COAL FIRED POWER PLANT
TRACE ELEMENT STUDY
VOLUME III
STATION II
-------
at
11* 06qq
908R75008
m - *
[coal fired power plant
TRACE ELEMENT STUDY
VOLUME III
STATION II
ch p .
/) ' '^a'l 17 -
°e^er
' %^vit
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. Olanam.
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 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 i^O (4°C)
Pounds
/XtTTT
L, W / iJ ^ W
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/s tandagd
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 Qnrn
Jm • W ^ J X.
0.45359
15.155
0.90719
0.9144
-------
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
Mercury
Chlorine
Antimony
Chromium
Fluorine
Selenium
Lead
Molybdenum
Nickel
Boron
Zinc
Cadmium
The following elements appear to be uniformly dis-
tributed in the ash streams:
Barium
Beryllium
Vanadium
Aluminum
Calcium
Iron
Magnesium
Manganese
Titanium
-2-
-------
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-
-------
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-
-------
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-
-------
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 105 lb/hr (225 gpm) of cooling tower blowdown
-6-
-------
INLET STREAMS OUTLET STREAMS
Coal x
Sluice Solids v
/
Inlet Sluice Water x
/
Outlet Sluice Water
/
Refractory Cooling
Water (Not Sampled) x
Refractory Cooling
Water (Not Sanroled)
/
/
Precipitator Ash
/
Fly Ash and Flue Gas v
/
FIGURE 2-1
INLET AND OUTLET STREAMS
AT STATION II
-7-
-------
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 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 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 meter readings and corrected for the moisture
content of the coal to give a dry feed rate.
-9-
-------
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 7870-22% split between sluice
ash and precipitator ash estimated by plant personnel.
-10-
-------
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-
-------
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 filte
during four WE? 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+70.
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.
-------
TABLE 2-1
CALCIUM AND TITANIUM ANALYSES* OF
ANDERSEN IMPACTOR PARTICLE SIZE FRACTIONS (DA-105)
Particle Diameter Ca Ti
um wt% 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-
-------
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
TTZ
XWL(Ca)
+
XW, (Ti)
cfiy
xw
Ash'
(2-1)
wnere,
= volume of the WEP liquor (ml)
V
q = volume of flue gas sampled by WEP (scf)
XW,
^(Ca) = concentration of calcium in WEP liquor (yg/ml)
XWAsh^a) = 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-
-------
The point to average grain loading correction factor
is then th.e 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
SO2 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 limics 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 177>-837o and 277o-7370. 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-
-------
TABLE 2-2
FLOW RATES FOR STREAMS AROUND STATION II
Stream Flow Rate Error Limit
Coal 2.75 x 105 Ib/hr ±10%
Inlet Sluice Water 5.02 x 10s lb/hr ±15%
Sluice Solids 4.4 x 103 lb/hr ±257„
Sluice Liquid 5.02 x 105 lb/hr ±15%
Precipitator Ash 1.53 x 101* lb/hr. ±10%
Flue Gas 5.46 x 107 scfh ±10%
Fly Ash 1.40 x 102 lb/hr ±10%
Method Used for
Flow Determination
Metered at coal feeders
Pump heads and pump
curves
Plant personnel esti-
mate of ash distribution
and total ash from coal
Rate set equal to inlet
sluice water
Plant personnel estimate
of ash distribution and
total ash from coal
Measured by stack traverses
Determined from.cumulative
grain loadings
-------
point sample
continuous 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
7. Flue Gas Particulate
Loading
Flue Gas WEP
Particulate Collection
(••••)
(- -)
(- -)
(:
Oct. 21 Oct. 22 Oct. 23
FIGURE 2-3
SAMPLING SCHEDULE AT STATION II
-17-
-------
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
other 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-
-------
HNO -H-SO,-HC10.
