SEPTEMBER 1975
COAL FIRED POWER PLANT
TRACE ELEMENT STUDY
STATION I
STATION II
STATION Ili
ENVIRONMENTAL PROTECTION AGENCY jfl \
ROCKY MOUNTAIN PRAIRIE REGION | g
REGION VIII % *
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•fci
z?3>
e&
c, I
COAL FIRED POWER PLANT
TRACE ELEMENT STUDY
VOLUME II
STATION I
SEPTEMBER 1975
U.S. EPA Region 8 Library
80C-L
999 18lh St., Suite 500
Denver, CO 80202-2468
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
REGION VIII
DENVER, COLORADO
BY
RADIAN CORPORATION
AUSTIN, TEXAS
TS-Ib
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FOREWORD
The four volumes comprising this document describe a
coal-fired power plant trace element study prepared under EPA
Contract 68-01-2663.
This work was conducted under the direction of Mr.
Terry L. Thoem, Project Officer, Environmental Protection Agency,
Region VIII, Denver, Colorado. The Radian program staff included
Dr. F. G. Mesich as Program Manager and Dr. K. Schwitzgebel as
Technical Project Director. Principle contributors were Mr.
R. A. Magee, Dr. F. B. Meserole and Mr. R. G. Oldham.
Acknowledgement is given to the station personnel from
each utility company whose full cooperation greatly facilitated
the field work. Mr. R. M. Mann, Mrs. G. E. Wilkin and Mrs.
C. M. Thompson contributed significantly to the program during
sampling and analysis.
i
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VOLUME II
Ti bl-. OF CONTENTS
PaSe
TABLE OF CONVERSION UNITS 1
STATION I SUMMARY 2
1.0 INTRODUCTION 4
2.0 SAMPLING AND SAMPLE HANDLING 6
2.1 Plant Description 6
2.2 Sampling Points and Flow Rate
Determination 6
2.3 Summary of Flow Rates and
Estimated Errors 16
2.4 Sampling Schedule 18
2.5 Sample Analysis 18
3 . 0 DATA E VALU AT ION. . 26
3.1 Trace Element Material Balances 26
3.2 Error Propagation Analysis 29
4.0 RESULTS 30
5.0 DISCUSSION OF RESULTS 44
5.1 Material Balance Closure 44
5.2 Distribution of Elements in the
Exit Streams 45
APPENDIX A - SAMPLING AT STATION I
APPENDIX B - ANALYTICAL PROCEDURES
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TABLE OF CONVERSION UNITS
To Convert From
BTU
BTU/pound
Cubic feet
Cubic yards
Feet
Feet/second
Gallons (U.S. liq.)
Gallons (U.S. liq.)
Gallons/minute
Grains/cubic foot
Inches
Inches of 1^0 (4°C)
Pounds
Pounds/BTU
Pounds/hour
Pounds/s tandard
cubic foot (60°F,
29.92 inches Ilg)
Tons
Yards
To
Calories, kg
Calories, kg/kilogram
Cubic meters
Cubic meters
Meters
Meters/second
Cubic meters
Liters
Cubic meters/minute
Grams/cubic meter
Centimeters
Millimeters Hg (0°C)
Kilograms
Kilogram/Calorie, kg
Kilo gr ams/hour
Kilograms/standard
cubic meter (0 C,
760 mm Hg)
Metric tons
Meters
Multiply By
0.25198
0.55552
0.028317
0.76455
0.30480
0.30480
0.0037854
3.7854
0.0037854
2.2884
2.5400
1.8683
0.45359
1.8001
0.45359
15.155
0.90719
0.9144
-1-
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STATION I SUMMARY
Station I is an example of a sub-bituminous coal-fired
boiler using venturi wet scrubbers for particulate control. The
sampling and characterization of trace elements in Station I
streams resulted in closure of material balances for some 24
of the 27 elements examined in detail. Additional information
of a semi-quantitative nature was obtained for a total of 53
elements using spark source mass spectrometry.
The distribution of the trace elements among the
station exit streams as a function of coal composition and station
operating configuration is essential information for the eventual
development of predictive techniques. For Station I the following
elements were found to be concentrated in the flue gas stream
and depleted in the bottom ash stream.
Sulfur
Boron
Mercury
Zinc
Chlorine
Cadmium
Antimony
Chromium
Fluorine
Copper
Selenium
Cobalt
Lead
Arsenic
Molybdenum
Silver
Nickel
Vanadium
The following elements are distributed in proportion
to the total ash flows with no concentration or depletion evi-
dent.
Barium Iron
Beryllium Magnesium
Aluminum Manganese
Calcium Titanium
-2-
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The results for uranium were somewhat anomalous as it was
concentrated in the bottom ash and depleted in the precipitator
ash.
A detailed comparison of this station with generating
stations using hot-side electrostatic precipitators and mechanical
particulate collection is given in Volume I of this series.
-3-
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1.0 INTRODUCTION
The use of the extensive coal resources in the Northern
Great Plains area of the United States may provide a significant
part of the country's energy growth for the foreseeable future.
As natural gas and oil resources become less available and more
costly, coal will receive increasing emphasis as a primary energy
source. A coal-fired generating station produces a variety of
emissions and effluents ranging from sulfur and nitrogen oxides
and particulates in the flue gas to solid and liquid wastes.
In addition to carbonaceous material, coal contains
inorganic matter which becomes part of the emissions and efflu-
ents from the generating station. The overall objective of this
program was to define the sources, levels, and disposition of
potentially toxic trace and minor elements in power plant streams.
The levels of trace elements in various streams may be expected
to be a function of both coal composition and plant operating
configuration.
This volume describes the detailed characterization
with respect to trace and minor elements of a tangentially-fired,
balanced draft boiler fired with Wyoming sub-bituminous coal
and using venturi wet scrubbers for particulate collection.
This unit is one of four located at the power plant designated
as Station I. The station has a total generating capacity of
750 MW of which the unit tested .contributes 330 MW.
The following trace and minor elements were examined
in detail:
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Aluminum
Calcium
Lead
Silver
Antimony
Chlorine
Manganese
Sulfur
Arsenic
Chromium
Magnesium
Titanium
Barium
Cobalt
Mercury
Uranium
Beryllium
Copper
Molybdenum
Vanadium
Boron
Fluorine
Nickel
Zinc
Cadmium
Iron
Selenium
A material balance was calculated for each element to
provide a sound basis for evaluating the reliability of the
emissions measurements. In addition, each sample was surveyed
using spark source mass spectrometry to provide a semi-
quantitative assessment of additional trace elements.^ V-O
The following sections give a description of the plant,
a discussion of the sampling, analytical strategies, and pre-
sentation and discussion of the experimental data. Appendices
are provided which describe the sampling of the plant and the
analytical methodology.
-5-
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2.0
SAMPLING hND SAMPLE HANDLING
The procedures used to sample Station I are described
briefly in this section. Details are given in Appendix A
"Sampling at Station I". Sampling was performed during the
period 2-5 September 1974.
2.1 Plant Description
Unit No. 4 at Station I is a 330 MW, tangentially-
fired, balanced draft boiler with three venturi scrubbers for
particulate collection. The boiler is fired with Wyoming sub-
bituminous coal mined near the station, transported by rail,
crushed and fed to storage silos. Bottom ash is sluiced
to a nearby settling pond. The scrubber slurry discharge
is pumped to the same settling pond, which is the first
in a series of three ponds. Ash sluice water and scrubber
make-up are recycled to the plant from the last pond. The
station is a base load unit. Boiler load ranged from
285-298 MW during the entire sampling period.
2.2 Sampling Points and Flow Rate Determination
The streams sampled are shown schematically in Figure
2-1. The incoming streams are coal, ocutom ash sluice water,
cooling tower blowdown, scrubber make-up water, and lime. Out-
going streams are bottom ash, bottom ash sluice water, economizer
ash, scrubber solids, scrubber liquid, and flue gas containing
fly ash. The physical location of the points for sampling these
streams at the station are schematically shown in Figure 2-2.
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INGOING STREAMS
OUTGOING STREAMS
Coa 1
Bottom Ash Sluice.
Water
Cooling; Tower
Blowdown
Scrubber Make-up
Water
Lime
BOILER NO. 4
SCRUBBER
SYSTEM
Bottom Ash Solids
>- ©
Bottom Ash Sluice
Economizer Ash
Scrubber Solids w
to Fond ^
Scrubber Liquid ^
to Pond
Fly Ash and Flue Gas
Through Stack
•0
FIGURE 2-1
IN AND OUTGOING STREAMS AT THE
BOILER NO. 4 AND SCRUBBER SYSTEM AT STATION I
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Sample Point 1 Coal
Coal samples were collected from pneumatic transfer
lines transporting coal from four of the seven mills to the
boiler. A cyclone sampler was used to collect a sample from
one line every 15 minutes. The individual samples were stored
in closed plastic containers and divided using riffle buckets
into two samples for analysis at the end of the sampling period.
The flow rate of coal to each of the mills was recorded
hourly in the control room. The average total coa-l feed to the
mills was corrected for moisture content to yield a dry coal
feed rate. This rate compared with the coal-burn requirement
calculated from unit load, unit heat rate and coal heat value
within 170.
Sample Point 2: Bottom Ash Sluice Water Inlet
Bottom ash was sluiced continuously with water from
the last settling pond in a series of two ponds. A sample
from the point of intake was collected, acidified to prevent
wall adsorption of trace constituents and stored in a polypro-
pylene bottle for analysis. This sample is referred to as clear
pond return.
The flow rate of bottom ash sluice water was determined
from the power requirements of the centrifugal pump used to
transport the water from the settling pond. The power was cal-
culated from periodic readings of an ammeter and read directly
from a wattmeter. The average of the two determinations of power
were converted to flow rate from the pump curves provided by the
manufacturer.
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Sample Point 3: Cooling Tower Blowdown
A portion of the cooling tower blowdown is used as
pump seal water, demister wash in the scrubbers and for induced
draft-fan sprays. A sample was collected at the bottom of the
cooling tower, acidified to prevent wall adsorption of trace
constituents and stored in a polypropylene bottle for analysis.
The flow rate of cooling tower blowdown to the scrubbers
was determined from the total dynamic head developed across the
two pumps transporting the water stream. The pump heads were
recorded hourly and converted to flow rates with pump curves
provided by the manufacturer.
Sample Point 4: Scrubber Make-Up Water
The scrubber make-up water is identical to the bottom
ash sluice water inlet since both come from the same settling
pond intake. One sample was therefore collected and analyzed
for both streams. This sample is referred to as clear pond
return.
The flow rate of make-up water to each of the three
scrubbers was monitored by flowmeters. Hourly readings were
taken and the total averaged over the sampling period.
Sample Point 5: Lime
Samples of lime were collected hourly between the lime
storage silo and the scrubber slurry make-up tanks. The indi-
vidual samples were combined in a polypropylene container for a
composite sample for analysis.
The lime feed rate to the scrubber system was calculated
from a calcium material balance around the system
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Sample Point 6: Bottom Ash Solids
Samples of the bottom ash sluice stream were collected
every 15 minutes at the point of discharge into the settling
pond. The individual samples were combined in a plastic con-
tainer, and the solids and liquid later separated by filtration.
The bottom ash production rate could not be directly
measured due to the random variations in size distribution of
the ash particulates and solids content of the stream which
prevented the accurate determination of the solids content of
the sluice stream. The bottom ash rate was calculated from a
total ash balance. The total ash production was determined
from the coal feed rate and ash content. The ash content of
the scrubber solids was determined from the titanium analyses
of the scrubber solids, economizer ash, and lime. See Appendix
A for a detailed description of this calculation. The bottom
ash is then the difference between the total coal ash and the
sum of the ash in the scrubber solids, economizer ash, and fly
ash leaving in the flue gas.
Sample Point 7: Bottom Ash Sluice Water Outlet
A portion of the filtrate collected during the separa-
tion of solids and liquids in the bottom ash sluice stream
described above was acidified to prevent wall adsorption of
trace components and stored in polyethylene containers for
analysis.
The bottom ash sluice water outlet flow is equal to
the inlet flow described above as Sample Point 2.
Sample Point 8: Scrubber Solids
Samples were collected at 30-minute intervals from the
exit stream of the scrubber slurry discharge line to the first
-11-
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settling pond. The solids were separated by filtration and the
individual samples combined to form a composite sample for
analysis.
The discharge rate of solids from the scrubber system
was determined from the average solids content of the discharge
stream and the discharge rate of liquid from the scrubber system.
Sample Point 9: Scrubber Liquid
Following the collection of the scrubber slurry sample
the solids were allowed to settle, A portion of the supernatant
liquid was decanted, filtered to remove fine particulates,
acidified to prevent wall adsorption, and stored in a polypropy-
lene container for analysis.
The flow rate of liquid from the scrubber system was
calculated from a total water balance around the scrubber system.
The inlet water to the system consists of the scrubber make-up
water, cooling tower blowdown, and water from the moisture conr-
tent and combustion of coal. The outlet water streams include
the moisture in the exiting flue gas and the water discharged a«
part of the scrubber slurry discharge. The scrubber liquid
discharge rate is then the difference between the sum of the
inlet streams and the moisture in the exiting flue gas.
Sample Point 10: Economizer Ash
The accumulation of ash in the economizer hopper during
the sampling period was collected in two large plastic containers.
Random cores of ash from the two containers were combined and
divided using riffle buckets to provide a composite sample for
analysis.
-12-
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The accumulation rate of economizer ash was determined
from the volumetric measurement of the accumulation during the
sampling period and the packing density of the ash.
Sample Point 11: Flue Gas and Fly Ash
Samples of the flue gas and particulate matter exiting
the stack were collected using a wet electrostatic precipitator
(WEP) as a particulate collection device. This sampling device
is described in detail in Appendix A. This method of collection
permits sampling over extended periods at isokinetic conditions
without plugging as occurs in a filter. Thus, a sufficient
quantity of fly ash can be recovered to permit repeated analyses
and problems of trace element contamination by a filter substrate
are avoided. To confirm the comparability of this sampling
approach with the filter technique recommended by EPA, an EPA
filter was run in series with the TOP at Station III. A 125 mm
class "A" Gelman glass fiber filter was used in a glass filter
holder immediately after the WEP in the sampling train. The
filter holder was heated to avoid condensation on the filter.
The particulate matter collected by the filter during four WEP
runs was equivalent to a grain loading of 0.0009 grains/scf.
The inlet particulate loading to the WEP was 0.21 grains/scf,
giving a collection efficiency of the WEP of 99+%.
Samples of the mercury vapor in the flue gas were
collected by a gold amalgamation technique. The sulfur in the
gas stream was collected as per EPA Method 6 by absorption in a
hydrogen peroxide solution in a glass frit bubbler and determined
as the sulfate. Orsat analysis of the flue gas for oxygen and
carbon dioxide was performed to determine gas density as per EPA
Method 3. Flue gas moisture content was determined using an
efficient copper-tubing condenser immersed in an ice bath.
-13-
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The veolocity profile in the stack was determined using
an S-type pitot per EPA Method 2. Traverses were made over 20
points on each of two perpendicular diameters of the stack per
EPA Method 1.
The average particulate loading was obtained from
cumulative sampling with "in-stackM Gelman filter devices over
the same set of sampling points. Four cumulative samples were
required to cover the 40 points and the results of the four were
averaged.
The WEP samples were collected at a single point in
the stack and a correction made from this point to the average
grain loading. The dust concentration at the sampling point was
determined from the titanium concentration in the WEP sample
assuming that titanium is evenly distributed in the particulates
with respect to particle size. This assumption is based on work
performed by Davison, et al. (DA-105) in which fly ash samples
were collected from the duct of a coal-fired station. Andersen
impactor samplers were used to separate the particulates into
seven size fractions. The results of this work for titanium are
presented in Table 2-1. It is evident from these data that the
assumption of uniform as composition with respect to titanium
holds within experimental limits.
The relationship between particle size and titanium
concentration in the fly ash is important to this correction
because the economizer ash has a larger average particle size
than the exiting fly ash. If the titanium concentration were
dependent on particle size, then the assumption made in Equation
(2-1) that the titanium concentration in the fly ash is the same
as in the economizer ash is invalid.
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TABLE 2-1
TITANIUM ANALYSES* OF ANDERSEN IMPACTOR
PARTICLE SIZE FRACTIONS (DA-105)
Particle Diameter
um wt7o Ti
>11.3 1.12
7.3 - 11.3
4.7 - 7.3 0.92
3.3 - 4.7
2.06 - 3.3 1.59
1.06 - 2.06
0.65 - 1.06 1.08
* Analysis by X-ray fluorescence spectrometry
-15-
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The point grain loadings were determined from the
titanium concentration in the WEP samples and the titanium weight
fraction in the economizer ash using the relation:
rcmt -ram - ^ W""
wC(P/sSf) ""V- »WTi>
where,
= volume of the WEP liquor (ml)
VG = volume of flue gas sampled by WEP (scf)
XW^(Ti) = concentration of Ti in the WEP liquor (ug/ml)
^Ash^^ = we^Sht fraction of Ti in the economizer ash (ppm)
The point to average grain loading correction factor
is then the ratio of the average grain loading to the point grain
load calculated from Equation (2-1). The correction factor was
1.4.
2. 3 Summary of Flow Rates and Estimated Errors
A summary of the flow rates is given in Table 2-2. The
error limits presented in this table are largely based on Radian
field experience. The error limits presented for those flows
calculated from material balances were calculated by propagation
of analytical and flow rate error limits through the balance
calculation. Also summarized in this table are the procedures
used to obtain the listed rates.
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TABLE 2-2
FLOW RATES FOR STREAMS
AROUND STATION I
Stream
Coal
Flow Rate
2.83 x 105 lb/hr.
Error Limit
±10%
Method Used For
Flow Determination
Control room print-out
and heat balance
1.29 x 106 lb/hr,
Bottom Ash
Sluice Water
Inlet
Cooling Tower
Blowdown
Scrubber Make-up 4.00 x 106 lb/hr.
Water
4.39 x 10s lb/hr.
Lime
Bottom Ash
Bottom Ash
Sluice Water
Outlet
4.78 x 103 lb/hr.
1.15 x 10" lb/hr.
1.29 x 106 lb/hr.
Scrubber Solids 5.00 x 10^ lb/hr,
Scrubber Liquid 4.18 x 106 lb/hr.
Economizer Ash
Flue Gas
Fly Ash
2.63 lb/hr.
5.01 x 107 scfh
1.65 x 102 lb/hr.
±15%
±15%
± 10%
±15%
±40%
±15%
±20%
±10%
±10%
±10%
±10%
Pump power consumption
and pump curves
Pump heads and pump
curves
Flowmeters
Calculated from calcium
material balance
Calculated from total
ash balance
Rate was set equal to
inlet sluice water
Calculated from slurry
solids content and flow
rate of scrubber liquid
Calculated from total
water balance around
scrubbers
Measured directly by
volume and known density
Measured by stack traverses
Determined from cumulative
grain loadings
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2.4
Sampling Schedule
All of the streams around Unit No. 4 at Station I with
the exception of the economizer ash were continuous with short
residence times. The total accumulation of economizer ash during
the sampling period was collected to provide a representative
sample. Time phasing of sampling was therefore not necessary.
The samples and measurements described briefly in the
preceding sections were taken during the period September 2nd,
3rd, and 4th according to the schedule shown in Figure 2-3.
Those samples enclosed in parenthesis were analyzed, the rest
were retained in reserve.
2•5 Sample Analysis
The techniques used for the quantitative determination
of the elements of interest were based on:
(1) atomic absorption
(2) X-ray fluorescence
(3) ion selective electrodes
(4) fluorometry, and
(5) colorimetry
The methods are described in greater detail in Appendix B
"Analytical Procedures".
Figures 2-4 through 2-7 summarize the dissolution and
analytical methods used for trace element determination in coal
samples, ash/sludge samples, lime/limestone samples, and WEP
and aqueous samples.
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1
2
3
4
5
6
7
8
9
10
11
12
13
Coal
Bottom Ash Sluice Water
Inlet
Cooling Tower Blowdown
Scrubber Makeup Water
Lime
Bottom Ash
Bottom Ash Sluice Water
.Outlet
Scrubber Solids
Scrubber Liquid
Economizer Ash
Flue Gas Velocity
Flue Gas Particulate
Loading
Flue Gas WEP
Particulate Collection
continuous sampling
point sampling
( —
(•)
(• •)
(•)
(•
(
(
* • • • » «
( • • « *
(•
)
| Sept. 2 | Sept. 3 | Sept. 4
FIGURE 2-3
Sampling Schedule at Station I
-19-
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CI, F
HNOj-HClO^ Digestion
Fluorescence
Se
Oxygen Bomb Digestion
Titrimetry
- S
Flameless
Atomic Absorption
Hg
Primary Digestion
(Thermal Oxidation,
JHF-HNO3-H2SO4 Digestion)!
Spectrophotometry
Ti, B
Ai. $ 1 f &
Atomic Absorption Ca|
Mn, Cu, Zrv
Extraction/Atomic Absorption C0j Be, Pb
Mo, Cd, Sb,'
Ni
FIGURE 2-1
ANALYSIS PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL
-20-
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HN03-H2S04-HC104
Atomic Absorption
Reflux Digestion
HNO3 Digestion
Atomic Absorption
Li-C0_-Na„B.0_ Fusion
2 J 2 4 7
X-Rav Fluorescence
Ba
^2^2 Fusion
Ion Selective Electrode
CI, F
NaF Fusion
Fluorescence
Ash/
Sludge
HN03 - HC104 Digestion
Fluorescence
¦U
Se
SCI Digestion
Titrimetry
Flameless
Gold Amalgamation
Atomic Absorption
•Hg
Primary Digestion
(Thermal Oxidation,
HF-HN03-H2S04 Digestion)
Spectrophotometry
Atomic Absorption
Extraction/Atomic Absorption
Ti, B
Al, Mg, Fe,
Ca, V, As,
Mn, Cu, Zn
Co, Be, Pb,
Mo, Cd, Sb
Ni
FIGURE 2-2
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL ASH AND SLUDGE
-21-
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Ion
Splectivr F1 orfrode-
WEP
or
Aqueous
Samples
Primary
Digestion
(Filtration
Thermal
Oxidation,
HF-HNO3-
h2S04
Digestion)
Li«CO<,
X-Ray
2 ¦>
viunrescence
Na2B4°7
Fusion
Atomic Absorption
Extraction/
Afomic Absorption,
Ba
Ti, B
Al, Mg, Fe,
Ca, V, As,
"Mn, Cu, Zn
Ag, Cr
Selective Electrode
Co, Be, Pb,
Mo, Cd, Sb,
Ni
•CI
FIGURE 2-4
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF WET ELECTROSTATIC PRECIPITATOR LIQUORS AND AQUEOUS SAMPLES
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Mo, Cd, Sb,
Ni
FIGURE 2-3
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF LIME
-23-
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The accuracies of Che analytical techniques are sum-
marized in Table 2-3. These values were derived by comparing
analytical results with NBS standards where availa
other cases, recovery studies and/or precision values are the
basis for the estimated confidence level.
Semiquantitative analyses based on spark source mass
spectrometry for 53 elements were performed by Accu
+-his method is strongly
Denver, Colorado. Since the accuracy of
i,-™-?*- onuld not be estimated
dependent on the matrix, an error limit
in the framework of the present study-
-24-
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TABLE 2-3
ERROR LIMITS FOR THE CHEMICAL ANALYSES
WEP
Aqueous
Coal and
Scrubber
Liquor
Samples
Coal Ash
Lime
Sludge
Aluminum
±10%
±10%
± 8%
± 8%
± 8%
Antimony
±10%
±10%
±15%
±12%
±12%
Arsenic*
± 8%
± 8%
±10%
±10%
±10%
Barium
±20%
±20%
±20%
±20%
±20%
Beryllium
±10%
±10%
±12%
±12%
±12%
Boron
± 8%
±8%
± 8%
± 8%
± 8%
Cadmium*
±12%
±12%
±12%
±12%
±12%
Calcium
± 2%
±2%
± 2%
± 2%
± 2%
Chlorine
±10%
±10%
± 8%
±10%
±10%
Chromium *
±10%
±10%
±12%
±12%
±12%
Cobalt
±10%
±12%
±10%
±12%
±12%
Copper*
±10%
±10 %
±12%
±12%
±12%
Fluorine
± 8%
±8%
± 8%
± 8%
± 8%
Iron *
± 6%
±6%
± 6%
± 6%
± 6%
Lead *
±10%
±10%
±18%
±18%
±18%
Manganese *
±10%
±10 %
± 8%
±10%
±10%
Magnesium
± 2%
± 2 %
± 2%
± 2%
± 2%
Mercury *
±20%
±10 %
±10%
±10%
±10%
Molybdenum
±12%
±12 %
±15%
±15%
±15%
Nickel *
±12%
±12 %
±12%
±18%
±18%
Selenium *
± 5%
± 5 %
± 5%
±7%
± 7%
Titanium
± 8%
± 8 %
± 8%
±8%
± 8%
Silver
±10%
±10 %
±10%
±10%
±10%
Sulfur
±10%
± 2 %
± 2%
± 2%
± 2%
Uranium*
± 8%
± 8 %
± 6%
± 6%
± 6%
Vanadium *
±12%
±12 %
±10%
±10%
±10%
Zinc*
±10%
±10 %
±12%
±12%
±12%
By comparison with NBS Standard Reference Materials 1633 and 1634.
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3.0 DATA EVALUATION
The flow rates and chemical analyses are used to
calculate the transport rate of the elements of interest through
the boiler and their discharge rates in the effluent streams.
A material balance is made around the boiler for each of the
elements to substantiate the individual measurements. The
mathematical correlation forms are given in the next sections.
3.1 Trace Element Material Balances
The transport rates of the elements of interest
through the steam station are calculated from the chemical
analyses of the samples and the flow rates of the incoming and
exiting streams. A material balance is calculated for each of
the trace elements to verify the determined emission values.
Equating the trace element flow into the system to
the flow out of the system gives the following expression:
VcO) + MSWiX¥wi<« + Mctb»ctbO> +
+ M^O) - (3-1)
"ba^ba^ + "swoXwswo + +
+ +
where,
-26-
-------
M = the mass flow rate of coal into the boiler on
a dry weight basis (lb/hr)
XWc(j) = the weight fraction of the element j in the coal
on a dry weight basis
Mgwi = the mass flow rate of bottom ash sluice water
into the ash sluice system (lb/hr)
XWswi(j) = the weight fraction of the element j in the
inlet bottom ash sluice water which is the same
as clear pond return
Mctk = the mass flow rate of cooling tower blowdown
to the scrubber system (lb/hr)
XWctbO) = the weight fraction of the element j in the
cooling tower blowdown
= the mass flow rate of the make-up water from
the settling pond to the scrubber system (lb/hr)
W„(J) 83 the weight fraction of the element j in the
make-up water to the scrubber system which is
the same as clear pond return
= the mass flow rate of lime into the scrubber
system (lb/hr)
XW^(j) = the weight fraction of the element j in the
lime
M^a - the discharge rate of bottom ash from the
boiler (lb/hr)
-27-
-------
^ba^ = t^le weight fraction of the element j in the
bottom ash
^swo = t*ie mass flow rate of the bottom ash sluice
water from the sluice system which is equal to
Mswi (lb/hr)
™swo(j) = the weight fraction of the element j in the
outlet bottom ash sluice water
^ss = discharge rate of solids from the scrubber
system (lb/hr)
XWss(j) = the weight fraction of the element j in the
scrubber discharge solids
= the discharge rate of liquid from the scrubber
system (lb/hr)
XWsiU) - the weight fraction of the element j in the
scrubber discharge liquid
= the discharge rate of economizer ash (lb/hr)
^ea^) * the weight fraction of the element j in the
economizer ash
Vfg = the volumetric flow rate of the flue gas in
the stack (scfh)
xvfg(j) = the weight of element j per unit volume of flue
gas (lb/scf)
-28-
-------
3.2 Error Propagation Analysis
An error propagation analysis was performed on the
material balance equations for each element. Error limits are
calculated for the total inlet and outlet rates of each element
indicating the magnitude of variation to be expected due simply
to random measuring errors.
Only errors random in nature are considered in this
treatment. A variance is calculated for a given value according
to the following standard definition.
32(Q) - qf§-'2 S2(q.) (3-2)
i\3qi/ 1
where,
S(Q) = the variance in Q
Q = the material balance value which is a
function of the q^s
^ ~ the i~ independent flow rate or composition
used to calculate Q.
Confidence intervals can then be assigned to the trace element
flow rates calculated for the various streams based on the
errors associated with each measurement used in the calculation
of these quantities. These limits will be included with the
calculated rates discussed in the following section. The error
limits for the flow rates were given in Table 2-2 and those
assigned to the chemical analyses are ""isted in Table 2-3 and
are in both cases as 2S.
-29-
-------
4.0 RESULTS
The values for the proximate and ultimate analysis of
the coal are presented in Table 4-1, the coal ash analysis in
Table 4-2.
The quantitative analysis results are listed m
Table 4-3. The element concentrations in the coal and the flow
rates are reported on a dry weight basis. Host of the values
in Table 4-3 are presented in parts per million on a dry weight
basis for the solid samples or micrograms per milliliter for
liquids. Some elements present in higher concentrations are
listed as percent. The WEP results are presented in pounds per
standard cubic foot of dry flue gas, where standard conditions
are a temperature of 60°F and pressure of 29.92 inches of
mercury.
Table 4-4 presents the analytical results obtained by
SSMS. The economizer ash sample was analyzed in duplicate to
estimate the precision of this method of analysis. Blind dupli-
cates were also submitted for the WEP sample. The differences
between duplicates were large for some of the elements as
evidence by a factor of 6 for Ge, 5 for Nd, 5 for Sn, and 270
for Zn. However, these data (SSMS) are useful for order-of-
magnitude estimates of trace element flows.
The trace element flow rates in lb/hr are listed in
Table 4-5, using the quantitative analysis methods and in Table
4-6, using the SSMS results. The sum of the elemental flow rates
of all incoming streams, coal and ash sluice water, are given
-30-
-------
TABLE 4-1
STATION I
COAL ANALYSIS
Proximate
As Received
Dry
% Moisture
26.95
0.00
7o Ash
15.06
20.62
% Volatile Matter
31.13
42.61
% Fixed Carbon
26 R6
36.77
Total
100.00
100.00
70 Sulfur
0. 52
0.72
BTU/lb
6948
9511
Moisture and Ash
Free BTU/lb
11,982
Ultimate
% Carbon
42.00
57.48
7» Hydrogen
6.87
4.49
7o Nitrogen
0.47
0.65
% Oxygen
35.08
16.04
7o Sulfur
0.52
0.72
70 Ash
15.06
20.62
Total
100.00
100.00
-31-
-------
TABLE 4-
¦2
STATION I ASH
ANALYSIS
Mineral Analysis of Ash
Percent
Silicon Dioxide, Si02
50.10
Aluminum Oxide, A1203
20.29
Titanium Dioxide, Ti02
0.77
Iron Oxide, Fe203
3.69
Sodium Oxide, Na20
0.15
Potassium Oxide, K20
1.31
Calcium Oxide, CaO
12.98
Magnesium Oxide, MgO
2.11
Phosphorus Pentoxide, P20s
0.23
Sulfur Trioxide, S03.
5.23
Other
3.14
Total
100.00
Ash Viscosity Calculations
Basic Content (percent)
22.14
Acidic Content (percent)
77.86
Base-to-Acid Ratio
0. 28
Silica-to-Alumina Ratio
2.47
Temperature for 250 Poise Viscosity, °F
2580
-32-
-------
TABLE 4-3
ANALYTICAL RESULT'' THE STATION I SAMPLES1
Element
Coal
Clear
Pond
Cooling
Tower
Lime
Bottom
Ash
Ash
Sluice
Water
Scrubber
Slurry
Solids
Scrubber
Slurry
r.< nii-t
Economizer
Ash
Combined
WEP
Aluminum
2.37.
5.0
2.2
.30%
10.3%
2.4
10.8%
4.8
10.0%
20.
Antimony
.53
;024
.024
<.6
•39
.041 .
2.3
.036
2.1
<.002
Arsenic
.83
.0045
.003
<.06
1.3
.0041
5.2
.0013
3.3
.026
Barium
130.
<•5
<.5
<40.
670.
<.5
840.
<.5
800.
<.5
Berylliuu
.82
.0013
.0036
1.2
2.5
.0013
3.2
.0015
3.2
.0014
Boron
51.
3.2
.27
6.8
160.
2.5
220.
2.8
260.
.81
Cadmitro
.18
.0054
.001
.46
1.0
.0038
1.8
.0068
7.3
.0095
Calcium
1.761
790.
140.
53.5%
8.66%
790.
11.8%
910.
11.5%
68.
Chlorine
44.
28.
25.
125.
140.
28.
89.
28.
200.
22.
Chromium
21.
.074
< .056
12.
67.
.12
118.
.14
,114
.92
Cobalt
2.1
. 01)81
.026
1.4
7.0
.005
8.1
.011
15.
.016
Copper
34.
.036
.24
17.
93.
.024
155.
.049
105.
.07
Fluorine
1140.
1 20.
.91
520.
100.
16.
820.
20.
120.
1.2 2
Iron
. 407.
.31
1.2
,127.
2.517.
.30
2.257.
.74
2.15%
10.
Lead
! 4.2
.008
.016
11.
7.1
.007
49.
.023
15.
.061
Manganese
170.
.86
.10
77.
690.
.79
.10%
.88
.10%
.27
Magnesium
.29%
68.
37.
. 46%
1.20%
68.
1.36%
62.
1.47%
11.
Mercury
.13
<•0005
<. 0004
¦ 057
.014
<.0005
.053
.0007
<.010
.004
Molybdenum
4.0
.035
.05
4.5
3.7
.056
10.
.015
34.
.43
Nickel
9.0
.025
.005
3.3
39.
.015
38.
.015
47.
.12
Selenium
2.2
.048
.0037
.27
.70
.031
8.7
.12
.46
.020
Titanium
.117.
<•1
<.1
1 87.
.45%
<.1
.40%
<.1
.48%
.96
Stiver
.045
.0003
.0003
< :013
.11
0004
.23
.0005
.093
. 0008
Sulfur
.727.
785.
.271
29.
.11
770,
1.44%
865.
.30
2 370
Uranium
1.3
.010
.015
7.8
13.
.0058
3.6
.0087
7.6
.0069
Vanadium
51. .
.16
.14
31.
230.
.19
268.
.23
275.
.50
*¦ "
.10
.40
6.3
41.
.076
190.
.089
57.
.30
Values represent Che a..rage of duplicate determinations. Values for liquid samples are reported
as ug/ml and solids samples as ppm on a dry basis, unless otherwise sioted. WEP analysis in 10
lb/scf <60°F. 29.92" Hg).
^Analysis from reserve WEP (529).
-33-
-------
TABLE 4-4 STATION I. ANALYTICAL RESULTS BY SS-MS*
Element
Coal
Cl^ar
Pond
Return
Cooling
Tower
Blowdown
Lime
Bottom
Ash
Bottom
Ash Sluice
Water
Scrubber
Slurry
Solids
Scrubber
Slurry
Liquid
Economizer
Ash 1
Flue Gas
WEP 1
Aluminum
:8600
2.1
.44
77
> 1%
13
>17.
4.1
>.57.
>U
11
2.8
Antimony
.43
.011
--
< . 06
.49
.021
.82
.016
1.2
.53
.012
.0016
Arsenic
1.3
< .005
< .001
< .71
5.4
< .003
17
.002
10
6
.0098
.0098
Barium
130
.15
.067
6.9
320
.34
110
.22
100
130
.16
. 15
Beryllium
1.9
--
--
.28
11
--
7.5
—
5.6
5.6
<.0016
<.0016
Bismuth
< : 70
--
--
< .10
.21
--
.46
—
.35
.74
.0016
<.0016
Boron
110
< .Is
.2"
1.4
800
< .1"
530
< ; 1*
500
500
<.16"
¦c. le**
Bromine
1.7
.026
--
.22
1.5
. 035
. 98
.018
1.6
1.6
<.0016
<.0016
Cadmium
.62
.048
.13
.18
.67
.15
.89
.048
3.3
1.4
.31
.033
Calcium
>1%
740
. no
>12
>1%
720
>17.
840
>17.
>1%
66
68
Cerium
56
.006
—
10
200
.003
100
.004'
100
35
.026
.026
Cesium
.66
.002
.005
¦01
4.3
. 005
2.8
.001
2.1
2.1
.012
.053
Chlorine
100
.018'
. 003®
13
26
. 28J
17
.093'
9.8
5.6
.016'
.0032'
Chromium
29
.004
.002
.57
110
.002
180
.004
160
57
1.2
.51
Cobalt
5.9
.023
.041
.37
26
.010
17
.014
20
13
.051
.046
Copper
25
.052
.13
1.2
120
.14
340
.18
120
60
.15
.068
Dysprosium
1.6
--
—
.21
4.2
--
2.8
—
4.2
2.1-
<.0016
<.0016
NOTES: 'Concentration in ppm by weight in solids and yg/ml in liquids. UEP analysis in 10"' lb/scf (60°F, 29.92" He).
Blind duplicate analysis.
'Possibly inaccurate due to loss from acidic solution.
¦"Approximate value only due to interference from preservative.
'Insufficient sample for determination.
--All elements not reported <0.1 ppm weight in solids or <0.001 wg/ml in liquids.
Maj. - Major component.
-------
TABLE 4-4 STATION I. ANALYTICAL RESULTS BY SS-MS' (Cont'd)
Element
Coal
Clear
Pond
Return
Cooling
Tower
Blowdown
Lime
Bottom
Ash
Bottom
Ash Sluice
Water
Scrubber
Slurry
Solids
Scrubber
Slurry
Liquid
Economizer
Ash1
Flue
WE
Gas
P »
Erbium
.51
„
.07
.48
„ _
.48
_ _
.51
.51
<.0016
<.0016
Europium
.83
—
—
.07
1
--
.69
—
1.2
1.2
<.0016
<.0016
Fluorine
330
2.2'
3
450
91
3
300
. 813
80
120
.0065'
Gadolinium
.13
--
.003
.08
.69
--
1. 1
--
.34
.90
<.0016
.0032
Gallium
3.7
.014
.003
.67
27
.006
48
.045
13
13
.15
.069
Germanium
.57
.033
.001
.04
2.8
.069
4
.049
1.4
3
.018
.0032
Gold
--
--
--
--
--
--
--
--
—
--
<.0016
<.0016
Hafnium
.31
--
--
.67
5.7
--
1.8
--
2.9
2
<.0016
<.0016
Holmium
.15
--
--
.02
.31
--
.20
--
.27
.37
<.0016
<.0016
Iodine
1.2
--
—
.18.
.60
.004
. 20
.001
.15
.18
<.0016
<.0016
Iridium
--
--
• --
--
--
--
--
--
--
—
<.0016
<.0016
Iron
>.51
.46
1.1
•v-5700
>1%
1.2
>1%
.92
>1%
>1Z
14
13
Lanthanum
9
.003
--
.87
31
.010
20
.003
24
15
.025
.023
Lead
2.9
.004
.005
< .10
8
.013
27
.003
8.5
8.6
.031
.028
Lithium
67
.029
.001
7.5
860
.13
2
.044
430
430
.013
<.0016
Lutetium
.08
--
--
.04
. 15
--
. 10
--
.11
.15
<.0016
<.0016
Magnesium
m
70
35
-*.5000
>17.
69
>i'/.
65
>17.
>17.
14
15
Manganese
80
.52
.037
170
-v.3300
.40
¦V2200
1
•x-3300
•*.3300
.36
.33
Mercury
. 12'
5
s
--
--
9
--
5
.03'
—
<.0016
t
Molybdenum
14
.066
.012
8.7
35
. 14
23
10
17
17
.069
. 16
NOTES: 'Concentration in ppm by weight in solids and tig/ml in liquids. WliP unalysls in 10 ' lb/scf (60 F, 29.92" Hg) .
'Blind duplicate analysis.
