FUEL

PROCESSING
TECHNOLOGY
ELSEVIER Fuel Processing Technology 39 (1994) 259-263

Multiple metals stack emission measurement methodology

for stationary sources, current status
T h o m a s E. W a r d
Source Methods Research Branch, Methods Research and Development Division, Atmospheric Research and
Exposure Assessment Laboratory, US Environmental Protection Agency,
Research Triangle Park, NC 27711, USA

(Received 19 April 1993; accepted in revised form 20 January 1994)

Abstract

This paper presents an overview of the current status of measurement methodology for the
purpose of determining multiple metals stack emissions of up to sixteen metals using one
sampling train developed by the Atmospheric Research and Exposure Assessment Laboratory
of the United States Environmental Protection Agency (US EPA). In the methodology
isokinetic sampling from a grid of points produces a representative sample from which the
multiple metal emissions can be measured in the sample from one train. Metals in the stack
particulate matter are measured separately from those in the stack gases. The samples are
prepared by digestion for subsequent analysis by inductively coupled plasma or atomic
absorption spectroscopy. The train was developed for measuring the following sixteen metals:
total Cr, Cd, As, Ni, Mn, Be, Cu, Zn, Pb, Se, P, TI, Ag, Sb, Ba, and Hg. Emission factor
development, research requiring measurement of metals emissions, and determining emission
compliance are important potential applications of this type of methodology.

1. Introduction

Stack emissions of metals from stationary sources are of interest to the US EPA, to
state and local governments, to industries, and to the public. A broad overview of the
current status of measurement methodology for determining multiple metals stack
emissions of up to sixteen metals using only a single sampling train is presented. US
EPA methods exist currently for use when prescribed by regulations for measurement
of emissions of a single metal in one sampling train. These include a separate train and
methodology for either Pb [1], Be [2], Hg [3], or As [4]. The multiple metals
methodology would be particularly useful in sampling situations in which one
sampling train can be used instead of two or more trains to measure metals because of
the significant potential for reduced cost and increased efficiencies in emissions
measurement.

SSD1 0 3 7 8 - 3 8 2 0 ( 9 3 ) 0 0 0 2 6 - P
260 T.E. Ward/Fuel Processing Technology 39 (1994) 259-263

2. Discussion

The Office of Air Quality Planning and Standards of US EPA is considering

plans to propose the multiple metals measurement methodology as Method 29,
in 40 CFR 60, Appendix A I-5]. A condensed description of the methodology
is given here. A representative sample of the stack multiple metals emissions
is acquired by using a single train by isokinetic sampling from a grid of
sampling points. As many as sixteen metals can be measured in the sample
produced by this one train. The stack emission sample is drawn through the train
in which a filter captures the metals in the particulate matter and acidic im-
pinger solutions capture the metals in the gases. The particulate matter and
acidic impinger samples are then recovered separately from the train, prepared
for analysis by separate digestions, and analyzed by inductively coupled plasma
and/or atomic absorption spectroscopy (AAS) including graphite furnace AAS
(GFAAS) or cold vapor AAS (CVAAS) as applicable. Calculations are then performed
to determine concentrations of the metals in the stack effluent from which stack
emissions may be determined. The train was developed for measurement of as many
as sixteen metals including total Cr, Cd, As, Ni, Mn, Be, Cu, Zn, Pb, Se, P, T1, Ag, Sb,
Ba, and Hg. An important use of the methodology would occur should government
entities or others develop regulations in the form of limitations of metals in stack
emissions and determine that the methodology be used to determine compliance to
the emission limits. Emission factor development and other research requiring quan-
tification of metals emissions are other important potential applications of this
methodology.
The current status of the methodology includes developments which increase
understanding of the design of the testing to yield the desired detection limits for
metals concentrations in the stack gas emissions: these are termed in-stack detection
limits as defined in the methodology. Procedures were developed, also, which decrease
chances for contamination of the sample, and increase understanding of the measure-
ment of metals emissions especially mercury emissions and of the limits to corrections
allowed by the methodology for certain blank reagent values.
The methodology includes acquisition of a representative source sample from a grid
of points in the sampling plane. In a one hour sampling period at a typical average
nominal stack aerosol sampling rate of 21 liters per minute, a sample of 1.25 m 3 will be
obtained which can yield the in-stack detection limits (I.tg/m3) shown in Table 1. The
in-stack detection limits are calculated by first multiplying the volume (ml) of the
digestion (from which the aliquot for analysis would be taken) times the analytical
detection limit of measurement of concentration 0ag/ml) of metal in the aliquot, and
then dividing by the volume (m 3) of the stack gas sample. For multiple metals
sampling, a Method 5 type sampling train I-6] which can produce isokinetically the
above described nominal sampling rates and sample volume was modified as shown in
Fig. 1 to have glass components including a glass probe tip, glass probe and glass filter
holder, low metals content quartz fiber filter, Teflon filter support, and glass imping-
ers. The Method 5 train was selected for modification because of its ease of operation,
availability of equipment to all source samplers, and low cost. Acidic absorbing
 T.E. Ward~FuelProcessing Technology 39 (1994) 259-263 261

Table 1
In-stack method detection limits (ktg/m3) for train fractions using ICP and AAS

Metal Front-half Back-half Back-half Total train

fraction 1 fraction 2 fractions,
probe and f i l t e r impingers 1-3 'Hg, only'
impingers 4-6

Antimony 7.7 (0.7)a 3.8 (0.4)a 11.5 (1.1)"