3 2 4 4
Reflux Digestion
Atomic Absorption
Cr
HNO^ Digestion
Atomic Absorption
Ag
Li„C0. -Na.B.O., Fusion
2 3 2 4 7
' X-Rav Fluorescence
Ba
Na?C0^ Fusion
Ion Selective Electrode
CI, F
NaF Fusion
Fluo rescence
Coal
HNO - HCIO^ Digestion
Fluorescence
Se
Oxygen Bomb Digestion
Titrimetrv
Flameless
Atomic Absorption
Hg
Primary Digestion
(Thermal Oxidation,
HF-HNO3-H2SO4 Digestion"
SDectrophotometry
Atomic Absorption
Extraction/Atomic Absorption
Ti, B
Al, Mg, Fe,
Ca, V, As,
Mn, Cu, Zn
Co, Be, Pb,
Mo, Cd, Sb,
Ni
FIGURE 2-1
ANALYSIS PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL
-19-
-------
HN03-H2S04-HC10a
Atomic Absorption
Reflux Digestion
HNO3 Digestion
Atomic Absorption
LioC0,-Na_B,0_ Fusion
2 3 2 4 7
X-Rav Fluorescence
Ion Selective Electrode
^2^2 Fusion
Ba
CI, F
Ash/
Sludge
NaF Fusion
Fluorescence
HNO^ - HCIO^ Digestion
Fluorescence
Se
RC1 Digestion
Titrimetry
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
_ ?n_
-------
Ion Selective Electrode
F
Al, Mg, Fe,
Ca, V, As,
Mn, Cu, Zn
Ag, Cr
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
-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 7°
Mercury *
±20
±107°
±10 %
Molybdenum
±12 7,
±l20/°
±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-
-------
3.0 DATA EVALUATION
The flow races 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)
MssXWss(j) + MslXWsl(j) +.MpaXWpa(j) + VfgXVfg(j)
where,
= the mass flow rate of c6al into the boiler on a
c
dry weight basis (lb/hr)
^c(j) = the weight fraction of the element j in the coal
on a dry weight basis
-23-
-------
Masw = t^ie mass flow rate of the inlet sluice water to
the ash sluice system (Ib/hr)
XW (i) = the weight fraction of the element i in the inlet
asw J 0 J
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
M , = the discharge rate of sluice water from the ash
si °
sluice system equal to ^asw (lb/hr)
XW8i(j> = weight fraction of the element j in the sluice
water
I-I = the collection rate of ash in the electrostatic
P ®
precipitators (lb/hr)
XW (j) = the weight fraction of the element j in the pre-
pa
cipitator ash
= the volumetric flue gas flow rate in the stack
(scfh)
XVfg(j) = the weight of the element j per unit volume of
flue gas (lb/scf)
-24-
-------
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.
where
S(Q) = the variance in Q
Q = the material balance value which is a function
of the q^'s
q^ = 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
and are in both cases as 2S.
-25-
-------
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 Al, 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 flow rates in lb/hr are listed in
Table 4-5, using the quantitative analysis results and in Table
-26-
-------
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
% Sulfur
0.35
0.49
BTU/lb
8290
11,708
Moisture and Ash
Free BTU/lb
12,621
Ultimate
% Carbon
48.31
68. 23
7o Hydrogen
6.53
4.64
7» Nitrogen
0.67
0.95
7o Oxygen
39.02
18.46
7o Sulfur
0.35
0.49
7o Ash
5.12
7.23
Total
100.00
100.00
-27-
-------
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-
-------
TABLE 4-3 ANALYTICAL RESULTS OF THE STATION II SAMPLES1
Element
Coal
Inlet Sluice |
Water
Precipitator
Ash
Sluice
Ash
Sluice
Ash
Filtrate
Combined
WEP
Aluminum
.717.
<.1
12%
10.9%
9.2
31.
Antimony
.16
.0023
2.3
< .08
.0038
.0029
Arsenic
2.5
<.0001
48.
1.4
<.0001
.0007
Barium
460.
<.6
.78%
.52%
<.6
.26
Beryllium
.29
<.002
5.6
4.1
<.002
.0042
3oron
31.
.17
550.
240.
.49
.92
Cadmium
<.L
<.002
1.2
< .8
<.002
.0016
Calcium
1.09%
57.
19.5%
15.1%
113.
55.
Chlorine
9.4
3.6
47,
<1.
15.
29.
Chromium
9.3
<.053
116.
< . 053
.59
Cobalt
1.5
<.003
27.
13.
<.003
.015
Copper
31.
.012
460.
230.
.022
. 12
Fluorine
67 .
.45
1130
19.
.70
2.7
Iron
.. 217,
.12
2.95%
4.06%
.01
9.5
Lead
2.3
.017
22.
11.
.006
.060
Manganese
24.
.034
406.
310.
.016
. 18
Magnesium
.15%
15 •
2.30%
2.06%
16-
8.1
Mercury
. 14
.08
< .010
< .010
<.0004
.017
Molybdenum
.64
<.0002
8.4
3.5
.015
.031
Nickel
2.1
<.02
37.
27.