'Possibly inaccurate due to loss from acidic solution.
11 Approximate value only due to interference from preservative.
'Insufficient sample for determination.
--All elements not reported <0.1 ppm weight in solids or <0.001 Mg/ml in liquids.
Maj. - Major component.
-------
TABLE 4-4 STATION I. ANALYTICAL RESULTS BY SS-MS1 (Cont'd)
Element
Coal
Clear
Pond
Return
Cooling
Tower
Blowdown
Lime
Bottom
Ash
Bottom
Ash Sluice
Water
Scrubber
Slurry
Solids
Scrubber
Slurry
Liquid
Economizer
Ash 2
Flue
K
Gas
EP »
Neodymium
75
.005
1.3
130
.011
84
.003
63
63
.053
.0098
Nickel
13
.46
.077
1.4
28
.077
19
.69
10
11
.69
.86
Niobium
5.4
--
--
.39
18
--
24
--
18
18
.016
.036
Osmium
--
--
--
--
--
--
--
--
--
--
<.0016
<•0016
Palladium
--
--
--
--
--
--
--
--
--
<.0016
<.0016
Phosphorus
640
.064
-v..41
100
¦*¦1800
. 11
1700
.097
1-2400
¦v-1800
8.1
1.3.6
Platinum
--
--
--
--
--
--
--
--
--
--
<.0016
<•0016
Potassium
¦*-2600
11
8.2
'51
•*.2400
12
>5%
12
1200
>.5%
4
4
Praseodymium
6 9
.001
--
.24 .
11
. 001
7.6
--
5.7
5.7
.0016
.0049
Rhenium
--
--
--
--
--
--
--
--
--
--
<.0016
<.0016
Rhodium
—
--
--
T-
--
--
--
--
--
--
<.0016
<•0016
Rubidium
9
.45
.041
.11
23
.089
32
.029
11
11
.10
.092
Ruthenium
--
--
--
--
--
--
--
--
—
<.0016
<•0016
Samarium
. 33
--
--
.06
1.9
--
1.3
--
.97
.97
<.0016
<.0016
Scandium
13
--
• --
1.7
80
--
53
--
40
40
<.0016
<.0016
Selenium
1.6
.15
.066
. 22
.87
. 19
5.8
. 13
.22
.93
.46
.41
Silicon
>1X
Maj .
-*-2.5
•v.7800
>U
Maj .
>1%
Ma j .
>1*
>1Z
Maj.
1.56
Silver
.24
--
.008
.04
. 14
.001
. 19
.001
.10
.30
<.0016
<.0016
Sodium
510
76
86
240
1-2200
78
>17.
80
-*¦2400
>.5%
26
28
Strontium
150
6.6
.60
320
970
4.5
860
9:8
1400
1-1400
1.5
1.8
NOTES: 'Concentration In ppm by weight in solids and pg/ml in liquids. WKP analysis in 10"" lb/scf (60°F, 29.92" Hg).
2Blind duplicate analysis.
'Possibly inaccurate due to loss from acidic solution.
""Approximate value only due to interference from preservative.
'Insufficient sample for determination.
—All elements not reported <0.1 ppm weight in solids or <0.001 Mg/ml in liquids.
Maj. - Major component.
-------
TABLE 4-4 STATION I. ANALYTICAL RESULTS BY SS-MS' (Cont'd)
Clement
Coal
Clear
Pond
Return
Cooling
Tower
Blowdown
Lime
Bottom
Ash
Bottom
Ash Sluice
Water
Scrubber
Slurry
Solids
Scrubber
Slurry
Liquid
Economizer
Ash *
Flue Gas
WEP'
Sulfur
>lt
MaJ.
MaJ.
470
-\-9300
MaJ.
>1%
MaJ .
•\-9300
-v.9300
MaJ.
•*.127
Tantalum
—
.007
--
.61
2.6
--
.80
.001
1.3
3
.0065
.0032
Tellurium
.10
—
--
< . 07
. 16
--
.09
.001
.07
< .07
<.0016
.0016
Terbium
.09
—
--
.02
.46
--
.15
--
.27
.11
<.0016
<.0016
Thallium
< .10
--
--
< .10
.19
--
.25
--
.28
.40
.012
<.0016
Thorium
2.6
--
--
.64
13
--
18
--
14
14
.0016
<.0016
Thulium
.04
--
--
.02
.26
--
. 12
--
1.3
. 13
<.0016
<.0016
Tin
1.8
.004
.007
.17
2
. 004
3.1
.012
2.3
2.3
.18
.038
Titanium
•v.1900
.23
.075
57
>1%
--
>17.
. 22
^8500
-v.6800
4.3
2.6
Tungsten
3.4
.005
--
1.1
3.7
.003
5
.003
8
6.2
.0049
.0098
Uranium
2.5
.002
--
1.2
23
.002
7.2
.003
5.4
12
.0049
.0098
Vanadium
73
.19
.006
1.3'
180
.067
280
.29
160
260
.89
.86
Ytterbium
.27
--
--
.15
1
--
1.4
--
.38
1.1
<.0016
<.0016
Yttrium
17
.001
--
2.1
75
.016
50
.002
110
58
.0082
.015
Zinc
.87
.10
.40
.21
10
.074
66
.051
27
18
.87
.0032
Zirconium
31
.003
l.l
62
.006
76
.004
57
57
.016
.028
NOTES:
MaJ
Concentration In ppm by weight In solids and |ig/ml in liqu.lds. WliP analysis In 10"" lb/scf (60°F, 29.92" Hi').
Blind duplicate analysis. '
Possibly Inaccurate due to loss from acidic solution.
Approximate value only due to interference from preservative.
Insufficient sample for determination.
All elements not reported <0.1 ppm weight in solids or <0.001 tJg/ml in liquids.
- Major component.
-------
TABLE 4"5 STATION I ma'IKKIAI. UAI.ANCtS*
U>
00
1
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chlorine
Chromium
Cobalt
Copper
• Fluorine
Iroa
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sulfur
Titanium
Uranium
Vanadium
Zinc
Coal
6509
.15
.23
37
.23
14
.051
4980
12
5.9
.59
9.6
40
1132
1.2
821
48
.037
1.1
2.5
.62
.013
2038
311
.37
14
6.8
Ash
Sluice
Water
6.5
.03
.0058
.65
.0017
4.1
.0070
1019
36
.095
.010
.046
26
.4
.010
88
1.1
.0006
.045
.032
.062
.0004
1013
<•13
.013
.20
.13
Coollng
Tower
Blowdowii
1.0
.01
.0013
.22
.0016
.12
.0004
61
11
< .025
.011
.11
.40
. 5
.007
16
.044
.0002
.022
.002
.0016
.0001
1185
<•04
.0066
.062
.18
Make-Up
Water
Mine
20
.096
.018
2
.0052
13
.022
3160
112
.30
.032
.14
80
1
.032
272
3.4
.002
.14
.10
.19
.0012
3140
<•4
.04
.63
.40
14
.003
.0003
.19
.0057
.01
r_hi
6550 • 830
.29 ! .03
.26 1 .03
40 1 8
.25 » .03
32 1 3
.0022 .082 i .009
2557 11.800 i 700
.60 170 1 17
.057 6.4 I .8
.0067 .66 1 .08
.081 10 I 2
2 150 ± 12
6 1140 t 130
.053 1.3 1 .2
22 1200 1 90
.37 53 1 6
.0003 .040 1 .005
.022 1.4 ± .2
.016 2.7 1 .4
.0013 .88 1 .07
.00006 .014 t .002
.14 7380 1 410
.42 310 1 40
.037 .46 ± .04
.15 15 ± 2
.030 8 11
1 Jul I < HU
A :i! I
1 i 8H
.00', 5
.01',
7.7
• 01!9
1.8
.012
995
2
.77
.081
1.1
1.2
289
.082
138
8.0
.0002
.043
.45
.008
.0013
.001
52
.15
2.6
.47
Asli
blnUic grubber
Uuii-r Sullda
1
.05)
.0053
.65
.0011
3.2
.0049
1 o l y
36
. 15
.0065
.031
21
.4
.009
88
1.0
.0006
.072
.019
.040
.0005
993
<¦13
.007
.25
.098
5400
. 1 2
.26
42
.16
11
.09
5900
4
5.9
.4 1
7.8
41
1125
2.5
680
50
.0027
.52
1.9
.44
.012
720
200
.18
13
9.5
Scrubber
l.lquld
20
.15
.0054
2
.0063
12
.028
3804
117
.59
.046
.20
84
3
.096
259
3.7
.0029
.063
.063
.50
.002
3615
<¦4
.036
.97
.37
Ecuitouilzer
Ash
2.6
.00005
. 00008
.02
.00008
.0068
.0002
3
.005
.0030
.0004
.0028
.0032
.6
.0004
.4
.026
2 x 10"7
.0009
.001
.00001
2 * 10~6
7 * 10~6
.13
.0002
.007
.0015
Flue
(jus
16.5
.0017
.021
.41
.0012
.67
.0078
56
18
.76
.013
.058
.85
9
.05
'9
.22
.022
.36
. .099
.017
.0007
1185
.79
.0057
.41
.25
E Out
6630 1 1260
.33 t .04
.31 1 .06
53 1 12
.20 1 .04
28 i 3
.14 1 .02
11,800 1 1300
180 1 18
8 11
.6 1 .1
9+2
150 i 14
1430 t 260
2.7 t .7
1170 i 150
60 ± 10
.029 i .004
1.1 ± .1
2.5 ± .5
1.0 + .1
.016 t .003
6510 t 440
250 1 50
.38 t .07
18 t 3
11 t 2
I Out/E In
1.01
1.14
1.19
1.33
.80
.88
1.71
1.00
1.06
1.25
.91
.90
1.00
1.25
2.08
.98
1.13
.73
.79
.93
1.14
1.14
.88
.81
.83
1.20
1.38
* All Viluii la lb/far.
-------
TABLE 4-6 1RACE ELEMENT FLOWS* AND MATERIAL BALANCE RESULTS AROUND STATION I FROM SPARK SOURCE MASS SPECTROMETRY ANALYSES
Cooling
Element
Coal
Bottom Ash
Sluice Hater
Tower
Blcwdcwn
Make-up
Water
lime
E In
Bo t tan
Ash
Bottom Ash
Sluice Water
Scrubber
Solids
Scrubber
Liquid
Economizer
Ash
Flue
Gas
E Out
Alunintni
115
17
>500
17
>.26
3.5
>650
Antimony
.12
.014
< .0004
.044
<.0002
.18
.006
.027
.041
.067
.00002
.003
.14
Arsenic
.37
<006
< .0004
<.02
< . 003
.40
.062
< .004
.85
.008
.0002
.005
.93
Bariun
37
.19
.029
.60
.033
38
3.7
.44
5.5
.92
.003
.079
11
Berylliun
.54
< . 001
< .0004
< .004
.001
.54
.13
< .001
.38
< . 004
.0001
< .0008
.51
Bismuth
< . 20
< . 001
< .0004
< . 004
< .0004
< .20
.002
< . 001
.023
< . 004
.00001
.0008
.032
Boron
31
< .13
.088
< . 40
.007
32
9.2
< .13
27
< . 42
.013
<
.083
36
Bromine
.48
.034
< .0004
.10
.001
.62
.017
.071
.049
.075
.00004
<
.0008
.21
Cadtidon
.18
.062
.057
.19
.0008
.49
.008
.19
.045
.20
.00006
.091
.54
Calciun
>2830
955
48
2960
>48
>6800
>115
929
>500
3511
>.26
34
>5100
Cerium
16
.008
< .0004
.024
.049
16
2.3
.004
5
.017
.002
.013
7.3
Cesium
.19
.003
.002
.008
.00004
.20
.049
.006
.14
.004
.00005
.017
.22
Chlorine
28
.023
.001
.072
.062
28
.30
.36
.85
.39
.0002
.005
1.9
Chromium
8.2
.005
.0008
.016
.003
8.2
1.3
.003
9
.017
.003
.42
11
Cobalt
1.7
.030
.018
.092
.002
1.8
.30
.013
.85
.059
.0004
.025 ¦
1.2
Copper
7.1
.067
.057
.21
.006
7.4
1.4
.18
17
.75
.002
.055
19
Eysprosiun
.45
< . 001
< .0004
< . 004
.001
.46
.048
< . 001
.14
< . 004
.00008
<
.0008
.19
Erbium
.14
< . 001
< .0004
< .004
.0003
.15
.006
< . 001
.024
< .004
.00001
<
.0008
< . 036
Europiun
.23
< .001
< .0004
< . 004
.0003
.24
.012
< . 001
.035
< .004
.00003
<
.0008
.052
Fluorine
93
2.8
—
8.8
2.1
110
1.0
—
15
3.4
.003
.003
19
Cadoliniuan
.037
< . 001
.001
< . 004
.0003
< . 044
.008
< .001
.055
< . 004
.00001
.002
.070
Gallium
1.0
.018
.001
.056
.003
1.1
.31
.008
2.4
.19
.0003
.056
3.0
Germaniun
.16
.043
.0004
.13
.0001
.34
.032
.089
.20
.20
.00005
.006
.53
Gold
< . 028
< .001
<.0004
< . 004
< .0004
< , 034
< . 001
< .001
< .005
< . 004
< 2 x 10"6
<
.0008
< .012
Hafniun
.088
< . 001
< .0004
< .004
.003
.096
.066
< .001
.090
<.004
.00006
<
.0008
.16
Holmiun
.042
< . 001
<.0004
< . 004
.00009
< . 048
.004
< . 001
.01
< . 004
8 x 10~6
<
.0008
< .020
*A11 flows in lb/hr.
-------
TABLE 4-6 TRACE ELEMENT FLOWS* AND MATERIAL BALANCE RESULTS AROUND STATION I FROM SPARK SOURCE MASS SPECTROMETRY ANALYSES (Cont'd
Cooling
Bottom Ash Tower Make-up Bottom Bottom Ash Scrubber Scrubber Economizer Flue
Element
Coal
Sluice Water
Blcwdown
Water
Lime
I In
Ash
Sluice Water
Solids
Liquid
Ash
Gas
£ Out
Iodine
.34
< . 001
< .0004
. 004
.0008
.35
.007
.005
.01
.004
4 x 10"6
c .0008
.027
Iridiun
A
©
00
< .001
<.0004
< . 004
< .0004
< .034
< . 001
< .001
< .005
< . 004
< 2 x 10"6
< .0008
< .012
Iron
>1415
.59
.48
1.8
>1400
>115
1.5
>500
3.8
>.26
6.7
>630
Lanthanum
2.5
.004
< .0004
.012
.004
2.6
¦ .36
.013
1.0
.013
.0005
.012
1.4
Lead
.82
.005
.002
.016
< .0004
.84
.092
.017
1.4
.013
.0002
.015
1.5
Lithium
19
.037
.0004
.62
.036
19
9.9
.17
.10
.18
.011
.007
10
Lutetian
.023
< .001
< .0004
< . 004
.0001
< . 029
.002
< .001
.005
A
O
o
3 x 10"6
< .0008
< .013
Magnesium
>2800
90
15
280
-v-24
>3200
>115
89
>500
272
>.26
7.3
>980
Manganese
23
.67
.016
2.1
.81
26
<38
.52
250
50
>.13
2
>350
Praseodymium 2.0
.001
< .0004
.004
.001
2.0
.13
.001
.38
< .004
.0001
.002
.51
Rhenium
< . 028
< . 001
< .0004
< . 004
< .0004
< . 034
< .001
< . 001
< . 005
< . 004
< 2 x 10"6
< .0008
< .012
Rhodium
< .028
< .001
< .0004
< . 004
< .0004
< . 034
< . 001
< .001
*< .005
< .004
< 2 x 10"6
< .0008
< .012
Rubidiun
2.5
.58
.018
1.8
.0005
4.9
.26
.11
1.6
.12
.0002
.050
2.2
Rutheniun
< . 028
< . 001
< .0004
<.004
< .0004
< . 034
< . 001
< .001
< 005
< . 004
< 2 x 10*6
< .0008
< .012
~All flows in lb/hi-
-------
TABLE 4-6 TRACE ELEMENT FLOWS* AND MATERIAL BALANCE RESULTS AROUND STATION I FROM SPARK SOURCE MASS SPECTROMETRY ANALYSES (Cont'd)
Element
Ccal
Bottom Ash
Sluice Mater
Cooling
Tower
Blowdown
Make-up
Water
Lime
E In
Bottom
Ash
Bottom Ash
Sluice Water
Scrubber
Solids
Scrubber
Liquid
Economizer
Ash
Flue
Gas
I Out
Samariun
.093
<
.001
<.0004
< . 004
.0002
.099
.022
< .001
.065
< . 004
.00002
< .0008
.093
Scandiun
3.7
<
.001
< .0004
< . 004
.008
3.7
.92
< . 001
2.7
< . 004
.001
< .0008
3.6
Seleniun
.45
.19
.029
.60
.001
1.3
.010
.25
.29
.54
.00001
.22
1.3
Silver
.068
<
.001
.004
< .004
.0001
.077
• .002
.001
.010
.OWi
5 x 10*6
< .0008
.017
Sodium
144
98
38
304
1.1
590
<25
101
>500
334
>.13
14
>974
Strontiun
42
8.5
.26
26
1.5
79
11
5.8
43
41
.037
.83
102
Tantalun
< . 028
.009
< .0004
.028
.003
< .068
.030
< .001
.04
.004
.00005
.002
.078
Tellurian
.028
<
.001
< .0004
< . 004
< .0003
< .034
.002
< . 001
.005
.004
1 x 10"6
.0008
.013
Terbiun
.025
<
.001
< .0004
< . 004
.00009
< . 031
.005
< . 001
.008
< . 004
4 x 10"6
< .0008
< .019
Thalliun
00
CM
©
V
<
.001
< .0004
< .004
< .0004
<.034
.002
< .001
.013
< . 004
.000008
.006
.026
Thorixm
.74
<
.001
< .0004
< .004
.003
.74
.15
< .001
.90
< .004
.0003
.0008
1.1
Thuliun
.011
<
.001
< .0004
< .004
.00009
< .017
.003
< .001
.006
< .004
.00001
< .0008
< .015
Tin
.51
.005
.003
.016
.0008
.53
.023
.005
.16
.050
.00006
.055
.29
Tltaniun
^538
.30
.033
.92
.27
-v540
115
< .001
>500
.92
-v20
1.7
>620
Tungsten
'.96
.006
< .0004
.02
.005
.99
.042
.004
.25
.013
.0001
.004
.31
Uranivm
.71
.003
< .0004
.008
.006
.72
.26
.003
.36
.013
.0002
.004
.64
Vanadiun
21
.25
.003
.76
.006
22
>2.1
.086
14
1.2
.005
.44
18
Ytterbiun
.076
<
.001
< .0004
< .004
.0007
< .083
.012
< .001
.07
< .004
.00001
< .0008
.088
Yttriun
4.8
.001
< .0004
.004
.010
4.8
.86
.021
2.5
.008
.002
.006
3.4
Zinc
.25
.13
.18
.40
.001
.95
.12
.095
3.3 -
.21
.0006
.22
3.9
Zircordvm
8.8
.004
< .0004
.012
.005
8.8
.71
.008
3.8
.017
.001
.012
4.6
*A11 flows in Ib/hr.
-------
as Z In. The elemental flow rates in the outgoing streams,
bottom ash, bottom ash sluice water, scrubber solid and liquid
discharge, economizer ash and flue gas, also were added and are
listed as Z Out. The error limits given were calculated from
the estimated errors in the analyses and the estimated errors
in the flows according to the procedures described in Section 3.0.
The emissions results for sulfur and particulates are
summarized in Table 4-7 since these are the two emission parameters
of greatest immediate importance. The results are provided on a
lb/BTU basis to facilitate comparison to other stations.
-------
TABLE 4-7
EMISSION RESULTS FOR PARTICULATES AND
SULFUR DIOXIDE AT STATION I
Particulates
(Ash) Sulfur Dioxide
.023 gr/scf 280 ppm (v/v)
21.7 lb/106 BTU 1.51 lb/106 BTU
.061 lb/106 BTU .88 lb/106 BTU
Concentration in flue
gas
Quantity in coal per
unit heat value
Emissions in flue gas
per unit heat value
of coal burned
-43-
-------
5.0 DISCUSSION OF RESULTS
The distribution of trace elements in station exit
streams is affected by the properties of individual elements,
the boiler configuration on the flue gas emission controls. The
ability to distinguish the distribution patterns is dependent on
the overall quality of the results. The criteria for acceptability
of the trace element flow data used in this section is the degree
of closure of individual element material balances.
5.1 Material Balance Closure
cates a high degree of confidence of the individual trace element
flows. Closure within the error limits is indicated by an
overlap of the error bands for Z In and Z Out presented in Table
4-5. Twenty-four out of twenty-seven elemental material balances
close within the error limits. These elements are:
Closure of the balances within the error limits indi-
Aluminum
Antimony
Arsenic
Barium
Chromium
Cobalt
Nickel
Selenium
Fluorine
Iron
Copper
Silver
Sulfur
Calcium
Chlorine
Beryllium
Boron
Magnesium
Manganese
Molybdenum
Titanium
Uranium
Vanadium
Zinc
The balances are out of limits for:
Cadmium
Lead
Mercury
0.082 ± .009 lb/hr in
1.3 ± .2 lb/hr in
0.040 ± .005 lb/hr in
.14 ± .02 lb/hr out
2.7 ± .7 lb/hr out
029 ± .004 lb/hr out
-44-
-------
This must be attributed to inaccuracies in sampling,
sample handling and/or sample analysis particularly mercury which
is in the gas phase in the flue gas making collection and analysis
difficult. Normalized deviations in the material balances
imm = £in(,i) - Sout(i)
{£ in (j ) + Eout(j)}/2
(5-1)
were calculated using Equation 5-1 for the results obtained
from the quantitative analyses and by spark source mass spectro-
metry. The results are given in Table 5-1. The average of the
normalized deviations were -0.06 and 0.26 for the quantitative
methods and for SSMS respectively. These provide some measure
of the overall material balance closure for each of the two
analytical approaches
The root mean square of the normalized deviations
calculated by Equation (5-2)is 0.24 for the quantitative methods
and 0.86 for the SSMS results.
RMS
ND
Ein(j) - Eout(j)\
) + Zout( j) ,
L J
%
(5-2)
The same calculations for 48 elements analyzed by
SSMS resulted in an average for the normalized deviations of
0.31 and a RMS value of 0.82. Analytical results less than or
greater than a certain value were considered inconclusive and
therefore not included in the latter calculations.
5.2 Distribution of Elements in the Exit Streams
The elements entering the station with the coal stream
are distributed in the various ashes according to the individual
element properties.
-45-
-------
TABLE 5-1
DEVIATIONS FROM MATERIAL BALANCE CLOSURE FOR
QUANTITATIVE ANALYSES AND
SPARK SOURCE MASS SPECTROMETRY ANALYSES
FOR STATION I
Elements
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chlorine
Chromium
Cobalt
Copper
Fluorine
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sulfur
Titanium
Uranium
Vanadium
Zinc
Average of Normalized
Deviations
RMS of Deviations2
Quantitative
Normalized'
Deviation
-0.01
-0.13
-0.18
-0.28
0.22
0.13
-0.52
0
-0. 06
-0.22
0.10
0.11
0
-0. 23
-0. 70
0.03
-0.12
0.32
0.24
-0.08
-0.13
-0.13
. .0.13
0.21
0.19
-0.18
-0.32
¦0.06
0.24
SSMS
Normalized1
Deviation
1.15
0.25
-0.80
1.10
0.06
-0.12
-0.10
0.29
1.75
-0.29
0.40
-0. 38
1.41
0. 76
-0.56
1.06
-1.42
1.40
0.67
0.30
0
1.28
-0.14
0.12
0.20
-1.22
0.26
0.86
NOTES: ^ Normalized Deviation ** Ein^
£out«'
2. Root Mean Square of
Normalized Deviations
z
j
+ Eout
-------
The average total ash distribution for Station I is
as follows:
Bottom ash 21.3%
Ash in scrubber slurry 78.47,
Economizer ash 0.05%
Flue gas 0.3%
The distribution of each element in these ashes is
given in Table 5-2. A fraction of an element which exceeds the
above values in an ash stream indicates enrichment of this
element. An element concentration smaller than the above values
indicates a depletion of this element in the corresponding ash
stream. Corrections for leaching effects of the ashes in con-
tact with water during the sluicing operation were applied by
subtracting the element flows in the sluice water inlet' from
the element flows in the sluice water outlet. An increase in
the sluice water outlet concentrations was assumed to arise
from leaching effects. The amount leached was added for com-
parison purposes to the corresponding ash stream. This was
possible for all elements with the exception of chlorine and
sulfur. The mass flows of these elements in the inlet and out-
let liquid streams are high in comparison to the flow in the
solids. As a consequence, the errors in the corrected terms
are high compared to the mass flow in the solids. Therefore,
uncorrected values were used.
The trace element flows in the scrubber sludge were
corrected for the contribution from both the lime addition and
the water streams. The values listed in Table 5-2 show, there-
fore, the distribution of elements entering the boiler with the
coal among the ash solids.
47-
-------
TABLE 5-2
DISTRIBUTION OF ELEMENTS AMONG BOTTOM ASH,
SCRUBBER SLURRY, ECONOMIZER ASH,
AND FLUE GAS AT STATION I
Element
lb/hr
in Coal
Bottom Ash %
(Average 21.3%)
Scrubber
Slurry %
(Average 78.4%)
Economizer Ash °L
(Average .05%)
Flue G
(Average
Aluminum
6510
18.0
81.7
0.04
— I - _
0. 25
Antimony-
0.15
9.9
89.4
0. 02
0.61
Arsenic
0. 23
5.0
87. 6
0. 03
7.5
Barium
37
15.4
83. 6
0. 04
<0. 84
Beryllium
0. 23
15. 7
83. 8
0. 04
0. 65
Boron
14
7.9
86. 2
0. 06
5.9
Cadmium
0.051
8.9
84. 0
0. 18
7.0
Calcium
4980
15. 1
84. 0
0.05
0. 35
Chlorine
12
8.3
16. 7
0. 02
75.0
Chromium
5.9
10. 7
79.4
0. 04 ;
9.9
Cobalt
0. 59
15. 5
81. 7
0. 08
2.6
Copper
9.6
12. 4
87. 0
0. 03
0. oo
Fluorine
40
0
98. 0
0. 007
2. 0
Iron
1130
20.4
80. 0
0. 04
0.63
Lead
1.2
3.1
94. 9
0. 01
1.9
Magnesium
821
17. 7
81.1
0. 05
1.2
Manganese
48
13.6
85.9
0. 04
0. 38
Mercury
0.037
0. 78
12.5
0.0008
86.8
Molybdenum
1.1
8.4
48'. 3
0. 11
43. 2
Nickel
2.5
18. 3
77.6
0. 04
4. 1
Selenium
0.62
0
97. 8
0. 001
2.2
Silver
0.013
9.5
86. 1
0. 01
4. 7
Sulfur
2038
0
37.8
0
62. 2
Titanium
311
20. 6
79.0
0. 05
0. 30
Uranium
0.37
50. 1
47. 7
0. 07
2.0
Vanadium
14
16.3
81.1
0. 04
2.5
Zinc
6.8
4.4
93. 0
0. 02
2.5
-48-
-------
MANGANESE
MAGNESIUM
TITANIUM
100%
FIGURE 5.1
DISTRIBUTION OF ELEMENTS AMONG BOTTOM ASH,
ASH IN SCRUBBER SLURRY
AND FLUE GAS AT STATION I
-49-
-------
The results obtained in this fashion are graphically
displayed in Figure 5-1. Element concentrations in the econo-
mizer ash are omitted since the contribution of this stream is
insignificant, 0.057o of the total. The average concentration
of the bottom ash (21.3%), the ash in the scrubber slurry (78.4%)
and the fly ash (0.3%) are shown as vertical green, blue, and
red lines.
The distribution of the individual elements in these
streams are shown as horizontal lines (bottom ash - green, ash
in scrubber slurry - blue, fly ash plus flue gas - red).
The crossing of a total ash line and an elemental bar of the
same color indicates enrichment of that element in the ash
stream.
From the exit distributions, the elements can be
divided into two groups. Group one comprises the compounds
enriched in the flue gas and depleted in the bottom ash. They
are:
Sulfur
Boron
Mercury
Zinc
Chlorine
Cadmium
Antimony
Chromium
Fluorine
Copper
Selenium
Cobalt
Lead
Arsenic
Molybdenum
Silver
Nickel
Vanadium
The balances for cadmium, lead and mercury did not close within
the error limits, placing a degree of uncertainty in the enrich-
ment data.
-50-
-------
Uranium seems to be enriched in the bottom ash. The
reasons for this enrichment are not clear. The rest of the
elements are evenly distributed among the ashes. This group
includes:
Probable mechanisms for the element enrichment are':
(1) volatilization of an element or compound
in the boiler, or
(2) chemical changes with formation of a
volatile element or compound.
The volatilized compounds can subsequently:
(1) leave the plant without recondensation,
(2) recondense partially, or
(3) recondense completely onto the available
particulate surface area.
These mechanisms lead to a depletion of the bottom ash
and an enrichment in the flue gas and/or precipitator ashes.
Element concentration as a function of particle size can eluci-
date the underlying phenomena. In addition, the types of com-
pounds volatilized would be of extreme practical interest. Both
areas were, however, outside the scope of the present study.
Barium
Beryllium
Aluminum
Calcium
Magnesium
Manganese
Titanium
Iron
-51-
-------
APPENDIX A
SAMPLING AT STATION I
-------
TABLE OF CONTENTS
Page
1.0 INTRODUCTION A-l
2.0 PLANT DESCRIPTION A-2
2.1 Plant Operation During Sampling A-2
2.2 Time Phasing During Sampling A-4
3.0 DESCRIPTION OF SAMPLING POINTS A-5
3.1 Coal Sampling A-5
3.2 Bottom Ash Sluice Water Inlet A-5
3.3 Cooling Tower Blowdown A*7
3.4 Scrubber Makeup Water A-7
3 . 5 Lime A-7
3.6 Bottom Ash A-3
3.7 Bottom Ash Sluice Water Outlet .... A-8
3.8 Scrubber Solids A-8
3.9 Scrubber Liquids A-9
3.10 Economizer Ash A-9
3.11 Fly Ash A-9
3.12 Sampling Schedule A-13
4.0 FLOW RATE MEASUREMENTS A-15
4.1 Coal A-15
4.2 Bottom Ash Sluice Water Inlet A-15
4.3 Cooling Tower Blowdown A-16
4.4 Scrubber Makeup Water A-16
4.5 Lime A-16
4.6 Bottom Ash A-19
4.7 Bottom Ash Sluice Water Outlet A-21
4.8 Scrubber Solids A-21
-------
Page
4.9 Scrubber Liquid A-21
4.10 Economizer Ash A-22
4.11 Fly Ash A-22
4.12 Summary of Flow Rates A-23
-------
1.0 INTRODUCTION
Sampling at Station I was performed by Radian personnel
during the period September 2-5, 1974. Units using different
coals and particulate collection devices were selected for
sampling under the trace elements' portion of the Northern Great
Plains Resources Program. This plant is typical of a plant
burning Wyoming coal and equipped with a venturi scrubber for
particulate control.
Representative samples of all inlet and outlet streams
around the power plant were collected with the objective of
quantifying the trace element emissions from the plant. Analyses
of the samples for the trace elements of interest in combination
with flow rate data for each stream during the sample period
allows a material balance to be performed for each element. The
material balances serve two main functions: (1) closure of the
material balances lends credibility to the sampling and analytical
techniques and, therefore, to the emission data produced, and
(2) data is generated which allows the ultimate fate of individual
trace elements to be determined and their flow through the plant
system to be traced.
The following sections provide descriptions of Station
I, the sampling techniques used, and the flow rate measurements
performed.
A.-1
-------
2.0 PLANT DESCRIPTION
The unit sampled at Station I consists of a 330 MW,
tangentially fired, balanced draft boiler with three venturi
scrubbers for fly ash control. A schematic of the plant is
shown in Figure 2-1. The boiler is fired with subbituminous
coal which is mined about 15 miles from the plant site and
transported by rail. The coal for Unit 4 is stored in seven
storage silos and gravity fed to seven mills where it is crushed
prior to delivery to the boiler through a pneumatic conveyer
system.
The three venturi scrubbers use a combination of clear
settling pond water and cooling tower blowdown as scrubber
liquor with the addition of lime to control the pH to approxi-
mately 6.5. The scrubber liquor was recycled to each scrubber
at a rate of 6500 gpm during Che sampling period. The three
scrubbers have a total inlet flue gas capacity of 1.43 x 106
acfm. The flue gas exits the scrubbers through spray demister
systems to a stack with a diameter of 32 feet and a decreased
diameter orifice at the top to increase exit velocity.
The bottom ash and scrubber sludge from Unit No. 4
are deposited in a settling pond, the clear return from which
provides both sluice water and scrubber makeup water. The
small quantity of ash collected in the economizer hopper is
trucked away periodically.
2.1 Plant Operation During Sampling
Unit No. 4 was operated at an essentially constant load
during the sampling period on September 4th varying between 298 MW
A-2
-------
-------
and 285 MW. This constant
representative samples and
rates .
load facilitated the collection of
the measurement of accurate flow
2 .2 Time Phasing During Sampling;
The time phasing of sample collection around Station I
was unnecessary since all of the flows were continuous except
the scrubber liquor which had a residence time of only 20 minutes
in the recycle system, which is negligible in the time frame of
the sampling period.
A-4
-------
3.0
DESCRIPTION OF SAMPLING POINTS
The samp1^ point locations are indicated in Figure
2-1, and the inlet and outlet streams are shown in Figure 3-1.
The following sections provide detailed descriptions of the
sample points and the techniques used to obtain samples repre-
sentative of the streams during the sampling period.
31 Coal Sampling
Samples of pulverized coal were taken from the pneu-
matic transfer lines between the mills and the boiler. A cyclone
sampler was used to obtain approximately 1.5 lb. of hot, dry
coal dust from one of four transfer lines in sequence every 15
to 20 minutes from 8:30 AM to 5:00 PM on September 4, 1974.
The individual samples were combined in a large polyethylene
container and riffled to yield two one-liter bottles of sample
for analysis.
In addition, 3 lb. samples of the coal fed to the
storage silos were periodically taken off the conveyer belt from
the ready pile. These samples were also combined and riffled
to provide two one-liter polyethylene bottles for moisture con-
tent determination. This data is necessary for the determination
of the dry coal feed rate.
3.2 Bottom Ash Sluice Water Inlet
The sluice water for transporting the bottom ash was
pumped from a settling pond located approximately one-half mile
A-5
-------
INGOING STREAMS
OUTGOING STREAMS
(D
Coal
&
CD
Bottom Ash Sluice,
Water
Cooling Tower .
Blowdown
Scrubber Make-u.D .
Water
Lime
BOILER NO. 4
SCRUBBER
SYSTEM
Bottom Ash Solids ^
Bottom Ash Sluice ^ ^
Economizer Ash
Scrubb'er Solids
to Pond
Scrubber Liquid
-^(9;
to Pond
Flv Ash and Flue
Gas Through Stack
•©
0
FIGURE 3-1
In and Outgoing Streams at the
Boiler No. 4 Scrubber System at Station I
A-6
-------
from the plant. The particular pond sampled was one of three
used for settling of bottom ash and scrubber sludge solids.
A two-liter sample was taken from the settling pond in a poly-
ethylene bottle at a point about 15 feet from the intake to
the plant. The sample was acidified with nitric acid to
preserve it for subsequent analysis.
3.3 Cooling Tower Blowdown
A portion of the cooling tower blowdown is used as
pump seal water, demister wash, and induced draft fan spray
in the scrubbers. The cooling towers are located next to the
settling ponds on the west side of the plant. A two-liter
sample was taken at the bottom of the cooling tower, acidified
with nitric acid for preservation, and stored in a polyethylene
bottle for subsequent analysis.
3.4 Scrubber Makeup Water
The scrubber makeup water comes from the same pond as
the bottom ash sluice water and, therefore, the same sample was
be used for analysis of both streams. For the sampling procedure
and handling of the sample, see Section 3.2.
3 • 5 Lime
The lime feed to the scrubber slurry makeup tanks was
sampled between the lime storage silo and makeup tanks. Samples
of approximately 100 g each were taken every hour from 9:20 AM
to 4:20 PM on September 4, 1974, with a small scoop. The lime
was dry and appeared clean, no discoloration. The individual
samples were combined for a composite sample.
A-7
-------
3 . 6 Bottom Ash
Bottom ash from the boiler was continuously sluiced
with clear pond water via a 10 in. pipe about one-half mile
to the first of two settling ponds. The flow from the pipe
was sampled using a 500 ml wide mouth polyethylene bottle. In
order to obtain a representative sample, the bottle was passed
from bottom to top through the stream three times with the
bottle held perpendicular to the direction of flow and the
mouth tilted slightly into the flow. Three passes accumulated
approximately 350 ml which was emptied into a five gallon poly-
ethylene container. Samples were collected every 15 minutes
from 10:00 AM to 5:00 PM on September 4th and combined in the
rive gallon container. The sample was filtered in the laboratory
and the bottom ash solids dried and ground for analysis.
3•7 Bottom Ash Sluice Water Outlet
Two liters of the liquid portion of the bottom ash
sluice were removed from the five gallon sample described in
Section 3.6, filtered, acidified for preservation, and returned
to the laboratory for analysis.
3.8 Scrubber Solids
Scrubber slurry was continuously pumped via an 18 in.
diameter pipe about one-half mile to the first of three settling
ponds. The stream exiting the pipe was sampled concurrently
with bottom ash sampling with a one-liter polyethylene bottle
in a manner similar to that described for bottom ash in Section
3.6. Samples were collected every 30 minutes from 10:00 AM to
5:00 PM on September 4th. The longer sampling interval was
A-8
-------
possible because the density of the scrubber slurry was much
more constant than that of the bottom ash sluice. The solids
were separated by filtration in the laboratory and dried and
ground for analysis.
3 .9 Scrubber Liquids
Following the scrubber slurry sample collection
described in Section 3.8, the five gallon sample was allowed
to stand until most of the solids had settled. A. two-liter
sample of the supernatant liquor was removed, filtered to remove
any fine solids, acidified with nitric acid for preservation,
and stored in polyethylene bottles for subsequent analysis.
3.10 Economizer Ash
The ash accumulation in the economizers is periodically
emptied into an ash storage silo from which the ash is trucked
away. At the beginning of the sampling period the economizer
and the storage silo were emptied. At the end of the period
the accumulation in the economizer was emptied into the silo
and the silo emptied into two large polyethylene containers.
The ash was randomly cored and the sample riffled to provide
a two-liter sample for analysis
3.H Fly Ash
Particulate matter in the exiting flue gas was sampled
through four ports located at the ends of two perpendicular
diameters of the stack serving Unit No. 4. These ports were
approximately 100 feet above ground level; the stack internal
A-9
-------
diameter was 32 feet at this point: The flue gas was relatively
cool, 114°F, following passage through the venturi scrubbers
and had a large amount of entrained water from the spray de-
mister system. The moisture content was found to be 16.0% by
condensation measurements. This is above the saturation level
of 11.7% at the gas temperature indicating a significant quantity
of entrained mist.
Since the sample ports were only 2% stack diameters
downstream from the point of entry of the flue gas, a total of
40 traverse points were necessary to statistically sample the
stream. The stack cross-section was divided into ten con-
centric sections of equal area and the samples were taken at
the centroid of each section along the two perpendicular
diameters as per EPA Method 1. The sampling points were the
following distance from the inner wall of the stack at each of
the four ports :
1. 5 in. 6. 5ft.3 in.
2. 1 ft. 3 in. 7. 6 ft. 6 in.
3. 2 ft. 2 in. 8. 8 ft. 0 in.
4. 3 ft. 1 in. 9. 9 ft. 10 in.
5. 4 ft. 2 in. 10. 12 ft. 5 in.
