP or AAS



analysis as described in Sections 5.4.1 and/or 5.4.2.



Fraction IB is for determination of front-half mercury as



described in Section 5.4.3.   The back-half of the train was used



to prepare the third through seventh samples.   The third and



fourth samples, labeled Fractions 2A and 2B, contain the digested



samples from the moisture knockout, if used, and HNO3/H202



Impingers 1 through 3.  Fraction 2A is for ICAP or AAS analysis.



Fraction 2B will be analyzed for mercury.  The fifth through



seventh samples, labeled Fractions 3A, 3B, and 3C, consist of the



impinger contents and rinses from the empty and permanganate





                                40

-------
impingers 4, 5, and 6.  These samples are analyzed for mercury as

described in Section 5.4.3.  The total back-half mercury catch is

determined from the sum of Fraction 2B and Fractions 3A, 3B,

and 3C.

     5.4.1   ICAP Analysis.   Fraction  1A  and  Fraction  2A  are

analyzed by ICAP using Method 6010 or Method 200.7 (40 CFR 136,

Appendix C).  Calibrate the ICAP, and set up an analysis program

as described in Method 6010 or Method 200.7.  The quality control

procedures described in Section 7.3.1 shall be followed.

Recommended wavelengths for use in the analysis are listed below.

           Element	Wave 1 ength (nm)
           Aluminum                   308.215
           Antimony                   206.833
           Arsenic                    193.696
           Barium                     455.403
           Beryllium                  313.042
           Cadmium                    226.502
           Chromium                   267.716
           Copper                     324.754
           Iron                       259.940
           Lead                       220.353
           Manganese                  257.610
           Nickel                     231.604
           Phosphorous                214.914
           Selenium                   196.026
           Silver                     328.068
           Thallium                   190.864
           Zinc                       213.856

The wavelengths listed are recommended because of their

sensitivity and overall acceptance.  Other wavelengths may be

substituted if they can provide the needed sensitivity and are

treated with the same corrective techniques for spectral

interference.  Initially, analyze all samples for the desired

target metals (except mercury) plus iron and aluminum.  If iron

and aluminum are present, the sample may have to be diluted so

                                41

-------
that each of these elements is at a concentration of less than
50 ppm to reduce their spectral interferences on arsenic,
cadmium, chromium, and lead.   NOTE:  When analyzing samples in a
HF matrix, an alumina torch should be used; since all front-half
samples will contain HF, use an alumina torch.
     5.4.2  AAS by Direct Aspiration and/or Graphite Furnace.  If
analysis of metals in Fraction 1A and Fraction 2A using graphite
furnace or direct aspiration AAS is desired, Table 29-2 should be
used to determine which techniques and methods should be applied
for each target metal.  Table 29-2 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.
                               42

-------
Table 29-2 .   Applicable techniques, methods and minimization of  i
Metal
Fe
Pb
Pb


tin
Hi



Se




AS




Tl

Tl




Zn

Tech.fl.iq.ue
Aspiration
Aspiration
Furnace


Aspiration
Aspiration



Furnace




Acpi.raT.don




Aspiration

Furnace




Aspiration

SW-846 Wavel ength
Method No, CGnO
7380 248,3
7420 283 . 3
7421 283.3


7460 279 . 5
7520 232 . O



7740 196. O




77fiQ 32S. 1




7840 276 , 8

7841 276.8




7950 213.9

Interferences
Cause Minimization,
Contamination
217. O nm alternate
Poor recoveries