<.02
.29
Selenium
1.6
.0017
6.3
.35
.0038
" . 12
Titanium
565.
<.1
.96%
.91%
<.1
2.2
Silver
. 048
<•0003
.90
• 11
< -0003
.0003
Sulfur
. 49%
14.
.80%
910.
108.
2380.
Uranium
.89
.0084
3.8
5.0
.0044
.0031
Vanadium
20.0
0.058
295
190
0.071
.26
Zinc
4.1
.39
77.
156.
.0084
.084
/alues represent the average of duplicate determinations. Values for liquid
samples are reported as vg/ml and solids samples as ppm on a dry basis, unless
jtherwise noted, values are reported as 10"^ lb/scf (60°F, 29.92" Hg).
-29-
-------
TABLE 4-4
STATION It ANAI.YTTCA1. RKSH.TS
BY SS-fLS'
El eircnt
Co j 1
Inlet Sluice
Water
Precipitator
Ash'
Sluice Ash
Sluice Ash
Filtrate
Combined
WE?
Aluminum
670
-.57,
. 18
> 17.
¦¦-1.100
>17.
2.5
13
Antimony
. 43
. 87
.001
2.7
1.1
1.1
.001
<.0007
Arsenic
.89
.98
.004
21
9.1
9.1
.003
<.0016
Barium
400
400
.022
"'4900
>.57.
>17.
.22
.66
Beryllium
.32
1.4
--
1.2
.90
2.6
--
<.0007
Bismuth
<.47
<.47
--
12
2.3
5
--
<.0007
Boron
15
53
.016
1-1200
¦n-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%
>1?.
49
>1%
>17.
>17.
100
35
Cerium
5.3
11
--
400
150
530
--
.0073
Cesium
. 13
. 30
--
.81
.81
.81
--
<.0007
Chlorine
410
89
i
47
47
20
1
1
Chromium
7.4
4.9
.053
61
61
61
.053
.44
Cobalc
3
3
--
16
8.9
14
--
.0054
Copper
25
9.3
.013
250
200
120
.013
.055
Dyspros ium
3 7
1.6
--
19
3.7
19
--
<.0007
Erbium
.40
.40
—
2.8
1 2
1. 2
--
<.0007
Europium
.39
. 12
--
4.3
2. 1
4. S
--
<.0007
Fluorine
560
210
j
'.2100
"'2100
210
3
j
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
Gold
—
--
--
--
--
--
--
<.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
^2300
"'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
Lithium
3.5
17
.009
120
210
120
.002
.0016
Lutetium
<.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
58
64
36
.02
.29
Niobium
5.4
2. 5
--
32
16
57
--
.0036
Osmium
--
--
--
--
--
--
--
<.0007
Palladium
--
--
--
--
--
--
--
<.0007
Phosphorus
moo
-1300
. 13
>17.
>17.
"-4800
. 20
4.4
Platinum
--
--
--
--
--
--
-'.0007
Notes :
'Concentration in sc;r. weight: in solids ami pg/ml in liquids. UK? anaivsis in 10"s lb/scf (60° f, 29 92"
lis)
Blind duplicnce analysis.
1 Hoc recorded clue Co loss from acidic solution.
'"Approximate vnl'u op.1v due Co inter Coronet: frorr. preservative
f'Insuf f icietic .sa-y.plc Cor dc to r:r: aci on
--All elements not reported 0 1 ppm weip.hc in solids or 0 001 5/ml in liquid?
Maj - Major corr.nonunc .
-30-
-------
TABLE 4-4 STATION II AN'AT.YTTCAI. RF.SIiT.TS 3Y SS-HS1
Inlet Sluice Precipitator Sluice Ash Combined
Element
Coal
2
Water
Ash:
Sluice Ash
Filtrate
WEP
Potassium
470
280
2.3
"t.1200
--1200
¦U400
4.*
.75
Praseodymium
i 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
--
r—
O
o
O
V
Scandium
7.3
7.3
--
40
40
40
—
0036
Selenium
3. 7
1.5
.002
13
4. 7
1.3
.009
.040
Silicon
> 57.
>IZ
6.1
>1%
>12
>17.
11 ••
9.2
S Liver
< 10
12
--
.30
.21
14
<.C01
<.0007
Sodium
-.2400
> 1"
27
>17.
>17.
>17.
43
1.8
S trontium
310
310
2
>. 5%
>.5%
>.57.
3.6
1.6
Sulfur
>17.