Velocity traverses of the stack were made on
September 2nd and in conjunction with the particulate loading
determinations on September 3rd and 4th as per EPA Method 2.
The average velocity was found to be 25.9 fps over the three-day
A-10
-------
period with less than ten percent variation over the time period
or from point-to-point in the traverses. The velocity traverses
determined the total flow in the stack and the conditions neces-
sary for isokinetic sampling.
Particulate loading determinations were made on
September 3rd and 4th with "in stack" Gelman filter devices at
the end of a heat traced sample probe. These determinations
were a combination of dynamic grain loadings, for which the
loadings at the points from each port were physically averaged
by sampling for an equal time interval at each point with the
accumulation of all ten points on a single filter, and single
point grain loadings at point 8 to define the actual particulate
concentration at the point used for particulate sample collection.
During particulate loading determinations, the moisture content
of the flue gas was measured by condensation in an efficient
copper tubing condenser maintained in an ice bath.
Particulate matter in the stack gas stream was
sampled at point 8 from the south 'and east ports on September 4th
during the period when the other plant streams were sampled.
The wet electrostatic precipitator (WEP) sampling system used
for sample collection is shown schematically in Figure 3-2. A
five percent sulfuric acid solution is circulated in this
sampling device by a peristaltic pump. A voltage of 12-14 KV
is applied between a thin platinum wire and the wetted wall
to induce electrostatic collection. The sampling probe from
the sampling nozzle to the WEP was lined with teflon tubing
to prevent trace element contamination of the sample. A gas
stream is isokinetically drawn from the stack and through the
sampling equipment by a vacuum pump and metered by a dry gas
meter. Approximately three hours of sampling was required to
obtain sufficient particulate matter for analysis.
A-11
-------
Precipitator
FIGURE 3-2
SCHEMATIC OF STATION I
ARRANGEMENG FOR DUCT SAMPLING
-------
Samples for mercury were taken in the middle and at
the end of the last WEP run by diverting the exit gas flow
from the WEP through a mesh of gold wire where the mercury is
collected by amalgamation with the gold. Samples were also
taken during the WEP runs for the determination of the sulfur
concentration in the flue gas by bubbling a known volume of gas
through a hydrogen peroxide solution as per EPA Method 6. Orsat
analysis of the flue gas for oxygen and carbon dioxide was per-
formed to provide gas density information as per EPA Method 3.
3.12 Sampling Schedule
The samples described in the preceding sections were
taken during the period September 2, 3, and 4, 1974, according
to the schedule shown in Figure 3-3. Those samples enclosed in
parenthesis are to be analyzed, the rest being held in reserve.
A-13
-------
1. Coal
2. Bottom Ash Sluice Water
Inlet
3. Cooling Tower Blowdown
4. Scrubber Makeup Water
5. Lime
6. Bottom Ash
7. Bottom Ash Sluice Water
Outlet
8. Scrubber Solids
9. Scrubber Liquid
10. Economizer Ash
11. Flue Gas Velocity
12. Flue Gas Particulate
Loading
13. Flue Gas WEP
Particulate Collection
(~
(•)
(• •)
(•)
(•
")
J Sept. 2 | Sept. 3 | Sept. 4
FIGURE 3-3
Sampling Schedule at Station I
A-14
-------
4.0 FLOW RATE MEASUREMENTS
The mass flow rate of each of the sampled streams
described in Sections 3.0 to 3.11 was determined as described
in the following sections.
4.1 Coal
The feed rate of coal to each of seven mills is
recorded in the master printout in the control room. The totals
for each mill on an hourly basis are provided. The hourly-
total coal feed rate to the boiler is calculated by averaging
the seven mills during the sampling period. Samples were col-
lected of the coal feed to the silos and moisture content deter-
mined to allow the coal feed rate to the boiler to be corrected
to dry weight basis. The feed rate determined by this method
was 2.83 x 10s lb/hr.
This rate was checked by calculating the fuel require-
ments of the boiler from the hourly plant load in the control
room printout, unit heat rate, and the heating value of
the coal. This method gives a coal feed rate of 2.84 x 10s lb/hr.
4 . 2 Bottom Ash-Sluice Water Inlet
The bottom ash sluice water was pumped from the
settling pond by a centrifugal pump with a 19-3/8 in. impeller
driven by a three phase 4160 volt motor. The electrical power
requirements of the pump motor were measured by a wattmeter and
an ammeter both of which were read hourly during the sampling
period on September 4th. The motor power requirement was read
A-15
-------
directly from the wattmeter in kilowatts and calculated from
the ammeter readings. The averages of these two determinations
were converted to the pump horsepower requirement using a 937o
motor efficiency. The pump curves provided by the manufacturer
were used to convert horsepower to a flow of 1.55 x 105 gal/hr
,(2580 gpm) or 1.29 x 106 lb/hr.
^^ Cooling Tower Blowdown
A portion of the cooling tower blowdown is transported
to the scrubbers by two pumps. The pressure on the suction and
discharge side of each pump was recorded hourly from 9:00 AM
to 5:00 PM on September ith. The total dynamic head developed
across the duuids was then used to determine from pump curves supplied
by the manufacturer a total flow of 5.27 x 10* gal/hr (379 gpm)
or 4.39 x 105 lb/hr.
^Scrubber Makeup Water
The scrubber makeup water was measured by a flowmeter
on the inlet line to each of the three scrubbers. Readings
were taken from these meters hourly from 9:00 AM to 5:00 PM on
September 4th. The total flow rate to the three was averaged
over the entire period and found to be 4.80 x 10s gal/hr (3002
gpm) or 4.00 x 106 lb/hr.
4.5 Lime
The lime feed to the scrubber slurry makeup tank was
calculated from a material balance for calcium around the boiler-
A-16
-------
scrubber system. The calcium material balance is expressed as
M XW (Ca) + M .XW . (Ca) + M^vXW ., (Ca)
c c swx swiv ctb ctb
+ M XW (Ca) + M-iXW, (Ca) = M,XW, a(Ca)
mw mw II ba ba
+ M XW (Ca) + M XW (Ca) + M ,XW , (Ca)
swo swo ss ss si si
+ M XW _(Ca) + V- XV- (Ca)
ea eaN fg fgv '
where,
= the mass flow rate of coal into the boiler on
c
a dry weight basis (Ib/hr)
XWc(Ca) » the weight fraction of calcium in the coal on a
dry weight basis
M . = the mass flow rate of bottom ash sluice water
swi
into the ash sluice system (lb/hr)
XWswi(Ca) " the weight fraction of calcium in the inlet
bottom ash sluice water which is the same as
clear pond return
Mctk » the mass flow rate of cooling tower blowdown to
the scrubber system (lb/hr)
XWctb(Ca) - the weight fraction of calcium in the cooling
tower blowdown
" the mass flow rate of the make-up water from the
settling pond to the scrubber system
A-17
-------
XW (Ca) = the weight fraction of calcium in the make-up
mw °
water to the scrubber system which is the same
as clear pond return
= the mass flow rate of lime into the scrubber
system (lb/hr)
XW^(Ca) = the weight fraction of calcium in the lime
M^a = the discharge rate of bottom ash from the boiler
(lb/hr)
XWba(Ca) = the weight fraction of calcium in the bottom ash
M = the mass flow rate of the bottom ash sluice water
swo
from the sluice system which is equal to
(lb/hr)
XW (Ca) = the weight fraction of calcium in the scrubber
oWO
discharge solids
Mg^ = the discharge rate of liquid from the scrubber
system (lb/hr)
XWgi(Ca) = the weight fraction of calcium in the scrubber
discharge liquid
Mga = the discharge rate of economizer ash (lb/hr)
XWea(Ca) « the weight fraction of calcium in the economizer
ash
Vf = the volumetric flow rate of the flue gas in the
stack (scfh)
A-18
-------
XV^g(j) = the weight of calcium per unit volume of flue
gas (lb/scf)
The lime flow rate is calculated by solving this
equation for The concentrations of calcium, flowrates, and
resulting mass flows of calcium used to calculate are presented
in Table 4-1. This gives a lime flowrate of 4.78 x 103 lb/hr.
4.6 Bottom Ash
Determination of the bottom ash production rate
directly was impossible because no sample of the bottom ash
sluice stream could be obtained which accurately represented
the percent solids in the stream. Random fluctuations in the
solids content of the sluice stream were evident throughout the
sampling period. The bottom ash production rate was, therefore,
determined indirectly from the ash content of the coal, the
coal feed rate (Section 4.1), the economizer ash flow rate
(Section 4.10), the scrubber solids flow rate (Section 4.8),
and the ash content of the scrubber solids. The ash content of
the scrubber solids was determined by analysis of the economizer
ash, the scrubber solids, and the lime feed for titanium. Assum-
ing that the concentration of Ti in the ash in the scrubber
solids is equal to the Ti concentration in the economizer ash,
the ash content of the scrubber solids was calculated. The
accuracy of this technique was greatly enhanced by the high Ti
concentration in the ash compared to the lime Ti concentration.
From an ash content of the dry scrubber solids of 84.9% and ash
content of the coal of 19.12"U (dry basis), the production rate
of bottom ash was found to be 1.15 x 101* lb/hr.
A-19
-------
TABLE 4-1
SUMMARY OF CALCIUM MATERIAL BALANCE DATA
Stream
Coal
Bottom Ash Sluice
Water Inlet
Cooling Tower
Blowdown
Scrubber Make-up
Water
Lime
Bottom Ash
Bottom Ash Sluice
Water Outlet
Scrubber Solids
Scrubber Liquid
Economizer Ash
Flue Gas
Calcium
Concentration
I.767,
790 ppm
140 ppm
790 ppm
53.5%
8.6 67,
790 ppm
II.87,
910 ppm
11.57,
1.12 x 10"6
lb/scf
Flow Rate
2.83 x 10s lb/hr
1.29 x 10s lb/hr
4.39 x 105 lb/hr
4.00 x 10s lb/hr
Mi
1.15 x 10u lb/hr
1.29 x 10s lb/hr
5.00 x 10* lb/hr
4.18 x 105 lb/hr
26.3 lb/hr
5.01 x 107 scfh
Calcium
Flow Rate
4.98 x 10 3 lb/hr
1.02 x 103 lb/hr
61.5 lb/hr
3.16 x 103 lb/hr
.535 M]_
9.96 x 102 lb/hr
1.02 x 103 lb/hr
5.9 x 103 lb/hr
3.80 x 103 lb/hr
3 lb/hr
56 lb/hr
A-20
-------
4.7 Bottom Ash Sluice Water Outlet
The bottom ash sluice water outlet flow rate is equal
to the inlet flow rate determined as described in Section 4.2
to be 1.55 x 10s gal/hr (2580 gpm) or 1.29 x 106 lb/hr.
4.8 Scrubber Solids
The flow rate of scrubber solids from the three venturi
scrubbers to the settling pond was determined from the weight
percent solids in the scrubber sludge stream to the pond and the
volumetric flow of liquid from the scrubber. The volumetric
flow of liquid from the scrubber was determined by a water
material balance which will be described in Section 4.9. With
a slurry stream solids concentration of 1.18%, the mass flow of
solids from the scrubbers was found to be 5.00 x 10" lb/hr.
4.9 Scrubber Liquid
As mentioned in Section 4.8, the liquid flow from the
scrubber was determined from a water material balance around
the scrubber system. The inlet water streams to the system con-
sist of the scrubber makeup water (see Section 4.4), the cooling
tower blowdown added to the scrubber system (see Section 4.3),
and the water originating in the boiler from the combustion
reactions and the moisture content of the coal. The outlet
water flow from the scrubber system is the sum of the liquid
portion of the sludge stream to the pond snd the evaporation
and entrainment losses to the exiting flue gas. The water
leaving the system in the flue gas was determined by condensation
during stack sampling (Section 3.11). Since all of the flow
A-21
-------
rates are known or calculable except the scrubber liquid flow,
this flow can be determined. This water balance indicates a
scrubber liquid flow to the sett ling,pond of 4.18 x 10s lb/hr.
4.10 Economizer Ash
The amount of economizer ash produced during the
eight hour sampling period on September 4th was measured by
emptying the economizers and economizer ash silo at the beginning
of the test period and measuring the accumulation over the period.
The ash was collected in two large polyethylene containers and
its volume determined to be 2.70 cu. ft. From this volume and
a packed density of 1.25 g/ml (73.0 lb/cu. ft.), the proauccion
rate of economizer ash during the sampling period was calculated
to be 26 . 3 lb/hr.
4-11 Fly Ash
The flow rate of fly ash from the Unit No. 4 stack
at Station I was determined from the flue gas velocity and par-
ticulate loading measurements discussed in Section 3.11. The
total quantity of flue gas, corrected to standard conditions,
passing through the stack is calculated from the average gas
velocity in the stack and the cross-sectional area of the stack
at the point of measurement. -From the average velocity given
in Section 3.11 of 25.9 fps and a cross-sectional area of 804
square feet, the total flow from the stack on a dry basis was
8.35 x 10s scfm. The fly ash emissions were then found from
the total flow and an average particulate loading of 0.023 gr/scf
to be 164 lb/hr.
A-22
-------
4.12 Summary of Flow Rates
The mass flow of each of the streans sampled at
Station I are summarized in Table 4-2. The flow rates of all
solids are based on a dry weight basis.
A-23
-------
TABLE 4-2
FLOW RATES FOR STREAMS AROUND STATION I
Stream
Coal
Bottom Ash Sluice Water Inlet
Cooling Tower Blowdown
Scrubber Makeup Water
Lime
Bottom Ash
Bottom Ash Sluice Water Outlet
Scrubber Solids
Scrubber Liquid
Economizer Ash
Flue Gas
Fly Ash
Flow Rate
2.83 x 10s lb/hr.
1.29 x 10s lb/hr.
4.39 x 105 lb/hr.
4.00 x 103 lb/hr.
4.78 x 103 lb/hr.
1.15 x 10" lb/hr.
1.29 x 10s lb/hr.
5.00 x 104 lb/hr.
4.18 x 103 lb/hr.
26.3 lb/hr.
5.01 x 107 scfh
164 lb/hr.
A-24
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APPENDIX B
ANALYTICAL PROCEDURES
-------
APPENDIX B
TABLE OF CONTENTS
Page
1.0 SAMPLE PREPARATION B-l
1.1 Coal, Coal Ash, and Sludge
Preparation B-l
1.2 Lime/Limestone Preparation B-l
1.3 WEP Preparation B-2
1.4 Aqueous Streams and Filtrates
Preparation B-2
2.0 ANALYTICAL PROCEDURES B-3
2.1 Determination of Fluoride by the
Ion-Selective Electrode Technique B-3
2.2 Determination of Chloride by Ion-
Selective Electrode B-9
2.3 Spectrophotometric Determination
of Titanium. B-9
2.4 Determination of Copper and Zinc
by Atomic Absorption B-10
2.5 Determination of Molybdenum by
Atomic Absorption B-10
2.6 Determination of Nickel and Cobalt B-10
2.7 Determination of Arsenic by
Flameless Atomic Absorption B-ll
2.8 Determination of Antimony by
Flameless Atomic Absorption B-ll
2.9 Determination of Beryllium by
Atomic Absorption B-ll
2.10 Fluorometric Determination of Uranium... B-12
2.11 Determination of Lead and Cadmium
by Atomic Absorption B-12
2.12 Fluorometric Determination of
Selenium B-13
2.13 Determination of Vanadium and
Silver by Flameless Atomic Absorption... B-13
-------
APPENDIX B
TABLE OF CONTENTS (Cont'd)
Page
2.14 Determination of Barium by-
X-ray Fluorescence B-14
2.15 Determination of Chromium, Calcium,
Iron, Magnesium, Manganese and
Aluminum by Atomic Absorption B-14
2.16 Determination of Mercury by
Flameless Atomic Absorption B-15
2.17 Sulfur Determination by Titrimetry B-16
2.18 Spectrophotometric Determination
of Boron B-16
BIBLIOGRAPHY
-------
Trace element analyses on samples from three power
plants were performed using dissolution and analytical techniques
adapted specifically for these matrices.
1.0 SAMPLE PREPARATION
Preparation procedures were performed ^on the following
types of samples to provide the primary digestion solution:
Coal
Coal Ash
Sludge
Lime
Wet electrostatic precipitator
Aqueous streams and filtrates
1 1 Coal, Coal Ash, and Sludge Preparation
The dissolution of coal, coal ash, and sludge is
achieved by a two-step method. The samples are oxidized at
850-950°C in the presence of air utilizing a quartz pipe reactor.
Volatile trace elements are retained via an acetone-dry ice trap
at the end of the reactor. Dissolution of the remaining solids
is accomplished by treatment with hydrofluoric, nitric, and
sulfuric acid. The dissolved solids are then combined with the
washings from the cold trap.
1.2 Lime/Limestone Preparation
Lime is dissolved by treatment with 57o hydrochloric
acid. Any remaining undissolved material is removed by filtra-
tion and treated with hydrofluoric, nitric, and sulfuric acids
to achieve dissolution.
-------
1.3 WEP Preparation
An .8y millipore filter was used to remove particulates
from aqueous WEP samples. The particulates were then treated
similar to coal (through the quartz pipe reactor acid dissolution
steps). The filtrates, dissolved solids, and cold trap washings
were quantitatively transferred to a single container to form the
primary digestion sample.
1.4 Aqueous Streams and Filtrates Preparation
Nitric acid was added as a preservative to all aqueous
samples.
B-2
-------
2.0 ANALYTICAL PROCEDURES
The following analytical procedures were utilized for
the determination of trace elements in the various samples.
Each analytical technique has been screened for accuracy and
reliability by standard addition and interference studies.
The complete analytical scheme for the analysis of
trace elements in the samples are found in Figures 2-1, 2-2,
2-3, and 2-4. Detection limits for each procedure are summarized
in Table 2-1.
2.1 Determination of Fluoride by the Ion-Selective
Electrode Technique
The determination of fluoride utilizes a sodium car-
bonate fusion for solid samples (TH-060) and direct analysis of
aqueous samples. The technique of standard addition using a
fluoride specific-ion electrode, mentioned by several workers
(BA-131, BA-137), is used for measurement of the fluoride ion.
A citrate buffer is used to release complexed fluoride ions and
to stabilize the pH and ionic strength. Addition of a standard
quantity of fluoride is characterized by a change in the potential
of the solution. The specific ion electrode senses this change
in potential which is related to the initial fluoride concentra-
tion. The relationship between potential and fluoride concen-
tration follows the Nernst equation:
AE » A log (CF + Xi)/CF
where,
AE is the change in potential
B-3
-------
\JV y uc , r u ,
Mo, Cd, Sb,
Ni
FIGURE 2-1
ANALYSIS PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL
B-4
-------
Ash/
Sludge
HN03-H2S04-HC104
Reflux Digestion
Atomic Absorption Cr
NaF Fusion
Fluorescence
¦U
HNO^ - HCIO^ Digestion
Fluorescence
Se
•Hg
Primary Digestion
(Thermal Oxidation,
HF-HN03~H^S0^ Digestion)
Spectrophotometry
Atomic Absorption
Extraction/Atomic Absorption
Ti, B
Al, Mg, Fe,
Ca, V, As,
Mn, Cu, Z11
Co, Be, Pb,
Mo, Cd, Sb
Ni
FIGURE 2-2
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL ASH AND SLUDGE
B-5
-------
Mo, Cd, Sb,
Ni
FIGURE 2-3
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF LIME
B-6
-------
FIGURE 2-4
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF WET ELECTROSTATIC PRECIPITATOR LIQUORS AND AQUEOUS SAMPLES
B-7
-------
TABLE 2-1
DETECTION LIMITS FOR TRACE ELEMENT ANALYSIS
Detection Limit (ppm)
Element Analytical Procedure
A1 Atomic Adsorption (AA)
Sb Extraction/AA
As AA
Ba X-Ray Fluorescence
Be Extraction/AA
B Ion Exchange/Spectropbotomet
Cd Extraction/AA
Ca AA
CI Ion Selective Electrode
Cr AA
Co Extraction/AA
Cu Standard Addition/AA
F Ion Selective Electrode
Fe AA
Pb Extraction/AA
Mn AA
Mg AA
Hg Flameless AA
Mo Extraction/AA
Ni Extraction/AA
Se Fluorometry
Ti Spectrophotometry
Ag Standard Addition/AA
S Ion Exchange/Titrimetry
U Fluorometry
V Standard Addition/AA
Zu Standard Addition/AA
Coal
Ash
Sludge
Lime
WEP
Aqueous
100
400
650
1.9
.04
. 16
.6
.002
.1
.5
.06
.001
5
50
40
.5
. 2
1.6
1.0
.001
y i
3
3
.05
. l
.2
.2
.0002
10
40
65
.1
5
10
10
.5
10
40
65
.1
.2
.8
1
.003
1
4
6.5
.1
.5
1.2
1.2
.1
10
40
65
.1
.4
.8
5
.004
10
40
65
.01
5
20
30
.5
.01
.01
.01
.0005
.4
1.6
16
.004
2
8
2
.006
.1
.1
.1
.0005
5
20
20
.1
.05
.2
.3
.0005
100
100
200
5
.0001
.0001
.0001
.0001
1
4
6.5
.005
1
4
6.5
.01
B-8
-------
A is the constant = 59 mV at 25°C
CF is concentration of free fluoride in solution
is additional fluoride concentration added.
2. 2 Determination of Chloride by Ion-Selective Electrode
Chloride is determined by a known standard addition
method (OR-016). Sample preparation is the same as fluoride
with a sodium carbonate fusion for all solid samples and direct
analysis of aqueous solutions. A known amount of the species
being measured is added to a known volume of sample and the
resulting change in potential is observed. The original sample
concentration is computed using a known addition table. The
method allows samples to be analyzed which have variable ionic
strength.
2. 3 Spectrophotometry Determination of Titanium
Titanium is determined in the primary digestion solution
as a yellow complex formed with tiron (disodium -1, 2- dihydroxy-
benzene -3, 5- disulfonate). This method is based on the pro-
cedure of Yoe and Armstrong, and is further extended to include
shales by Rader (RA-125). An acetate buffer is used to regulate
the pH. The only major interference is the complex tiron forms
with Fe. This interference is eliminated by addition of sodium
dithionite, reducing ferric to ferrous ion. The absorbance of
the complex is read on a double beam spectrophotometer and
samples compared with a standard calibration curve.
B-9
-------
2.4
Determination of Copper and Zinc by Atomic Absorption
Copper and zinc are determined by direct aspiration
of the primary digestion into the flame of the atomic absorption
spectrophotometer (PE-115)- Quantitative determinations are
achieved by comparing the samples to their respective standards
and by the use of standard additions to the primary digestions,.
2.5 Determination of Molybdenum by Atomic Absorption
Molybdenum analysis is based on organic extraction
atomic absorption technique and method of Joyner (JO-012) which
has been modified by Kinrade and Van Loon (KI-085). Molybdenum
in the primary digestion readily forms a complex with ammonium
pyrrolidinedithiocarbamate at an acidic pH. Extraction of this
complex with methyl isobutyl ketone offers a convenient method
of concentration of the element. The signal is further enhanced
by use of a nitrous oxide-acetylene flame. Concentration was
determined by use of a standard calibration curve.
2. 6 Determination of Nickel and Cobalt
Nickel and cobalt analyses are based on the organic
extraction atomic absorption technique and method of Joyner (JO-
012) . An ammonium tartrate buffer is used to stabilize the
primary digestions. Nickel and cobalt are complexed with the
chelating agent sodium diethyldithiocarbamate and extracted with
methyl isobutyl ketone.
Once the metal complex has been separated and concen-
trated in the organic phase, the solution can be directly
aspirated into atomic absorption spectrophotometer for measure-
ment of the metal concentration.
B-10
-------
2.7
Determination of Arsenic by Flameless Atomic Absorption
Arsenic is determined by a Radian modified flameless
atomic absorption procedure based on the method of Ramakrishna,
Robinson and West (RA-147) incorporation the techniques of
Ediger (ED-027). The usually volatile arsenic present in the
primary digestion is complexed as the molybdenum heteropoly acid
with ammonium molybdate in a nitric acid medium. The complex
formation enables the complex to be analyzed on the graphite
furnace by reducing the volatility of the arsenic so that high
temperature charring can be used to rid the sample of matrix
interferences.
2.8 Determination of Antimony by Flameless Atomic Absorption
Antimony determination is based on a Radian flameless
atomic absorption method modifying the extraction procedure of
Burke (BU-136) and Headridfa^ and Smith (HE-094) while utilizing
the techniques of Ediger (ED-027) to reduce the volatility of
antimony. After complexation with iodide, antimony is extracted
from the primary digestion into a methyl isobutyl ketone and
tributyl phosphate mixture (MIBK-TBP). TBP increases the extrac-
tion efficiency. As with arsenic, ammonium molybdate is used
to increase the thermal stability of the complex during the
charring cycle in the graphite furnace.
2.9 Determination of Beryllium by Atomic Absorption
The method of Bokowski (BO-027) is used for the
determination of beryllium by atomic absorption. After addition
of EDTA to the primary digestion to mask interferences, the
beryllium present in the aqueous sample is chelated with acetyl-
acetone. The complex is then extracted with methyl isobutyl
ketone and the organic phase directly aspirated into the atomic
B-11
-------
absorption spectrophotometer for the determination of beryllium.
The solvent extraction procedure allows one to conveniently
separate and concentrate the beryllium present.
2.10 Fluorometric Determination of Uranium
Radian's uranium procedure is a modification of the
fluorometric determination of Thatcher (TH-049) updated by
Turner (TU-025). Hexavalent uranium ions have a native fluo-
rescence that may be used for analysis in relatively high
concentrations. However, when fused with fluoride salts, uranyl
ions produce an intense specific fluorescence detectable at
levels of 10"10 grams of uranium. In general, the solid sample
is mixed with'a sodium fluoride flux and fused to a translucent
disc in a platinum crucible. Aqueous primary digestions are
evaporated in platinum crucibles and the residue fused with the
flux. Once cooled, its fluorescence is measured with a Turner
filter fluorometer. The method of standard additions is used to
compensate for quenching.
2.11 Determination of Lead and Cadmium by Atomic Absorption
The procedure for analysis of lead and cadmium is
similar to that for copper and zinc found in Section 2.4. Trace
elements present in the primary digestion are separated and
concentrated by chelation and extraction. Kinrade and Van Loon's
method (KI-085) utilizing two chelating agents, ammonium pyrro-
lidine dit hi o carbamate (APDC) and diethyl ammonium diethyldiothio-
carbamate (DDDC) to complex lead and cadmium has been highly
successful. A citrate buffer was used due to its stability,
strong buffering capacity, and nonparticipation in any reaction.
The sample solution was extracted into methyl isobutyl ketone
B-12
-------
and the organic solution injected into the graphite furnace on
the atomic absorption spectrophotometer. Concentration was
determined by use of a standard calibration curve.
2.12 Fluorometric Determination of Selenium
Selenium in the form of selinite reacts with aromatic
orthodiamines to form piazselenols which fluoresce in various
organic solvents. This method of determination of selenium is
a Radian modification of a procedure published by Levesque and
Vendette (LE-068). The solid sample is digested with nitric and
perchloric acids in the Parr acid digestion bomb (HA-258).
Aqueous samples are heated with .nitric and perchloric acids. In
both cases this oxidizes selenium to selenate and is followed by
hydrochloric acid reduction to selinite. Isolation of selenite
from interferring substances is accomplished by adding hydroxy1-
amine, EDTA, and formic acid. The selenite is then reacted with
2, 3-diaminonaphthalene to form the organic extractable piazselenol,
naphtho-(2, 3-d)-2 selena-1, 3-diazole, which is determined
fluorometrically. This method is free of any interferences and
is capable of detecting nanograms of selenium by use of a
calibration curve.
2.13 Determination of Vanadium and Silver by Flameless
Atomic Absorption
Vanadium is determined by flameless atomic absorption
using the heated graphite atomizer. The method is a Radian
adaptation of the work of Cioni, Innocente and Mazzioli (CI-002).
Standard additions are performed on the primary digestion solu-
tion. Experimentation conducted on National Bureau of Standards
samples of coal and coal ash yield results within 10% of the
certified values.
B-13
-------
Huffman (HU-095) recommends the same procedure for
silver. Solid samples are dissolved in concentrated nitric acid
and the method of standard additions is utilized.
2.14 Determination of Barium by X-ray Fluorescence
Barium is determined by a Radian method utilizing.
X-ray fluorescence. Samples are pelletized in a solid flux of
lithium carbonate-sodium borate which are then introduced directly
into the X-ray unit. Quantitative determinations are achieved by
comparing the samples to a barium standard calibration curve
prepared in the same manner and by the use of the method of
standard additions to correct for matrix interferences, if any
are present.
2.15 Determination of Chromium, Calcium, Iron, Magnesium,
Manganese and Aluminum by Atomic Absorption
Chromium, calcium, iron, magnesium, manganese and
aluminum (PE-115) are determined by direct aspiration into the
flame of the atomic absorption spectrophotometer. Calcium and
magnesium are diluted with lanthanum chloride to mase inter-
ferences . All elements are compared with standard calibration
curves. All analyses are performed on the primary digestion
solutions except chromium.
Chromium requires a special preparation for solid
samples. Digestion of coal, ash, limestone, and sludge is
accomplished with nitric, sulfuric, and perchloric acids in a
reaction flash. A packed reflux column is attached to prevent
any loss of -chromium. Perchloric acid oxidizes all the chromium
+s
to Cr . This method was developed by Rains and Menis (RA-155)
as a mercury determination procedure. Radian has applied the
method to the determination of chromium in NBS standard reference
B-14
-------
materials of coal and coal ash and the results were comparable
to the reported values.
2.16 Determination of Mercury by Flameless Atomic Absorption
Two methods were used for mercury analysis:
(1) acid permanganate
(2) gold amalgamation
Mercury is determined by a flameless atomic absorption
technique. Liquid samples are treated with acid potassium permanga-
nate to oxidize all of the mercury present to the +2 oxidation
state. The excess KMnOi» is removed with the addition of
H|.
hydroxylamine hydrochloride, and the Hg 2 is reduced to elemental
mercury by the addition of stannous chloride, which is swept
through the absorption cell of the atomic absorption unit for
determination.
Gold amalgamation collection of mercury has been
reported by several workers (KA-086, DI-043). Radian utilizes
a double amalgamation technique in which mercury is collected
on a gold wire plug in a quartz tube either from flue gas passed
through the tube or from thermal desorption into a stream of
argon from solid samples. The mercury thus collected is desorbed
by heating and amalgamated on a second tube to minimize inter-
ferences. Upon desorption from the second tube, the mercury is
passed into an absorption cell positioned in the atomic absorp-
tion spectrophotometer.
B-15
-------
2.17 Sulfur Determination by Titrimetry
The method of sulfur analysis consists of determining
the total sulfur as sulfate by titrimetry. Initial sample pre-
paration for coal is performed by ignition in a Parr Ignition
Bomb and sorption of the evolved SO2 in a sodium carbonate solu-
tion. Sludge and ash samples are mixed with hydrochloric acid
and the solids filtered. In both cases, hydrogen peroxide is
added to oxidize sulfite to sulfate. The sample is passed through
a cation exchange column to form sulfuric acid. The acid is
titrated with standard sodium hydroxide and the sulfur concentra-
tion determined.
Nitrate and phosphate ions interfere. Heat applied
with hydrochloric acid at pH 2-4 avoids nitrite interference in
the column. If the sample is heated at 275°C for 30 minutes to
drive off sulfuric acid, phosphate can be determined and the
value subtracted from the total to give sulfate ions.
2.18 Spectrophotometrie Determination of Boron
Radian's boron procedure combines the separation method
of Carlson (CA-084) and the spectrophotometrie determination of
Mair and Day (MA-190). An ion-exchange column is prepared using a
boron specific resin, Amberlite XE-243, to separate boron in the
primary digestion from interfering ions and allow complete boron
recovery. It is then extracted into chloroform with 2-ethyl-l,
3-hexanediol. Boron in the organic phase is converted to the
highly absorbing rosocyanin complex using glacial acetic acid
followed by sulfuric acid. The absorbance of the complex is read
on a double-beam spectrophotometer and samples compared with a
standard calibration curve.
B-16
-------
BIBLIOGRAPHY
BA-131 Baker, R. L., "Determination of Fluoride in Vegetation
Using the Specific Ion Electrode", Anal. Chem.
44(7), 1326 (1972).
BA-137 Baumann, Elizabeth W., "Trace Fluoride Determination
With Specific Ion Electrode", Anal. Chim. Acta 42,
127-32 (1968).
BO-027 Bokowski, D. L., "Rapid Determination of Beryllium by
a Direct-Reading Atomic Absorption Spectrophoto-
meter", Am. Ind. Hyg. Assoc. J. 29(5), 474-81
(1968) .
BU-136 Burke, Keith E., "Determination of Microgram Amounts
of Antimony, Bismuth, Lead and Tin in Aluminum,
Iron and Nickel-Base Alloys by Nonaqueous Atomic-
Absorption Spectroscopy", Analyst 97, 19-28 (1972).
CA-084 Carlson, R. M. and J. L. Paul, "Potentiometric Deter-
mination of Boron as Tetrafluoroborate", Anal.
Chem. 40(8), 1292 (1968).
CI-002 Cioni, R., F. Innocenti, and R. Mazzuoli, "The Deter-
mination of Vanadium in Silicate Rocks with the
HGA-70 Graphite Furnace", Atomic Absorption
Newsletter 11(5), 102 (1972).
DA-105 Davison, Richard L., et al., "Trace Elements in Fly
Ash, Dependence of Concentration on Particle Size",
Env. Sci. and Tech. 8 (13), 1107, (1974).
DI-043 Diehl, R. C., et al., Fate of Trace Mercury in the
Combustion of Coal, RPR-54, Pittsburgh, Pa.,
Pittsburgh Energy Research Cntr., 1972.
B-17
-------
ED-027 Ediger, Richard, "Atomic Absorption Analysis with the
Graphite Furnace Using Matrix Modification",
Atomic Absorption Application Study No. 584,
Perkin-Elmer, 1975.
HA-258 Harstein, A. M. , R. W. Freedman, and D. W. Platter,
"Novel Wet-Digestion Procedure for Trace-Metal
Analysis of Coal by Atomic Absorption", Anal.
Chem. 45(3), 611 (1973).
HE-094 Headridge, J. B. and D. Risson Smith, "Determination
of Trace Amounts of Antimony in Mild Steels by
Solvent Extraction Followed by Atomic Absorption
Spectrophotometry", Lab. Practice 20(4), 312
(1971).
HU-095 Huffman, Claude, Jr., J. D. Mensik, and L. F. Rader,
"Determination of Silver in Mineralized Rocks by
Atomic-Absorption Spectrophotometry", U.S.G.S.
Prof. Paper 550-B, B189-191, (1966).
JO-012 Joyner, T., et al., Env. Sci. and Tech.l, 417 (1967).
KA-086 Kalb, G. 'Win. and Charles Baldeck, The Development of
the Gold Amalgamation Sampling and Analytical
Procedure for Investigation of Mercury in Stack
Gases, PB 210 817, Columbus, Ohio, TraDet, Inc.,
1972.
KI-085 Kinrade, John D. and Jon C. Van Loon, "Solvent Extrac-
tion for Use with Flame Atomic Absorption Spec-
trometry", Anal. Chem. 46(13), 1894 (1974).
B-18
-------
LE-068 Levesque, M. and E. D. Vendette, "Selenium Determination
in Soil and Plant Materials", Canad. J. Soil Sci.
51, 85-93 (1971).
MA-190 Mair, James W. , Jr. and Harry G. Day, "Curcumin
Method for Spectrophotometry Determination of
Boron Extracted From Radiofrequency Ashed Animal
Tissues Using 2-Ethyl-l, 3-Hexanediol", Anal.
Chem. 44(12), 3015 (1972).
OR-016 Orion Research, Inc., Analytical Methods Guide, 3rd
ed., Cambridge, Mass., 1972.
PE-115 Perkin-Elmer, Instructions, Model 503, Atomic Absorp-
tion Spectrophotometer, Norwalk, Conn., 1974.
RA-125 Rader, L. F. and F.. S. Grimaldi, Chemical Analyses for
Selected Minor Elements in Pierre Shale, U.S.G.S.
Professional Paper 391-A, Washington, D. C., GPO,
1961.
RA-147 Ramakrishna, T. V. , J. W. Robinson, and Philip W. West,
"Determination of Phosphorus, Arsenic or Silicon
by Atomic Absorption Spectrometry of Molybdenum
Heteropoly Acids", Anal. Chim. Acta 45, 43-49
(1969).
ft
RA-155 Rains, Theodore C. and Oscar Menis, "Determination of
Submicrogram Amounts of Mercury in Standard
Reference Materials by Flameless Atomic Absorption
Spectrometry", J. Assoc. Offic. Anal. Chem. 55(6),
1339-1344, (1972).
B-19
-------
TH-049
Thatcher, L. L. and F.. B. Barker, "Determination of
Uranium in Natural Waters", Anal. Chem. 29(11),
1575 (1957).
TH-060 Thomas, Josephus, Jr. and Harold J. Gluskoter, "Deter-
mination of Fluoride in Coal with the Fluoride
Ion-Selective Electrode", Anal. Chem. 46(9),
1321 (1974).
TU-025 (G. K.) Turner Associates, "Uranium", Fluorometry
Reviews Series, Palo Alto, Ca. , Feb.. 1968.
B-20
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COAL FIRED POWER PLANT
TRACE ELEMENT STUDY
VOLUME III
STATION II
SEPTEMBER 1975
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
REGION VIII
DENVER, COLORADO
BY
RADIAN CORPORATION
AUSTIN, TEXAS
TS-lc
-------
FOREWORD
The four volumes comprising this document describe a
coal-fired power plant trace element study prepared under EPA
Contract 68-01-2663.
This work was conducted under the direction of Mr.
Terry L. Thoem, Project Officer, Environmental Protection Agency,
Region VIII, Denver, Colorado. The Radian program staff included
Dr. F. G. Mesich as Program Manager and Dr. K. Schwitzgebel as
Technical Project Director. Principle contributors were Mr.
R. A. Magee, Dr. F. B. Meserole and Mr. R. G. Oldham.
Acknowledgement is given to the station personnel from
each utility company whose full cooperation greatly facilitated
the field work. Mr. R. M. Mann, Mrs. G. E. Wilkin and Mrs.
C. M. Thompson contributed significantly to the program during
sampling and analysis.
i
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VOLUME III
TABLE OF CONTENTS
Page
TABLE OF CONVERSION UNITS 1
STATION II SUMMARY 2
1.0 INTRODUCTION 4
2.0 SAMPLING AND SAMPLE HANDLING 6
2.1 Plant Description 6
2.2 Sampling Points and Flow Rate
Determinations 6
2.3 Summary of Flow Rates and Estimated Errors. 15
2.4 Sampling Schedule 15
2.5 Sample Analysis 18
3.0 DATA EVALUATION 23
3.1 Trace Element Material Balances 23
3.2 Error Propagation Analysis 25
4.0 RESULTS 26
5.0 DISCUSSION OF RESULTS 37
5.1 Material Balance Closure 37
5.2 Distribution of Elements in the Exit
Streams 40
APPENDIX A - SAMPLING AT STATION II
APPENDIX B - ANALYTICAL PROCEDURES
-------
TABLE OF CONVERSION UNITS
To Convert From
BTU
BTU/pound
Cubic feet
Cubic yards
Feet
Feet/second
Gallons (U.S. liq.)
Gallons (U.S. liq.)
Gallons/minute
Grains/cubic foot
Inches
Inches of 1^0 (4°C)
Pounds
Pounds/BTU
Pounds/hour
Pounds/standard
cubic foot (60 F,
29.92 inches Ilg)
Tons
Yards
To
Calories, kg
Calories, kg/kilogram
Cubic meters
Cubic meters
Meters
Meters/second
Cubic meters
Liters
Cubic meters/minute
Grams/cubic meter
Centimeters
Millimeters Hg (0°C)
Kilograms
Kilograms/Calorie, kg
Kilo gr ams/hour
Kilograms/standard
cubic meter (0 C,
760 mm Hg)
Metric tons
Meters
Multiply By
0.25198
0.55552
0.028317
0.76455
0.30480
0.30480
0.0037854
3.7854
0.0037854
2.2884
2.5400
1.8683
0.45359
i Qnm
J- « W ±.