403.1 nm alternate
352.4 nm alternstt
Fet Co., and Cr

Nonlinear response
Volatility


Adsorption & scam

Adsorption & ccatt
AgCl insoluble





Hydrochl ori c acid
or chloride



High Si , Cu . A P
Cont ami nation
Great care taken to avoid ctmtaminatio
Background correction required
Matrix modifier, add 10 ul of phosphor
acid to 1 ml of prepared sample in
sampler cup
Background correction required
Background correction required
Matrix matching or nitrous-oxide/
acetylene flame
Sample dilution or use 352.3 nm line
Spi he sampl es and reefer ence mat efi als
add nickel nitrate to minimize
volatilization
fiBactground correction is required and
Zeeman background correction can "be US'
dSsacigro-und correction is required
Avoid hydrochloric acid unless silver
!n solution as a chloride complex
Sample and standards monitored for
aspiration rate
Background correction is required
Hydrochloric acid should not be used
Background correction is required
Verify that losses are not occurring f
volatizstion by spiked samples or stan
addition.; Palladium is a suitable matr
modifier
Strontium removes Cu and phosphate
Great care taJcen to avoid contaminatio:
L

us







and



jful

.s






ir
lard
-X


1
                                      43

-------
Table 29-2 cont.
Iletal
Sb


Sb
As



Ba


B*

Be
Cd

Cd



Cr


Cr

Cu
Technique
Aspiration


Furnace
Furnace



Aspiration


Aspi.ratd.oii

Furnace
Aspiration

Furnace



Aspiration


Furnace

Aspiration
SW-846
Method Ho,
7040


7041
7O6O



7080


7090

7091
7130

7131



7190


71S1

7Z10
Wavelength
(mO
217.6


217.6
193.7



553.6


234.9

2.34.9
2.2.8.8

22.8.8



3S7.9


357.9

324.7
Interferences
Cause Minimization
1000 mgXmi Pb
Hi , Cu , or acid

High Pb
Arsenic volatilize

Al-uaifiiiu

Calcium

Barium ionizakion
500 ppm Al
Bigll Mg and Si
Be in optical patt
Absorption and lig
scattering
As aoove
Excess chloride

Pipet tips
Alkali metal


200 mg/L Ca and P

Absorption a scatt
Use secondary wavelenthe of Z31.1 urn;
match sample & standards ' acid concent
tion or use nitrous oxide/acetylene fl
Secondary waveleagtJ) or Zeeman correct
t£tpiifced samples and add nickel nitrate
lution to
digestates prior to analysis
Use Zeeman background correction
High hollow cathode current and narrow
band set
2 ml of KC1 per 100 ml of sample
Add O.l« fluoride
Use method of standard additions
Optimize parameters to minimize effect
tftackoround correction is required

As above
Ammonium phosphate used as a matrix
modifier
Use cadmium-free tips
KC1 ioniaation suppressant in samples
and standards
Consult manufacturer 's literature
All calcium nitrate for a known consta
effect and to eliminate effect of phos
SEonsult manufacturer 's manual


ra-
ame
.on
3O-








s









at
phafce

       44

-------
     5.4.3  Cold Vapor AAS Mercury Analysis.  Fractions IB, 2B,



3A, 3B, and 3C should be analyzed separately for mercury using



CVAAS following the method outlined in EPA SW-846 Method 7470 or



in Standard Methods for Water and Wastewater Analysis, 15th



Edition, Method 303F.  Set up the calibration curve (zero to



1000 ng) as described in SW-846 Method 7470 or similar to Method



303F using 300-ml BOD bottles instead of Erlenmeyers.   Dilute



separately, as described below, an aliquot sized from 1 ml to



10 ml of each original sample to 100 ml with water.  Record the



amount of the aliguot used for dilution to 100 ml.  If no prior



knowledge exists of the expected amount of mercury in the sample,



a 5-ml aliquot is suggested for the first dilution to 100 ml and



analysis.  In determining the emission value for mercury, the



size of the sample aliquot used for dilution and analysis is



dependent upon its mercury content.  The total amount of mercury



in the aliquot shall be less than 1 pq and within the range (zero



to 1000 ng) of the calibration curve.  Place each sample aliquot



into a separate 300-ml BOD bottle, and add enough water to make a



total volume of 100 ml.  Then analyze the sample for mercury by



adding to it sequentially the sample preparation solutions and



performing the sample preparation and analysis as described in



the procedures of SW-846 Method 7470 or Method 303F.  If the



reading maximums are off-scale (because mercury in the aliquot



exceeded the calibration range), including the dilution of l-ml



aliquots of the original sample, then perform the following:





                                45

-------
dilute the original sample (or a portion of it) with 0.15 percent



HN03 (1.5 ml  concentrated HN03 per liter aqueous solution) so



that when a 1- to 10-ml aliquot of the original sample is further



diluted to 100 ml and analyzed by the procedures described above,



it will yield an analysis within the range of the calibration



curve.



6.   Calibration



     Maintain a laboratory log of all calibrations.



     6.1  Sampling Train Calibration.  Calibrate the sampling



train components according to the indicated sections of Method 5:



Probe Nozzle (Section 5.1); Pitot Tube (Section 5.2); Metering



System (Section 5.3); Probe Heater (Section 5.4); Temperature



Gauges (Section 5.5); Leak-Check of the Metering System



(Section 5.6); and Barometer (Section 5.7).



     6.2  Inductively Coupled Argon Plasma Spectrometer



Calibration.   Prepare standards as outlined in Section 4.5.



Profile and calibrate the instrument according to the



manufacturer's recommended procedures using the above standards.



The calibration should be checked once per hour.  If the



instrument does not reproduce the standard concentrations within



10 percent, the complete calibration procedures should be



performed.



     6.3  Atomic Absorption Spectrometer - Direct Aspiration,



Graphite Furnace and Cold Vapor Mercury Analyses.  Prepare the



standards as outlined in Section 4.5 and use to calibrate the



spectrometer.  Calibration procedures are also outlined in the





                                46

-------
EPA methods referred to in Table 29-2 and in SW-846 Method 7470

or Standard Methods for Water and Wastewater Method 303F (for

mercury).  Each standard curve should be run in duplicate and the

mean values used to calculate the calibration line.  The

instrument should be recalibrated approximately once every 10 to

12 samples.

7.   Quality Control

     7.1  Sampling.  Field Reagent Blanks.  When analyzed, the

blanks in Container Nos. 7 through 12 produced previously in

Sections 5.2.14 through 5.2.19, respectively, shall be processed,

digested, and analyzed as follows.  Digest and process one of the

filters from Container No. 12 per Section 5.3.1, 100 ml from
Container No. 7 per Section 5.3.2, and 100 ml from Container
No. 8A per Section 5.3.3.  This produces Fraction Blanks 1A and
IB from Fraction Blank 1.  [If desired, the other two filters may

be digested separately according to Section 5.3.1, diluted
separately to 300 ml each, and analyzed separately to produce a
blank value for each of the two additional filters.  If these
analyses are performed, they will produce two additional values

for each of Fraction Blanks 1A and IB.  The three Fraction Blank
1A values will be calculated as three values of M£hb in Eguation 3
of Section 8.4.3, then the three values shall be totalled and
divided by 3 to become the value MfM> to be used in computing Mt
by Equation 3.  Similarly, the three Fraction Blank IB values
will be calculated separately as three values, totalled,

averaged, and used as the value for Hgfhb in Equation 8 of
                                     \
                                47

-------
Section 8.5.3.  The analyses of the two extra filters are



optional and are not a requirement of this method, but if the



analyses are performed, the results must be considered as



described above.]  Combine 100 ml of Container No. 8A with 200 ml



from Container No. 9, and digest and process the resultant volume



per Section 5.3.4.  This produces concentrated Fraction Blanks 2A



and 2B from Fraction Blank 2.  A 100-ml portion of Container




No. 8A is Fraction Blank 3A.  Combine 100 ml from Container



No. 10 with 33 ml from Container No. 8B.  This produces Fraction



Blank 3B (use 400 ml as the volume of Fraction Blank 3B when



calculating the blank value.  Use the actual volumes when



calculating all the other blank values).  Dilute 225 ml from



Container No. 11 to 500 ml with water.  This produces Fraction



Blank 3C.  Analyze Fraction Blank 1A and Fraction Blank 2A per



Section 5.4.1 and/or 5.4.2.  Analyze Fraction Blank IB, Fraction



Blank 2B, and Fraction Blanks 3A, 3B, and 3C per Section 5.4.3.