-.40
--
>17.
> . 5%
--100
>32
Tantalum
l
.49
--
6.1
1.3
3
--
<.0007
Tellurium
< 10
<.10
< 001
.93
. 13
. 16
<.001
.oon
TerfcLuai
<. 10
. 19
--
2 3
. 30
1
--
<.000 7
Thai lium
<.10
<.10
--
.57
. 13
A
o
--
<.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
Titanium
600
300
.020
> . 5%
>.57.
>17.
. 044
1.6
Tungs ten
.90
1.5
--
3
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 pom weight in solids and ug/nl in liquids. WEP analysis in 10 * lb/scf (60°?, 29.-92"
Hg).
'Blind duplicate analysis.
'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/ffil in liquids.
Maj. - Major component.
-31-
-------
TABLE 4-5 STATION II MATEHIAI. IIAI.ANC.KS*
Coal
Itolet Sluice
Outlet Sluice
KlueCaa
E Out
£ Out/E In
Aluminum
1950
<•05
*• "¦
1950 t 250
•ictipiiaiui
1830
480
4.6
17
2330 ±
270
1.19
Antimony
.044
.0012
.045 t .008
.031
<¦0004
. OOj.9
.0016
.040 t
.006
.89
Araenlc
.70
<•00005
.7 t .1
.73
.0062
<.00005
.0004
.7 ±
.1
1.00
Barium
127
*•30
130 ± 28
119
23
<. 30
14
140 ±
28
1.08
Berylllum
.080
<•0010
.08 ± .01
. 0U6
.018
<.0010
<•0023
.11 ±
.013
1.38
Boron
8.5
.09
8.6 t 1
8.4
1.1
.25
.50
10 t
1
1.16
Cadmium
<•028
<•0010
<•029
.018
.0037
<.0010
<.000»
<.024
—
Calcium
3000
29
3030 ± 310
2980
660
57
30
3730 i
350
1.23
Chlorine
2.6
4.3
6.9 t .8
.72
<•004
7.5
16
25 ±
3
3.62
Chromium
2.5
<.027
2.6 t .4
1.8
.34
<.027
.32
2.5 t
.3
.96
Cobalt
.41
<.0015
.41 t .06
.41
.079
<•0015
• 0081
.5 ±
.06
1.22
Copper
8.5
.0060
8.5 t i
7.0
1.0
.011
.068
8 ±
1
.94
Fluorine
18
.23
19 * 2
17
.084
.35
1.3
19 ±
2
1.00
Iron
560
.060
580 ± 70
450
180
.0050
5.2
640 ±
70
1.10
Lead
.63
.0085
.64 * .13
.34
.048
.0030
.033
.42 ±
.07
.66
Magnesium
413
7.4
420 t 40
428
91
7.9
A. 4
530 ±
50
1.26
Manganese
6.6
.017
6.6 ± .8
6.2
1.4
.0080
.10
7.7 ±
.9
1.17
Mercury
.037
.040
.077 t .009
<-0002
<.00004
<• 0002
.0093
.010 ±
.002
.13
Molybdenum
.18
<.0001
.18 ± .03
.13
.015
.0075
.017
.17 ±
.02
.94
Nickel
.58
<•010
.59 ± .09
.57
.12
<.010
.16
.86 ±
.1
1.46
Selenium
.44
.0009
.44 ± .05
.10
.0015
.0019
.068
.17 t
.01
.39
Silver
.013 •
<.0001
.013 ± .002
.014
.0005
<¦0001
.0002
.015 ±
.002
1.15
/Sulfur ^
L^i?
7
1350 * 140
(Q5T|
4.0
54**)
/l300j
1480 i
180
1.10
Titanium
160
<.05
160 * 20
146
41)
<.05
1.2
190 ±
20
1.19
Uranium
.24
.0042
.25 1 .03
. OH9
.022
.0022
.0017
.11 ±
.01
.44
Vanadium
5.5
.029
5.5 1 .8
4.5
.84
.036
• 14
5.5 t
.7
1.00
Zlnn
1.1
.20
1.3 * .2
1.2
.69
.0042
. 046
1-9 t
.3
1.46
All values in lb/hr.
v -
rr
-------
4-6, using the SSMS results. The sum of the elemental flow rates
of all incoming streams, coal and ash sluice water, are given
as I In. -The flow rates of the outgoing streams, sluice ash,
sluice ash filtrate, precipitator 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 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 para-
meters of greatest immediate importance. The results are
provided on a lb/BTU basis tc facilitate comparison to other
stations.