0.45359
15.155
0.90719
0.9144
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STATION II SUMMARY
Station II is representative of a generating station
firing sub-bituminous coal and using a hot-side electrostatic
precipitator for particulate control. All station streams
were sampled and analyzed to determine the trace element content.
Material balance closure was achieved for some 23 of the 27
elements characterized in detail. In addition, semi-quantita-
tive results were obtained by spark source mass spectrometry for
a total of 53 elements.
Development of correlations permitting the prediction
of emissions from coal-fired generating stations will require
an extensive data base relating the .distribution of trace elements
as a function of coal composition and operating conditions. For
Station II, the following elements were found to be concentrated
in the flue gas emissions over the amount expected from the mass
of the ash:
Sulfur
Lead
Mercury
Molybdenum
Chlorine
Nickel
Antimony
Boron
Chromium
Zinc
Fluorine
Cadmium
Selenium
The following elements appear to be uniformly dis-
tributed in the ash streams:
Barium Iron
Beryllium Magnesium
Vanadium Manganese
Aluminum Titanium
Calcium
-2-
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The elements copper, cobalt, uranium, arsenic, and
silver display intermediate behavior and are enriched in the
precipitator ash stream.
These results are compared and contrasted in Volume
I with Stations I and III using wet scrubbing and mechanical
particulate collection, respectively.
-3-
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1.0 INTRODUCTION
The use of the extensive coal resources in the
Northern Great Plains area of the United States may provide a
significant part of the country's energy growth for the foreseeable
future. As natural gas and oil resources become less available
and more costly, coal will receive increasing emphasis as a
primary energy source. A coal-fired generating station produces
a variety of emissions and effluents ranging from' sulfur and
nitrogen oxides and particulates in the flue gas to solid and
liquid wastes.
In addition to carbonaceous material, coal contains
inorganic matter which becomes part of the emissions and
effluents from the generating station. The overall 'Objective
of this program was to define the sources, levels, and dis-
position of potentially toxic trace and minor elements in power
plant streams. The levels of trace elements in various streams
may be expected to be a function of both coal composition and
plant operating configuration.
This volume describes the detailed characterization,
with respect to trace and minor elements, of a tangentially-
fired boiler firing Wyoming sub-bituminous coal and using a hot-
side electrostatic precipitator for fly ash control. The
particular plant designated as Station II operates at a design
rating of 350 MW.
The following trace elements were examined in detail:
-4-
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Aluminum
Calcium
Lead
Silver
Antimony
Chlorine
Magnesium
Sulfur
Arsenic
Chromium
Manganese
Titanium
Barium
Cobalt
Mercury
Uranium
Beryllium
Copper
Molybdenum
Vanadium
Boron
Fluorine
Nickel
Zinc
Cadmium
Iron
Selenium
A material balance was calculated for each element to
provide a sound basis for evaluating the reliability of the
emissions measurements. In addition, each sample was surveyed
using spark source mass spectrometry to provide a semi-
quantitative assessment of 53 trace elements.
The following sections give a description of the plant,
a discussion of the sampling, analytical strategies, and pre-
sentation and discussion of the experimental data. Appendices
are provided which describe the sampling of the plant and
analytical methodology.
-5-
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2.0
SAMPLING AND SAMPLE HANDLING
The procedures used to sample Station II are presented
briefly in this section. Details are given in depth in Appendix
A, "Sampling at Station II". Sampling was performed during the
period October 21-23, 1974.
2.1 Plant Description
Station II consists of a 350 MW unit with a tangentially-
fired boiler. The boiler is fired with Wyoming sub-bituminous
coal delivered to the plant site by rail and stored in an open pile
from which it is conveyed to storage silos. From the silos, the
coal is fed to mills for pulverizing prior to delivery to the
boiler. Bottom ash, economizer ash and pyrites from the mills
are sluiced intermittently to a nearby settling pond using
cooling-tower blowdown. Hot-side electrostatic precipitators
provide fly ash control. The collected ash is pneumatically
conveyed to a storage silo and trucked away from the plant site.
Plant load ranged from 335-350 MW during the sampling period.
2. 2 Sampling Points and Flow Rate Determinations
The streams sampled are shown schematically in Figure
2-1. The incoming streams are coal and sluice water. Outgoing
streams are sluice ash, including pyrites from the mills, dis-
charged sluice water, precipitator ash, and flue gas containing
fly ash. The physical location of the points for sampling these
streams at the station are schematically shown in Figure 2-2.
Immediately prior to the sampling effort and after
the preliminary plant inspection, a special refactory cooling
system was installed in the boiler-bottom ash hopper area.
Approximately 1.13 x 10s lb/hr (225 gpm) of cooling tower blowdown
-6-
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INLET STREAMS OUTLET STREAMS
Coal ^
Sluice Solids \
Inlet Sluice Water ,
Outlet Sluice Water ^
/
Refractory Cooling
Water (Not Sampled)
Refractory Cooling
Water (Not Sacraled)
, . y
Precipitator Ash
/
Fly Ash and Flue Gas
)
FIGURE 2-1
INLET AND-OUTLET STREAMS
AT STATION II
-7-
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FIGURE 2-2 SCHEMATIC OF STATION II
-------
was directed to the refactory region in the bottom ash hopper
and the overflow pumped to the ash pond separately from the
regular ash sluice stream. The existence of these inlet and
outlet streams was not noted during the sampling effort and they
were, therefore, not sampled. These were then not included in
either the inlet or outlet portions of the material balances to
be presented in Table 4-5. The composition of the refactory
cooling water inlet and outlet streams should be similar to the
inlet and outlet sluice water. With the exception of chlorine,
the levels of the elements are low enough that an increase of
227, (the quantity of water flow neglected) would npt significantly
alter the elemental mass flows presented. In addition to this
inlet and outlet water flow, several other small water streams
such as clarifier underflow from the lime softener, boiler
blowdown, and miscellaneous plant drains were considered insig-
nificant or were not related to the combustion process and were
not sampled.
Sample Point 1: Coal
The coal was stored in five storage silos from which it
was conveyed to the mills. Three of the coal streams to the mills
were sampled at the metering feeders; one feeder being sampled
every fifteen minutes. The individual samples were combined and
stored in closed plastic containers. Two samples of the composite
were obtained at the end of the sampling period by sequential
splitting using riffle buckets.
The coal flow rate was metered to each of the mills
at the coal feeders. The meter readings were recorded every
hour in the control room. An average hourly flow rate was cal-
culated from the matsr readings and corrected for the moisture
content of the coal to give a dry feed rate.
-9-
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Sample Point 2: Inlet Sluice Water
The sluice water was a combination of plant service
water, recycle water from the ash pond, and cooling tower blow-
down which were combined in a storage tank. Individual samples
were collected from the storage tank every three hours and
combined to form two composite samples which were acidified to
prevent wall adsorption of trace constituents.
The flow rate of sluice water was determined from the
pressure drops across the two sluice pumps recorded during the
sluicing periods. The intermittent flow rate was averaged over
the four-hour sluicing cycle to give an equivalent continuous
flow rate.
Sample Points 3 and 4: Ash Sluice
The ash sluice slurry stream was sampled every 2.5
minutes at the point of discharge to the ash pond during the
pumping periods which were on a regular four-hour cycle. The
combined sluice samples provided a composite sample of bottom
ash, economizer ash, and pyrites from the mills. The solids and
liquid were separated by filtration. The solids were retained
and a portion of the filtrate was acidified to prevent wall
adsorption of trace components.
The exit sluice water flow rate was equal to the inlet
sluice water rate previously discussed.* The ash sluice solids
flow rate was calculated from the total ash in the coal, the fly
ash discharge (Sample Point 6) and a 78%*22% split between sluice
ash and precipitator f.sh estimated by plant personnel.
-10-
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Sample Point 5: Precipitator Ash
Samples of the precipitator ash were collected from a
portal in the top of the ash storage silo hourly during the
sampling period. The individual samples were combined to form
a composite sample. Two samples were obtained for analysis by
sequential splitting using riffle buckets.
The precipitator ash flow rate was calculated from the
estimated split between sluice ash and precipitator ash described
above.
Sample Point 6: Flue Gas
The flue gas containing fly ash is discharged from a
500-foot double-walled stack. The stack was equipped with four
sampling ports, two at each end of two perpendicular diameters
of the stack at the 375-foot level.
The velocity profile in the stack was determined as per
EPA Method 2 using S-type pitot tube and thermocouple measure-
ments. Individual values obtained at 16 points in the stack were
averaged to determine an integral velocity. The sampling points
were located according to EPA Method 1 for sample point location
in a circular duct. Sample point location is described in detail
in Appendix A.
The dust loadings were measured at the same set of
points. Gelman filter devices were used to determine cumulative
dust loadings for four points from each sample port. The average
grain loading in the stack was then calculated from the individual
determinations.
-11-
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Particulate matter for analysis was collected with wet
electrostatic precipitators (WEP). This method of collection
permits sampling over an extended time at isokinetic conditions
without plugging, as occurs in a filter. Thus, a sufficient
quantity of sample can be collected to permit repeated analyses.
In addition, problems of trace element contamination by the
filter substrate are avoided. A detailed description of the WEP
device is given in Appendix A. To confirm the comparibility of
this sampling approach with the filter technique recommended by
EPA,, an EPA filter was run in series with the WEP at Station III.
A 125 mm Gelman class "a" glass filter was used in a glass filter
holder. The whole assembly was heated to avoid condensation of
sulfuric acid mist. The particulate matter collected by the filter
during four WEP runs was equivalent to a grain loading of 0.0009
grains/scf. The inlet particulate loading to the WEP was 0.21
grains/scf, giving a collection efficiency of the WEP of 99+%.
The WEP samples were collected at a single point in
the stack and a correction made from the grain loading at this
point to the average grain loading. The dust concentration at
the sampling point was determined from the calcium and titanium
concentrations in the WEP sample assuming that these elements
are evenly distributed in the particulates with respect to par-
ticle size. This assumption is based on work performed by
Davison, et al. (DA-105) in which fly ash samples were collected
from the duct of a coal-fired station. Andersen impactor samplers
were used to separate the particulates into seven size fractions.
The results of this work for calcium and titanium are presented
in Table 2-1. It is evident from these data that the assumption
of uniform ash composition with respect to calcium and titanium
holds within experimental limits.
-12-
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TABLE 2-1
CALCIUM AND TITANIUM ANALYSES* OF
ANDERSEN IMPACTOR PARTICLE SIZE FRACTIONS (DA-105^
Particle Diameter Ca Ti
H55 wt%
>11.3 4.9 1.12
7.3 - 11.3
4.7 - 7.3 4.2 0.92
3.3 - 4.7
2.06-3.3 5.0 1.59
1.06 - 2.06
0.65 - 1.06 2.6 1.08
Analysis by X-ray fluorescence spectrometry
-13-
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The relationship between particle size and titanium
and calcium concentrations in the fly ash is important to this
correction because the precipitator ash has a larger average
particle size than the exiting fly ash. If the titanium and
calcium concentrations were dependent on particle size, the
assumption made in Equation (2-1) that the titanium and calcium
concentrations in the fly ash is the same as in the precipitator
ash is not valid.
The point grain loadings were determined from the
calcium and titanium concentrations in the WEP samples and the
calcium and titanium weight fractions found in the precipitator
ash using the relation:
Point grain
load (gr/scf)
15.4 VT
TT7
"XWL(Ca)
+
XWL(Ti)
(2-1)
where,
VL = volume of the WEP liquor (ml)
Vq = volume of flue gas sampled by WEP (scf)
XW^(Ca) = concentration of calcium in WEP liquor (yg/ml)
XWAsh(Ca) = weight fraction of calcium in the precipitator
ash (ppm)
XW^(Ti) = concentration of titanium in WEP liquor (yg/ml)
XWAsh(Ti) = weight fraction of titanium in the precipitator
ash (ppm)
-14-
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The point to average grain loading correction factor
is then the ratio of the average grain load in the stack to the
point grain load calculated from equation (2-1). The correction
factor was 1.13.
Gaseous mercury in the flue gas was collected by gold
amalgamation. Hydrogen peroxide bubblers were used to absorb
SC>2 in the flue gas as per EPA Method 6.
2.3 Summary of Flow Rates and Estimated Errors
A summary of the flow rates is given in Table 2-2.
The error limits presented in this table are largely based on
Radian field experience and the typical errors expected with
the flow measuring devices. The error limits for the sluice
water inlet and outlet flows are estimated from the accuracy
of the dynamic pressure head measurements and the slope of the
pump curves in that region. The error limits for precipitator
and sluice ash are based on the assumption that the maximum range
around the 22%-78% ash split estimated by plant personnel is
between 17%-83% and 27%-73%. Also summarized in this table are
the procedures used to obtain the listed rates.
2.4 Sampling Schedule
With the exception of the ash sluice stream, all plant
streams were continuous with short residence times in the system.
Bottom ash and economizer ash were sluiced on a four-hour cycle
and pyrites sluiced every eight hours, Sampling was time-phased
to collect samples from the sluice stream representative of the
ash which had accumulated during the sampling period.
Sampling was performed during the period October 21-
23rd according to. the schedule shown in Figure 2-3. Those
samples enclosed in parenthesis were analyzed, the rest were
retained in reserve.
-15-
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TABLE
FLOW RATES FOR STREAMS
Stream
Coal
Inlet Sluice Water
Sluice Solids
Sluice Liquid
Precipitator Ash
Flue Gas
Fly Ash
Flow Rate
2.75 x 105 lb/hr
5.02 x 105 lb/hr
4.4 x 103 lb/hr
5.02 x 10s lb/hr
1.53 x 10" lb/hr.
5.46 x 107 scfh
1.40 x 102 lb/hr
STATION H
Method Used for
rror Limit Flow Determination
10% Metered at coal feeders
±157. Pump heads and pump
curves
125 70 Plant personnel esti-
mate of ash distribution
and total ash from coal
J157, Rate set equal to inlet
sluice water
tlOT. Plant personnel estimate
of ash distribution and
total ash from coal
±107. Measured by stack traverses
±107. Determined from cumulative
grain loadings
-------
point sample
continuous sampling
Coal Feeder A
Feeder C
Feeder E
Inlet Sluice Water
Sluice Solids
4. Outlet Sluice Water
5. Precipitator Ash
6. Flue Gas Velocity
Flue Gas Particulate
Loading
Flue Gas WEP
Particulate Collection
(- ~)
(- -)
Oct. 21
Oct. 22
Oct. 23
FIGURE 2-3
SAMPLING SCHEDULE AT STATION II
-17-
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2. 5 Sample Analysis
The techniques used for the quantitative determinations
were based on:
(1) atomic absorption
(2) X-ray fluorescence
(3) ion selective electrodes
(4) fluorometry, and
(5) colorimetry
The methods are described in greater detail in Appendix B,
"Analytical Procedures".
Figures 2-4 through 2-6 give a brief summary of
dissolution and analytical methods used for trace element deter-
mination in the samples.
The analytical accuracies of the techniques are sum-
marized in Table 2-3. These values were derived by comparing
analytical results with NBS standards where available. In the
oth'er cases, recovery studies and/or precision values are the
basis for the estimated confidence level.
Semi-quantitative analyses based on spark source mass
spectrometry (SSMS) for 53 elements were performed by Accu-Labs,
Inc., Denver, Colorado. Since the accuracy of this method is
strongly dependent on the matrix, an error limit could not be
estimated in the framework of the present study.
-18-
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M°» Cd, Sb,
Ni
FIGURE 2-1
ANALYSIS PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL
-19-
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HN03-H2S04-HC104
Atomic Absorption
Reflux Digestion
HNO3 Digestion
Atomic Absorption
Li„CO,-Na B.0, Fusion
^3 2 4 7
X-Rav Fluorescence
Ion Selective Electrode
^2^2 Fusion
Ba
CI, F
NaF Fusion
Fluorescence
Ash/
Sludge
HNO^ - HCIO^ Digestion
Fluorescence
¦ U
Se
HC1 Digestion
Titrimetry
Gold Amalgamation
Atomic Absorption
•Hg
Primary Digestion
(Thermal Oxidation,
HF-HNO3-H2SO4 Digestion)
Spectrophotometry
Atomic Absorption
Extraction/Atomic Absorption
Ti, B
Al, Mg, Fe,
Ca, V, As,
Mil, Cu, Zn
Co, Be, Pb,
Mo, Cd, Sb
Ni
FIGURE 2-2
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL ASH AND SLUDGE
-20-
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FIGURE 2-4
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF WET ELECTROSTATIC PRECIPITATOR LIQUORS AND AQUEOUS SAMPLES
-21-
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TABLE 2-3
ESTIMATED ERROR LIMITS FOR THE CHEMICAL ANALYSES
WEP
Aqueous
Coal and
Liquor
Samples
Coal Ash
Aluminum
±10
±10
± 8
Antimony
±10
±10
±15
Arsenic *
± 8
± 8
±10
Barium
±20
±20
±20
Beryllium
±10
±10
±12
Boron
± 8
± 8
± 8
Cadmium *
±12
±12
±12
Calcium
± 2
± 2
± 2
Chlorine
±10
±10
± 8
Chromium *
±10
±10
±12
Cobalt
±10
±12
±10
Copper *
±10
±10
±12
Fluorine
± 8
± 8
± 8
Iron*
± 6
± 6
± 6
Lead*
±10
±10
±18
Manganese*
±10
±10
± 8
Magnesium
± 2
± 2
± 2
Mercury *
±20
±10
±10
Molybdenum
±12
±12
±15
Nickel*
±12
±12
±12
Selenium*
± 5
± 5
± 5
Titanium
± 8
± 8
± 8
Silver
±10
±10
±10
Sulfur
±10
± 2
± 2
Uranium*
± 8
± 8
± 6
Vanadium*
±12
±12
±10
Zinc*
±10
±10
±12
—
By comparison with NBS Standard Reference Materials 1633 and 1634.
-22-
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3.0 DATA EVALUATION
The flow rates and chemical analyses are used to
calculate the transport rate of the elements of interest through
the boiler and their discharge rates in the effluent streams.
A material balance is made around the boiler for each of the
elements. The mathematical correlation forms are given in the
next sections.
3.1 Trace Element Material Balances
The transport rates of the elements of interest through
the steam station are calculated from the chemical analyses of
the samples and the flow rates of the incoming and exiting streams.
A material balance is calculated for each of the trace elements
to verify the determined emission values.
Equating the trace element flow into the system to the
flow out of the system gives the following expression:
Mc • XWc(j) + Masw • XWasM(j) - (3-1)
«ba ' ^ba^ + "basw ' ^basw^ + Mea ' *»««> + Measw
+ Mca ' ^caO' + Vfgs ' XV£gs + Vfgn • XVfgn(j)
where
Mc - the mass flow rate of coal into the boiler on
a dry weight basis (lb/hr.)
XWgCj) " the weight fraction of the element j in the coal
on a dry weight basis
-23-
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M = the mass flow rate of the inlet sluice water to
qSW
the ash sluice system (lb/hr)
XW (j) = the weight fraction of the element j in the inlet
ciSW
sluice water
M = the mass flow rate of sluice solids from the
ss
system (lb/hr)
XW (j) = the weight fraction of the element j in the sluice
b O
solids
= the discharge rate of sluice water from the ash
sluice system equal to Masw (lb/hr)
XW8i(j) = weight fraction of the element j in the sluice
water
= the collection rate of ash in the electrostatic
pa
precipitators (lb/hr)
^(3) = the weight fraction of the element j in the pre-
cipitator ash
Vfg = the volumetric flue gas flow rate in the stack
(scfh)
XV£g(j) = the weight of the element j per unit volume of
flue gas (lb/scf)
-24-
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3.2 Error Propagation Analysis
An error propagation analysis was performed on the
material balance equations for each element. Error limits are
calculated for the total inlet and outlet rates of each element
indicating the magnitude of variation to be expected due simply
to random errors.
Only errors random in nature are considered m this
treatment. A variance is calculated for a given value according
to the following standard definition.
s!
-------
4.0 RESULTS
The values for the proximate and ultimate analysis of
the coal are presented in Table 4-1, the coal ash analysis in
Table 4-2.
The quantitative analysis results are listed in Table
4-3. The element concentrations in the coal and the flow rates
are reported on a dry weight basis. Most of the values in
Table 4-3 are presented in parts per million on a weight
basis for the solid samples or micrograms per milliliter for
liquids. Some elements present in higher concentrations are
listed as percent. The WEP results are presented in pounds per
standard cubic foot of dry flue gas, where standard conditions
are a temperature of 60°F and pressure of 29.92 inches of
mercury.
Table 4-4 presents the analytical results obtained by
SSMS. The coal sample was analyzed in duplicate to estimate the
precision of this method of analysis. The duplicate results
differ in some cases by factors of three or greater as indicated
for A1, Be, B, Cd, CI, Eu, Ho, Li, and Nd. Systematic errors
caused by matrix effects could not be determined within the
scope of the present work. Blind duplicate samples were also
submitted for the precipitator ash samples. The differences
between duplicate samples were fairly large as evidenced by a
factor of 5 for Bi, 3 for Ce, 5 for Dy, 5 for Hf, 3 for I and
3 for Pb. However, these data (SSMS) are useful for order-of-
magnitude estimates of trace element flows.
The trace element flov rates in lb/hr are listed in
Table 4-5, using the quantitative analysis results and in Table
-26-
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TABLE 4-1
STATION II COAL ANALYSIS
Proximate
As Received
Dry
7o Moisture
29.19
0.00
% Ash
5.12
7.23
% Volatile Matter
30.15
42.58
% Fixed Carbon
35.54
50.19
Total
100.00
100.00
7o Sulfur
0.35
0. 49
BTU/lb
8290
11,708
Moisture and Ash
Free BTU/lb 12,621
Ultimate
% Carbon 48.31 68.23
7. Hydrogen 6.53 4.64
7o Nitrogen 0.67 0.95
7, Oxygen 39.02 18.46
% Sulfur 0.35 0.49
% Ash 5.12 7.23
Total 100.00 100.00
-27-
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TABLE 4-2
STATION II ASH ANALYSIS
Mineral Analysis of Ash Percent
Silicon Dioxide, Si02 28.68
Aluminum Oxide, A1203 18.25
Titanium Dioxide, Ti02 1.73
Iron Oxide, Fe203 4.75
Sodium Oxide, Na20 1.32
Potassium Oxide, K20 0.40
Calcium Oxide, CaO 21.97
Magnesium Oxide, MgO 3.60
Phosphorus Pentoxide, P205 1.49
Sulfur Trioxide, S03 14.43
Other 3.38
Total 100.00
Ash Viscosity Calculations
Basic Content 39.69
Acidic Content 60.31
Base-to-Acid Ratio 0.66
Silica-to-Alumina Ratio 1.57
Temperature for 250 Poise Viscosity, °F 2230
-28-
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TABLE 4-3 ANALYTICAL RESULTS OF THE STATION II SAMPLES1
Element
Coal
Inlet Sluice I
Water
Precipitator
Ash
Sluice
Ash
Sluice
Ash
Filtrate
Combined
WEP
^uminum
.717.
<.1
12%
10.9%
9.2
31.
Antimony
.16
.0023
2.3
00
o
V
.0038
• 0029
Arsenic
2.5
<.0001
48.
1.4
<.0001
OOO 7
Barium
460.
<.6
.78%
.52%
< .6
.26
Beryllium
.29
<.002
5.6
4.1
<.002
.004.2
3oron
31.
. 17
550.
240.
.49
.92
Cadmium
<.1
< .002
1.2
<.8
<.002
OOls
Calcium
1.09%
57.
19. 5%
15.1%
113.
55.
Chlorine
9.4
VD
OO
47.
<1.
15.
29.
Chromium
9.3
< .053
116.
< . 053
.59
Cobalt
1.5
<.003
27.
18.
<.003
.015
C.oooer
31.
.012
460.
230.
.022
• 12
Fluorine
67 •
.45
1130
19.
. 70
2.7
Iron
.21%
.12
2.95 %
4.06%
.01
9.5
Lead
2.3
.017
22.
11.
.006
•06q
Manganese
24.
.034
406.
310.
.016
.18
Magnesium
.15%
15 ¦
2.80%
2.06%
16-
8.1
Mercurv
. 14
.08
<.010
< .010
<.0004
• 017
Molybdenum
.64
. <.0002
8.4
3.5
.015
• 03i
Nickel
2.1
A
O
N>
37.
27.
A
O
N>
• 29
Selenium
1.6
.0017
6.8
.35
.0038
•12
Titanium
565.
<.1
.96 %'
.91%
<.1
2.2
Silver
.048
<• 0003
.90
. 11
< .0003
o
O
O
U>
Sulfur
.49%
14.
.80%
910.
108.
2380.
Uranium
.89
.0084
5.8
5.0
.0044
•°Q3i
Vanadium
20.0
0.058
295
190
0.071
• 26
Zinc
4.1
.39
77.
156.
.0084
•0fc<^
Values represent the average of duplicate determinations. Values for liq
samples are reported as yg/ml and solids samples as ppni on a dry basis, un
otherwise noted. wEP values are reported as 10 ® lb/scf (60 F, 29.92 Hg)
-29-
-------
To
Id£L!L :,-h station it amai.yttcat. hi-spt.ts by ss-ms'
F. ] oment
Coal
Inlet Sluice
Water
Precipitator
Ash-'
Sluice Ash
Sluice Ash
Filtrate
Combine
WEP
Aluminum
670
-. 5?,
. 18
-17.
-7.'00
> 17»
2.5
18
An riir.ony
. 4 3
. 37
.001
2.7
1.1
1.1
.001
<.000 7
Arsenic
.89
. 98
.004
21 •
9.1
9.1
.003
<.0016
Barium
400
400
.022
A-4900
> . 5%
>1%
.22
.66
Beryllium
. 32
1.4
--
1.2
. 90
2.6
--
<.0007
Bismuth
<-. 47
<.47
--
12
2.3
5
--
<.0007
Boron
15
53
.016
¦\-1200
1-1500
750
.086
.071
Bromine
2.9
6.1
. 003
2.8
. 73
. 73
.018
.0036
Cadmium
5.7
1. 7
<.005
14
1.4
1.4
<.005
.0054
Calcium
'1%
>17.
49
>1%
>17.
>17.
100
35
Cerium
5.3
11
--
400
150
530
--
.0073
Cos ium
. 13
. 30
--
. 81
.81
. 81
--
<.0007
Chlorine
410
89
3
47
47
20
3
3
Chromium
7.4
4.9
.053
61
61
61
.053
. 44
Cobalt
3
3
--
16
8.9
14
--
.0054
Copper
25
9.3
.013
250
200
120
.013
.055
Dys p ros ium
1 7
1.6
--
19
3. 7
19
--
<.0007
Erb ium
.40
. 40
--
2.3
1.2
1.2
--
<.0007
Europium
. 39
. 12
--
4.3
2.1
4. S
--
<.0007
Fluorine
560
210
o
o
CnJ
-.2100
210
3
3
Gadolinium
. 13
. 13
--
2.1
. 75
2. 4
--
< .0007
Gallium
1.9
4
--
24
8.7
3.7
.021
.033
Germanium
. 37
22
--
3.6
' 3
3
. 004
. 0016
Go Ld
--
--
--
--
--
--
<.0007
Ha fnium
1.2
. 70
--
6. 7
1.3
6.7
--
<.0007
Holmium
. 11
.03
--
1.4
. 60
1.4
<.0007
Iodine
.80
1. 6
.001
.3
<.10
.64
.001
<.0007
Iridium
--
--
--
--
--
--
<.0007
Iron
-v2300
¦^2300
. 17
>17.
>17.
>17.
.53
5.3
Lanthanum
6
2.6
.003
77
42
77
.002
.0054
Lead
13
5.6
.005
120
35
15
.006
.011
Li thiurn
3.5
17
.009
120
210
120
.002
.0016
Lutetium
C. 10
. 14
--
. 77
.30
.77
—
<.0007
Magnes ium
--
>17.
15
>17.
>17.
>17.
16
5.9
Manganese
17
40
.013
.250
250
49
.013
.092
Mercury
--
--
--
--
--
--
--
<.0007
Molybdenum
18
7.9
.005
86
30
20
.047
.016
Neodymium
24
4. 7
--
250
130
250
--
.011
Nickel
2.2
4.5
.004
98
64
36
.02
.29
Niobium
5.4
2.5
--
32
16
57
--
.0036
Osmium
--
--
--
--
--
--
<.0007
Palladium
--
--
--
--
--
--
--
<.0007
Phosphorus
:i300
'¦1300
. 13
>17.
•• 1%
-.4800
. 20
4.4
Platinum
--
--
--. 0007
No t.es :
'Concentration in p~;r. weight in solids and .r/
-------
TABLE 4-4 STATION II ANAT.YTTCAT, RF.S1H.TS BY SS-MS'
Inlet Sluice Precipitator Sluice Ash Combined
Element
Coal
2
Water
AshJ
Sluice Ash
Fi ltrate
WEP
Potassium
470
280
2. 8
¦\.1200
^izon
¦*.1400
4.8
. 75
Praseodymium
5.3
5.3
--
40
20
20
--
.0016
Rhenium
--
--
--
--
--
--
--
--
Rhodium
--
--
--
--
--
--
--
<.0007
Rubidium
1.6
.69
. 003
43
43
87
.006
.0054
Ruthenium
--
--
--
--
--
--
--
<.0007
Samarium
.67
.33
--
9
1.8
4.2
--
A
o
o
o
Scandium
7.3
7.3
--
40
40
40
—
.0036
Selenium
3. 7
1.6
.002
13
4.7
1.3
.009
. 040
Silicon
>.57.
>1".
6.1
>1%
>17.
>17.
U
9.2
Silver
<.10
.12
--
.30
.21
, . 14
<.G01
<.0007
Sodium
- 2400
>1%
27
>1%
>17.
>17.
43
1.8
S trontium
310
310
2
>. 5%
>. 57.
>,57.
3.6
1.6
Sulfur
-1%
>17.
>
o
--
>17.
> . 57.
>100
>82
Tantalum
1
.49
--
6.1
1.3
3
--
<.0007
Tellurium
< . 10
<.10
< . 001
.93
. 13
. 16
: .001
.001^
Terbium
-.10
. 19
--
2.3
.80
1
--
<.000 7
Thallium
<.10
<.10
--
.57
. 13
<.10
--
< 0007
Thorium
1.9
4.3
--
24
3.6
18
--
<.0007
Thulium
<.10
.11
--
.3
. 14
. 70
--
<.0007
Tin
1.6
. 73
. 006
4.6
2
2.3
.002
.0054
Ti tanium
600
300
.020
>. 57;
>. 57.
>17.
.044
1.6
Tungs ten
.90
1.5
--
8
3.7
8
--
<.0007
Uranium
2
2
.001
12
2.3
12
<.001
<.0007
Vanadiuu
40
14
.003
500
210
210
.059
.099
Ytterbium
1
. 75
--
5
1.3
2.9
--
<.0007
Yttrium
24
10
--
300
60
160
.002
.082
Zinc
4.9
4.9
.37
110
38
58
.079
.066
Zirconium
lb
16
.002
57
31
170
.002
.033
Notes:
'Concentration in ppm weight in solids and ug/ml in liquids. WEP analysis in 10 ' lb/scf (60°F, 29.92"
Hg) •
Blind duplicate analysis.
5 Not recorded duo to loss from acidic solution.
'Approximate value only due to interference from preservative.
'Insufficient sample for determination.
--All elements not reported <0.1 ppm weight in solids or <0.001 ug/ml in liquids.
Maj . - Major component.
-31-
-------
TABLE 4-5 STATION II MATKKIAI. bAI.ANCKS*
Element
Alumlnun
And Bony
Arsenic
Barium
Beryl Hub
Boron
Cadalua
Calclua
Chlorine
Chromlun
Cobalt
Copper
Fluorine
Iron
Lead
Magneslua
Manganese
Mercury
Kolybdenua
Nickel
Selenlua
Silver
Sulfur
Tltanlua
Uranlua
Vanadlua
Zinc
Coal
1950
.044
.70
127
.080
8.5
<•028
3000
2.6
2.5
.41
8.5
18
580
.63
413
6.6
.037
.18
.58
.44
.013 •
1350
160
.24
5.5
1.1
Italet Sluice
Water
<•05
.0012
<.00005
<•30
<•0010
.09
<•0010
29
4.3
<•027
<.0015
.0060
.23
.060
.0085
7.4
.017
.040
<.0001
<.010
.0009
<.0001
7
<.05
.0042
.029
.20
£ In
1950 * 250
.045 ± .008
.7 t .1
130 ± 28
.08 t .01
8.6 ± 1
<•029
3030 i 310
6.9 ± .8
2.6 ± .4
.41 ± .06
8.5 ± !
19 ± 2
580 ± 70
.64 * .13
420 * 40
6.6 * .8
.077 ± .009
.18 t .03
.59 * .09
.44 ± .05
.013 ± .002
1350 * 140
160 ± 20
.25 ± .03
5.5 1 -8
1.3 * .2
Precipitator Ash Sluice Aati
1830
.035
.73
119
. 086
8. A
.018
2480
.72
1.8
.41
7.0
17
4 50
.34
428
6.2
<¦0002
.13
.57
.10
.014
120
146
.089
4.5
1.2
480
<.0004
.0062
23
.018
1.1
.0037
660
<.004
.34
.079
1.0
.084
180
.048
91
1.4
<.00004
.015
.12
.0015
.0005
4.0
40
.022
..84
.69
Outlet Sluice
Water
4.6
. 00i9
<•00005
<¦ 30
<•0010
.25
<. 0010
57
7.5
<¦027
<.0015
.011
.35
.0050
.0030
7.9
.0080
<•0002
.0075
<•010
.0019
<¦0001
54
<¦05
.0022
.036
.0042
Flue Gas
17
.0016
.0004
14
<•0023
.50
<.0009
30
16
.32
.0081
.068
1.5
5.2
.033
4.4
.10
.0093
.017
.16
.068
.0002
1300
1.2
.0017
• 14
. 046
£ Out
2330 ± 270
.040 t .006
.7 ± .1
140 ± 28
.11 ± .013
10 i 1
<.024
3730 ± 350
25 ± 3
2.5 ± .3
.5 ± .06
8 t 1
19 ± 2
640 ± 70
.42 ± .07
530 ± 50
7.7 ± .9
.010 ± .002
.17 ± .02
.86 ± .1
.17 ± .01
.015 ± .002
1480 ± 180
190 ± 20
.11 ± .01
5.5 t .7
1.9 ± .3
t Out/E In
1.19
.89
1.00
1.08
1.38
1.16
1.23
3.62
.96
1.22
.94
1.00
1.10
.66
1.26
1.17
.13
.94
1.46
.39
1.15
1.10
1.19
.44
1.00
1.46
~All values In lb/hr.
-------
4-6, using the SSMS results. The sum of the elemental flow rates
of all incoming streams, coal and ash sluice water, are gi
as 2 In. The flow rates of the outgoing streams, sluice ash,
sluice ash filtrate, precipitator ash and flue gas, also w
added and are listed as E Out. The error limits given were
calculated from the estimated errors in the analyses and i
the flows according to the procedures described in Section
The emission results for sulfur and particulates are
summarized in Table 4-7 since'these are the two emission para
meters of greatest immediate importance. The results are
provided on a lb/BTU basis to facilitate comparison to other
stations.
-33-
-------
TABLE 4-6 STATION II MATERIAL BALANCE BASED ON
SPARK SOURCE MASS SPECTROGRAPHS DATA *
Element
Coal
Inlet Sluice
Water
I In
Precipitator
Ash
Sluice Ash
Sluice Ash
Filtrate
WEP
Z Out
Aluminum
>1175
.090
>1400
-162
>46
. 1.3
9.9
>220
Antimony
. 17
.0005
. 17
. 31
. 005
. 0005
<.0004
.037
Arsfuic
26
.002
26
. 24
.042
.002
<.0009
. 29
Bari um
110
.011
110
a.79
>46
. 11
.36
>126
Beryllium
.25
<.0005
.25
.018
. 012
<.0005
<.0004
.031
Bismuth
< . 13
<.0005
<.13
12
. 023
<.0005
<.0004
. 14
Boron
9.4
.008
9.4
*.23
3. 5
.043
.039
'-26
Bromine
1.2
.004
1.2
. 029
. 003
.009
.002
.043
Cadmium
1.0
<.003
1.0
. 12
. 006
<.003
.003
. 14
Calcium
>2750
25
>2800
>162
>46
50
19
>280
Cerium
2.3
<.0005
2.3
4.5
2.4
<.0005
.004
6.9
Cesium
.061
<.0005
.061
.013
. 004
<.0005
<.0004
.018
Chlorine
69
--
69
. 76
.092
--
--
.85
Chromium
1.7
.027
1.7
. 99
. 28
. 027
. 24
1.5
Cobalt
.83
<.0005
.83
. 21
. 065
<.0005
.003
. 28
Copper
4. 7
.007
4. 7
3.6
.55
.007
.030
4.2
Dysprosium
. 74
<.0005
. 74
. 18
.088
<.0005
<.0004
.27
Erbium
. 11
<.0005
. 11
. 0!i2
. 006
<.0005
<.0004
.039
Europium
.072
<.0005
.072
.057
. 022
<.0005
<.0004
.080
Fluorine
106 •
--
106
34
. 97
--
--
¦v-35
Gadolinium
.036
<.0005
.036
.023
.011
<.0005
<„ 0004
.035
Gallium
. 83
<.0005
.83
. 26
.040
.011
.018
.33
Germanium
.083
<.0005
.083
.053
.014
.002
.0009
^70
Cold
<.028
<.0005
<.028
<.002
<.0004
<.0005
<.0004
<.003
Hafnium
.28
<.0005
.28
. 065
.031
< .0005
<.0004
.097
Holmium
.019
<.0005
.020
.016
.006
<.0005
<.0004
.024
Iodine
.33
.0005
. 33
. 005
. 003
<.0005
<.0004
. 009
Iridium
<.028
<.0005
<.028
<.002
<.0004
<.0005
<.0004
< .003
I ron
'-633
.085
^630
>162
>46
. 27
2.9
>210
Lanthanum
1.2
.002
1.2
.97
. 35
.001
.003
1.3
Lead
2.6
.003
2.6
1.2
.069
.003
.006
1.3
Lithium
2.8
.005
2.8
2.7
. 55
.001
.0009
3.2
Lutecium
.039
<.0005
.039
.009
. 004
<.0005
<.0004
.013
Magnesium
>2750
7.5
>2800
>162
>46
8.0
3.2
>220
Manganese
8.0
.007
8.0
4. 1
.23
.007
.050
4.3
Mercury
<.028
<.0005
<.028
<.002
<.0004
<.0005
<.0004
<.003
*A11 values in lb/hr.
-------
Element
Coal
InleC Sluice
Uacer
Molybdenum
3.6
.003
Neodymiu.il
4.0
<.0005
Nickel
,"94
.002
Niobium
1.1
<.0005
Op aiium
<.028
<.0005
Palladium
<.028
<.0005
Phosphorus
^358
.065
Platinum
<,028
<.0005
Potassium
99
1.4
Praseodymium
1.5
<.0005
Rhenium
<.028
--
Rhodium
<.028
<.0005
frubidium
.33
.002
Puthenium
< .028
<.0005
Samarium
. 14
<.0005
Scandium
2.0
<.0005
Selenium
. 74
.001
Si licon
>2750
3. 1
Silver
.033
<.0005
Sodium
>2750
14
Strontium
85
1.0
Sulfur
>2750
"-20
Tar.talur.i
. 22
<.0005
Tellurium
<.028
<.0005
Terbium
.052
<.0005
Th a 11 i uin
<.028
-.0005
Thorium
.85
<.0005
Thulium
.030
<.0005
Tin
.33
.003
Titanium
124
.010
Tungsten
.33
<.0005
Uranium
. 55
.0005
Vanadium
7.4
.002
Ytterbium
.24
<.0005
Yttrium
4.7
.0005
Zinc
1.3
.19
Zirconium
4.4
.001
*A11 values in lb/hr.