The analysis of Fraction Blank 1A produces the front-half reagent



blank correction values for the metals except for mercury; the



analysis of Fraction Blank IB produces the front-half reagent



blank correction value for mercury.  The analysis of concentrated



Fraction Blank 2A produces the back-half reagent blank correction



values for the metals except for mercury, while separate analyses



of Fraction Blanks 2B, 3A, 3B, and 3C produce the back-half



reagent blank correction value for mercury.



     7.2  An attempt may be made to determine if the laboratory



reagents used in Section 5.3 caused contamination.  They should





                                48

-------
be analyzed by the procedures in Section 5.4.  The Administrator



will determine whether or not the laboratory blank reagent values



can be used in the calculation of the test results.



     7.3  Quality Control Samples.  The following quality control



samples should be analyzed.



     7.3.1  ICAP Analysis.  Follow the quality control shown in



Section 8 of Method 6010.  For the purposes of a three run test



series, these requirements have been modified to include the



following:  two instrument check standard runs, two calibration



blank runs, one interference check sample at the beginning of the



analysis (must be within 25 percent or analyze by standard



additions), one quality control sample to check the accuracy of



the calibration standards (must be within 25 percent of



calibration), and one duplicate analysis (must be within 10



percent of average or repeat all analyses).



     7.3.2  Direct Aspiration and/or Graphite Furnace AAS



Analysis for Sb, As, Ba, Be, Cd, Cu, Cr, Pb, Ni, Mn, Hg, P, Se,



Ag, Tl, and Zn.  All samples should be analyzed in duplicate.



Perform a matrix spike on at least one front-half sample and one



back-half sample or one combined sample.  If recoveries of less



than 75 percent or greater than 125 percent are obtained for the



matrix spike, analyze each sample by the method of additions.  A



quality control sample should be analyzed to check the accuracy



of the calibration standards.  The results must be within



10 percent or the calibration repeated.
                                49

-------
     7.3.3  Cold Vapor AAS Analysis for Mercury.  All  samples



should be analyzed in duplicate.  A quality control  sample  should



be analyzed to check the accuracy of the calibration standards



(within 15 percent or repeat calibration).  Perform  a  matrix



spike on one sample from the HN03 impinger portion (must be



within 25 percent or samples must be analyzed by the method of



standard additions).   Additional information on quality  control



can be obtained from EPA SW-846 Method 7470 or  in Standard



Methods for Water and Wastewater Method 303F.



8.   Calculations



     8.1  Dry Gas Volume.  Using the data from  this  test,



calculate Vn(std),  the dry gas sample volume at standard conditions



as outlined in Section 6.3 of Method 5.



     8.2  Volume of Water Vapor and Moisture Content.  Using the



data obtained from this test, calculate the volume of  water vapor



vw(Std>  and the moisture content Bws of the stack gas.  Use



Equations 5-2 and 5-3 of Method 5.



     8.3  Stack Gas Velocity.  Using the data from this test and



Equation 2-9 of Method 2, calculate the average stack  gas



velocity.



     8.4  Metals (Except Mercury) in Source Sample.



     8.4.1  Fraction 1A, Front-Half, Metals (except  Hg).



Calculate separately the amount of each metal collected in



Fraction 1 of the sampling train using the following equation:



             M«, = Cal Fd Vsoln^                     Eq. 29-1



where:





                                50

-------
             Mfh = Total mass of each metal  (except Hg)  collected



                  in the front half of the  sampling  train



                  (Fraction 1) , jug.