-33-
-------
TABLE 4-6 STATION II MATERIAL BALANCE BASED ON
SPARK SOURCE MASS SPECTROGRAPHIC DATA *
Element;
Coal
Inlet Sluice
Water
E In
Preci pi tacor
Ash
Sluice Ash
Sluice Ash
Filtrace
WEP
T. Out
Aluminum
: 1175
.090
>1400
>162
>46
1. 3
9.9
>220
Ancimony
. 17
.0005
. 17
. 31
.005
. 0005
<.0004
.037
Arsenic
26
.002
26
. 24
.042
.002
<.0009
.29
Bai'i um,
110
.011
110
¦v-79
>46
. 11
. 36
>126
Bery 1 Hum
.25
<.0005
.25
.018
. 012
<.0005
<.0004
.031
Bismuch
•=.13
<.0005
<.13
. 12
023
<.0005
<.0004
. 14
Boron
9.4
.008
9.4
¦1-23
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
Cer i um
2.3
<.0005
2.3
4.5
2.4
<.0005
.004
6.9
Ces ium
.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
Cobalc
.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
. 032
.006
<.0005
<.0004
.039
Europium
.072
<.0005
.072
057
.022
<.0005
<.0004
. 080
Fluorine
106 .
--
106
•*-34
.97
--
--
•*-3 5
Gadolinium
.036
<.0005
.036
. 023
.011
<.0005
<.0004
.035
Ca11ium
.83
<.0005
.83
. 26
040
.011
.018
. 33
Germanium
.083
<.0005
.083
. 053
.014
.002
.0009
.070
Cold
< . 028
<.0005
<.028
<.002
<.0004
<.0005
<.0004
<.003
Hafnium
.28
<.0005
.28
.065
.031
<.0005
<.0004
.097
llolmium
.019
<.0005
.020
. Olfc
.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
] . 2
.069
.003
.006
1.3
Lithium
2.8
.005
2.8
2. 7
. 55
.001
. 0009
3.2
Lu c e L i um
.039
<.0005
.039
.009
.004
<.0005
<.0004
.013
Magnes iuiu
>2750
7.5
>2800
>162
>46
8.0
3. 2
>220
Manganese
8.0
.007
8.0
4.1
. 23
.007
.050
4. 3
tlercury
<.028
<.0005
<.028
<.002
<.0004
<.0005
<. 0004
<.003
'-'•"All values in lb/hr.
-------
Element
Coal
Inlet Sluice
Water
Molybdenum 3.6 .003
Neodymlum 4.0 <.0005
Nickel .94 .002
Niobium 1.1 <.0005
Op.nium <.028 <.0005
Palladium <.028 <.0005
Phosphorus -^358 .065
Platinum <.028 <.0005
Potass ium 99 1.4
Praseodymium 1.5 <.0005
Rhenium <.028
Rhodium <.028 <.0005
Rubidium .33 .002
Ruthenium <.028 <.0005
Samarium .14 <.0005
Scandium 2.0 <.0005
f Selenium .74 .001
Silicon >2750 3.1
_n
P Silver .033 <.0005
Sodium >2750 14
Strontium 85 1.0
Sulfur >2750 '<-20
Tintdlurj .22 -..0005
Tellurium <.028 <.0005
Terbium .052 <.0005
Thallium <.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
'•All values in lb/hr.