4-6 STATION XI MaTLRIAL BALANCE BASED ON
SPARK SOURCE MASS Sl-KCTROGRAHIIC DATA (Cont'd)*
Sluice Ash
I In
Preci pi uror
Ash
Sluice Ash
3.6
4.0
.94
1.1
< .028
<.028
^358
<.028
100
1.5
<028
<.028
.33
<.028
. 14
2.0
. 74
>2800
. 034
>2800
86
>2800
22
<.028
. 053
< . 028
.85
.031
. 33
124
. 33
. 55
7.4
. 24
4. 7
1.5
4.4
. 94
3. 1
1.3
.39
<.002
< . 0(J2
>1 62
<. 002
'-19
. 49
v . 002
<.002
. 70
<.002
. 087
. 65
. 14
> lo2
. 0U4
-- lo L
•81
11/2
. UcO
. 009
. 024
. UU6
. 004
. U51
>B1
.096
. 12
5 . b
.052
2.9
1. 2
. 71
. 092
1.2
. 17
,2b
<.0004
<.0004
¦>-22
-.0004
i-6. 5
.092
<.0U04
<.0004
.40
-.0004
. 019
. 18
. OUo
46
. 0006
-4o
-23
2 J
. 014
. 0007
. 005
..0004
. oai
. 003
oil
-4o
.01 '
.055
.9/
.011
. 74
. 2/
. 78
Filtrace
WEP
I Out
.024
.009
1.1
.0005
.006
.4-2
.010
.16
1.6
<.0005
.002
.65
<.0005
<.0004
< . 003
<.0005
<.0004
<003
. 10
2.4
>187
<.0005
<.0004
< .003
2.4
.41
•v-29
<.0005
.0009
. 58
--
<.0004
o
o
V
<.0005
<•0004
<.003
.003
.003
, 1.1
<.0005
< 0004
<.003
<.0005
<.0004
. 11
-'.0005
.002
.84
.005
.022
. ia
5. 5
5.0
>220
<.0005
<.0004
.006
22
1.0
>230
1.8
.90
-107
SO ¦
45
2S0
<.0005
<.0004
.0/5
<.0005
.001
.011
<.0005
< .0004
. 030
<.0005
<.0004
.007
<.0005
<.0004
.31
<.0005
<.0004
. 008
. 001
.003
. 068
.022
.90
>128
<.0005
<.0004
. 13
<.0005
<.0004
. 17
. 030
.054
6.8
< .0005
< .0004
.066
.001
.045
3.7
. 040
.036
1.5
.001
.018
1. 5
-------
TABLE 4-7
EMISSION RESULTS FOR PARTICULATES AND
SULFUR DIOXIDE AT STATION II
Particulates
(Ash) Sulfur Dioxide
0.018 gr/scf 280 ppm (v/v)
6.18 lb/10s BTU 0.8'4 lb/105 BTU
0.044 lb/105 BTU 0.81 lb/105 BTU
Concentration in
flue gas
Quantity in coal
per unit heat value
Emissions in flue
gas per unit heat
value of coal
burned
-36-
-------
5.0 DISCUSSION OF RESULTS
The results given in Section 4.0 can be used to
establish the distribution of each trace element in the station
exit streams. The degree of closure of the individual element
material balances provides a measure of the overall reliability
of the results.
3.1 Material Balance Closure
Closure of the balances within error limits indicates
a high reliability for the emissions measurements. Closure
within the error limits is indicated by an overlap of the error
bands for E In and Z Out presented in Table 4-5. Some 23 elements
closed within error limits:
Molybdenum
Nickel
Silver
Sulfur
Titanium
Vanadium
Zinc
The balances were outside the error limits for chlorine,
mercury, selenium, and uranium. The degree of closure is as
follows:
Aluminum
Chromium
Antimony
Cobalt
Arsenic
Copper
Barium
Fluorine
Beryllium
Iron
Boron
Lead
Cadmium
Magnesium
Calcium
Manganese
Chlorine 6.9 ± .7 lb/hr in
Mercury .077 ± .008 lb/hr in
Selenium .44 ± .05 lb/hr in
Uranium .25 ± .03 lb/hr in
25 ± 3 lb/hr out
.010 ± .002 lb/hr out
.18 ± .02 lb/hr out
.12 ± .02 lb/hr out
-37-
-------
These discrepancies must be attributed to random errors in
sampling, sample handling and/or analysis. Sampling is a
particular problem for chlorine, mercury and selenium which
may be present in the vapor state.
The degree of balance closure obtained by the
quantitative analyses and by the spark source emission spectro-
metry method are compared in Table 5-1. A normalized deviation
was calculated for each element according to:
_ Ein(i) - Eout(i) ,c
ND(J) "(Zin(j) + Eout(j))/2 (5"1)
The average of the normalized deviations is 0.007 for
the quantitative procedures and +0.89 for the SSMS method. A
negative average indicates some systematic bias toward the out-
let flowrates and a positive average indicates bias toward the
inlet streams. The root mean square of the normalized devia-
tions according to:
RMS
ND
Zin(j) - Eout(j)
Zin('j) + Zout(i),
L J
%
(5-2)
is 0.46 for the quantitative methods and 1.18 for SSMS. These
provide some measure of the overall material balance closure for
each of the two analytical approaches.
The average of the ND values for 53 entries based on
SSMS results is 0.66 and the RMS equals 0.99. Results less than
or greater than a certain value were considered inconclusive
and not included in these calculations.
-38-
-------
TABLE 5-1
DEVIATIONS FROM MATERIAL BALANCE CLOSURE FOR
QUANTITATIVE ANALYSES AND
SPARK SOURCE MASS SPECTROMETRIC ANALYSES
FOR STATION II
Elements
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chlorine
Chromium
Cobalt
Copper
Fluorine
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sulfur
Titanium
Uranium
Vanadium
Zinc
Quantitative
Normalized1
Deviation
-0.18
0.12
0
-0.07
-0.32
-0.15
0.19
-0.21
-1.1
0.04
-0.20
0.06
0
-0.10
0.42
-0.23
-0.15
1.5
0.06
-0.37
0.88
-0.14
-0.09
-0.17
0.77
0
-0.38
Average of Normalized
Deviations 0.007
RMS of Deviations2 0.46
SSMS
Normalized1
Deviation
1.46
1.29
1.96
-0.14
1.56
-0.94
1.51
1.64
1.95
0.13
0.99
0.11
1.01
1.00
0.67
1. 71
0.60
1.61
1.06
-0.52
1.22
1.40
1.64
-0.03
1.06
0.08
0
0.89
1. 18
NOTES:
1. Normalized Deviation
"in
0) - =oue
(lin^ioutfE)
2. Root Mean Square of
Normalized Deviations
fm
+ Eout(^
l\
2
-39-
-------
5.2
Distribution of Elements in the Exit Streams
The coal ash was distributed among the exit streams
as follows:
Sluice ash 22.2%
Precipitator ash 77.1%
Flue gas 0.7%
The sluice ash is th*a sum of bottom ash, economizer
ash and pyrites originating from the mills. The degree of
leaching of the elements during the sluice operation was cal-
culated from the concentration increase of an element in the
exit sluice water stream compared to the inlet sluice water.
The increase in the exit water stream was added to the value
of the elements in the total sluice ash. These corrections
were negligible with the exceptions of antimony, calcium,
chlorine, fluorine, selenium, and sulfur.
The distribution of the individual elements is shown
in Table 5-2. Values greater than 22.2% in the sluice ash,
greater than 77.1%> in the precipitator ash and greater than
0.7% in the flue gas indicate enrichments of the element in
the corresponding stream; values smaller than these numbers
indicate a depletion. The total amount of an incoming element
in the coal in pounds per hour is also shown in this table.
The results of these distributions are graphically
shown in Figure 5-1. The average amount of sluice ash, precip-
itator ash and flue gas plus fly ash are represented as green,
blue and red vertical lines respectively. The distribution of
an element within these streams is shown as green (sluice ash),
blue (precipitator ash) and red (flue gas and fly ash) horizon-
tal lines. Crossing of a horizontal and vertical line of the
-40-
-------
SULFUR
MERCURY
TITANIUM
25%
50%
75%
100
FIGURE 5.1
DISTRIBUTION OF ELEMENTS AMONG SLUICE ASH,
PRECIPITATOR ASH, AND FLUE GAS AT STATION EI
-41-
-------
TABLE 5-2
DISTRIBUTION OF ELEMENTS AMONG SLUICE ASH,
PRECIPITATOR ASH, AND FLUE GAS AT STATION II
Coal in Sluice Ash Precipitator Ash Flue Gas
Elements lb/hr (Average 22.2%) (Average 11.1%) (Average 0.7%)
Aluminum
1950
20.5
78.8
0.7
Antimony
0.044
2.7
93.4
3.9
Arsenic
0.70
0.8
99.1
0.05
Barium
127
16.0
83.9
<0.09
Beryllium
0.080
16.9
81.0
<2.0
Boron
8.5
12.1
83.2
4.7
Cadmium
<0.028
<15.7
80.5
<3.8
Calcium
3000
18.5
80.7
0.8
Chlorine
2.6
16.0
3.8
80.2
Chromium
2.5
13.9
73.7
12.4
Cobalt
0.41
15.6
82.9
1.5
Copper
8.5
12.7
86.5
0.8
Fluorine
18
1.1
91.3
7.6
Iron
578
27.9
71.3
0.8
Lead
0.63
10.3
82.2
7.5
Magnesium
413
17.2
82.0
0.8
Manganese
6.6
17.3
81.5
1.2
Mercury
0.037
2.1
0
97.9
Molybdenum
0.18
12.8
77.8
9.4
Nickel
0.58
13.6
68.2
18.2
Selenium
0.44
1.4
60.9
37.7
Silver
0.013
3.2
95.5
1.3
Sulfur
1350
3.4
8.8
87.8
Titanium
155
21.1
78.3
0.6
Uranium
0.24
18.0
80.5
1.5
Vanadium
5.5
15.3
82.3
2.4
Zinc
1.1
29.4
68.0
2.6
-42-
-------
same color indicates enrichment of an element in the corresponding
exit stream. The contrary indicates a depletion.
The elements can be divided into three broad classes.
The first class includes those elements enriched in flue gas
plus fly ash. Elements belonging to this group are:
Sulfur
Mercury
Chlorine
Antimony
Chromium
Fluorine
Selenium
Lead
Molybdenum
Nickel
Boron
Zinc
Cadmium
The material balances for chlorine, mercury, and selenium were
outside error limits; therefore, the exact magnitude of the
enrichment in these cases may be uncertain, but the general
trend is evident.
The following elements, class two, are depleted in
the bottom ash and preferably enriched in the precipitator ash.
Copper
Cobalt
Uranium
Arsenic
Silver
Only the balance for uranium failed to close for these elements
Elements belonging to class three show normal dis-
tribution in the exit streams. These are:
Barium
Beryllium
Aluminum
Calcium
Vanadium
Iron
Magnesium
Manganese
Titanium
-43-
-------
Although a detailed investigation of the mechanisms
of enrichment for the trace elements in a given stream is beyond
the scope of this study, several general comments can be made.
Enrichment in the precipitator ash or flue gas is
expected in those cases for which:
(1) species are partly or completely
evaporated at the boiler temperature
(2) species change to other compounds
within the boiler atmosphere with
subsequent volatilization.
The volatilized species can subsequently
(1) leave the plant in the vapor state,
(2) partly redondense, or
(3) recondense completely on the available
particulate surface area.
In the last two cases, enrichment in the exit flue gas
and the precipitator ash will be observed; in the first case,
enrichment in the flue gas is observed with depletion in the
bottom ash and precipitator ash. Sulfur, mercury and chlorine
are good examples for this behavior. The evaporation-recondensation
mechanism will lead to a concentration dependence as function of
particle size.
--44—
-------
APPENDIX A
SAMPLING AT STATION II
-------
APPENDIX A
TABLE OF CONTENTS
Page
1.0 INTRODUCTION A-1
2.0 PLANT DESCRIPTION A-2
2.1 Plant Operation During Sampling A-2
2.2 Time Phasing During Sampling A-4
3.0 DESCRIPTION OF SAMPLING POINTS A-5
3.1 Coal A-7
3.2 Inlet Sluice Water A-7
3.3 Sluice Solids A-8
3.4 Outlet Sluice Water A-9
3.5 Precipitator Ash A-9
3.6 Fly Ash A-10
3.7 Sampling Schedule A-14
4.0 FLOW RATE MEASUREMENT A-1.7
4.1 Coal A-17
4.2 Inlet Sluice Water A-17
4.3 Sluice Solids A-18
4.4 Outlet Sluice Water A-18
4.5 Precipitator Ash A-19
4.6 Fly Ash A-19
4.7 Summary of Flow Rates A-19
-------
1.0 INTRODUCTION
Sampling at Station II was performed by Radian per-
sonnel during the period of October 21-23, 1974. Station II
was selected as part of the Northern Great Plains Resources
Program trace elements study to be representative of a plant
with hot-side electrostatic precipitator for fly ash control.
Representative samples of all inlet and outlet streams
around the power plant were collected with the objective of
quantifying the trace element emissions from the plant. Analyses
of the samples for the trace elements of interest in combination
with flow rate data for each stream during the sample period
allows a material balance to be performed for each element around
the plant. These material balances serve two main functions:
(1) closure of the material balances lends credibility to the
sampling and analytical techniques and, therefore, to the emis-
sion data produced, and (2) data is generated which allows the
ultimate fate of individual trace elements to be determined
and their flow through the plant to be traced.
The following sections provide descriptions of the
station, the sampling techniques utilized, and the flow rate
measurements performed.
-------
2.0 PLANT DESCRIPTION
Station II consists of one 350 MW tangentially-fired
boiler. A second boiler, essentially identical to the first,
is presently under construction. Hot-side electrostatic pre-
cipitators designed for 350 MW at an inlet gas temperature of
828°F are used for fly ash control. The boiler is fired with
sub-bituminous coal transported by rail from Wyoming, where it
is strip-mined. The coal typically contains 30% moisture, 5%
ash, 0.5% sulfur, and 33% volatile matter and has a heating
value of 8400 BTU/lb. The coal is initially stored in an open
pile from which it is conveyed to five storage silos. From the
storage silos the coal is fed to the mills where it is pulverized
prior to delivery to the boiler through a pneumatic conveyer
system.
Pyrites from the mills, economizer ash, and bottom
ash are sluiced alternately to an ash pond at approximately
four hour intervals. The ash collected in the electrostatic
precipitators is transferred to an ash storage silo by a pneu-
matic conveyer system and removed from the plant site by truck.
Flue gas exits the system through a 500 ft. stack, approximately
25 ft. in diameter.
A schematic of the station with all sampled streams
is presented in Figure 2-1.
2.1 Plant Operation During Sampling
During the period of sampling the plant load varied
between 335 and 350 MW. This consistency of operation provided
very steady conditions allowing collection of representative
A-2
-------
FIGURE 2-1 SCHEMATIC OF STATION II
-------
samples and flow rate measurement without the difficulties
introduced by operational fluctuations. The electrostatic pre-
cipitators operated with very little variation in efficiency
as evidenced by consistent particulate load determinations over
the sampling period. No major upsets in precipitator operation
were in evidence; however, a slight increase in loading from
.015 gr/scf to .020 gr/scf was noticed during the period.
2.2 Time Phasing During Sampling
The only plant stream requiring some degree of time
phasing was the ash sluice stream. Bottom ash and economizer
ash were sluiced on a four hour cycle during the sampling
period and pyrites were sluiced every eight hours. The only
time phasing required was to sample the sluice stream during
the period when the ash and pyrite accumulated during the sampl-
ing period were sluiced.
A-4
-------
3.0 DESCRIPTION OF SAMPLING POINTS
The sample point locations are indicated schematically
in Figure 2-1 and the process streams are summarized schematically
in Figure 3-1. The following sections provide detailed descrip-
tions of the sample points and the techniques employed to obtain
samples representative of the streams during the sampling perio-d.
All samples were collected both during a preliminary sampling on
October 22nd and the primary sampling on October 23rd.
Immediately prior to the sampling effort and after the
preliminary plant inspection, a special refactory cooling system
was installed in the boiler-bottom ash hopper area. Approximately
1.13 x 10s Ib/hr (225 gpm) of cooling tower blowdown was directed
to the refactory region in the bottom ash hopper and the overflow
pumped to the ash pond separately from the regular ash sluice
stream. The existence of these inlet and outlet streams was not
noted during the sampling effort and they were, therefore, not
sampled. These were then not included in either the inlet or
outlet portions of the material balances to be presented in Table
4-5. The composition of the refactory cooling water inlet and
outlet streams should be similar to the inlet and outlet sluice
water. With the exception of chlorine, the levels of the elements
are low enough that an increase of 22% (the quantity of water
flow neglected) would not significantly alter the elemental mass
flows presented. In addition to this inlet and outlet water
flow, several other small water streams such as clarifier under-
flow from the lime softener, boiler blowdown, and miscellaneous
plant drains were considered insignificant or were not related
to the combustion process and were not sampled.
A-5
-------
INLET STREAMS
OUTLET STREAMS
Coal ^
2 Inlet Sluice Water
Refractory Cooling
Water (Not Sampled) s
Sluice Solids ^ 3
Outlet Sluice Water 4
Refractory Cooling
Water (Not Sampled)
Precipitator Ash ^
Fly Ash and Flue Gas v ,
— } 5
FIGURE 3 -1
INLET AND OUTLET STREAMS
AT STATION II
A-6
-------
3.1 Coal
Five coal feeders (A, B, C, D, E) meter the coal from
each of five storage silos to the respective mills for pulveriz-
ing prior to delivery to the boiler. Coal samples were col-
lected every 15 minutes from one of feeders A, C, and E, con-
secutively, such that each of these three was sampled every
45 minutes. The samples were collected by passing a container
of approximately 700 ml volume through the stream of coal fall-
ing from a conveyer in the feeder to the mill. The samples
were combined in a large polyethylene container to form an
integral sample for the entire period. This integral sample was
riffled until two one-liter polyethylene bottles of representa-
tive sample remained for analysis.
3. 2 Inlet Sluice Water
The sluice water was a cooling tower blowdown from a
storage tank. Samples were collected from the storage tank by
lowering a 250 ml polyethylene bottle through a portal in the
top of the tank. Two 250 ml samples were collected every three
hours from 8:30 AM to 5:30 PM during the primary sampling period
on October 23rd and from 12:30 PM to 5:30 PM during preliminary
sampling on October 22nd. The individual samples during each
period were combined to form two integral samples which were
acidified with nitric acid for preservation until analysis.
A-7
-------
3.3
Sluice Solids
Samples of the ash sluice slurry stream were col-
lected at the point of discharge into the ash pond during the
pumping periods of both the preliminary and primary sampling.
In reality the ash sluice stream was composed of three distinct
streams: bottom ash sluice, economizer ash sluice, and pyrites
from the coal mills. There were several variations in the
mixing and order of pumping of each of the three streams.
Bottom ash sluice was generally pumped separately, and economizer
ash and pyrites were pumped both separately and combined. Due
to the random nature of these combinations, a total ash sluice
sample was the optimum method of obtaining a representative
sample. Sluice pumping occurred at approximately four hour
intervals on a 24 hour basis. The ash and pyrites accumulated
during the preliminary sample period were sluiced from 4:22 PM
to 5:51 PM on October 22nd. The ash and pyrites accumulated
during the primary sample period were sluiced from 12:43 PM to
2:13 PM and from 4:10 PM to 5:31 PM on October 23rd. Samples
were collected during each of these pumping intervals by pass-
ing a one-half liter polyethylene container vertically from
top to bottom and bottom to top through the discharge stream
every 2.5 minutes collecting a mixture of solids and liquid.
The samples from each pumping interval were combined in a five
gallon polyethylene container providing three integral samples.
Upon arrival at our Austin laboratories, the solids and liquid
in each sample were separated by filtration. The solids from
the two samples collected during the primary sampling were
combined to form an integral sample for analysis. The solids
from the preliminary sample were retained as a reserve sample.
A-8
-------
3.4
Outlet Sluice Water
The liquid portion of the ash sluice stream was sampled
as described in Section 3.3. Following filtration two liters
of the filtrate from the preliminary sample were acidified for
preservation and retained as a reserve sample. The filtrates
from the two primary samples were combined and a two liter
portion of this integral sample was acidified for preservation
and retained for analysis.
3.5 Precipitator Ash
Precipitator ash samples were collected from the ash
storage silo through a portal in the top of the silo. Approxi-
mately one liter samples were collected hourly during the pre-
liminary and primary sampling periods. The initial sample for
each period was collected by dragging a polyethylene container,
lowered through the portal by a rope, across the top of the ash
in the silo until an adequate quantity was collected. The
container was then left in the silo positioned such that the
ash falling into the silo from the pneumatic conveyer system
slowly filled the container over the period of an hour. The
individual samples were combined to form an integral sample for
each of the two sampling periods. These integral samples were
riffled until two one-liter polyethylene containers remained
of each. The two liters of ash from the primary sampling were
retained for analysis and the two liters from the preliminary
period were held as a reserve sample.
A-9
-------
3. 6 Fly Ash
Fly ash exiting Che 500-foot stack in the flue gas
stream at Station II was sampled through four four-inch sample
ports. These were located on both ends of two perpendicular
stack diameters at a height of 375 feet. A work platform was
located at this level. The internal diameter of the stack was
25 feet at this point. The flue gas was at an average tempera-
ture of 324°F. The moisture content was determined by conden-
sation during the sampling period to be 8.57o.
The sample ports were greater than ten stack diameters
downstream from the point of entry of the flue gas and, there-
fore, a minimum of 12 traverse points, six on each diameter,
were required to provide statistically valid sampling of the
flue gas stream according to EPA Method 1. A total of 16 tra-
verse points were sampled by dividing the cross-sectional area
of the stack into four equal concentric areas and sampling at
the centroid of each area along each of two perpendicular
diameters. The sampling points were then the following dis-
tances from the inner stack wall:
1. 10 in.
2. 2 ft. 7 in.-
3. 4 ft. 10 in.
4. 8 ft. 0 in.
The four inch pipe forming the sample port extended seven inches
into the stack and was, therefore, so close to the first point
that nohrepresentative turbulence was .produced in the flue gas
stream at the first point. In order to avoid the turbulence,
the first sample point was moved an additional six inches into
the stack.
A-10
-------
Velocity measurements were taken at each point on
October 21st and in conjunction with particulate loading deter-
minations on October 22nd and 23rd as per EPA Method 2. The
average velocity was found to be 61 fps with less than 10%
variation over the three-day period. The velocity traverse
results were used to determine the total flow in the stack
and the conditions necessary for isokinetic sampling of the
particulates. The velocity profile is shown schematically
in-Figure 3-2.
Particulate loading determinations were made on
October 21, 22, and 23 with "in-stack" Gelman filter devices
mounted at the end of a heat traced probe. These determinations
were a combination of cumulative grain loadings and point grain
loadings. During the cumulative grain loadings, the loadings
at the individual points were physically averaged by sampling
for equal time intervals at each point on a half diameter with
the accumulation from all four points on a single filter. The
single point grain loadings were taken at Point 4 to define the
actual particulate concentration at the point used for particulate
collection. The results of the cumulative grain loading deter-
mintations are shown in Figure 3-3. During particulate loading
determinations, the moisture content of the flue gas was measured
by condensation in an efficient copper tubing condenser maintained
in an ice bath.
Particulate concentration determinations were made
from all four ports on October 21st and 22nd and the average
loading was found to be 0.018 gr/scf from the cumulative
determinations. Cumulative and single point determinations
were made during the particulate sample collection periods on
October 22nd and 23rd from one sample port to detect any
significant variations during sample collection.
A-11
M
-------
FIGURE 3-2 - VELOCITY PROFILE AT STATION II
FOR OCTOBER 21, 1974
AVERAGE VELOCITY - 61 fps
59
58
SAMPLE POINTS
- 4' 41/2"
- 7> 7"
R - 9' 9|/2"
3
R - II1 1/2"
4
A-12
-------
FIGURE 3-3 - GRAIN LOADING AT STATION II
AVERAGE - 0.018 gr/scf
C
R - 41 41/2"
1
R - 7' 7"
2
R - 9' 91/2"
3
R - II' 1/2"
4
A-13
-------
Particulate matter in the flue gas stream was sampled
at Point 4 on two perpendicular diameters during the preliminary
sample period on October 22nd and the primary sample perio
October 23rd. The wet electrostatic precipitator (WEP) sampl^
ing system used for sample collection is shown schematically m
Figure 3-4. A five percent sulfuric acid solution is circulated
in this sampling device by a peristaltic pump. A voltage
12-14 KV is applied between a thin platinum wire and the wette
wall to induce electrostatic collection. The sampling probe
from the sampling nozzle to the WEP was lined with teflon tub-
ing to prevent trace element contamination of the .s p
gas stream is isokinetically drawn from the stack by a vacu
pump and metered by a dry gas meter. Approximately four h
of sampling was required to obtain sufficient particulate mat
for analysis.
Samples for mercury vapor were taken during each WEP
run by diverting the exit gas from the WEP through a mesh of
gold wire where the mercury is collected by amalgamation with
the gold. Samples were also taken during the WEP runs for the^
determination of.sulfur concentration in the flue gas by bubbling
a known volume of gas through a 37«, hydrogen peroxide solution, by
EPA Method 6. Orsat analysis of the flue gas ror oxygen and^
carbon dioxide was performed to provide gas density information
according to EPA Method 3.
3.7 Sampling Schedule
The samples described in the preceding sections were
taken during the period of October 21, 22 and 23, 1974, accord-
ing to the schedule shown in Figure 3-5. Those samples enclosed
-in parenthesis were analyzed, the rest being nela in reserve.
A-14
-------
Wet Electrostatic
Precipitator
FIGURE 3-4
SCHEMATIC OF STATION II
ARRANGEMENG FOR DUCT SAMPLING
-------
1. Coal Feeder A
Feeder C
Feeder E
2. Inlet Sluice Water
3. Sluice Solids
4. Outlet Sluice Water
5. Precipitator Ash
6. Flue Gas Velocity
Flue Gas Particulate
Loading
Flue Gas WEP
Particulate Collection
point sampling
continuous sampling
(•*••)
(- -)
(- -)
Oct. 21 |Oct. 22 |Oct. 23
FIGURE 3-5
Sampling Schedule at Station II
A-16
-------
4.0 FLOW RATE MEASUREMENTS
The mass flow rate of each of the sampled streams
described in Sections 3.0 to 3.6 was determined as described in
the following sections.
4.1 Coal
The feed rate of coal to each of the mills is monitored
by counters in the control room which record the revolutions of
each of the five coal feeders. Each revolution of a feeder has
been determined previously to be equivalent to 100 lb of coal.
The readings of the five counters were recorded every hour dur-
ing the sampling period and the total averaged over the period
was found to be 3.88 x 105 lb/hr. From the moisture content of
the coal of 29.2%, the dry coal flow rate was 2.75 x 105 lb/hr.
4.2 Inlet Sluice Water
The outlet pressure of the sluice pumps moving the
sluice water from the sluice water storage tank to the economizer
hopper, the bottom ash hopper and the pyrite storage area at
the mills was recorded continuously during the pumping times for
which samples were collected as described in Section 3.3. From
an inlet head pressure of 10 psig and the pump curves supplied
by the manufacturer, the inlet sluice water flow rate averaged
over the two four-hour sluicing cycles on October 23rd was
found to be 6.02 x 101* gph or 5.02 x 105 lb/hr.
A-17
-------
4.3
Sluice Solids
The flow rate of the sluice solids was determined from
an ash balance around the boiler and a split between sluice ash
and precipitator ash of 227, sluice ash and 787, precipitator
ash provided by plant personnel.
The average solids concentration in the sluice sample
described in Section 3.3 was determined to be 1.487® by weight.
Assuming this concentration to be representative of the sluice
stream and a liquid flow rate in the stream (Section 4.2) of
5.02 x 10s Ib/hr, the sluice solids flow rate was then 7.6 x
103 Ib/hr by this method.
The coal burn rate was found to be 2.75 x 103 Ib/hr on
a dry weight basis (Section 4.1) and the ash content 1.22%.
This predicts a total ash generation of 1.99 x 101* lb/hr. . This
ash is divided among precipitator ash, fly ash, economizer ash,
bottom ash, and pyrites from the mill. The latter three comprise
the sluice solids. Subtracting the fly ash rate of 1.40 x 10*
lb/hr (Section 4.6) from the total and dividing the remainder
between sluice ash and precipitator ash gives a sluice solids
flow rate of 4.4 x 103 lb/hr. Assuming that the split between
sluice ash and precipitator ash is between 177,-837, and 287.-73%,
the error in the sluice solids flow is ±25%.
4.4 Outlet Sluice Water
The water losses in the sluicing system are negligible
so the outlet sluice water flow rate is equal to the inlet sluice
water flow rate of 5.02 x 10s lb/hr (Section 4.2).
A-18
-------
4.5
Precipitator Ash
Similar to the sluice solids (Section 4.3), the pre-
cipitator ash mass flow rate was determined from an ash balance
around the boiler.
The precipitator ash flow rate was determined from the
difference between the total ash from the coal and the sum of
the fly ash (Section 4.6) and the sluice solids (Section 4.3).
This gives a precipitator ash production rate of 1.53 x 10*1
Ib/hr ±10%.
4. 6 Fly Ash
The flow rate of fly ash from the stack at Station II
was determined from the flue gas velocity and particulate
loading measurements discussed in Section 3.6. The total
quantity of flue gas, corrected to standard conditions, is
calculated from the average gas velocity in the stack and
the cross-sectional area of the stack at the point of measure-
ment. From the average velocity given in Section 3.6 of 61 fps
and a cross-sectional area of 481 square feet, the total flow
from the stack on a dry basis was 5.46 x 107 scfh. The fly ash
emissions were then found from the total flow and an average
particulate loading of 0.018 gr/scf to be 140 Ib/hr.
4.7 Summary of Flow Rates
The mass flow of each of the streams sampled at the
Station II are summarized in Table 4-1. The flow rates of all
solids are based on dry weight.
A-19
-------
TABLE 4-1
FLOW RATES FOR STREAMS
AROUND STATION XI
Stream
Coal
Inlet Sluice Water
Sluice Solids
Outlet Sluice Water
Precipitator Ash
Flue Gas
Fly Ash
Flow Rate
2.75
X
10s
lb/hr
5.02
X
10 s
lb/hr
4. 4
X
103
lb/hr
5 .02
X
10 s
lb/hr
1. 53
X
10"
lb/hr
5.46
X
107
scfh
o
t—i
X
102
lb/hr
A- 20
-------
APPENDIX B
ANALYTICAL PROCEDURES
-------
APPENDIX B
TABLE OF CONTENTS
Page
1.0 SAMPLE PREPARATION B-l
1.1 Coal, Coal Ash, and Sludge
Preparation B-l
1.2 Lime/Limestone Preparation B-l
1.3 WEP Preparation B-2
1.4- Aqueous Streams and Filtrates
Preparation B-2
2.0 ANALYTICAL PROCEDURES B-3
2.1 Determination of Fluoride by the
' Ion-Selective Electrode Technique....... B-3
2.2 Determination of Chloride by Ion-
Selective Electrode B-9
2.3 Spectrophotometry Determination
of Titanium.' . .. B-9
2.4 Determination of Copper and Zinc
by Atomic Absorption B-10
2.5 Determination of Molybdenum by
Atomic Absorption B-10
2.6 Determination of Nickel and Cobalt B-10
2.7 Determination of Arsenic by
Flameless Atomic Absorption B-ll
2.8 Determination of Antimony by
Flameless Atomic Absorption B-ll
2.9 Determination of Beryllium by
Atomic Absorption B-ll
2.10 Fluorometric Determination of Uranium... B-12
2.11 Determination of Lead and Cadmium
by Atomic Absorption B-12
2.12 Fluorometric Determination of
Selenium B-13
2.13 Determination of Vanadium and
Silver by Flameless Atomic Absorption... B-13
! )
-------
APPENDIX B
TABLE OF CONTENTS (Cont'd)
gage
2.14 Determination of Barium by-
X-ray Fluorescence B-14
2.15 Determination of Chromium, Calcium,
Iron, Magnesium, Manganese and
Aluminum by Atomic Absorption B-14
2.16 Determination of Mercury by
Flameless Atomic Absorption B-15
2.17 Sulfur Determination by Titrimetry B-16
2.18 Spectrophotometric Determination
of Boron B-16
BIBLIOGRAPHY
-------
Trace element analyses on samples from three power
plants were performed using dissolution and analytical techniques
adapted specifically for these matrices.
1.0 SAMPLE PREPARATION
Preparation procedures were performed on the following
types of samples to provide the primary digestion solution:
Coal
Coal Ash
Sludge
Lime
Wet electrostatic precipitator
Aqueous streams and filtrates
1 ]_ Coal, Coal Ash, and Sludge Preparation
The dissolution of coal, coal ash, and sludge is
achieved by a two-step method. The samples are oxidized at
850-950°C in the presence of air utilizing a quartz pipe reactor.
Volatile trace elements are retained via an acetone-dry ice trap
at the end of the reactor. Dissolution of the remaining solids
is accomplished by treatment with hydrofluoric, nitric, and
sulfuric acid. The dissolved solids are then combined with the
washings from the cold trap.
1. 2 Lime/Limestone Preparation
Lime is dissolved by treatment with 570 hydrochloric
acid. Any remaining undissolved material is removed by filtra-
tion and treated with hydrofluoric, nitric, and sulfuric acids
to achieve dissolution.
-------
1.3
WEP Preparation
An .8v millipore filter was used to remove particulates
from aqueous WEP samples. The particulates were then treated
similar to coal (through the quartz pipe reactor acid dissolution
steps). The filtrates, dissolved solids, and cold trap washings
were quantitatively transferred to a single container to form the
primary digestion sample.
1.4 Aqueous Streams and Filtrates Preparation
Nitric acid was added as a preservative to all aqueous
samples.
B-2
-------
2.0 ANALYTICAL PROCEDURES
The following analytical procedures were utilized for
the determination of trace elements in the various samples.
Each analytical technique has been screened for accuracy and
reliability by standard addition and interference studies.
The complete analytical scheme for the analysis of
trace elements in the samples are found in Figures 2-1, 2-2,
2-3, and 2-4. Detection limits for each procedure are summarized
in Table 2-1.
2.1 Determination of Fluoride by the Ion-Selective
Electrode Technique
The determination of fluoride utilizes a sodium car-
'bonate fusion for solid samples (TH-060) and direct analysis of
aqueous samples. The technique of standard addition using a
fluoride specific-ion electrode, mentioned by several workers
(BA-131, BA-137) , is used for measurement of the fluoride ion.
A citrate buffer is used to release complexed fluoride ions and
to stabilize the pH and ionic strength. Addition of a standard
quantity of fluoride is characterized by a change in the potential
of the solution. The specific ion electrode senses this change
in potential which, is related to the initial fluoride concentra-
tion. The relationship between potential and fluoride concen-
tration follows the Nernst equation:
AE - A log (Cp + Xi)/CF
where,
AE is the change in potential
n
B-3
-------
Coal
Oxygen Bomb Digestion
Titrimetrv
Flameless/
Atomic Absorption
S
Hg
Primary Digestion
(Thermal Oxidation,
HF-HN03-H2S04 Digestion:
Spectrophotometry
| Atomic Absorption
Extraction/Atomic Absorption
Ti, B
A1> Mg, Fe,
Ca» V, As,
Mn, Cu, Zn
Co, Be, Pb,
Mo, Cd, Sb,
Ni
FIGURE 2-1
ANALYSIS PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL
B-4
-------
Mo, Cd, Sb
Ni
FIGURE 2-2
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL ASH AND SLUDGE
B-5
-------
HNO.-H-SO.-HCIO.
3 2 4 4
Reflux Digestion
Atomic- AhsnmMnn Cr
HNO3 Digestion
Atomic Absorption
¦Ag
Li-CO,- Na^B.O., Fusion
2 3 2 4 7
X-Ray Fluorescence
Ba
Lime
HC1 Digestion
Titrimetry
Gold Amalgamation
Atomic Absorption
•Hg
Primary Digestion
Spectrophotometry
(HC1 Digestion)
Atomic Absorption
Extraction/Atomic Absorption
Ti,B
Al. Mg, FSf
Ca, V, Asj
Mn, Cu, zn
Co. Be, Pb,
Mo» Cd, Sb,
Ni
FIGURE 2-3
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF LIME
B-6
-------
FIGURE 2-4
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF WET ELECTROSTATIC PRECIPITATOR LIQUORS AND AQUEOUS SAMPLES
B-7
-------
TABLE 2-1
DETECTION LIMITS FOR TRACE ELEMENT ANALYSIS
Detection Limit (ppm)
Ash WEP
Element
Analytical Procedure
Coal
Sludge
Lime
Aqueoi
Al
Atomic Adsorption (AA)
100
400
650
1.0
Sb
Extraction/AA
.04
.16
.6
.002
As
AA
.1
.5
.06
.001
Ba
X-Ray Fluorescence
5
50
40
.5
Be
Extraction/AA
.2
1.6
1.0
.001
B
Ion Exchange/'Spectropho tome try
1
3
3
.05
Cd
Extraction/AA
. 1
.2
.2
.0002
Ca
AA
10
40
65
.1
CI
Ion Selective Electrode
5
10
10
.5
Cr
AA
10
40
65
. 1
Co
Extraction/AA
.2
.8
1
.003
Cu
Standard Addition/AA
1
4
6.5
. 1
F
Ion Selective Electrode
.5
1.2
1.2
.1
Fe
AA
10
40
65
.1
Pb
Extraction/AA
.4
.8
5
.004
Mn
AA
10
40
65
.01
Mg
AA
5
20
30
.5
Hg
Flameless AA
.01
.01
.01
.0005
Mo
Extraction/AA
.4
1.6
16
.004
Ni
Extraction/AA
2
8
2
.006
Se
Fluorometry
.1
.1
.1
.0005
Ti
Spectrophotometry
5
20
20
.1
Ag
Standard Addition/AA
.05
.2
.3
.0005
S
Ion Exchange/Titrimetry
100
100
200
5
U
Fluorometry
0001
.0001
.0001
.0001
V
Standard Addition/AA
1
4
6.5
.005
Zu
Standard Addition/AA
1
4
6.5
.01
B-8
-------
A is the constant = 59 mV at 25°G
Cp is concentration of free fluoride in solution
is additional fluoride concentration added.
2.2 Determination of Chloride by Ion-Selective Electrode
Chloride is determined by a known standard addition
method (OR-016). Sample preparation is the same as fluoride
with a sodium carbonate fusion for all solid samples and direct
analysis of aqueous solutions. A known amount of the species
being measured is added to a known volume of sample and the
resulting change in potential is observed. The original sample
concentration is computed.using a known addition table. The
method allows samples to be analyzed which have variable ionic
strength.
2.3 Spectrophotometric Determination of Titanium
Titanium is determined in the primary digestion solution
as a yellow complex formed with tiron (di'sodium -1, 2- dihydroxy-
benzene -3, 5- disulfonate). This method is based on the pro-
cedure of Yoe and Armstrong, and is further extended to include
shales by Rader (RA-125). An acetate buffer is used to regulate
the pH. The only major interference is the complex tiron forms
with Fe. This interference is eliminated by addition of sodium
dithionite, reducing ferric to ferrous ion. The absorbance of
the complex is read on a double beam spectrophotometer and
samples compared with a standard calibration curve.
B-9
-------
2.4 Determination of Copper and Zinc by Atomic Absorption
Copper and zinc are determined by direct aspiration^
of the primary digestion into the flame of the atomic absorption
spectrophotometer (PE-115). Quantitative determinations are
achieved by comparing the samples to their respective standards
and by the use of standard additions to the primary digestions.