             Cal = Concentration of metal  in sample Fraction  1A as



                  read from the standard  curve,  jug/ml.



              Fd = Dilution factor  (Fd = the inverse of the



                  fractional portion of the concentrated sample



                  in the solution actually  used  in the  instrument



                  to produce the reading  Cal.   For example, when



                  2 ml of Fraction 1A are diluted to 10 ml,



                  Fd = 5).



          vsoin,i = Total volume of digested  sample solution



                  (Fraction 1), ml.



NOTE:  If Fractions 1A and 2A are combined,  proportional aliquots



must be used.  Appropriate changes must be  made  in Equations 29-1



to 29-3 to reflect this approach.



     8.4.2  Fraction 2A, Back-Half, Metals  (except Hg).



Calculate separately the amount of each metal collected in



Fraction 2 of the sampling train using the  following equation.



             Mbh = Ca2 Fa Va                         Eq.  29-2



where:



             Mbh = Total mass of each metal  (except Hg)  collected



                  in the back-half of the sampling train



                  (Fraction 2) , //g.
                                51

-------
             Ca2 = Concentration of metal  in  sample  concentrated



                  Fraction 2A as read  from the  standard curve,



                  (jug/ml).



              Fa = Aliquot factor, volume  of  Fraction  2  divided  by



                  volume of aliquot Fraction 2A (see



                  Section 5.3.4).



              Va = Total volume of digested sample solution




                  (concentrated Fraction  2A), ml  (see



                  Section 5.3.4.1 or 5.3.4.2, as applicable).



     8.4.3  Total Train, Metals  (except Hg).  Calculate the total



amount of each of the quantified metals collected in  the sampling



train as follows:



              Mt = (Mfh - Mehb) + (Mbh - Mbhb)        Eq.  29-3
where:



              Mt = Total mass of each metal  (separately stated for



                  each metal) collected  in  the  sampling train,



                  jug.



            M£hb = Blank correction value for mass  of  metal



                  detected in front-half field  reagent blank, //g.







            Mbhb = Blank correction value for mass  of  metal



                  detected in back-half  field reagent blank,  jug.



NOTE:  If the measured blank value for the  front half (m^) is  in



the range 0.0 to A nq [where A /Ltg equals the value determined by





                                52

-------
multiplying 1.4 jug/in.2 times the actual area  in  in.2 of the



filter used in the emission  sample],  mfhb may be used to correct



the emission sample value  (mfh) ;  if mfhb exceeds A jug, the greater



of the two following values  may  be used:



     I.   A nq, or



     II.   the lesser of  (a)  mfhb,  or  (b) 5 percent of mfh.



     If the measured blank value for  the back-half (mbhb) is in



the range 0.0 to 1 jug,  mbhb may be  used to  correct the emission



sample value (mbh) ; if mbhb  exceeds  1 jug, the greater of the two



following values may be used:  1 jug or 5 percent of mbh.



     8 . 5  Mercury in Source  Sample .



     8.5.1  Fraction IB, Front-Half,  Mercury.   Calculate the



amount of mercury collected  in the front-half, Fraction 1, of the



sampling train using the following eguation:







                                                   Eq' 29~4
                                flB
where:



            Hgfh = Total mass  of  mercury collected in the front-



                  half of  the sampling train (Fraction 1), //g.



             Qfh = Quantity of mercury in analyzed sample, fj,g.



           Vsoin,i - Total volume of digested sample solution



                  (Fraction 1),  ml.



            VflB = Volume of Fraction IB analyzed, ml.  See the



                  following Note.
                                53

-------
Note:  VflB is the actual amount of Fraction IB analyzed.   For



example, if 1 ml of Fraction IB were diluted  to  100  ml  to bring



it into the proper analytical range, and  1 ml of the 100-ml



dilution were analyzed, VflB would be 0.01.