Arsenic 12.7 (0.3) 6.4 (0.1)a 19.1 (0.4)"
Barium 0.5 0.3 0.8
Beryllium 0.07 (0,05)~ 0.04 (0.03)a 0.11 (0.08)a
Cadmium 1.0 (0.02)~ 0.5 (0.01)~ 1.5 (0.03)a
Chromium 1.7 (0.2)a 0.8 (0.1)~ 2.5 (0.3)~
Copper 1.4 0.7 2.1
Lead 10.1 (0.2)~ 5.0 (0.1)~ 15.1 (0.3)a
Manganese 0.5 (0.2)~ 0.2 (0.1)a 0.7 (0.3)~
Mercury 0.6b 3.0b 2.0b 5.6b
Nickel 3.6 1.8 5.4
Phosphorous 18 9 27
Selenium 18 (0.5)~ 9 (0.3)a 27 (0.8)a
Silver 1.7 0.9 2.6
Thallium 9.6 (0.2)a 4.8 (0.1)~ 14.4 (0.3)~
Zinc 0.5 0.3 0.8

Note: Actual in-stack method detection limits will be determined based on actual source sampling
parameters and analytical results as described in this paper.
a Detection limit when analyzed by GFAAS.
b Detection limit when analyzed by CVAAS, estimated for back-half and total train.

solutions for the metals are used in four of the seven impingers in the multiple metals
train. As described in the m e t h o d a n a q u e o u s solution of c o m b i n e d 5 % nitric acid a n d
10% h y d r o g e n peroxide is used in the second a n d third impingers which follow the
e m p t y first impinger, a n d a n a q u e o u s s o l u t i o n of c o m b i n e d 4 % p o t a s s i u m p e r m a n g a -
nate a n d 10% sulfuric acid is used in the fifth a n d sixth impingers which follow the
e m p t y fourth impinger.
The multiple metals m e t h o d o l o g y describes how the sampler m a y design the
sampling, digestion a n d analytigal c o n d i t i o n s to meet the specific needs of the test.
The in-stack detection limits s h o w n in T a b l e 1 are for n o m i n a l s a m p l i n g conditions.
However, the in-stack detection limits p r o d u c e d in the actual test m a y be lowered,
that is, m a d e m o r e sensitive t h a n those s h o w n in T a b l e 1. F o r example, if the actual
sample v o l u m e is 2 . 5 0 m 3 instead of 1.25m 3, the in-stack detection limits will be
o n e - h a l f those s h o w n in T a b l e 1. By using the other design o p t i o n s described in the
m e t h o d o l o g y , the in-stack detection limits could be o n e - t e n t h or lower t h a n those
s h o w n in T a b l e 1.
If desired or required, b l a n k corrections according to the strict guidelines/limita-
tions described in the m e t h o d o l o g y m a y be performed.
 F,J
All glass sample exposed surlace to here.
(Except when Teflon filter support is used.]

Thermometer
Glass
Thermocouple - Fitef Thermocouple
Holder
Glass /
Probe =Z' Glass wobe Implngers with
Tip . - ~ . . - ~ Absorbing Solutions

e~
Healed Area
Pitot Tube
R•everse-Type Ice
2

Emply (Opbonal Moisture Knockout) - - - - I SWc,,a Gel

Empb/
5%HNO 3 /10% H 2 O 2
4% KMnO 4 /10%H 2SO4
Vacuum
Bypass Vacuum Line--
Thermocoupies Valve Gauge

Orifice
I

alve

Fig. 1. Schematic of multiple metals sampling train configuration.

 T.E. Ward/Fuel Processing Technology 39 (1994) 259-263 263

3. Summary

In its c u r r e n t status the m u l t i p l e metals m e t h o d o l o g y allows m e a s u r e m e n t of

c o i n c i d e n t a l stack emissions of u p to sixteen d e s c r i b e d metals in one s a m p l i n g train.
T h e m e t h o d o l o g y describes a p p r o a c h e s for designing the s a m p l i n g c o n d i t i o n s to meet
the needs of the test. P r e p a r a t i o n for s a m p l i n g a n d the acquisition, digestion a n d
analysis of the s a m p l e are described. B l a n k c o r r e c t i o n s a c c o r d i n g to the strict
g u i d e l i n e s / l i m i t a t i o n s m a y be p e r f o r m e d .

4. Disclaimer

T h e i n f o r m a t i o n in this d o c u m e n t has been f u n d e d w h o l l y o r in p a r t by the U n i t e d

States E n v i r o n m e n t a l P r o t e c t i o n Agency. It has been subjected to A g e n c y review a n d
a p p r o v e d for p u b l i c a t i o n . M e n t i o n of t r a d e n a m e s o r c o m m e r c i a l p r o d u c t s does n o t
c o n s t i t u t e e n d o r s e m e n t o r r e c o m m e n d a t i o n for use.

References

[1] Code of Federal Regulations, 1992. Title 40 - Protection of Environment, Part 60, United States
Government Printing Office, Washington, DC., Appendix A, Method 12.
[2] Code of Federal Regulations, 1992. Title 40 - Protection of Environment, Part 61, United States
Government Printing Office, Washington, DC., Appendix B, Method 104.
[3] Code of Federal Regulations, 1992. Title 40 - Protection of Environment, Part 61, United States
Government Printing Office, Washington, DC., Appendix B, Method 101A.
[4] Code of Federal Regulations, 1992. Title 40 - Protection of Environment, Part 61, United States
Government Printing Office, Washington, DC., Appendix B, Method 108.
[5] EMTIC Bulletin Board System, 1993. United States Environmental Protection Agency, Office of Air
Quality Planning and Standards, Technology Transfer Network, Research Triangle Park, NC 27711.
[6] Code of Federal Regulations, 1992. Title 40 - Protection of Environment, Part 60, United States
Government Printing Office, Washington, DC,. Appendix A, Method 5.