2.5 Determination of Molybdenum bv Atomic Absorption
Molybdenum analysis is based on organic extraction^
atomic absorption technique and method of Joyner. (JO 012) which
has been modified by Kinrade and Van Loon (KI-085). Molybdenum
in the primary digestion readily forms a complex with ammonium
pyrrolidinedithiocarbamate at an acidic pH. Extraction o t s
complex with methyl isobutyl ketone offers a convenient met o
of concentration of the element. The signal is further enhanced
by use of a nitrous oxide-acetylene flame. Concentration was
determined by use of a standard calibration curve.
2.6 Determination of Nickel and Cobalt
Nickel and cobalt analyses are based on the organic
extraction atomic absorption technique and method of Joyner (JO-
012). An ammonium tartrate buffer is used to stabilize the
primary digestions. Nickel and cobalt are complexed with the
chelating agent sodium diethyldithiocarbamate and extracted with
methyl isobutyl ketone.
Once the metal complex has b«en separated and concen-
trated in the organic phase, the solution can be directly
aspirated into atomic absorption spectrophotometer for measure-
ment of the metal concentration.
B-10
-------
2.7
Determination of Arsenic by Flameless Atomic Absorption
Arsenic is determined by a Radian modified flameless
atomic absorption procedure based on the method of Ramakrishna,
Robinson and West (RA-147) incorporation the techniques of
Ediger (ED-027). The usually volatile arsenic present in the
primary digestion is complexed as the molybdenum heteropoly acid
with ammonium molybdate in a nitric acid medium. The complex
formation enables the complex to be analyzed on the graphite
furnace by reducing the volatility of the arsenic so that high
temperature charring can be used to rid the sample of matrix
interferences.
2.8 Determination of Antimony by Flameless Atomic Absorption
Antimony determination is based on a Radian flameless
atomic absorption method modifying the extraction procedure of
Burke (BU-136) and. Headridge and Smith (HE-094) while utilizing
the techniques of Ediger (ED-027) to reduce the volatility of
antimony. After complexation with iodide, antimony is extracted
from the primary digestion into a methyl isobutyl ketone and
tributyl phosphate mixture (MIBK-TBP). TBP increases the extrac-
tion efficiency. As with arsenic, ammonium molybdate is used
to increase the thermal stability of the complex during the
charring cycle in the graphite furnace.
2.9 Determination of Beryllium by Atomic Absorption
The method of Bokowski (BO-027) is used for the
determination of beryllium by atomic absorption. After addition
of EDTA to the primary digestion to mask interferences, the
beryllium present in the aqueous sample is chelated with acetyl-
acetone. The complex is then extracted with methyl isobutyl
ketone and the organic phase directly aspirated into the atomic
B-ll
-------
absorption spectrophotometer for the determination of beryllium.
The solvent extraction procedure allows one to conveniently
separate and concentrate the beryllium present.
2.10 Fluorometric Determination of Uranium
Radian's uranium procedure is a modification of the
fluorometric determination of Thatcher (TH-049) updated by
Turner (TU-025). Hexavalent uranium ions have a native fluo-
rescence that may be used for analysis in relatively high
concentrations. However, when fused with fluoride salts, uranyl
ions produce an intense specific fluorescence detectable at
levels of 10~l° grams of uranium. In general, the solid sample
is mixed with a sodium fluoride flux and fused to a translucent
disc in a platinum crucible. Aqueous primary digestions are
evaporated in platinum crucibles and the residue fused with the
flux. Once cooled, its fluorescence is measured with a Turner
filter.fluorometer. The method of standard additions is used to
compensate for quenching.
2.11 Determination of Lead and Cadmium by Atomic Absorption
The procedure for analysis of lead and cadmium is
similar to that for copper and zinc found in Section 2.4. Trace
elements present in the primary digestion are separated and
concentrated by chelation and extraction. Kinrade and Van Loon's
method (KI-085) utilizing two chelating agents, ammonium pyrro-
lidinedithiocarbamate (APDC) and diethyl ammonium diethyldiothio-
carbamate (DDDC) to complex lead and cadmium has been highly
successful. A citrate buffer was used due to its stability,
strong buffering capacity, and nonparticipation in any reaction.
The sample solution was extracted into methyl isobutyl ketone
B-12
-------
and the organic solution injected into the graphite furnace on
the atomic absorption spectrophotometer. Concentration was
determined by use of a standard calibration curve.
2.12 Fluorometric Determination of Selenium
Selenium in the form of selinite reacts with aromatic
orthodiamines to form piazselenols which fluoresce in various
organic solvents. This method of determination of selenium is
a Radian modification of a procedure published by Levesque and
N
Vendette (LE-068). The solid sample is digested with nitric and
perchloric acids in the Parr acid digestion bomb (HA-258).
Aqueous samples are heated with nitric and perchloric acids. In
both cases this oxidizes selenium to selenate and is followed by
hydrochloric acid reduction to selinite. Isolation of selenita
from interferring substances is accomplished by adding hydroxy1-
amine, EDTA, and formic acid. The selenite is then reacted with
2, 3-diaminonaphthalene to form the organic extractable piazselenol,
naphtho-(2, 3-d)-2 selena-1, 3-diazole, which is determined
fluorometrically. This method is free of any interferences and
is capable of detecting nanograms of selenium by use of a
calibration curve.
2.13 Determination of Vanadium and Silver by Flameless
Atomic Absorption
Vanadium is determined by flameless atomic absorption
using the heated graphite atomizer. The method is a Radian
adaptation of the work of Cioni, Innocente and Mazzioli (CI-002).
Standard additions are performed on the primary digestion solu-
tion. Experimentation conducted on National Bureau of Standards
samples of coal and coal ash yield results within 10% of the
certified values.
B-13
-------
Huffman (HU-095) recommends the same procedure for
silver. Solid samples are dissolved in concentrated nitric acid
and the method of standard additions is utilized.
2.14 Determination of Barium by X-ray Fluorescence
Barium is determined by a Radian method utilizing_
X-ray fluorescence. Samples are pelletized in a solid flux of
lithium carbonate-sodiTim borate which are then introduced directly
into the X-ray unit. Quantitative determinations are achieved by
comparing the samples to a barium standard calibration curve
prepared in the same, manner and by the use of the method of
standard additions to correct for matrix interferences, if any
are present.
2• 15 Determination of Chromium, Calcium, Iron, Magnesium,
Manganese and Aluminum by Atomic Absorption
Chromium, calcium, iron, magnesium, manganese and
aluminum (PE-115) are determined by direct aspiration into the
flame of the atomic absorption spectrophotometer. Calcium and
magnesium are diluted with 1'anthafium chloride to mase inter-
ferences. All elements are compared with standard calibration
curves. All analyses are performed on the primary digestion
solutions except chromium.
Chromium requires a special preparation for solid
samples. Digestion of coal, ash, limestone, and sludge is
accomplished with nitric, sulfuric, and perchloric acids in a
reaction flash. A packed reflux column is attached to prevent
any loss of chromium. Perchloric acid oxidizes all the chromium
to Cr . This method was developed by Rains and Menis (RA-155)
as a mercury determination procedure. Radian has applied the
method to the determination of chromium in NBS standard reference
B-14
-------
materials of coal and coal ash and the results were comparable
to the reported values.
2.16 Determination of Mercury by Flameless Atomic Absorption
Two methods were used for mercury analysis:
(1) acid permanganate
(2) gold amalgamation
Mercury is determined by a flameless atomic absorption
technique. Liquid samples are treated with acid potassium permanga
nate to oxidize all of the mercury present to the +2 oxidation"
state. The excess KMnOi* is removed with the addition of
hydroxy1amine hydrochloride, and the Hg is reduced to elemental
mercury by the addition of stannous chloride, which is swept
through the absorption cell of the atomic absorption unit for
determination.
Gold amalgamation collection of mercury has been
reported by several workers (KA-086, DI-043). Radian utilizes
a double amalgamation technique in which mercury is collected
on a gold wire plug in a quartz tube either from flue gas passed
through the tube or from thermal desorption into a stream of
argon from solid samples. The mercury thus collected is desorbed
by heating and amalgamated on a second tube to minimize inter-
ferences. Upon desorption from the second tube, the mercury is
passed into an absorption cell positioned in the atomic absorp-
tion spectrophotometer.
B-15
-------
2.17
Sulfur Determination by Titrimetry
The method of sulfur analysis consists of determining
the- total sulfur as sulfate by. titrimetry. Initial sample pre-
paration for coal is performed by ignition in a Parr Ignition
Bomb and sorption of the evolved SC^ in a sodium carbonate solu-
tion. Sludge and ash samples are mixed with hydrochloric acid
and the solids filtered. In both cases, hydrogen peroxide^is
added to oxidize sulfite to sulfate. The sample is passed through
a cation exchange column to form sulfuric acid. The acid is
.titrated with standard sodium hydroxide and the sulfur concentra-
tion determined.
Nitrate and phosphate ions interfere. Heat applied
with hydrochloric acid at pH 2-4 avoids nitrite interference in
the column. If the sample is heated at 275°C for 30 minutes to
drive off sulfuric acid, phosphate can be determined and the
value subtracted from the total to give sulfate ions.
2.18 Spectrophotometric Determination of Boron
Radian's boron procedure combines the separation method
of Carlson (CA-084) and the spectrophotometry determination of
Mair and Day (MA-190). An ion-exchange column is prepared using a
boron specific resin, Amberlite XE-243, to separate boron in the
primary digestion from interfering ions and allow complete boron
recovery. It is then extracted into chloroform with 2-ethyl-l,
3-hexanediol. Boron in the organic phase is converted to the
highly absorbing rosocyanin complex using glacial acetic acid
followed by sulfuric acid. The absorbance of the complex is read
on a double-beam spectrophotometer and samples compared with a
standard calibration curve.
B-16
-------
BIBLIOGRAPHY
BA-I31 Baker, R. L., "Determination of Fluoride in Vegetation
Using the Specific Ion Electrode", Anal. Chem.
44(7), 1326 (1972).
BA-137 Baumann, Elizabeth W., "Trace Fluoride Determination
With Specific Ion Electrode", Anal. Chim. Acta 42,
127-32 (1968).
B0-027 Bokowski, D. L., "Rapid Determination of Beryllium by
a Direct-Reading Atomic Absorption Spectrophoto-
meter", Am. Ind. Hyg. Assoc. J. 29(5), 474-81
(1968) .
BU-136 Burke, Keith E., "Determination of Microgram Amounts
of Antimony, 3ismuth, Lead and Tin in Aluminum,
Iron and Nickel-Base Alloys by Nonaqueous Atomic-
Absorption Spectroscopy" , Analyst 97, 19-28 (1972).
CA-084 Carlson, R. M. and J. L. Paul, "Potentiometric Deter-
mination of Boron as Tetrafluoroborate", Anal.
Chem. 40(8), 1292 (1968).
CI-002 Cioni, R., F. Innocenti, and R. Mazzuoli, "The Deter-
mination of Vanadium in Silicate Rocks with the
HGA-70 Graphite Furnace", Atomic Absorption
Newsletter 11(5), 102 (1972).
DA-105 Davison, Richard L., et al., "Trace Elements in Fly
Ash, Dependence of Concentration on Particle Size",
Env. Sci. and Tech. 8 (13), 1107, (1974).
DI-043 Diehl, R. C., et al., Fate of Trace Mercury in the
Combustion of Coal. RPR-54, Pittsburgh, Pa.,
Pittsburgh Energy Research Cntr., 1972.
B-17
-------
ED-027 Ediger, Richard, "Atomic Absorption Analysis with the
Graphite Furnace Using Matrix Modification",
Atomic Absorption Application Study No. 584,
Perkin-Elmer, 1975.
HA-258 Harstein, A. M., R. W. Freedman, and D. W. Platter,
"Novel Wet-Digestion Procedure for Trace-Metal
Analysis of Coal by Atomic Absorption", Anal.
Chem. 45(3), 611 (1973).
HE-094 Headridge, J. B. and D. Risson Smith, "Determination
of Trace Amounts of Antimony in Mild Steels by
Solvent Extraction Followed by Atomic Absorption
Spectrophotometry", Lab. Practice 20(4), 312
(1971).
HU-095 Huffman, Claude, Jr., J. D. Mensik, and L. F. Rader,
"Determination of Silver in Mineralized Rocks by
Atomic-Absorption Spectrophotometry", U.S.G.S.
Prof. Paper 550-B, B189-191, (1966).
JO-012 Joyner, T., et al., Eiw. Sci. and Tech.l, 417 (1967).
KA-086 Kalb, G. Wm. and Charles Baldeck, The Development of
the Gold Amalgamation Sampling and Analytical
Procedure for Investigation of Mercury in Stack
Gases. PB 210 817, Columbus, Ohio, TraDet, Inc.,
1972.
KI-085 Kinrade, John D. and Jon C. Van Loon, "Solvent Extrac-
tion for Use with Flame Atomic Absorption Spec-
trometry", Anal. Chem. 46(13), 1894 (1974).
B-18
-------
LE-068 Levesque, M. and E. D. Vendette, "Selenium Determination
in Soil and Plant Materials", Canad. J. Soil Sci.
51, 85-93 (1971).
MA.-190 Mair, James W. , Jr. and Harry G. Day, "Curcumin
Method for Spectrophotometrie Determination of
Boron Extracted From Radiofrequency Ashed Animal
Tissues Using 2-Ethyl-l, 3-Hexanediol", Anal.
Chem. 44(12), 3015 (1972).
OR-016 Orion Research, Inc-. , Analytical Methods Guide, 3rd
ed., Cambridge, Mass., 1972.
PE-115 Perkin-Elmer, Instructions, Model 503, Atomic Absorp-
tion Spectrophotometer, Norwalk, Conn., 1974.
RA-125 Rader, L. F. and F. S. Grimaldi, Chemical Analyses for
Selected Minor Elements in Pierre Shale, U.S.G.S.
Professional Paper 391-A, Washington, D. C., GPO,
1961.
RA-147 Ramakrishna, T. V. , J. W. Robinson, and Philip W. West,
"Determination of Phosphorus, Arsenic or Silicon
by Atomic Absorption Spectrometry of Molybdenum
Heteropoly Acids", Anal. Chim. Acta 45, 43-49
(1969).
RA-155 Rains, Theodore C. and Oscar Menis, "Determination of
Submicrogram Amounts of Mercury in Standard
Reference Materials by Flameless Atomic Absorption
Spectrometry", J. Assoc. Offic. Anal. Chem. 55(6),
1339-1344, (1972).
B-19
-------
TH-049
Thatcher, L. L. and F., B. Barker, "Determination of
Uranium in Natural Waters", Anal. Chem. 29(ID.
1575 (1957).
TH-060 Thomas, Josephus, Jr. and Harold J. Gluskoter, "Deter-
mination of Fluoride in Coal with -the Fluoride
Ion-Selective Electrode", Anal. Chem. 46(9). •
1321 (1974).
TU-025 (G. K.) Turner Associates, "Uranium", Fluorometry
Reviews Series, Palo Alto, Ca. , Feb.. 1968.
B-20
-------
COAL FIRED POWER PLANT
TRACE ELEMENT STUDY
VOLUME IV
STATION III
SEPTEMBER 1975
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
REGION VIII
DENVER, COLORADO
BY
RADIAN CORPORATION
AUSTIN, TEXAS
TS-Id
-------
FOREWORD
The four volumes comprising this document describe a
coal-fired power plant trace element study prepared under EPA
Contract 68-01-2663.
This work was conducted under the direction of Mr.
Terry L. Thoem, Project Officer, Environmental Protection Agency,
Region VIII, Denver, Colorado. The Radian program staff included
Dr. F. G. Mesich as Program Manager and Dr. K. Schwitzgebel as
Technical Project Director. Principle contributors were Mr.
R. A. Magee, Dr. F. B. Meserole and Mr. R. G. Oldham.
Acknowledgement is given to the station personnel from
each utility company whose full cooperation greatly facilitated
the field work. Mr. R. M. Mann, Mrs. G. E. Wilkin and Mrs.
C. M. Thompson contributed significantly to the program during
sampling and analysis.
i
-------
VOLUME IV
TABLE OF CONTENTS
Page
TABLE OF CONVERSION UNITS 1
STATION III SUMMARY • 2
1.0 INTRODUCTION 4
2.0 SAMPLING AND SAMPLE HANDLING 6
2. I Plant Description 6
2.2 Sampling Points and Flow Rate
Determinations 6
2.3 Summary of Flow Rates and Estimated
Errors 14
2.4 Sampling Schedule 16
2.5 Sample Analysis 16
3.0 DATA EVALUATION 23
3.1 Trace Element Material Balances 23
3.2 Error Propagation Analysis 25
4.0 RESULTS 27
5.0 DISCUSSION OF RESULTS 39
5.1 Material Balance Closure 39
5.2 Distribution of Elements in the
Exit Streams 40
APPENDIX A - SAMPLING AT STATION III
APPENDIX B - ANALYTICAL PROCEDURES
-------
TABLE OF CONVERSION UNITS
To Convert From
BTU
BTU/pound
Cubic feet
Cubic yards
Feet
Feet/second
Gallons (U.S. liq.)
Gallons (U.S. liq.)
Gallons/minute
Grains/cubic foot
Inches
Inches of H20 (4°C)
Pounds
Pounds/BTU
Pounds/hour
Pounds/standard
cubic foot (60 F,
29.92 inches Hg)
Tons
Yards
To
Calories, kg
Calories, kg/kilogram
Cubic meters
Cubic meters
Meters
Meters/second
Cubic meters
Liters
Cubic meters/minute
Grams/cubic meter
Centimeters
Millimeters Hg (0°C)
Kilograms
Kilograms/Calorie, kg
Kilograms/hour
Kilograms/standard
cubic meter (0 C,
760 mm Hg)
Metric tons
Meters
Multiply By
0.25198
0.55552
0.028317
0.76455
0.30480
0.30480
0.0037854
3.7854
0.0037854
2.2884
2.5400
1.8683
0.45359
1.8001
0.45359
15.155
0.90719
0.9144
-1-
-------
STATION III SUMMARY
The detailed sampling and characterization of trace
elements in Station III streams resulted in excellent material
balance closure for some 21 of the 27 elements examined in
detail. A total of 53 elements were tested on a semiquantitative
basis using spark source mass spectrometry.
A long-range objective is the correlation of the trace
element content of each outlet stream with the coal input. A
wide variation was found between elements as to their relative
distribution in plant streams. The following elements were
found to be concentrated in the flue gas stream.
Sulfur Selenium Zinc
Mercury Lead Cadmium
Chlorine Molybdenum Chromium
Antimony Nickel Copper
Fluorine Boron Cobalt
In contrast, the following elements are more or less
distributed in direct proportion to the total ash content of
each stream.
Barium Iron
Beryllium Manganese
Vanadium Magnesium
Aluminum Titanium
Calcium
The elements uranium, arsenic, and silver display intermediate
behavior.
-2-
-------
These characteristics of a lignite-fired cyclone
boiler with mechanical ash collection are compared with other
plant configurations and coal compositions in Volume I of this
report series.
-3-
-------
1.0 INTRODUCTION
The use of the extensive coal resources in the Northern
Great Plains area of the United States may provide a significant
part of the country's energy growth for the foreseeable future.
As natural gas and oil resources become less available and more
costly, coal will receive increasing emphasis as a primary energy
source. A coal-fired generating station produces a variety of
emissions and effluents ranging from sulfur and nitrogen oxides
and particulates in the flue gas to solid and liquid wastes.
In addition to carbonaceous material, coal contains
inorganic matter which becomes part of the emissions and
effluents from the generating station. The overall objective
of this program was to define the sources, levels, and dis-
position of potentially toxic trace and minor elements in power
plant streams. The levels of trace elements in various streams
may be expected to be a function of both coal composition and
plant operating configuration.
This volume describes the detailed characterization,
with respect to trace and minor elements, of a lignite-fired,
cyclonic boiler using mechanical collection of particulate matter.
The particular plant designated as Station III operates at a
design rating of 250 MW.
The following trace elements were examined in detail:
Aluminum
Calcium
Lead
Silver
Antimony
Chlorine
Manganese
Sulfur
Arsenic
Chromium
Magnesium
Titanium
Barium
Cobalt
Mercury
Uranium
Beryllium
Copper
Molybdenum
Vanadium
Boron
Fluorine
Nickel
Zinc
Cadmium
Iron
Selenium
-4-
-------
A material balance was calculated for each element to
provide a sound basis for evaluating the reliability of the
emissions measurements. In addition, each sample was surveyed
using spark source mass spectrometry to provide a semi-
quantitative assessment of 53 trace elements.
The following sections give a description of the
plant, a discussion of the sampling, analytical strategies, and
presentation and discussion of the experimental data. Appendices
are provided which describe the sampling of the plant and the
analytical methodology.
-5-
-------
2.0
SAMPLING AND SAMPLE HANDLING
The procedures used to sample Station III are pre-
sented briefly in this section. Details are given in depth in
Appendix A, "Sampling at Station III". Sampling was performed
during the period 26-30 August 1974.
2.1 Plant Description
Station III is a 250 MW unit firing North Dakota
lignite. The lignite is mined in a nearby strip mine operation,
trucked to the plant, crushed and fed to the coal-storage silos.
The boiler arrangement is of the cyclonic type. Bottom ash and
economizer ash are sluiced intermittently to a nearby pond.
Cyclones are used as fly ash control devices. The station is
a base load unit. Fluctuation in plant load ranged from 245-2:30
MW during the entire sampling period.
2 • 2 Sampling Points and Flow Rate Determinations
The streams sampled are shown schematically in Figure
2-1. The incoming streams are coal and ash sluice water taken
from the cooling pond. Outgoing streams are bottom ash, bottom
ash sluice water, economizer ash, economizer sluice water, cy-
clone ash and flue gas containing fly ash. The physical location
of the points for sampling these streams at the station are
schematically shown in Figure 2-2.
Sample Point 1: Coal
The coal is stored in seven silos. A coal sample
was collected from silos number 2, 4, and 6 each 20 minutes
-6-
-------
INLET STREAMS
OUTLET STREAMS
CD-
CD
Coal
Ash Sluice Water
Bottom Ash
Bottom Ash Sluic
v©
Water
Economizer Ash^. q
Economizer Ash^ ^
Sluice Water ^
Cvclone Ash
Flv Ash
FIGURE 2-1
Inlet and Outlet Streams
at Station III
-7-
-------
FIGURE 2-2
SCHEMATIC OF STATION m
-------
in alternating fashion using a 2-inch diameter sampling port at
the silo exits prior to introduction to the mills. The individual
samples were combined and stored in closed plastic containers.
Two samples for analysis were obtained at the end of the sampling
period by sequential splitting of the composite coal using riffle
buckets.
The coal flow rate was metered into the plant at the
feed to the mills. An average hourly flow rate was calculated
from the meter readings.
Sample Point 2: Sluice Water Inlet
Bottom ash and economizer ash are sluiced every four
hours to an ash pond. A sample from the point of sluice water
intake was collected, acidified to avoid wall adsorption of trace
constituents and stored in a polypropylene bottle for analysis.
The discharge rate of the sluice water was measured
directly by measuring the time required to fill a known volume.
This rate was also used for the sluice water intake rate, assuming
no significant water losses during the sluicing operation.
Sample Points 3 and 4: Bottom Ash and Bottom Ash
Sluice Water
Accurate bottom ash rates could not be directly
measured, due to the inhomogeneous nature of the ash particles
and fluctuation of the solids content in the sluice stream
over the period of the sluicing operation. Therefore, the solids
rate was calculated from a total ash balance. The total ash
production was determined from the ash content of the coal and
the coal feed rate. The measured rates of the economizer ash,
cyclone ash and fly ash were then used to calculate the bottom ash
rate by difference.
-------
The liquid sluice water exit rate was determined by
measuring the time necessary to collect a known volume of the
total sluice stream.
Sample Points 5 and 6: Economizer Ash and
Economizer Sluice Water
Samples of this stream were collected at the sluice
outlet. The total flow rate of solids and liquids was determined
by timed volumetric collection of the total stream. Individual
discharge rates for economizer ash and economizer sluice water
were calculated from this value using the solids content of the
slurry input. The slurry in this case was sufficiently uniform
to permit - determination of both solids and liquid flow rates.
The liquid samples were stored in polypropylene bottles
and acidified after filtration. The solid portions were divided
and two samples retained for analysis.
Sample Point 7: Cyclone Ash
The cyclone ash was collected from the pneumatic
system used to transport the ash to the cyclone ash storage
silo. The pneumatic transport system was shut down each hour,
the sight glasses removed and samples taken from the hoppers of
Cyclones 1, 4 and 7. Two integral samples were obtained by
riffling at the end of the sampling period. The cyclone ash
flow rate was calculated from the ash disposal truck weights,
moisture content, density and the difference in the storage silo
levels determined during the sampling period.
-10-
-------
Sample Point 8: Flue Gas and Fly Ash
The flue gas and fly ash are discharged from the cyclones
to the stack through two ducts, differentiated as north and south
ducts in this report. Each duct was equipped with four sampling
ports.
The velocity profile was determined using S-type pitot
tube and thermocouple measurements as per EPA Method 2. Individual
values obtained in the center of 16 equal-sized rectangles
according to EPA Method 1 were then averaged to determine an
integral value for the south and the north ducts.
The dust loadings were measured at the same set of
points. Gelman filter devices were used to determine dust loadings
in each of the section squares for both ducts. Average grain
loadings for the north and south ducts were then calculated from
the individual flows found in the 16 rectangles.
Particulate matter for analysis was collected with wet
electrostatic precipitators (WEP). This method of collection
permits sampling over an extended time at isokinetic conditions
without plugging, as occurs in a filter. Thus, a sufficient
quantity of sample can be collected to permit repeated analyses.
In addition, problems of trace element contamination by the filter
substrate are avoided. A detailed description of the WEP device
is given in Appendix A. To confirm the comparability of this,
sampling approach with the filter technique recommended by EPA,
an EPA filter was run in series with the WEP. A 125 mm Gelman
class "A" glass filter was used in a glass filter holder which was
placed in the sampling train immediately after the WEP. The whole
assembly was heated to avoid condensation of sulfur acid mist.
The particulate matter collected by the filter during four WEP runs
was equivalent to a grain loading of 0.0009 grains/scf. The inlet
>11-
-------
particulate loading to the WEP -was 0.21 grains/scf, giving a
collection efficiency of the WEP pf 99+%.
The WEP samples were collected at a single point in
the duct and a correction made from the grain loading at this
point to the average grain loading. The dust concentration at
the sampling point was determined from the calcium and titanium
concentrations in the WEP sample assuming that these elements
are evenly distributed in the particulates with respect to
particle size. This assumption is based on work performed by
Davison, et al. (DA-105) in which fly ash samples-were collected
from the duct of a coal-fired station. Andersen impactor samplers
were used to separate the particulates into seven size fractions.
The results of this work for calcium and titanium are presented
in Table 2-1. In is evident from these data that the assump-
tion of uniform ash composition with respect to calcium and
titanium holds within experimental limits.
The relationship between particle size and titan-him
and calcium concentration in the fly ash is important to this
correction because the cyclone ash has a larger average particle
size than the exiting fly ash. If the titanium concentration
were dependent on particle size then the assumption made in
Equation (2-1) that the titanium and calcium concentration in
the fly ash is the same as in the cyclone ash is invalid.
The point grain loadings were determined from the
calcium and titanium concentrations in the WEP samples and the
calcium and titanium weight fractions found in the cyclone ash
using the relation:
Point grain
load (gr/scf)
15.4 Vj
2 V„
XWL(Ca)
XW
Ash
XCa)
+
XWL(Ti)
^Ash^J
(2-1)
-12-
-------
TABLE 2-1
CALCIUM AND TITANIUM ANALYSES* OF
ANDERSEN IMPACTOR PARTICLE SIZE FRACTIONS (DA-105)
Particle Diameter Ca Ti
ym wt7o wt%
>11.3
4.9
1.12
7.3 -
11.3
-
-
4.7 -
7.3
4. 2
0.92
3.3 -
4.7
-
-
2.06 ¦
- 3.3
5.0
1.59
1. 06 -
- 2.06
-
-
0.65 -
- 1.06
2.6
1.08
* Analysis by X-ray fluorescence spectrometry
-13-
-------
where,
= volume of the WEP liquor (ml)
Vq = volume of flue gas sampled by WEP (scf)
XWL(Ca) = concentration of calcium in WEP liquor, (yg/ml)
XWAgh(Ca) = weight fraction of calcium in the cyclone ash
(ppm)
XWL(Ti) = concentration of titanium in WEP^liquor (ug/ml)
XWAsh(Ti) = weight fraction of titanium in the cyclone ash
(ppm)
The point to average grain loading correction factor
is then' the ratio of the average grain load in each duct to the
point grain load calculated from equation (2-1). The correction
factors were 1.7 for the south duct and 2.4 for the north duct.
These factors not only compensate for spatial maldistribution
of the particulates but also for temporal variation since the'
WEP samples are taken over a longer period of time than the
grain loading determinations.
Gaseous mercury in the flue gas was collected by gold
amalgamation. Hydrogen peroxide bubblers were used to absorb
SO2 in the flue gas by EPA Method 6.
2.3 Summary of Flow Rates and Estimated Errors
A summary of the flow rates is given in Table 2-2.
The error limits presented in this table are largely based on
-14-
-------
TABLE 2-2
FLOW RATES FOR STREAMS
AROUND STATION III
Stream
Coal
Bottom ash and
economizer ash
sluice water
inlet
Bottom ash
Bottom ash
sluice water
outlet
Economizer ash
Economizer ash
sluice water
outlet
Cyclone ash
Flow Rate
2.34 x 10s lb/hr.
2.65 x 10s lb/hr.
1.68 x 10" lb/hr.
Flue gas
Fly ash
1.78 x 105 lb/hr.
154 lb/hr.
8.71 x 10* lb/hr.
6.23 x 103 lb/hr.
4.11 x 107 scfh
3.42 x 103 lb/hr.
Error Limit
±10%
±157.
±15%
±15%
±20%
±15%
±10%
± 10%
± 10%
Method Used For
Flow Determination
Revolutions of coal
feeders were measured
Rates were set equal
to sluice water outlet
rates
Difference of ash rate
in incoming coal and
discharge rates of econ-
omizer ash, cyclone ash
and fly ash
Directly measured by
vo lume
Calculated from economizer
ash sluice rate
Directly measured by
volume
Measured by weighing trucks
and from differences in
silo level
Measured by duct traverses
Determined from point
grade loadings
-------
Radian field experience and Che typical errors expected with
the flow measuring devices. Also summarized in this table are
the procedures used to obtain the listed rates.
2.4 Sampling Schedule
With the exception of the bottom ash and economizer
ash, all plant streams were continuous with short residence
times in the system. Bottom ash accumulated in the quench tanks
and was sluiced to the storage basin every four hours requiring
approximately thirty minutes to empty the tank. Economizer
ash accumulated in the economizer ash hopper for four hours
after which the accumulation was then sluiced to the storage
basin over a period of approximately thirty minutes. Sampling
of these' two streams was time-phased to collect samples from
the sluice stream representative of the ash which had accumu-
lated during the sampling period.
Sampling was performed during the period August 27-
29th according to the schedule shown in Figure 2-3. Those
samples enclosed in parenthesis were analyzed, the rest were
retained in reserve.
2.5 Sample Analysis
The techniques used for the quantitative determinations
based on:
(1)
atomic absorption
(2)
X-ray fluorescence
(3)
ion selective electrodes
(4)
fluorometry, and
(5)
colorimetry.
-16-
-------
1. Coal - Silo 2
Silo 4
Silo 6
2. Bottom Ash and Economizer
Ash Sluice Water Inlet
3. Bottom Ash
4. Bottom Ash Sluice
Water Outlet
5. Economizer Ash
6. Economizer Ash Sluice
Water Outlet
7. Cyclone Ash
8. Flue Gas Velocity
9. Flue Gas Particulate
Loading
10. Flue Gas WEP
Particulate Collection
point sampling
continuous sampling
( )
( )
( )
• (• )
• •(•)
• •( •)
• •(•)
• •(•)
• ( )
August 27 August' 28 August 29
FIGURE 2-3
Sampling Schedule at Station III
-17-
-------
The methods are described in greater detail in Appendix B,
"Analytical Procedures".
Figures 2-4 through 2-6 give a succinct survey of
dissolution and analytical methods used for trace element deter-
mination in the samples.
The analytical accuracies of the employed techniques
are summarized in Table 2-3. These values were derived by
comparing analytical results with NBS standards where available.
In the other cases, recovery studies and/or precision values are
the basis for the estimated confidence level.
Semiquantitative analyses based on spark source mass
spectrometry (SSMS) for 53 elements were performed by Accu-Labs,
Inc. Since the accuracy of this method is strongly dependent
on the matrix, an error limit could not be estimated in the
framework of the present study.
-18-
-------
Mo, Cd, Sb *
Ni *
FIGURE 2-1
ANALYSIS PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL
-19-
-------
Mo, Cd, Sb
Ni
FIGURE 2-2
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL ASH AND SLUDGE
-20-
-------
Ion Selective Electrode
Primary
Digestion
(FiltrationJ.
.Thermal
Oxidation,
HF-HNO3-
H2so4
Digestion)
Li2CV
X-Ray
Na„B,0_
Fluorescence
2 4 7
Fusion
NaF Fusion
Fluorescence
Fluorescence
Titrimetry
Acid Permanganate/
Atomic Absorption
Spectrophotometry
Ba
¦U
• Se
•Hg
•Ti, B
Atomic Absorption
Extraction/
Atomic Absorption
Al, Mg, Fe,
_Ca, V, As,
Mn, Cu, Zn
Ag, Cr
Co, Be, Pb,
-Mo, Cd, Sb,
Ni
Ion Selective Electrode
•CI
FIGURE 2-4
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF WET ELECTROSTATIC PRECIPITATOR LIQUORS AND AQUEOUS SAMPLES
-21-
-------
TABLE 2-3
ESTIMATED ERROR LIMITS FOR THE CHEMICAL ANALYSES
WEP
Aqueous
Coal and
Liquor
Samples
Coal Ash
Aluminum
±10%
±10%
±8%
Antimony
±10%
±10%
±15%
Arsenic *
± 8%
± 8%
±10%
Barium
±20%
±20%
±20 %
Beryllium
±10%
±10%
±12 %
Boron
±8%
± 8%
±8%
Cadmium *
±12%
±12%
±12%
Calcium
± 2%.
± 2%
±2%
Chlorine-
±10%
±10%
± 8 %
Chromium "
±10%
±10%
±12 %
Cobalt
±10%
±12%
±10 %
Copper *
±10%
±10%
±12 %
Fluorine
±8%
± 8%
± 8 %
Iron *
±6%
± 6%
± 6 %
Lead *
±10%
±10%
±18 %
Manganese *
±10
±10%
± 8 %
Magnesium
± 2%
± 2%
± 2 %
Mercury *
±20 7°
±10*
±10 7.
Molybdenum
±12*
±12*
±15 7-
Nickel *
±12%
±12%
±12 %
Selenium *
±5%
± 5%
± 5 %
Titanium
±8%
± 8%
± 8 %
Silver
±10
±10%
±10 %
Sulfur
±10%
± 2%
± 2 %
Uranium *
± 8 *
± 8*
± 6 *
Vanadium *
±12%
±12%
±10 %
Zinc *
±10%
±10%
±12 %
*By comparison with NBS Standard Reference Materials 1633 and 1634.
-22-
-------
3.0 DATA EVALUATION
The flow rates and chemical analyses are used to cal-
culate the transport rate of the elements of interest through
the boiler and their discharge rates in the effluent streams.
A material balance is made around the boiler for each of the
elements. The mathematical correlation forms are given in the
next sections.
3.1 Trace Element Material Balances
The transport rates of the elements of interest through
the steam station are calculated from the chemical analyses of
the samples and the flow rates of the incoming and exiting
streams. A material balance is calculated for each of the trace
elements to verify the determined emission values.
Equating the trace element flow into the system to the
flow out of the system gives the following expression:
McXWc(j) + MaswXWasw.(j) = (3-1)
MssXWssa) + Ms]XWsl(j) + MpaXWpa
-------
Masw = the mass flow rate of the inlet sluice water to
the ash sluice system (lb/hr.)
^asw^ = the wei§ht fraction of the element j in the inlet
sluice water
Mba = the discharge rate of bottom ash from the boiler
(lb/hr.)
XWba(j) = the weight fraction of the element j in the
bottom ash
Mbasw = the mass flow rate of the sluice water discharged
with the bottom ash (lb/hr.)
XWb w(j) = the weight fraction of the element j in the
bottom ash sluice water
Mea = the discharge rate of economizer ash from the
boiler (lb/hr.)
XW (j) = the weight fraction of element j in the econo-
6 di
mizer ash
M * the mass flow rate of the sluice water discharged
easw &
with the economizer ash (lb/hr.)
XW (i) = the weight fraction of the element i in the
easwVJ/
economizer ash sluice water
-24-
-------
Mca = the discharge rate of ash collected in the cyclone
dust collectors (lb/hr.)
XW (j) = the weight fraction of element j in the cyclone
C SL
ash
VfgS = the volumetric flue gas flow rate in the south
duct (scfh)
XVf (J) " the weight of the element j per unit volume of
flue gas in the south duct (lb/scf)
Vfgn ™ the volumetric flue gas flow rate in the north
duct (scfh)
XVfgn(j) « the weight of element j per unit volume of flue
gas in the north duct (lb/scf)
3. 2 Error Propagation Analysis
An error propagation analysis was performed on the
material balance equations for each element. Error limits are
calculated for the total inlet and outlet rates of each element
indicating the magnitude of variation to be expected due simply
to random errors.
Only errors random in nature are considered in this
treatment. A variance is calculated for a given value according
to the following standard definition.
S2(Q) - I S2(q.) (>3)
1 K1
-25-
-------
where
S(Q) = the variance in Q
Q = the material balance value which is a function
of the q^'s
- the i— independent flow rate or composition
used to calculate Q
Confidence intervals can then be assigned to the trace element
flow rates calculated for the various streams based on the
errors associated with each measurement used in the calculation
of these quantities. These limits will be included with the
calculated rates discussed in the following section. The error
limits for the flow rates were given in Table 2-2 and those
assigned to the chemical analyses were listed in Table 2-3.
-26-
-------
4.0 RESULTS
The values for the proximate and ultimate analysis of
the coal are presented in Table 4-1, the coal ash analysis in
Table 4-2.
The analysis results using the quantitative analytical
methods described in Section 2.5 and Appendix B are listed in
Table 4-3. The element concentrations in the coal and the flow
rates are reported on a dry weight basis. Most of the values
in Table 4-3 are presented in parts per million on a dry weight
basis for the solid samples or micrograms per milliliter for
liquids. Some elements present in higher concentrations are
listed as percent. The WEP results are presented in pounds per
standard cubic foot of dry flue gas, where standard conditions
are defined as a temperature of 60°F and pressure of 29.92 inches
of mercury.
Table 4-4 presents the analytical results obtained
by SSMS. The coal sample was analyzed in duplicate to estimate
the precision of this method of analysis. The duplicate results
differ in some cases by a factor up to three as indicated for
Br, Cd, Ce, Cu, Ni, Rb, and Zn. Systematic errors caused by
special matrices could not be determined within the scope of
the present work. Blind duplicate samples were also submitted
for the WEP samples from the south duct. The differences be-
tween duplicate samples were fairly large as evidenced by a
factor of 8 for Br, 5 for Cd, 22 for Cs, 20 for Cr, etc. How-
ever, these data (SSMS) are useful for order-of-magnitude
estimates of trace element flows.