     8.5.2  Fractions 2B, 3A, 3B, and  3C, Back Half, Mercury.



Calculate the amount of mercury collected in  Fractions  2  using



Equation 5 and in Fractions 3A, 3B, and 3C using Equation 6.



Calculate the total amount of mercury  collected  in the  back-half



of the sampling train using Eq. 29-7.
                                f2B





where :



            Hgbh2 = Total mass of mercury  collected  in  Fraction 2,



                  /ig.



            Qbh2 = Quantity of mercury  in analyzed  sample,  /Ltg.



           Vsoin,2 = Total volume of Fraction  2,  ml.



            V£2B = Volume of Fraction 2B  analyzed,  ml  (see  the



                  following note).



Note:  Vf2B is the actual amount of Fraction 2B analyzed.   For



example, if 1 ml of Fraction 2B were diluted to  10 ml to bring it



into the proper analytical range, and  5  ml  of  the  10-ml  dilution



was analyzed, Vf2B would be 0.5.  Use Equation  6  to calculate



separately the back-half mercury for Fractions 3A, then  3B,  then



3C.



where :
                                54

-------
                               bh3 (A, B, C)  / T7              p~   -5 Q _
                               T -  (VSoln,3(A,B.C.)     E(3 •  29
       Hgbh3(A,B,c>  = Total mass of mercury  collected separately in

                   Fraction 3A, 3B, or  3C,  jug.

              ,o  = Quantity of mercury  in separately analyzed

                   samples, /ug.

              ,o  = Volume of Fraction 3A, 3B,  or 3C analyzed, ml

                   (see note in Sections  8.5.1  and 8.5.2, and

                   calculate similarly) .

      vsoin,3
-------
Note:  If the total of the measured blank  values  (Hgfhb  +  Hgbhb)  is
in the range of 0 to 6 ng, then the total  may be  used to  correct
the sample value (Hgfh +  Hgbh);  if  it exceeds 6 ng, the greater of
the following two values may be used:  6  jxg or 5 percent of the
sample value (Hgfh + Hgbh).
     8.6  Metal Concentration  in  Stack Gas.   Calculate  each metal
separately for the Cd, total Cr,  As, Ni, Mn,  Be,  Cu,  Pb,  P, Tl,
Ag, Ba, Zn, Se, Sb, and  Hg concentrations  in  the  stack  gas (dry
basis, adjusted to standard conditions)  as follows:
                                 Vm(std)
                                               Eq. 29-9
where:
              Cs = Concentration of  each  metal  in the stack gas,
                  mg/dscm.
              K4 = 10"3  mg//ig.
              Mt = Total mass of each metal  collected in the
                  sampling train, /ng;  (substitute Hgt for  Mt for
                  the  mercury calculation).
           Vm(std) = Volume of gas sample as measured by the dry gas
                  meter, corrected  to dry standard conditions,
                  dscm.
     8.7  Isokinetic Variation and  Acceptable  Results.   Same as
Method 5, Sections 6.11 and 6.12, respectively.
9.  Bibliography
     1.  Method 303F in Standard Methods for the Examination of
Water Wastewater, 15th Edition, 1980.  Available from the
                                56

-------
American Public Health Association, 1015 18th Street N.W.,



Washington, D.C. 20036.



     2.  EPA Methods 6010, 7000, 7041, 7060, 7131, 7421, 7470,



7740, and 7841, Test Methods for Evaluating Solid Waste;



Physical/Chemical Methods.  SW-846, Third Edition.  September



1988.  Office of Solid Waste and Emergency Response, U. S.



Environmental Protection Agency, Washington, D.C. 20460.



     3.  EPA Method 200.7, Code of Federal Regulations, Title 40,



Part 136, Appendix C.  July 1, 1987.



     4.  EPA Methods 1 through 5,  Code of Federal Regulations,



Title 40, Part 60, Appendix A, July 1, 1991.
                               57

-------