The trace element flow rates in lb/hr are listed in
Table 4-5, using the quantitative analysis methods and in Table
4-6, using the SSMS results. The sum of the elemental flow rates
-27-
-------
TABLE 4-1
STATION III COAL ANALYSIS
Radian Sample No. 496
Proximate As Received Dry
% Moisture 36.84
% Fixed Carbon 29.08
0.00
7.84 12.40
% Ash
. Mat.f0r 26.24 41.54
% Volatile Matter
46.06
Total 100.00 10Q.00
% Sulfur 0.91 1.44
BTU/lb 6214 9333
Moisture and Ash
Free BTU/lb 11,230
Ultimate
% Carbon 41.91 66.52
% Hydrogen 6.77 4.24
% Nitrogen 0.60 0.95
70 Oxygen 41.97 14.59
% Sulfur °-91 1-30
% Ash 7-84 12.40
Total 100.00 100.00
-28-
-------
TABLE 4-2
STATION III ASH ANALYSIS
Radian Sample No. 496
Mineral Analysis of Ash Percent
Silicon Dioxide, Si02 30.21
Aluminum Oxide, A1203 11.90
Titanium Dioxide, Ti02 0.67
Iron Oxide, Fe203 14.27
Sodium Oxide, Na20 3.24
Potassium Oxide, iC20 1.10
Calcium Oxide, CaO 16.23
Magnesium Oxide, MgO 5.72
Phosphorus Pentoxide, P205 0.09
Sulfur Trioxide, S03 12.90
Other 3.67
Total 100.00
Ash Viscosity Calculations
Basic Content (percent) 48.66
Acidic Content (percent)- 51.34
Dolomite Content (percent) 54.13
Base-to-Acid Ratio 0.95
Silica-to-Alumina Ratio 2.54
Temperature for 250 Poise Viscosity, °F 2050
-29-
-------
TABLE 4-3
ANALYTICAL RESULTS OF THE STATION III SAMPLES 1
Element
Ash
Sluice
Water
Coal Inlet
Bottom
Ash
Bottom
Ash
Water
Sluice
Economizer
Ash
Economizer
Ash
Sluice Jgacer^
Cyclone
Ash
Souch
Ducc
WEP
North
Duct
WEP
Aluminum
741
.42
8.79%
1.7
8.48%
.58
7.44%
730
440
Antimony
40
.018
.8
.034
.56
.021
.79
.18
.13
Arsenic
S.
0
.006
20.
.0087
126.
.0012
188.
.67
1.3
Barium
440.
<.5
.57%
<.5
.83%
<•5
.77%
<5.8
<5.3
Beryllium
60
.0014
5.3
.0017
8.8
.003
8.3
.027
.021
Boron
150.
.26
520.
.25
740.
2.4
.16%
.71
.34
Cadmium
.20
.0003
.87
.0011
1.8
.0012
2.9
.054
.059
Calcium
1.
,38%
35.
13.0%
43.
12.0%
46.
13.1%
1800
1100
Chlorine
55.
12.
88.
16.
119.
17.
135.
29
43
Chromium
13.
< .053
95.
<.053
121
< .053
86.
3.5
3.6
Cobalt
, 75
.0003
10.
.0041
12.
.0039
13.
.28
.21
Copper
Fluorine
10.
,5
.0084
50.
.014
94.
.008
145.
1.9
1.6
57.
.21
< 10.
.25
65.
.21
670.
29
33
Iron
,757.
.43
6.54%
2.1
6.69%
1.4
5.76 %
930
550
Lead
Magnesium
Manganese
.36
.015
< .8
.024
8.3
.025
8.2
.23
.33
79.
.377.
26.
.082
3.71%
720.
26.
.055
3.77%
900.
24.
.096
3.63%
750.
7.1
450
4.3
260
Mercury
.074
< .0005
< .010
< .0005
.12
< .0005
.17
.080
.086
Molybdenum
Z,
.0
.033
18.
.016
44.
.012
61.
2.1
3.7
Nickel
5.
.4
.006
23.
.0014
36.
.007
38.
2.3
3.0
Selenium
1.
.3
.0012
.25
.0011
.14
.0012
9.5
.31
.26
Titanium
Silver
Sulfur
Uranium
350
1.
1
.034
.44%
.5
<.1
<.0003
68.
.0022
.35%
.11
95.
3.2
<.1
<.0003
74.
,0035
.38%
.32
.13%
11.
<•1
<.0003
77.
,0044
.30%
.75
.87%
12.
15
<.0031
7000
.15
2.5
18
<.0032
7400
.086
2.2
Vanadium
15
<.005
140.
<.005
110.
<•005
86.
3.5
2. 2
Zinc
7
.8
.013
18.
.013
140.
.028
120.
rwresent the average of duplicate determinations. Values for liquid samples are reported as ug/ol and
JSlids samples as ppm on a dry basis, unless otherwise noted. WEP values are reported as 10 lb/scf <60 F.
29.92" Hg).
-30-
-------
TABLE 4-4: STATION III. ANALYTICAL RESULTS BY SS-MS1 \ '
\. . v
Inlet Economizer
Ash Sluice Bottom Bottom Ash Economizer Ash Sluice North Duct
Coal2 Water Ash Sluice Water Ash Water Cyclone Ash South Duct WEP2 WEP
Elements
Aluminum
2200
^1200
1.2
>1%
0. 74
>1%
1.2
>17.
163
390
43
Antimony
0.47
0.35
_ _
2.5
0.003
2.5
2.5
0.13
0.34
0.075
Arsenic
9.4
6.0
0.005
12
0.012
57
0 020
120
1.1
2.6
0.59
Barium
260
490
0.31
730
0.40
-x-2600
0.31
-v-1800
8.8
0.49
2.3
Beryllium
2.1
3.2
_ __
56
- «.
11
11
0.012
<0.012
0.011
Bismuth
<0.77
<0.85
_ _
<0.17
« _
0.35
1.5
0.023
0.058
0.011
Boron
250
250
<0.1"
¦vlOOO
<0.1
-v2000
<0.1*
^2500
s
5
22
Bromine
1.9
4.4
0.025
3.1
0.070
3.1
0.012
5.5
0.023
0.19
0.022
Cadmium
1.4
3.4
0.029
1.3
0. 37
2.9
0.029
1.3
1.6
10.
1.0
Calcium
>1%
>1%
33
>1%
41
>1%
47
>1%
1000
1000
75
Cerium
7.5
17
0.005
40
0.002
71
0.001
71
0.31
0.19
0.19
Cesium
0.16
0.33
0.001
0.43
0.006
1.1
0.001
4.3
0.26
0.012
0.34
Chlorine
110
110
0.193
26'
2.03
92
0. 373
52
0.42
0.95
0.28
Chromium
11
11
0.001
53
0.32
53
0.010
110
1.4
27
1.9
Cobalt
2.4
2.4
0.047
15
0.003
40
0.005
40
0.12
0.70
0.35
Copper
7.7
17
0.013
42'
0.56
120
0.065
240
1.9
14
3.3
Dysprosium
1.2
1.5
_ _
4.2
8.4
4.2
0.035
<0.012
0.011
Erbium
0.16
0.16
_ «.
1.1
- _
1.0
0.48
0.012
<0.012
0.011
Europium
0.13
0.12
0.67
0.67
2.4
0.023
<0.012
0.011
Fluorine
66
130
0.503
91
0.203
91
0.0313
450
0.17
0.62
2.3
Gadolinium
0.14
0.27
0.69
1.6
1.0
0.046
<0.012
0.011
Gallium
0.86
0.86
0.003
13
0.008
27
0.006
47
1.6
3.1
0.45
Germanium
1.2
1.2
0.007
2.8
0.004
14
0.003
14
0.91
1.2
1.2
Gold
--
--
--
--
<0.012
<0.012
0.011
NOTES: 'Concentration in ppm weight in solids and pg/ml in liquids. WEP analysis in 10~# lb/scf (60°P, 29.92" Hg).
2Blind duplicate analysis.
'Possibly inaccurate due to loss from acidic solution.
'•Approximate value only due to interference from preservative.
'Insufficient sample for determination.
--All elements not reported <0.1 ppm weight in solids or <0.001 Mg/ml in liquids.
Maj. - Major component.
-------
TABLE 4-4: STATION III. ANALYTICAL RESULTS BY SS-MS1 (cont.)
Coal
2
Inlet
Ash Sluice
Water
Bottom
Ash
Bottom Ash
Sluice Water
Economizer
Ash
Economizer
Ash Sluice
Water
Cyclone Ash
North Duct
South Duct WEP2 WEP
Elements
Hafnium
0.25
0.34
. -
5.7
2.7
5.7
<0.012
<0.012
0.011
Holmium
0.04
0.08
- -
0.31
_ _
0.31
0. 31
<0.012
<0.012
0.011
Iodine
1.3
1.3
0.36
0.026
1.2
0.001
0.60
<0.012
<0.012
0.011
Iridium
_ _
- _
—
<0.012
<0.012
0.011
Iron
>17.
>0.5%
0.55
>17.
3.3
>17.
2.6
>17.
**-880
-woo
200
Lanthanum
2.0
4.3
0.010
8.7
0.014
17
0.002
8.7
0.13
0.13
0.033
Lead
0.48
0.96
0.009
0.80
0.15
40
0.005
40
0.31
1.9
0.11
Lithium
7.3
13
0.012
71
0.016
400
0.022
860
0.13
0.24
0.022
Lutetium
0.05
0.05
0.44
0.29
0.15
<0.012
<0.012
0.011
Magnesium
>1%
>17.
24
>17.
25
>17.
24
>17.
310
300
190
Mariganese
44
44
0.12
^2500
0.43
-v-3300
0.12
^1200
3.8
37
5.1
Mercury
_ _
_ _
5
—
5
--
5
%
s
s
Molybdenum
3.3
7.7
0.014
35
0.018
17
0.014
74
0.37
2.4
1.0
Neodymium
11
11
0.005
54
0.009
130
54
0.12
0.070
0.075
Nickel
14
2.8
0.18
28
0.046
28
0.036
49
1.0
56
1.3
Niobium
2.7
2.7
0.001
18
18
18
0.081
0.10
0.075
Osmium
—
--
—
—
<0.012
<0.012
0.011
Palladium
—
—
—
<0.012
<0.012
0.011
Phosphorus
70
70
0.086
960
0. 64
960
0.14
960
6.0
Maj
28
Platinum
--
—
--
--
<0.012
<0.012
0.011
Potassium
-v-1200
560
18
-V4800
18
^4800
18
^2400
200 1
190
180
Praseodymium
3.5
1.8
--
4.9
11
—
4.8
0.023
0.035
0.011
Rhenium
--
--
—
_ -
0.070
<0.012
0.011
Rhodium
—
_ _
_ _
— -
<0.012
<0.012
0.011
Rubidium 0.98 3.5 0.019 4J) 0.052 23 0.041 23 2^9 1.7 3.9
NOTES: 'Concentration in ppm weight in solids and pg/ml in liquids. WEP analysis in 10 * lb/scf (60°F, 29.92" Hg).
2Blind duplicate analysis.
3Possibly inaccurate due to loss from acidic solution.
11 Approximate value only due to interference from preservative.
5Insufficient sample for determination.
--All elements not reported <0.1 ppm weight in solids or <0.001 pg/ml in liquids.
Maj. - Major component.
-------
TABLE 4-4: STATION III, ANALYTICAL RESULTS BY SS-MS' (cont.)
Inlet Economizer
Ash Sluice Bottom Bottom Ash Economizer Ash Sluice North Duct
Coal2 ^ Water Ash Sluice Water Ash Water Cyclone Ash South Duct WEP2 WEP
Elements
Ruthenium
- -
_ _
_ _
—
<0.012
<0.012
0.011
Samarium
0.36
0.19
0.83
1.9
1.9
<0.012
<0.012
0.011
Scandium
5.3
2.9
- -
16
34
<0.012
<0.012
0.011
Selenium
1.8
4.0
0.042
1.9
0.024
4.3
0.043
8.7
0.73
17
1.4
Silicon
>1%
>11
3.3
>11
20
>1%
4.2
>11
Mai
Mai
Ma1
Silver
0.26
0.13
0.002
1.4
0.024
0.28
0.002
0.28
0.023
1.3
0.011
Sodium
>1%
>1%
130
>11
130
>11
130
>11
350
360
330
Strontium
310
620
1.4
->-2800
3.1
-W800
3.8
^9700
39
28
0.52
Sulfur
>1%
>1%
Ma1.
-v.1900
Mai.
--11
Mai ¦
>11
Ma1
Mai
Mai
Tantalum
0.003
2.6
0.002
1.2
0.001
1.2
0.012
0.046
0.022
Tellurium
0.11
0.10
0.002
0.52
— -
0.16
_ _
0.16
0.023
0.17
0.011
Terbium
0.10
0.09
0:53
-
0.53
«. _
0.80
<0.012
<0.012
0.011
Thallium
<0.12
<0.12
<0.10
0.003
<0.10
0.80
<0.012
0.34
0.011
Thorium
1.2
1.2
13
_ _
13
„ _
13
<0.012
<0.012
0.011
Thulium
0.07
0.07
0.26
- _
0.26
0.12
<0.012
<0.012
0.011
Tin
1.8
0.80
0.003
2.0
0.050
2.0
4.6
0.45
15
3.0
Titanium
490
490
0.097
<\.2300
0.18
^1900
0.14
-------
TABLE 4-5
TRACE ELEMENT FLOWS* AND MATERIAL BALANCE RESULTS
AROUND STATION
XII (8/29/74)
Flue
Ash Bottom Economizer Gas
Element
Coal
Sluice
t
In .
Bottom
Ash
Ash Sluice
Water
Economizer
Ash
Ash Sluice
Water
Cyclone
A:;h
Flue Gas
South Duct
Horth
Duct
I
Out
Z Cuz/T. In
Aluminum
1740
0.11
1740
±
220
1480
.30
13.
.05
463
164
82
2200
i 260
1.26
Antimony
.094
. 0048
.10
t
.02
.013
.0061
.00008
.0018
.0049
.040
.025
.09
t .01
.90
Arsenic
1.9
.0016
1.9
t
.3
.33
.0015
.019
.0001
1.2
.15
.25
1.9
£ .2
1.00
Barium
102
< . 13
103
4
23
96
< . 089
1.3
< .044
48.
< 1.3
< 1.0
147
- 26
1.43
Beryllium
.14
.0004
.14
1
.02
.089
.0003
.0014
.0003
.052
.006
.004
.15
t .02
1.07
Boron
36
.07
36
1
5
8.7
.045
.11
.21
10.
16.
6.4
42
i 3
1.17
Cadmium
.046
.00007
.046
t
.007
.015
.0002
.0003
.0001
.018
.012
.011
.056
: .005
1.22
Calcium
3220
9
3230
1
330
2180
8.
18.
4.
816.
397.
204.
3630
t 340*
1.12
Chlorine
13
3.2
16
1
2
1.5
2.8
.02
1.5
.84
6.4
8.0
21
2 2
1.31
Chromium
3. 1
<.014
3.1
t
.4
1.6
<.0094
.019
<.0046
.54
.78
.68
3.6
± .4
1.16
Cobalt
.18
.00007
.18
t
.02
.17
.0007
.0018
.0003
.081
.062
.039
.35
* .03
1.94
Copper
2.5
.002
2.5
t
.4
.84
.002
.014
.0007
.90
.42
.20
2.5
_ .2
1.00
Fluorine
13.
.05
13
1
2
<17
.044
.01
.02
4.2
6.4
6.1
17
* 2
1.31
Iron
1770
.11
1770
t
210
1100
.4
10.
. 12
358
2.08
103
1739
-• ltiO
1.01
Lead
.20
. 0040
.21
t
.04
<•013
.0043
.0013
.0022
.051
.062
.062
.20
s .02
.95
Magnesium
870
7
880
t
90
623
4.6
5.8
2.1
226
100
49
1010
i 100
1.15
Manganese
18
.022
18.
2
12
.0098
.14
.0084
4.7
1.6
.8
19
! 2
1.06
Mercury
.017
<.0001
.017
t
.002
<.0002
<.00008
.00001
<.00004
.0011
.018
.016
.03b
: .004
2.12
Molybdenum
.46
.0087
.47
+
.08
.30
.0028
.0068
.0010
.38
. 40
.70
1.9
; .1
4.04
Nickel
1.3
.0016
1.3
i
.2
.39
.0002
.0055
.0006
.24
.52
.56
1.7
i .2
1.31
Selenium
.31
.0003
. .31
t
.03
.0042
.0002
.00002
.0001
.059
.070
.049
.18
t .01
.58
Silver
.0079
<•00006
.008
j
.001
.0018
<.00004
.0004
<00002
.0047
<.0007
<.0006
.0078
; .0007
.98
Sulfur
3380
18
3400
+
340
1.6
13.
.20
6.7
54.
1560
1390
3020
i 300 .
.89
Titanium
82.
<•027
82
*
10
59
<•018
.59
<.0087
19'.
3.4
3.3
85
i 10
1.04
Uranium
.36
.0006
.36
±
.04
.054
.0006
.0017
.0004
.075
.034
.016
.18
i .02
.50
Vanadium
3.5
<.0013
3-5
+
.5
2.4
<¦0009
.017
<.0004
.54
.57
.41
3.9
i .4
1.11
Zinc
1.8
. 0034
1.8
±
.3
.30
.0023
.022
.0024
.75
.78
.41
2.3
t .3
1.28
*AU
flow ratea In lb/hr.
-------
TABLE 4-6 - TRACE ELEMENT FLOWS* AND MATERIAL BALANCE RESULTS AROUND STATION TTI FROM SPARK SOURCE MASS SPECTROMETRY ANALYSES
ELEMENT
COAL
ASH
SLUICE H20
j: in
BOTTOM
ASH .
BOTTOM ASH
SLUICE H20
. ECON ASH
ECON ASH
SLUICE H20
CYCLONE
ASH
FLUE GAS
SOUTH DUCT.
FLUE GAS
NORTH DUCT.
r out
ALUMINUM
410
0.32
410
>168
0.13
>1.5
0.10
>62
62
8
>300
ANTIMONY
0.095
<.0003
0.095
0.042
0.0005
0.0004
<0.00008
0.016
0.052
0.014
0.13
ARSENIC
1.8
0.0013
1.8
0.20
0.0021
0.0088
0.0017
0.75
0.42
0.11
1.5
BARIUM
88
0.082
88
12 *
0.071
i.0.40
0.27
1-11
1.0
0.43
1-25
BERYLLIUM
0.61
<0.0003
0.61
0.94
<0.0002
0.0017
<0.00006
0.G69
0.0026
0.0021
1.0
BISMUTH
<0.19
<0.0003
<0.19
<0.0029
<0.0002
0.0005
¦<0.00008
0.009 3
0.010
0.0021
0.025
BORON
59
<0.027
59
•>¦17
<0.018
1.0.34
<0.0087
>-16
4.1
1.37
BROMINE
0.72
0.0066
0.72
0.052
0.012
0 0005
0.0010
0.034
0.023
0.0041
0.13
CADMIUM
0.56
0.0077
0.57
0.022
0.066
0.0004
0 0025
0.0081
1.3
0.19
1.6
CALCIUM
>2560
8.7
>2570
>168
7.3
>1.5
4.1
>62
234
140
>620
CERIUM
3.1
0.0013
3.1
0.67
0.0004
O.Oil
0.00008
0.44
0.055
0.035
1.2
CESIUM
0.059
0.0003
0.059
0.0072
0 0011
0 0002
0 00008
0.027
0.029
0.064
0.13
CHLOPIME
26
0.05
26
0.44
0. 36
0 014
0.032
0. 32
0. 15
0.052
1.4
CHROMIUM
2.6
0.0003
2.6
0.89
0.057
0.0082
0.0009
0.69
3.1
0 . 35
5.1
COBALT
0.56
0.012
0.58
0.25
0.0005
0.0062
0.0004
0 25
0.091
0.066
0.67
COPPER
3.1
0.0034
3.1
0.71
0.10
0 018
0.0057
1. 5
1. 8
0. o2
4.7
DYSPROSIUM
0.33
<0.0003
0.33
0.071
<0.0002
0 0013
<0 00008
0 026
0.0078
<0.0021
0.11
ERBIUM
0.038
<0.0003
0.039
. 0.018
<0.0002
0.0002
<0 00008
0 0030
0.0026
<0.0021
0.027
EUROPIUM
0.031
<0.0003
0.031
0.011
<0 0002
0.0001
<0.00008
0.015
0 0052
<0.0021
0.034
FLUORINE
23
0.13
23
1.5
0.036
0.014
0.0027
2.8
0.088
0.43
4.9
CADOLINIUM
0.049
<0.0003
0.049
0.012
<0.0002
0 0002
<0.00008
0 0062
0.010
<0.0021
0.031
GALLIUM
0.20
0.0008
0.20
0.22
0.0014
0.0042
0.0005
0 . 29
0 . 55
0.84
1.1
GERMANIUM
0.28
0.0019
0.28
0.047
0.0007
0 0022
0.0003
0.087
0.23
0.23
0.60
COLD
'0.026
<0.0003
<0.026
<0.0017
<0.0002
<0.00001
<0.00008
<0.0006
<0.0026
<0.0021
<0.0072
HAFN'IUM
0.069
<0.0003
0.069
0.096
<0.0002
0.0004
<0.00008
0.036
<0.0026
<0.0021
0.14
HOLMIUM
0.015
<0.0003
0.016
0.0052
<0.0002
0.00004
<0.00008
0.0019
<0.0026
<0.0021
0.012
IODINE
0.31
<0.0003
0.31
0.0060
0.0046
0 0002
0.00008
0 0037
<0 0026
<0.0021
0.019
IRIDIUM
<0.026
<0.0C03
<0.026
<0.0017
<0.0002
<0.00001
<0.00008
<0.0006
<0.0026
<0.0021
<0.0072
IROIl
>1792
0.15
>1790
>168
0.59
>15
0.23
>62
179
37
>450
LANTHANUM
0 . 74
0.0027
0.74
0.15
0.0025
0.0026
0.0002
0.054
0.029
0.0062
0.24
LEAD
0.17
0.0024
0.17
0.013
0.027
0.0062
0.0004
0.25
0.24
0.021
0 . 56
LITHIUM
2.4
0.0032
2.4
1.2
0.0028
0.062
0.0019
5.4
0.042
0.0041
6.7 1
IJJT.Tl'1 ,JM
0 013
-•0.0003
0.013
0.0074
<0.0002
0.00004
<0 00008
0.0009
<0.0026
<0.0021
0.013
MAGNESIUM
>2560
6
>2570
>168
t.i
>1.5
£ . 1
>G2
70
35
>340
MANGANESE
10
0.032
10
•v. 42
0.077
1-0.51
0.010
1-7.5
4.7
0.95
1.56
* All flows In lb/hr.
-------
TABLE 4-6 - TR/.CE ELEMENT FLOWS"' AND MATERIAL BALANCE RESULTS AROUND STATION III FROM Sl'ARK SOURCE MASS SPECTROMETRY ANALYSES
(Cont.)
ASH rhtthm BOTTOM ASH ECON ASH .vn„ur
cj fiTfp u a BOTTOM nj ||T/in I. qi riT/^L' u r\ CYCLONE FLbE GAS i LUE CAS
ELEMENT COAL 5 "2. t IN . ASH . H2U . ECOH ASH.uu('b H2i. ASH .SOUTH DUCT .NORTH DUCT. I Ol'T
M'RCURY <0.026 -- <0.026 <0.0017 __<0 OflOCU : <0 0006 — <0 0023
MOLYBDENUM L. 3 0.0037 1.3 0.59 0.0032 0. 0')-6' 3 "01? P.':* 0.70 0¦ 19 2 0
L120n,riIU»^____ 2 6 0.0013 2 6 °-91 _JL 0?16 0 020 <0.00000 0.34 0.021 0.C14 1.3
•iirc^L 2/) o.Q/° n..!j o.oce:: rj"y o.o".n o.3i 6.2 0.25 7.3
NIOBIUM 0 ,64 0.0003 0.64 0.30 <0.0002 0.0028 <0.00008 0.11 0.021 0.014 0.45
OSMIUM <0.026 <0.0003 <0.026 <0.0017 <0.0002 <0 00001 -0.00008 <0.0006 <0.0026 <0.0021 <0.0072
PALLADIUM <0.026 <0.0003 <0.026 <0.0017 <0 0002^ -0.00001 <0.00008 <0 0006 <0.0026 <0.0021 <0.0072
PLATINUM <0.026 <0.0003 <0.026 <0.0017 <0.0002 <0^00001__ <0.00008 <0.0006 <0.0026 <0.0021 <0.0072
POTASSIUM 205 4JS 210 ->-81 3 . 2 ^180
PRASEODYMIUM 0.61 <0 .0003 0 .61 0.082 <0. 0002 0 . 0017 <0 .00008 0.030 0.0078 0.0021 0.12
RHENIUM <0.026 <0.0003 <0.026 <0.0017 <0.0002 vO OOOOl <0.00008 <0.0006 <0.0026 <0.0021 <0 0072
RHODIUM <0.026 <0.0003 <0.026 <0.0017 <0.0002 __£0 00001_ <0 00008 <0.0006 <0.0026 <0.0021 <0.0072
PUB I PI UM 0.54 0.0050 0.54 0.067 0 0093 0_ 0035 _ 0.0036 0.14 0.52 0.72 1.5
RUTH EM IUM <0.026 <0.0003 <0.026 <0.0017 <0.0002 <(KOOOO 1 <0.00008 <0.0006 <0.0026 <0.0021 <0 007 2
SAMARIUM 0.064 <0.0003 0.064 0.014 <0.0002 0.0003 <0.00008 0.012 <0,0026 <0.0021 0.031
SCANDIUM 0.97 <0.0003 0.97 1.3 <0.0002 0.0025 <0 00008 0.21 <0.0026 <0.0021 1.6
SELENIUM 0.69 0.011 0.70 0.032 0.0043 0 0007 0.003/ 0.054 2.0 0.27 2_4
SILVER 0.046 0.0005 0.04 7 0.024 0.004 3 0.00004 0.0002 0.0017 0.16 <0.0021 0. 19
SODIUM >2560 34 >2590 >168 23 >x . 5 U >62 78 62 >410
STHO-'ITIUM 110 0. 37 110 "-47 OJj^ 2 0.33 >-bO 7^5 9.7 ^130
TA'ITAI-UM <0.026 0.0008 <0.026 0.044 0.0004 0.0002 0.00003 0.0075 0.0078 0._004] 0.064
TELLURIUM 0.026 0.0005 0.026 0.0087 <0.0002 0.00002 -.0.00003 0.0010 0.023 0.0021 0.035
TERBIUM 0.023 <0.0003 0.023 0.0089 <0.0002 0_0000a 10^00008 0.0050 <0.0026 <0.0021 0.019
THALLIUM <0.028 <0.0003 <0.028 <0.0017 0. 000 5 < 0. 00001 <0.00008 0.0050 0.075 <0.0021 0.065
THORIUM 0.28 <0.0003 0.28 0.22 <0.0002 0_0020 <0 .00008 0.031 <0.0026 0.0021 0. 31
V'lJlJUy 0.015 <0.0003 0.016 0.0044 <0.0002 0^00004 <0. 00008 0.0007 <0.0026 <0.0021 0.010
TIN 0._31 0.0008 0.31 0.034 0 .0089 0 .0003 <0 .00008 0.029 1.7 0. 56 2.4
TITANIUM 115 0.026 115 M9 0.032 ^029 0. 012 -v-31 11 3.7 "84
TUNGSTEN 0.77 0.0019 0.77 0.27 0.0005 0.0057 0.0002 0.23 0.031 0,0062 0 54
URA.'.'IUM 0.20 <0.0003 0.21 0.18 0.0004 0.0017 <0.00008 0.069 0.010 0.006 0.27
VANADIUM 3JJ 0.0021 3.3 1.4 0.0018 0 J) 13 0.0027 1.1 5.2 0.56 8.3
YTTERBIUM 0.059 <0.0003 0.059 0.035 <0.0002 0.0003_ <0.00008 0.0062 <0.0026 <0.0021 0.047
YTTRIUM 1^6 0.0003 1.6 0.72 0 .0004 O.OU 0.00008 0.75 0.10 0.019 1. 6
ZINC 0.16 0.021 O.ia 0.034 0.18 0 0007 0.0070 0.34 3.4 1_1 5_._1
ZIRCONIUM 4_4 0.0008 4.4 1.0 0.0007 0.0095 0.00008 0.69 0.21 0,M9 2_0
* All flows in lb/hr.
-------
of all incoming streams, coal and ash sluice water, are given
as Z In. The flow rates of the outgoing streams, bottom ash,
bottom ash sluice water, cyclone ash, flue gas south duct and
flue gas north duct, also were added and are listed as Z Out.
The error limits given were calculated from the estimated errors
in the analyses and the estimated errors in the flows according
to the procedures described in Section 3.0.
The emission results for sulfur and particulates are
summarized in Table 4-7 since these are the two emission
parameters of greatest immediate importance. The results are
provided on a lb/BTU basis to facilitate comparison to other
stations.
-37-
-------
TABLE 4-7
EMISSION RESULTS FOR PARTICULATES AND
SULFUR DIOXIDE AT STATION III
Concentration in flue
gas
North Duct
South Duct
Quantity in coal per
unit heat value
Emissions in flue gas
per unit heat value
of coal burned
Particulates
(Ash')
Sulfur Dioxide
0.50 gr/scf
0.65 gr/scf
1.5 lb/106 BTU
880 ppm (v/v)
830 ppm (v/v)
12.6 lb/106 BTU 2.93 lb/106 BTU
2.56 lb/106 BTU
-38-
-------
5.0 DISCUSSION OF RESULTS
Two areas are of primary interest regarding the results
presented in Section 4.0. The first is the trace element levels
and their distribution among the exit streams; the second is the
level of confidence of the data as indicated by material balance
closure.
5.1
Material Balance Closure
The criteria used for judging overall reliability of
the data are the degree of closure of the material balances.
Closure within error limits, indicated by an overlap of the
error bands for Z In and S Out presented in Table 4-5, lends
support to the reliability of the individual element flows.
The balances close within error limits for the following 21
elements.
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Copper
Fluorine
Iron
Lead
Magnesium
Manganese
Nickel
Silver
Sulfur
Titanium
Vanadium
Zinc
The balance for chlorine is slightly out of the limits (16 ± 2
lbs/hr in versus 21 ± 2 lbs/hr out). Larger variations are
found for:
Cobalt
.18
Mercury
.017
Molybdenum
.47
Selenium
.31
Uranium
.36
± .02 lbs/hr in
±.002 lbs/hr in
± .08 lbs/hr in
± .03 lbs/hr in
± .04 lbs/hr in
.35 ± .03 lbs/hr out
036 ±.004 lbs/hr out
1.9 ± .2 lbs/hr out
.18 ± .01 lbs/hr out
.18 ± .02 lbs/hr out
>39-
-------
The nonclosure of these balances may be attributed to
errors in sampling, sample handling or sample analysis. Selenium,
mercury and chlorine present special sampling difficulties since
they may be present in the gaseous phase. The degree of closure
of the balances obtained by the quantitative analytical techniques
and by spark source mass spectrometry are compared in Table 5-1.
For each element a normalized deviation was calculated according
to :
vrrv t \ \ Sin(i) - Zout(i)
N (Zin(j) + £out(j))/2
(5-1)
The average of the normalized deviations was -0 14
for the quantitative methods and -0.29 for the SSMS results
indicating that the exit flows of the trace constituents were
measured on the average higher than the incoming flows The
root mean square of the normalized deviations according to
RMS
ND
+
T
(5-2)
are 0.37 for the quantitative methods and 1.1 for the SSMS
results. The RMS over 53 elements for SSMS was 0.87. Results
less than or greater than a certain value were not included in
the latter calculations. These deviation calculations provide
some measure of the overall material balance closure for each
of the two analytical approaches.
5.2
Distribution jf Elements in the Exit Streams
The incoming ash is distributed among the exit ashes
as follows
-40-
-------
TABLE 5-1
DEVIATIONS FROM MATERIAL BALANCE CLOSURE FOR QUANTITATIVE
ANALYSES AND SPARK SOURCE MASS SPECTROMETRY ANALYSES
SSMS
Normalized1
Deviation
Elements
Quantitative
Normalized
Deviation
Aluminum
-0.23
Antimony
0.11
-0.3L
Arsenic
0
0.18
Barium
-0.35
1.12
Beryllium
-0.069
-0.48
\
Boron
-0.15
0.46
Cadmium
-0.20
-0.95
Calcium
-0.12
--
Chlorine
-0.27
1.80
Chromium
-0.15
-0.65
Cobalt
-0.64
-0.14
Copper
0
-0.41
Fluorine
-0.27
1.30
Iron
-0.0056
--
Lead
0.049
-1.07
Manganese
-0.054
-1.39
Magnesium
-0.14
- —
Mercury
-0. 72
--
Molybdenum
-1.21
-0.42
Nickel
-0.27
-1.14
Selenium
0.53
-1.10
Silver
0.025
-1.21
Sulfur
0.12
--
Titanium
-0.036
0.31
Uranium
0.67
-0.25
Vanadium
-0.11
-0.86
Zinc
-0.24
-0.93
Averag
e of Normalized
Deviations
-0.14
-0.29
RMS of
Deviations2
0.37
1.1
NOTES: t
I (1)
Normalized Deviation ¦ in
" Eout
+ Eout(J>
9
2. Root Mean Square Oi
Normalized Deviations
N
I
[rin
- Eout«>]
fln
+
A
n
-41-
-------
Bottom Ash 63.17o
Economizer Ash 0.67,
Cyclone Ash 23.47,
Fly Ash 12.9%
The trace constituents entering the plant with the
coal would, in the simplest case, leave the plant in the same
ratios as the ashes. This will be the case, however, only if
no mechanism in the boiler leads to a preferential concentration
in one of the exit streams. Potential enrichment mechanisms
are
1) volatilization of an element or
compound and
2) chemical changes with formation of
a volatile element or compound.
The elements or compounds which vaporize can subsequently
1) leave the plant without recondensation,
2) recondense partially, or
3) recondense completely.
Those elements that are vaporized in the boiler are
subsequently enriched in the economizer ash, cyclone ash or
flue gas. The relative distribution in these streams is a
function of the degree of recondensation that occurs. The
volatile components that do not recondense are discharged pri-
marily with the flue gas. Condensation on the surface of
available particulate matter will result in a particular rela-
tive abundance of a given element in the various ash streams
dependent on the particulate size distribution in each stream
and the degree of recondensation.
-42-
-------
The element distribution in the bottom ash, in the
combined economizer and cyclone ash and in the flue gas for the
27 constituents quantitatively analyzed is shown on a percent
basis in Table 5-2. The values for bottom ash and economizer
ash were corrected for losses by leaching during the sluicing
operation. This correction was made by assuming that any in-
crease in concentration of a trace element in the liquid portion
of the bottom ash or economizer ash sluice stream was due to
leaching of that element from the respective ash. The concen-
tration difference (increase) between the inlet and outlet water
streams was converted to elemental mass flow using the outlet
bottom ash and economizer ash sluice water flows and added to
the mass flow in the ash solids. This total elemental mass
flow in the ashes was then used to calculate the distribution
shown in Table 5-2. The corrections were in most cases insig-
nificant .
The second column of Table 5-2 gives the total flow in
the coal of an incoming trace element in lbs/hr. The third column
is the portion in percent of the total outgoing flow of an element
found in the bottom ash. Values higher than 63.1% indicate an
enrichment of an element in the bottom ash; values lower than
63.1%, a depletion. The remaining columns present the fractions
in the other ash streams and the same reasoning holds true for
the economizer ash (gross average 0.67o), the cyclone ash (gross
average 23.4%), and the flue gas (gross average 12.9%). Values
for an element higher than these averages again indicate an
enrichment; values lower than these values, a depletion.
The results shown in .Table 5-2 are graphically dis-
played in Figure 5-1. The elements are approximately ordered
according to descending enrichment in the flue gas. The gross
average values for total fly ash (12.9%), cyclone plus economizer
-43-
-------
TABLE 5-2
DISTRIBUTION OF ELEMENTS AMONG BOTTOM ASH, ECONOMIZER ASH
CYCLONE ASH AND FLUE GAS AT STATION III
ELEMENT
lb/hr
in coal .
BOTTOM ASH 7»
(AVERAGE 63.1)
ECONOMIZER ASH %
(AVERAGE 0.67,)
CYCLONE ASH 7.
(AVERAGE 23.47.)
FLUE GAS 7o
.(AVERAGE 12.9%)
aluminum
1740
67.2
0.6
21.0
11.2
ANTIMONY
0.094
15.9
0.3
5.9
77.9
ARSENIC
1.9
16.9
1.0
61. 6-
20.5
BARIUM
102
64.9
0.9
32.4
< 1.6
BERYLLIUM
0. 14
58.2
1.0
34.0
6.5
BORON
36
21.0
0 . 7
24.1
54.1
CADMIUM
0.046
26. 8
0.4
32.1
41.1
CALCIUM
3220
60. 3
0.5
22.6
16.6
CHLORINE
13
12.2
2.9
4.7
80.0
CHROMIUM
3.1
44. 2
0.5
14.9
40.3
COBALT
0 . 18
48.0
0.5
' 22.9
28. 5
COPPER
2.5
34.1
0.6
36.6
28.9
FLUORINE
13
< 1.1
0.06
24.9
74.0
TRON
1770
61.8
0.6
20.1
17.5
lead
0.20
< 7.8
1.1
26.6
64.6
MANGANESE
13
62.5
0.7
24.5
12.5
MAGNESIUM
870
62.1
0.6
22.5
14.8
MERCURY
0.017
< 0.8
0.0 3
3.1
96.1
molybdenum
0.46
16.3
0.3
20.6
63.0
NICKEL
1.3
22.7
0.3
14.0
62.8
SELENIUM
0.31
2.3
0.01
32.4
65.4
SILVER
0.0079
22.0
4.9
57.3
<15.9
SULFUR
3380
0.09
0.03
1.8
98.1
TITANIUM
82
69.2
0.7
! 22.3
7.9
URANIUM
0. 36
29.8
1.0
41.4
27. 6
VANADIUM
3.5
60.9
0.4
13.7
24.9
ZINC
1.8
13. 3
1.0
33. 2
52.7
-44-
-------
SULFUR
MERCURY
CHLORINE
ANTIMONY
FLUORINE
SELENIUM
LEAD
MANGANESE
MAGNESIUM
TITANIUM
25%
50%
75%
100 %
FIGURE 5.1
DISTRIBUTION OF THE TRACE ELEMENT
AMONG STATION m PLANT EXIT ASHES
-45-
-------
ash (2470) , and bottom ash, (63.1%) are indicated as red, blue,
and green vertical lines respectively. The concentration of each
trace constituent in these three streams are given for each
element as horizontal bars. The concentration in the fly ash
plus flue gas on a percent basis is shown in red, the concentra-
tion of cyclone and economizer ash in blue, and the concentration
in the bottom ash in green. The crossing of two lines of the
sarafe color indicates enrichment.
The elements can, according to Table 5-2 and Figure
5-2, roughly be divided into three broad classes. Class one
contains the elements significantly enriched in the flue gas.
They are,in descending order of enrichment:
1)
Sulfur
6)
Selenium
11)
Zinc
2)
Mercury
7)
Lead
12)
Cadmium
3)
Chlorine
8)
Molybdenum
13)
Chromium
4)
Antimony
9)
Nickel
14)
Copper
5)
Fluorine
10)
Boron
15)
Cobalt
Material balances for four of the above elements, mercury, sele-
nium, molybdenum, and cobalt, exceeded the error limits. The
exact position of these elements in the above list may slightly
vary. However, the general trend should hold even for these
elements.
Class two elements seem to be enriched in the cyclone
plus economizer ash. This class includes:
1) Uranium
2) Arsenic
3) Silver
-46-
-------
The uranium material balance did not close within the stated
limits. Chemical compound identification and determination of
enrichment as a function of particle size would aid in clarifying
the enrichment mechanisms exhibited by this class.
Class three includes the elements which are more of
less evenly distributed among the ashes. These elements are:
1) Barium
6) Iron
2) Beryllium
3) Vanadium
4) Aluminum
5) Calcium
7) Manganese
8) Magnesium
9) Titanium
-47-
-------
APPENDIX A
SAMPLING AT STATION III
-------
TABLE OF CONTENTS
Page
1. 0 INTRODUCTION ' A-1
2.0 PLANT DESCRIPTION A-2
¦2.1 Plant Operation During Sampling a-2
2.2 Time Phasing During Sampling a-4
3.0 DESCRIPTION OF SAMPLING POINTS A-5
3.1 Coal A-5
3.2 Bottom Ash and Economizer Ash Sluice
Water Inlet A-5
3.3 Bottom Ash A-7
3.4 Bottom Ash Sluice Water Outlet A-7
3.5 Economizer Ash A-8
3.6 Economizer Ash Sluice Water Outlet a-8
3.7 Cyclone Ash A-8
3.8 Fly Ash A-9
3.9 Sampling Schedule A-14
4.0 FLOW RATE MEASUREMENTS A-16
4.1 Coal A-16
4.2 Bottom Ash and Economizer Ash Sluice
Water Inlet A-16
4.3 Bottom Ash A-17
4.4 Bottom Ash Sluice Water Outlet A-17
4.5 Economizer Ash A-17
4.6 Economizer Ash Sluice Water Outlet A-18
4.7 Cyclone Ash A-18
4. 8 Fly Ash A-19
4.9 Summary of Flow Rates A-19
-------
1.0 INTRODUCTION
Sampling at Station III was performed by Radian per-
sonnel during the period 26-30 August 1974. The station was
selected as part of the Northern Great Plains Resources Program
trace elements study to be representative of a plant with cyclone
dust collectors for fly ash control and a lignite-fired boiler
with cyclone burners.
Representative samples of all inlet and outlet streams
around the power plant were collected with the objective of
. pmissions from the plant. Analyses
quantifying the trace element emisbiuus f j
of the samples for the trace elements of interest in combination
with flow rate data for each stream during the sample period
. i , i m hp nerformed for each element.
allows a material balance to be ?eiiU1
T* . -i ce-ve two main functions: (1) closure
Tnese material balances se^ve
- , . i r. i ~ credibility to the sampling and
ot the material balance lends creu^u j
analytical techniques and, therefore, to the emission data
produced, and (2) data is generated which allows the ultimate
£ _ . .. . , , 0ipmpnts to be determined and their
fate of individual trace elements
flow through the plant system to be traced.
The following sections, provide descriptions of the
j-Qohm' ciues utilized and flow rate measure-
station, the sampling techniques,
ments performed.
-------
2.0 PLANT DESCRIPTION
Station III consists of one 250 MW boiler which fires
a medium sulfur lignite coal mined in an area immediately west of
the plant site and trucked to the plant. Following crushing,
the coal is conveyed to seven storage silos. The coal is re-
duced to a maximum size of one-fourth inch by mills prior to
being, fed to the cyclone burners in the furnace.
The bottom ash removal system consists of quench tanks
where the melted ash is quenched in pond water and a sluice
system to pump the bottom ash sluice to a storage basin. The
economizer ash is also handled by the same sluice system and
is pumped to the basin alternatively with the bottom ash.
The dust control system consists of six cyclone dust
collectors where a portion of the ash in the flue gas is col-
lected, stored in pressurized hoppers, and transferred pneu-
matically to a storage silo. The ash is periodically trucked
away from the storage silo after wetting to prevent dusting.
A schematic of the Station III is shown in Figure
2-1.
2.1 Plant Operation During Sampling
The plant was run at a constant load of 245-250 MW
during the entire sampling period. This consistency of opera-
tion allowed the collection of samples which were representative
of the entire period and the averaging of flow rates for all
streams over the sampling period.
A-2
-------
FIGURE 2-1
SCHEMATIC OF STATION HI
-------
2.2
Time Phasing During Sampling
All of the streams flowed continuously with short
residence times within the system with three exceptions. Bottom
ash accumulated in a storage tank and was sluiced to the
storage basin every four hours requiring 30 minutes to empty
the tank. Economizer ash was allowed to accumulate in the
economizer ash hopper for four hours after which the accumula-
tion was sluiced to the storage basin over a period of 30
minutes. The only time phasing required for these two streams
was to sample during the time when the ash which had accumulated
during the sampling period was sluiced.
Cyclone ash was stored in a silo to await trucking.
However, since the cyclone ash samples were taken from the
cyclone ash hoppers at the base of each cyclone where the
residence time was short, time phasing was unnecessary. Since
the plant load was constant, the accumulation of cyclone ash
in the storage silo could be averaged over a 48 hour period to
give a reliable rate of cyclone ash production.
A-4
-------
3.0
DESCRIPTION OF SAMPLING POINTS
The sample point locations are indicated in Figure
2-1 and the inlet and outlet streams in Figure 3-1. The follow-
ing sections provide detailed descriptions of the sample points
and the techniques employed to obtain samples representative
of the sampling period.
3.1 Coal
Coal samples were taken from 2" diameter sampling
ports in the transfer line between storage silos 2, 4, and 6
and the corresponding mills. The ports were closed with caps
between samples and when uncapped coal flowed freely into a
polyethylene collection bucket unless the port became obstructed-
by a large piece of coal. The first portion of this flow was
discarded to insure a fresh sample each time and approximately
two pounds retained. A coal sample was taken every 20 minutes
from 9:00 AM to 5:00 PM, August 29, 1974, such that each port
was sampled once every hour. The samples were combined in a
large polyethylene container. This composite sample was quartered
until two 1-liter polyethylene bottles of coal remained for
analysis.
3.2 Bottom Ash and Economizer Ash Sluice Water Inlet
Plant service water from the plant lake is used to
sluice bottom ash from the quench tanks and economizer ash from
the economizer hopper. The service water is taken directly from
the lake about 10 feet from shore and 100 feet from the inlet
pump. A two liter sample was taken in a polyethylene container
A-5
-------
INLET STREAMS
OUTLET ST REAilS
CD-
CD
Coal
Ash Sluice Water
Bottom Ash
Bottom Ash Sluic
Water
Economizer Ash^ q
Economizer Ash^ ^
Slu'ice Water ^
Cyclone Ash
Flue Gas
FIGURE 3-1
INLET AND OUTLET STREAMS
AT STATION III
A-6
-------
at 4:00 PM on August 29th at the inlet and acidified with nitric
acid for preservation.
3.3 Bottom Ash
Bottom ash was sluiced from the quench tanks via a
ten inch pipe to a disposal basin approximately 300 yards from
the plant at the upper end of the plant lake. There the sluice
water flows into the lake and the bottom ash solids collect to
be trucked away. Bottom ash sluice was pumped from holding
tanks every four hours (10:30, 2:30, and 6:30) on a 24 hour
basis until the holding tanks were emptied which took approxi-
mately 30 minutes. Representative sampling was accomplished by
passing a hose sampling device through the stream from too to
bottom and bottom to top every 2.5 minutes during the pumping
time. This was necessary because the bottom ash solids were
stratified in the effluent stream by settling dependent on
particle size and density. The hose was inserted into a five
gallon polyethylene container for the collection of the sample.
Approximately five gallons of the solid-liquid sluice stream
were collected during a pumping period.. The solid-liquid
mixture was filtered in the laboratory and the entire solid
portion of the sample was retained.
3.4 Bottom Ash Sluice Water Outlet
The bottom ash sluice water outlet was collected
with the bottom ash as described in Section 3.3. Two liters
of the filtrate was acidified for preservation and retained
in polyethylene bottles for analysis.
A-7
-------
3.5
Economizer Ash
The economizer ash from the economizer ash hopper
was sluiced with plant service water through the same system
as the bottom ash. Sluicing took place every four hours (10:00,
2:00, and 6:00) on a 24 hour basis for approximately 30 minutes.
Collection and handling of the samples was the same as that
followed for the bottom ash. After filtration, the solids were
retained for analysis.
3.6 Economizer Ash Sluice Water Outlet
The economizer ash sluice water outlet was collected
with the economizer ash described in Section 3.5. Two liters
of the filtrate were acidified for preservation and retained
in polyethylene bottles for analysis.
3.7 Cyclone Ash
Ash from the cyclone dust collectors was collected
from hoppers 1, 3, and 5 every hour from 10:00 AM to 5:00 PM
on August 29, 1974. Since the hoppers were pressurized, the
pneumatic ash transport system to the storage silo was shut down
for five to ten minutes every hour for sample collection.
Samples were obtained by removal of five inch glass observation
windows in the hoppers and one to two liters of ash removed
with a small scoop. The individual samples were combined in
a large polyethylene container and riffled to yield two,
one liter integral samples^one for analysis and one for reserve.
A-8
-------
3.8 Flue Gas
Particulate matter in the exiting flue gas was
sampled from two 12 ft. by 16 ft. ducts between the cyclone dust
collectors and the induced draft fans. At this point there
are four 4-inch diameter sampling ports in each duct to provide
access to the flue gas stream. The flue gas was at a tempera-
ture of 375-380°F, static pressure of -17.5 in. H20, and 12.5%
moisture during the sampling period.
For sampling purposes each duct was divided into 16
sections of equal areas as shown in Figure 3-2. The center
point of each section was the actual sampling point and assumed
to.be representative of the section.
Velocity traverses of the two ducts were made on
August 27th and in conjunction with the grain loading deter-
minations on August 28th and 29th as per EPA Method 2. Figure
3-2 presents .the average velocity at each sample point over the
three-day period. The average velocity in the north duct was
found to be 55 fps and in the south duct 67 fps. The velocity
traverses determined the total gas flow in the duct and the con-
ditions necessary for isokinetic sampling.
Particulate loading determinations were made with
Gelman filter devices on August 27, 28, and 29th. The majority
of the determinations were made on the 27th and 28th and those
made on the 29th were to detect any significant deviations from
the previous two days. Figure 3.3 presents the grain loading
data taken. It should be noted that in many cases there are
great differences between adjoining sections in both ducts and
some sections have two grain load concentrations shown. This
is due to the random blowing of soot from the boiler during the
A-9
-------
NORTH DUCT
68
t I
, 58 ,
54
72
4
55
' 50
1 1
52
1
63
3
59
1 1
, 47
54
65
2
54
1 37 1
i i
42
I
59
1
D
C
B
A
SOUTH
DUCT
77
i i
i 66 1
i _ _ _ _1 -
66
77
4
77
i i
67
i i
62 !
78
3
66
i i
• 63 '
' _ _ _ i _
62
79
2
60
i ¦
54
56
63
1
D C B A
FIGURE 3-2
Velocity Profile (fps) at
Station III
A-10
-------
4
3
2
1
D C B A
SOUTH DUCT
4
3
2
1
D C B A
FIGURE 3-3
Grain Loading Profile (grains per scf)
Station III
NORTH DUCT
0.27
0.48
0.27
0.34
0.35 , 0.94
0.42 1 0.42
I
0.35
0.88
0.49
0 .88 1 p. / n
0.41 ' 0,40
L.01
0.35
0.48 1 0.80
I
0.60
0.35
0.93
0.54
0.81
0.45
0.53
0.61
0.43 ' 0.38
1.15
0.36
0.57
0.41
1.00
0.52
0.32
0.51
1.55
A-11
-------
sampling period. The lower concentrations (< 0.61 grains per
scf) were apparently taken during periods when soot blowing was
not taking place and the higher concentrations (> 0.80 grains
per scf) were apparently taken during periods when soot blowing
was taking place. The random nature of the soot blowing makes
an exact analysis of the data difficult; however, the period
of grain loading sampling on August 27th was of sufficient length
for such random fluctuations.to be taken into account if we
take a time average of the grain loading data in each duct to
calculate an average grain loading over the entire sampling
period. This time averaging yields average particulate loads
of 0.50 grains per scf for the north duct and 0.65 grains per
scf for the south duct. During particulate loading determina-
tions, the moisture content of the flue gas was measured by
condensation in an efficient copper tubing condenser maintained
in an ice bath'.
Samples of the particulate matter in the flue gas
stream for analysis were taken at Point C-2 in each duct on
August 29th during the period when the other plant streams were
sampled. The wet electrostatic precipitator (WEP) sampling
system used for sample collection is shown schematically in
Figure 3-4. A 57o sulfuric acid solution is circulated in this
sampling device by a peristaltic pump. A voltage of 12-14 KV
is applied between a thin platinum wire and the wetted wall to
induce electrostatic collection. The sampling probe from the
sampling nozzle to the WEP was lined with teflon tubing to
prevent trace element contamination of the sample. A gas stream
is isokinetically drawn from the flue gas stream and through
the sampling equipment by a vacuum pump and metered by a dry
gas meter. Approximately one hour of sampling was required uo
obtain sufficient particulate matter for analysis.
A-12
-------
Wet Electrostatic
Precipitator
FIGURE 3- 4
SCHEMATIC OF STATION III
ARRANGEMENG FOR DUCT SAMPLING
-------
In addition to the particulate sampling, a sample for
mercury was taken following each WEP sample by diverting the
exit gas flow from the WEP through a mesh of gold wire where
the mercury is collected by amalgamation with the gold. Samples
were also taken during the WEP runs for the determination of
the sulfur concentration in the flue gas by bubbling a known
volume of gas through a hydrogen peroxide solution according to
EPA Method 6. Orsat analysis of the flue gas for oxygen and
carbon dioxide was performed to provide gas density information
by EPA Method 3.
3.9 Sampling Schedule
The samples and measurements described in the preceding
sections were taken during the period August 27, 28, and 29th
according to the schedule shown in Figure 3-5. Those samples en-
closed in parenthesis are to be analyzed, the rest being retained
in reserve.
A' 14
-------
. point samples
— continuous sampling
2.
Coal - Silo 2
Silo 4
Silo 6
Bottom Ash and Economizer
Ash Sluice Water Inlet
3. Bottom Ash
4.
Bottom Ash Sluice
Water Outlet
tconomxzei
Ash
6. Economizer Ash Sluice
Water Outlet
7. Cyclone Ash
8. Flue Gas Velocity
9. Flue Gas Particulate
Loading
10. Flue Gas WEP
Particulate Collection
( )
( )
( )
(• )
• (•)
•( •)
•(•)
( ........ )
August 27 August 28 ^ August 29
FIGURE 3-5
Sampling Schedule at Station III
A-15
-------
4.0
FLOW RATE MEASUREMENTS
The mass flow rate of each of the sampled streams
described in Sections 3.0 to 3.8 was determined as described in
the following sections.
4.1 Coal
The coal feed was metered by counting the revolutions
of the coal feeder which had empirically been determined by plant
personnel at a rate of 145 lb. per revolution. The flow rate
given by this method must be corrected for the moisture content
of Che coal to give the rate on a dry weight basis. The rate
found from this method roughly checked by comparison with the
coal delivery rate to the plant logged from the weighing of the
coal trucks. The rate from the coal feeder was found to be 3.71
x 10 lb/hr or 2.34 x 10 lb/hr on a dry basis after correction
for 377. moisture. The coal truck delivery log indicated 4630 tons
per day or an average of 3.86 x 10s lb/hr delivered to the plant.
4.2 Bottom Ash and Economxzer Ash Sluice Water Inlet
The losses in the bottom ash and economizer sluice
system were negligible. Therefore, the inlet sluice water flow
rate equals the sum of the bottom ash and economizer sluice water
outlet rates described in Sections 4.4 and 4.6 The sluice water
inlet rate was found to be 2.60 x 10s lb/hr.
A-16
-------
4.3 Bottom Ash
Determination of the bottom ash production rate
directly was impossible because of the difficulty of obtaining
a sample of the bottom ash sluice stream which accurately
represented the liquid-to-solid ratio in the stream over the
entire pumping time. During the periodic pumping time of
approximately 30 minutes, the solids content of the sluice
stream was high as pumping began and fell off rapidly as the
solids in the holding tanks were depleted. The bottom ash
production rate was, therefore, determined from the ash content
of the coal, the coal feed rate, and the ash accounted for as
economizer ash (Section 4.5), cyclone ash (Section 4.7), and
fly ash (Section 4.8). From a coal ash content of 11.4% (dry
basis), the bottom ash production rate was 1.68 x 10" lb/hr.
4.4 Bottom Ash Sluice Water Outlet
The flow rate of the bottom ash sluice water outlet
was determined from the time required to fill a known volume.
In this case the known volume was a 12 cubic yard front end
loader which was driven into the effluent stream from the sluice
pipe so as to catch the entire stream. 30.9 seconds were
required to fill the front loader to a level of 178.3 cubic feet
giving a flow of 2590 gpm during pumping. If this flow rate is
averaged over the four hour pumping cycle, a bottom ash sluice
water outlet flow of 1.78 x 105 lb/hr is indicated.
4.5 Economizer Ash
The economizer ash flow rate was determined from the
weight percent solids in the economizer ash sluice stream and
A-17
-------
the volumetric flow rate determined as described for the bottom
ash sluice water in Section 4.4. The economizer ash sluice stream
required 55.9 seconds to fill the 178.3 cubic foot volume of the
front loader to give a flow of 1440 gallons per minute during the
pumping time. This flow rate averaged over three four-hour in-
tervals for pumping with an average percent solids in the stream
of 0.187o yields an economizer ash production rate in the boiler
of 154 lb/hr.
4.6 Economizer Ash Sluice Water Outlet
The flow rate of the economizer ash sluice water
outlet stream was determined from the weight percent liquid and
the volumetric flow as described in Section 4.5 for the economizer
ash flow rate. If the flow rate is averaged over the four hour
cycle interval to give an average for the sampling period, we
have 8.70 x 10" lb/hr.
4. 7 Cyclone Ash
The production rate of cyclone ash in the cyclone
dust collector was determined as an average over the 48 hour
period from noon on August 27th to noon on August 29th. The
level of ash in the cyclone-ash storage silo was measured at the
beginning and end of the period. The ash removed from the silo
was measured by the record of ash truck weighings over the
period. The ash truck weighings were corrected for the water
added to the ash to prevent dusting by taking samples from the
trucks for moisture content determinations. The difference
between the dry ash removed by the ash trucks and the decrease
in the quantity of ash remaining in the storage silo is the
quantity of ash produced by the cyclones over the 48 hour period.
A-18
-------
This total production gives an average production rate of
6.23 x 103 lb/hr.
4.8 Fly Ash and Flue Gas
The flow rate of fly ash from the stack at Station
III was determined from the veolocity and particulate loading
measurements taken as discussed in Section 3.8. The total
amount of flue gas corrected to standard conditions passing
through the two ducts is determined from the average gas velo-
city and the area of the ducts. From the average velocities
given in Section 3.8 of 55 fps in the north duct and 67 fps in
the south duct, the total flow through both ducts is 6.87 x 105
scfm. The fly ash emissions were then determined from the flow
through each duct and an average particulate loading in the
north duct of 0.50 gr per scf and in the south duct of 0.65 gr
per scf from Section 3.8 to be 3.42 x 103 lb/hr.
4.9 Summary of Flow Rates
The mass flow of each of the sampled streams at Station
III is summarized in Table 4-1. 'The flow rates of all solids are
on a dry weight basis.
A-19
-------
TABLE 4-1
FLOW RATES FOR STREAMS
AROUND STATION III
Stream
Coal
Bottom Ash and Economizer
Ash Sluice Water Inlet
Bottom Ash
Bottom Ash Sluice Water Outlet
Economizer Ash
Economizer Ash Sluice Water Outlet
Cyclone Ash
Flue Gas
Fly Ash
Flow Rate
2.34 x 10s lb/hr.
2.65 x 105 lb/hr.
1.68 x 10" lb/hr.
1.78 x 105 lb/hr.
154 lb/hr.
8.71
X
10u
lb/hr
6.23
X
103
lb/hr
4.11
X
107
scfh
3.42
X
103
lb/hr
A-20
-------
APPENDIX B
ANALYTICAL PROCEDURES
-------
APPENDIX B
TABLE OF CONTENTS
Page
1.0 SAMPLE PREPARATION. B-l
1.1 Coal, Coal Ash, and Sludge
Preparation B-l
1.2 Lime/Limestone Preparation B-l
1.3 WEP Preparation B-2
1.4• Aqueous Streams and Filtrates
Preparation B-2
2.0 ANALYTICAL PROCEDURES B-3
2.1 Determination of Fluoride by the
Ion-Selective Electrode Technique B-3
2.2 Determination of Chloride by Ion-
Selective Electrode B-9
2.3 Spectrophotometric Determination
of Titanium.' B-9
2.4 Determination of Copper and Zinc
by Atomic Absorption B-10
2.5 Determination of Molybdenum by
Atomic Absorption B-10
2.6 Determination of Nickel and Cobalt B-10
2.7 Determination of Arsenic by
Flameless Atomic Absorption B-ll
2.8 Determination of Antimony by
Flameless Atomic Absorption B-ll
2.9 Determination of Beryllium by
Atomic Absorption B-ll
2.10 Fluorometric Determination of Uranium... B-12
2.11 Determination of Lead and Cadmium
by Atomic Absorption B-12
2.12 Fluorometric Determination of
Selenium B-13
2.13 Determination of Vanadium and
Silver by Flameless Atomic Absorption... B-13
-------
APPENDIX B
TABLE OF CONTENTS (Cont'd)
Page
2.14 Determination of Barium by
X-ray Fluorescence B-14
2.15 Determination of Chromium, Calcium,
Iron, Magnesium, Manganese and
Aluminum by Atomic Absorption B-14
2.16 Determination of Mercury by
Flameless Atomic Absorption . .. . . B-15
2.17 Sulfur Determination by Titrimetry B-16
2.18 Spectrophotometrie Determination
of Boron B-16
BIBLIOGRAPHY
-------
Trace element analyses on samples from three power
plants were performed using dissolution and analytical techniques
adapted specifically for these matrices.
1.0 SAMPLE PREPARATION
Preparation procedures were performed on the following
types of samples to provide the primary digestion solution:
Coal
Coal Ash
Sludge
Lime
Wet electrostatic precipitator
Aqueous streams and filtrates
1.1 Coal, Coal Ash, and Sludge Preparation
The dissolution of coal, coal ash, and sludge is
achieved by a two-step method. The samples are oxidized at
850-950 C in the presence of air utilizing a quartz pipe reactor.
Volatile trace elements are retained via an acetone-dry ice trap
at the end of the reactor. Dissolution of the remaining solids
is accomplished by treatment with hydrofluoric, nitric, and
sulfuric acid. The dissolved solids are then combined with the
washings from the cold trap.
1.2 Lime/Limes tone Preparation
Lime is dissolved by treatment with 5% hydrochloric
acid. Any remaining undissolved material is removed by filtra-
tion and treated with hydrofluoric, nitric, and sulfuric acids
to achieve dissolution.
-------
1.3
WEP Preparation
An .8u millipore filter was used to remove particulates
from aqueous WEP samples. The particulates were then treated
similar to coal (through the quartz pipe reactor acid dissolution
steps). The filtrates, dissolved solids, and cold trap washings
were quantitatively transferred to a single container to form the
primary digestion sample.
1.4 Aqueous Streams and Filtrates Preparation
Nitric acid was added as a preservative to all aqueous
s amples.
B-2
-------
2.0 ANALYTICAL PROCEDURES
The following analytical procedures were utilized for
the determination of trace elements in the various samples.
Each analytical technique has been screened for accuracy and
reliability by standard addition and interference studies.
The complete analytical scheme for the analysis of
trace elements in the samples are found in Figures 2-1, 2-2,
2-3, and 2-4. Detection limits for each procedure are summarized
in Table 2-1.
2.1 Determination of Fluoride by the Ion-Selective
Electrode Technique
The determination of fluoride utilizes a sodium car-
bonate fusion for solid samples (TH-060) and direct analysis of
aqueous samples. The technique of standard addition using a
fluoride specific-ion electrode, mentioned by several workers
(BA-131, BA-137), is used for measurement of the fluoride ion.
A citrate buffer is used to release complexed fluoride ions and
to stabilize the pH and ionic strength. Addition of a standard
quantity of fluoride is characterized by a change in the potential
of the solution. The specific ion electrode senses this change
in potential which is related to the initial fluoride concentra-
tion. The relationship between potential and fluoride concen-
tration follows the Nernst equation:
AE - A log (CF + Xi)/CF
where,
AE is the change in potential
B-3
-------
Ni
FIGURE 2-1
ANALYSIS PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL
B-4
-------
Mo, Cd, Sb
Ni
FIGURE 2-2
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL ASH AND SLUDGE
B-5
-------
Lime
/
HC1 Digestion
Titrimetry
Gold Amalgamation
Atomic Absorption
•Hg
Primary Digestion
(HC1 Digestion)
Spectrophotometry
Atomic Absorption
Extraction/Atomic Absorption
,Ti,B
Al, Mg, Fe,
Ca, V, As,
Mn, Cu, Zn
Co, Be, Pb,
Mo, Cd, Sb,
Ni
FIGURE 2-3
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF LIME
B-6
-------
FIGURE 2-4
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF WET ELECTROSTATIC PRECIPITATOR LIQUORS AND AQUEOUS SAMPLES
B-7
-------
TABLE 2-1
DETECTION LIMITS FOR TRACE ELEMENT ANALYSIS
Element
Analytical Procedure
Coal
Detection Limit
Ash
Sludge Lime
(ppm)
WEP
Aqueoi
Al
Atomic Adsorption (AA)
100
400
650
1.0
Sb
Extraction/AA
.04
.16
. 6
.002
As
AA
.1
.5
.06
.001
Ba
X-Ray Fluorescence
5
50
40
.5
Be
Extraction/AA
.2
1.6
1.0
.001
B
Ion Exchange/Spectrophotometry 1
3
3
.05
Cd
Extraction/AA
. 1
.2
.2
.0002
Ca
AA
10
40
65
.1
CI
Ion Selective Electrode
5
10
10
. 5
Cr
AA
10
40
65
.1
Co
Extraction/AA
.2
.8
1
.003
Cu
Standard Addition/AA
1
4
6.5
. 1
F
Ion Selective Electrode
.5
1.2
1.2
.1
Fe
AA
10
40
65
.1
Pb
Extraction/AA
.4
.8
5
.004
Mn
AA
10
40
65
.01
Mg
AA
5
20
30
.5
Hg
Flameless AA
.01
.01
.01
.0005
Mo
Extraction/AA
.4
1.6
16
.004
Ni
Extraction/AA
2
8
2
.006
Se
Fluorometry
.1
.1
.1
.0005
Ti
Spectrophotometry
5
20
20
.1
Ag
Standard Addition/AA
.05
.2
. 3
.0005
S
Ion Exchange/Titrimetry
100
100
200
5
U
Fluorometry
.0001
.0001
.0001
.0001
V
Standard Addition/AA
1
4
6.5
.005
Zu
Standard Addition/AA
1
4
6.5
.01
B-8
-------
A is the constant = 59 tnV at 25°C
Cj. is concentration of free fluoride in solution
is additional fluoride concentration added.
2.2 Determination of Chloride by Ion-Selective Electrode
Chloride is determined by a known standard addition
method (OR-016). Sample preparation is the same as fluoride
with a sodium carbonate fusion for all solid samples and direct
analysis of aqueous solutions. A known amount of the species
being measured is added to a known volume of sample and the
resulting change in potential is observed. The original sample
concentration is computed using a known addition table. The
method allows samples to be analyzed which have variable ionic
strength.
2.3 Spectrophotometric Determination of Titanium
Titanium is determined in the primary digestion solution
as a yellow complex formed with tiron (di'sodium -1, 2- dihydroxy-
benzene -3, 5- disulfonate). This method is based on-the pro-
cedure of Yoe and Armstrong, and is further extended to include
shales by Rader (RA-125). An acetate buffer is used to regulate
the pH. The only major interference is the complex tiron forms
with Fe. This interference is eliminated by addition of sodium
dithionite, reducing ferric to ferrous ion. The absorbance of
the complex is read on a double beam spectrophotometer and
samples compared with a standard calibration curve.
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2. 4 Determination of Copper and Zinc by Atomic Absorption
Copper and zinc are determined by direct aspiration
of the primary digestion into the flame of the atomic absorption
spectrophotometer (PE-115). Quantitative determinations are
achieved by comparing the samples to their respective standards
and by the use of standard additions to the primary digestions.
2. 5 Determination of Molybdenum by Atomic Absorption
Molybdenum analysis is based on organic extraction
atomic absorption technique and method of Joyner (JO-012) which
has been modified by Kinrade and Van Loon (KI-085). Molybdenum
in the primary digestion readily forms a complex with ammonium
pyrrolidinedithiocarbamate at an acidic pH. Extraction of this
complex with methyl isobutyl ketone offers a convenient method
of concentration of the element. The signal is further enhanced
by use of a nitrous oxide-acetylene flame. Concentration was
determined by use of a statldard calibration curve.
2.6 Determination of Nickel and Cobalt
Nickel and cobalt analyses are based on the organic
extraction atomic absorption technique and method of Joyner (JO-
012) . An ammonium tartrate buffer is used to stabilize the
primary digestions. Nickel and cobalt are complexed with the^
chelating agent sodium diethyldithiocarbamate and extracted with
methyl isobutyl ketone.
Once the metal complex has been separated and concen-
traced in Che organic phase, the solution can be directly
aspirated into atomic absorption spectrophotometer for measure-
ment of the metal concentration.
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2.7
Determination of Arsenic by Flameless Atomic Absorption
Arsenic is determined by a Radian modified flameless
atomic absorption procedure based on the method of Ramakrishna,
Robinson and West (RA-147) incorporation the techniques of
Ediger (ED-027). The usually volatile-arsenic present in the
primary digestion is complexed as the molybdenum heteropoly acid
with ammonium molybdate in a nitric acid medium. The complex
formation enables the complex to be analyzed on the graphite
furnace by reducing the volatility of the arsenic so that high
temperature charring can be used to rid the sample of matrix
interferences.
2.8 Determination of Antimony by Flameless Atomic Absorption
Antimony determination is based on a Radian flameles^
atomic absorption method modifying the extraction procedure of
Burke (BU-136) and Headridge and Smith (HE-094) while utilizing
the techniques of Ediger (ED-027) to reduce the volatility of
antimony. After complexation with iodide, antimony is extracted
from the primary digestion into a methyl isobutyl ketone and
tributyl phosphate mixture (MIBK-TBP). TBP increases the extrac-
tion efficiency. As with arsenic, ammonium molybdate is used
to increase the thermal stability of the complex during the
charring cycle in the graphite furnace.
2.9 Determination of Beryllium by Atomic Absorption
The method of Bokowski (BO-027) is used for the
determination of beryllium by atomic absorption. After addition
of EDTA to the primary digestion t-o mask interferences, the
beryllium present in the aqueous sample is chelated with acetyl-
acetone. The complex is then extracted with methyl isobutyl
ketone and the organic phase directly aspirated into the atomic
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absorption spectrophotometer for the determination of beryllium.
The solvent extraction procedure allows one to conveniently
separate and concentrate the beryllium present*
2.10 Fluorometric Determination of Uranium
Radian's uranium procedure is a modification of the
fluorometric determination of Thatcher (TH-049) updated by
Turner (TU-025). Hexavalent uranium ions have a native fluo-
rescence that may be used for analysis in relatively high
concentrations. However, when fused with fluoride salts, uranyl
ions produce an intense specific fluorescence detectable at
levels of 10"10 grams of uranium. In general, the solid sample
is mixed with a sodium fluoride flux and fused to a translucent
disc in a platinum crucible. Aqueous primary digestions are
evaporated in platinum crucibles and the residue fused with the
flux. Once cooled, its fluorescence is measured with a Turner
filter fluorometer. The method of standard additions is used to
compensate for quenching.
2.11 Determination of Lead and Cadmium by Atomic Absorption
The procedure for analysis of lead and cadmium is
similar to that for copper and zinc found in Section 2.4. Trace
elements present in the primary digestion are separated and
concentrated by chelation and extraction. Kinrade and Van Loon's
method (KI-085) utilizing two chelating agents, ammonium pyrro-
lidinedithiocarbamate (APDC) and diethyl ammonium diethyldiothio-
carbamate (DDDC) to complex lead and cadmium has be.en highly
successful. A citrate buffer was used due to its stability,
strong buffering capacity, and nonparticipation in any reaction.
The sample solution was extracted into methyl isobutyl ketone
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and the organic solution injected into the graphite furnace on
the atomic absorption spectrophotometer. Concentration was
determined by use of a standard calibration curve.
2.12 Fluorometric Determination of Selenium
Selenium in the form of selinite reacts with aromatic
orthodiamines to form piazselenols which fluoresce in various
organic solvents. This method of determination of selenium is
a Radian modification of a procedure published by Levesque and
Vendette (LE-068). The solid sample is digested with nitric and
perchloric acids in the Parr acid digestion bomb (HA-258).
Aqueous samples are heated with nitric and perchloric acids. In
both cases this oxidizes selenium to selenate and is followed by
hydrochloric acid reduction to selinite. Isolation of selenite
from interferring substances is accomplished by adding hydroxy1-
amine, EDTA, and formic acid. The selenite is then reacted with
2, 3-diaminonaphthalene to form the organic extractable piazselenol,
naphtho-(2, 3-d)-2 selena-1, 3-diazole, which is determined
fluorometrically. This method is free of any interferences and
is capable of detecting nanograms of selenium by use of a
calibration curve.
2.13 Detej-minati.on of Vanadium and Sxlver by Fl^meless
Atomic Absorption
Vanadium is determined by flameless atomic absorption
using the heated graphite atomizer. The method is a Radian
adaptation of the work of Cioni, Innocente and Mazzioli (CI-002).
Standard additions are performed on the primary digestion solu-
tion. Experimentation conducted on National Bureau of Standards
samples of coal and coal ash yield results within 10% of the
certified values.
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Huffman (HU-095) recommends the same procedure for
silver. Solid samples are dissolved in concentrated nitric acid
and the method of standard additions is utilized.
2.14 Determination of Barium by X-ray Fluorescence
Barium is determined by a Radian method utilizing
X-ray fluorescence. Samples are pelletized in a solid flux of
lithium carbonate-sodium borate which are then introduced directly
into the X-ray unit. Quantitative determinations are achieved by
comparing the samples to a barium standard calibration curve
prepared in the same manner and by the use of the method of
standard additions to correct for matrix interferences, if any
are present.
2.15 Determination of Chromium, Calcium, Iron, Magnesium,
Manganese and Aluminum by Atomic Absorption
Chromium, calcium, iron, magnesium, manganese and
aluminum (PE-115) are determined by direct aspiration into the
flame of the atomic absorption spectrophotometer. Calcium and
magnesium are diluted with lanthanum chloride to mase inter-
ferences. All elements are compared with standard calibration
curves. All analyses are performed on the primary digestion
solutions except chromium.
Chromium requires a special preparation for solid
samples. Digestion of coal, ash, limestone, and sludge is
accomplished with nitric, sulfuric, and perchloric acids in a
reaction flash. A packed reflux column is attached to prevent
any loss of chromium. Perchloric acid oxidizes all the chromium
to Cr+S This method was developed by Rains and Menis (RA-155)
as a mercury determination procedure. Radian has applied the
method to the determination of chromium in NBS standard reference
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materials of coal and coal ash and the results were comparable
to the reported values.
2.16 Determination of Mercury by Flameless Atomic Absorption
Two methods were used for mercury analysis:
(1) acid permanganate
(2) gold amalgamation
Mercury is determined by a flameless atomic absorption
technique- Liquid samples are treated with acid potassium permanga-
nate to oxidize all of the mercury present to the +2 oxidation-
state. The excess KMnCU is removed with the addition of
hydroxylamine hydrochloride, and the Hg"'"2 is reduced to elemental
mercury by the addition of stannous chloride, which is swept
through the absorption cell of the atomic absorption unit for
determination.
Gold amalgamation collection of mercury has been
reported by several workers (KA-086, DI-043). Radian utilizes
a double amalgamation technique in which mercury is collected
on a gold wire plug in a quartz tube either from flue gas passed
through the tube or from thermal desorption into a stream of
argon from solid samples. The mercury thus collected is desorbed
by heating and amalgamated on a second tube to minimize inter-
ferences. Upon desorption from the second tube, the mercury is
passed into an absorption cell positioned in the atomic absorp-
tion spectrophotometer.
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2.17
Sulfur Determination by Tjtrimetry
The method of sulfur analysis consists of determining
the total sulfur as sulfate by titrimetry. Initial sample pre-
paration for coal is performed by ignition in a Parr Ignition
Bomb and sorption of the evolved S02 in a sodium carbonate solu-
tion. Sludge and ash samples are mixed with hydrochloric acid
and the solids filtered. In both cases, hydrogen peroxide is
added to oxidize sulfite to sulfate. The sample is passed through
a cation exchange column to form sulfuric acid. The acid is
.titrated with standard sodium hydroxide and the sulfur concentra-
tion determined.
Nitrate and phosphate ions interfere. Heat applied
with hydrochloric acid at pH 2-4 avoids nitrite interference in
the column. If the sample is heated at 275°C for 30 minutes to
drive off sulfuric acid, phosphate can be determined and the
value subtracted from the total to give sulfate ions.
2.18 Spectrophotometrie Determination of Boron
Radian's boron procedure combines the separation method
of Carlson (CA-084) and the spectrophotometry determination of
Mair and Day (HA-190). An ion-exchange column is prepared using a
boron specific resin, Amberlite XE-243, to separate boron in the
primary digestion from interfering ions and allow complete boron
recovery. It is then extracted into chloroform with 2-ethyl-l,
3—hexanediol. Boron in the organic phase is converted to the
highly absorbing rosocyanin complex using glacial acetic acid
followed by sulfuric acid. The absorbance of the complex is read
on a double-beam spectrophotometer and samples compared with a
standard calibration curve.
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BA-13I Baker, R. L., "Determination of Fluoride in Vegetation
Using the Specific Ion Electrode", Anal. Chem.
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BA-137 Baumann, Elizabeth W., "Trace Fluoride Determination
With Specific Ion Electrode", Anal. Chim. Acta 42,
127-32 (1968).
BO-027 Bokowski, D. L., "Rapid Determination of Beryllium by
a Direct-Reading Atomic Absorption Spectrophoto-
meter", Am. Ind. Hvs;. Assoc. J. 29(5), 474-81
(1968) .
BU-136 Burke, Keith E., "Determination of Microgram Amounts
of Antimony, 3ismuth, Lead and Tin in Aluminum,
Iron and Nickel-Base Alloys by Nonaqueous Atomic-
Absorption Spectroscopy" , Analyst 97. 19-28 (1972).
CA-084 Carlson, R. M. and J. L. Paul, "Potentiometric Deter-
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CI-002 Cioni, R., F. Innocenti, and R. Mazzuoli, "The Deter-
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ED-027 Ediger, Richard, "Atomic Absorption Analysis with the
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HE-094 Headridge, J. B. and D. Risson Smith, "Determination
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HU-095 Huffman, Claude, Jr., J. D. Mensik, and L. F. Rader,
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LE-068
Levesque, M. and E. D. Vendette, "Selenium Determination
in Soil and Plant Materials", Canad. J. Soil Sci.
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MA-190 Mair, James W. , Jr. and Harry G. Day, "Curcumin
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Boron Extracted From Radiofrequency Ashed Animal
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OR-016 Orion Research, Inc-. , Analytical Methods Guide, 3rd
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PE-115 Perkin-Elmer, Instructions, Model 503, Atomic Absorp-
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RA-125 Rader, L. F. and F. S. Grimaldi, Chemical Analyses for
Selected Minor Elements in Pierre Shale, U.S.G.S.
Professional Paper 391-A, Washington, D. C., GPO,
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RA-147 Ramakrishna, T. V. , J. W. Robinson, and Philip W. West,
"Determination of Phosphorus, Arsenic or Silicon
by Atomic Absorption Spectrometry of Molybdenum
Heteropoly Acids", Anal. Chim. Acta 45, 43-49
(1969).
RA-155 Rains, Theodore C. and Oscar Menis, "Determination of
Submicrogram Amounts of Mercury in Standard
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1339-1344, (1972).
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TH-049 Thatcher, L. L. and F.. B. Barker, "Determination of
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