4-6
STATION 11 MATERIAL
BALANCE
UASED on
SPAKK
SOURCE MASS SPECTK0CRAW1IC
DATA (Cont'd)*
£ In
Preci pi taror
Ash
Sluice
Sluice Ash
Ash Filtrate
wi;p
E Oul
3.6
.94
.092
.024
.009
1.1
4.0
3 1
I 2
.0005
.006
4. 2
.94
1 3
. 17
.010
. 16
1.6
1.1
39
. 2b
< 0005
002
.65
< .028
< .002
< 0004
<.0005
<.0004
<.003
<.028
<.002
-.0004
<.0005
<.0004
< 003
¦v358
>162
•v-22
. 10
2.4
>187
<.028
< 002
<.0004
<.0005
<.0004
< .003
100
'*•19
¦v-6 5
2.4
.41
-x.29
1.5
.49
.092
<.0005
0009
. 58
<.028
< . 002
<.0004
--
<.0004
<.002
<.028
<.002
<.0004
<.0005
<.0004
< . 003
.33
70
.40
.003
.003
1. 1
<.028
< 002
<.0004
<.0005
< 0004
< . 003
. 14
.087
. 019
<.0005
<.0004
. 11
2.0
.65
18
<.0005
.002
. 84
. 74
14
. 006
.005
.022
. 18
>2800
>162
-46
5.5
5.0
>220
. 034
.004
0006
<.0005
<.0004
.006
>2800
>162
>46
22
1.0
>230
86
>81
>23
1.8
.90
••107
>2800
>10 2
>23
>¦>0
¦-45
¦280
22
060
.014
<.0005
<.0004
.075
<.028
. 009
. 0007
<.0005
.001
.011
.053
. 024
. 005
<.0005
<.0004
.030
<.028
.006
-.0004
< .0005
<.0004
.007
. 85
12
. oa 1
<.0005
<.0004
. 31
.031
004
. 003
<.0005
<.0004
. 008
. 33
.053
. 011
.001
. 003
.068
124
>81
>4 6
.022
.90
>128
. 31'
096
.03''
<.0005
<.0004
. 13
. 55
12
.055
<.0005
<.0004
. 17
7.4
5. a
.97 .
.030
.054
6.8
. 24
052
.013
<.0005
<.0004
.066
4. 7
2.9
.74
.001
.045
3.7
1.5
1.2
. 27
.040
036
1.5
4.4
. 7 1
78
.001
.018
1.5
-------
TABLE 4-7
EMISSION RESULTS FOR PARTICULATES AND
SULFUR DIOXIDE AT STATION II
Particulates
(Ash)
Sulfur Dioxide
Concentration in
flue gas
0.018 gr/scf
280 ppm (v/v)
Quantity in coal
per unit heat value
6.18 lb/105 BTU
0.8'4 lb/105 BTU
Emissions in flue
gas per unit heat
value of coal
burned
0.044 lb/105 BTU 0.81 lb/105 BTU
% Emitted*
0.71
96.4
* Emissions with flue gas ,
Quantity in coal x
-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.
5.1 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:
Aluminum
Chromium
Molybdenum
Antimony
Cobalt
Nickel
Arsenic
Copper
Silver
Barium
Fluorine
Sulfur
Beryllium
Iron
Titanium
Boron
Lead
Vanadium
Cadmium
Magnesium
Zinc
Calcium
Manganese
The balances were outside the error limits for chlorine,
mercury, selenium, and uranium. The degree of closure is as
follows:
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:
NDCj) -3"^ 1 (5-1)
(Im(j) + Eout (j )) / 2
The average of the normalized deviations is 0.007 for
the quantitative procedures and 4-0.89 for the SSMS mechod. 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:
PMc _ ~ £out(i)(
ND n / ( Zin( j) + ZouTTlT:
%
(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 -ROM MATERIAL BALANCE CLOSURE ;OR
QUANTITATIVE ANALYSES AND
SPARK SOURCE MASS SPECTROMETRY ANALYSES
FOR STATION II
Elements
Quantitative
Normalized1
Deviation
SSMS
Normalized1
Deviation
Aluminum
-0.18
1.46
Antimony
0.12
1.29
Arsenic
0
1.96
Barium
-0.07
-0.14
Beryllium
-0.32
1.56
Boron
-0.15
-0.94
Cadmium
0.19
1.51
Calcium
-0.21
1.64
Chlorine
-1.1
1.95
Chromium
0.04
0.12
Cobalt
-0.20
0.99
Copper
0.06
0.11
Fluorine
0
1.01
Iron
-0.10
1.00
Lead
0.42
0.67
Magnesium
-0.23
1. 71
Manganese
-0.15
0.60
Mercury
1.5
1.61
Molybdenum
0.06
1.06
Nickel
-0.37
-0.52
Selenium
0.38
1.22
Silver
-0.14
1.40
Sulfur
-0.09
1.64
Titanium
-0.17
-0.03
Uranium
0.77
1.06
Vanadium
0
0.08
Zinc
-0.38
0
Average of Normalized
0.007
Deviations
0.89
SMS of Deviations2
0.46
1.18
NOTES: ^^ Normalized Deviation - *in^ " ^out^
^tn(J) * totlC<
Root Mean Square of
Normalized Deviations
'in
" =o«c«>l
-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 the 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 77.170 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-
-------
100%
FIGURE 5.1
DISTRIBUTION OF ELEMENTS AMONG SLUICE ASH,
PRECIPITATOR ASH, AND FLUE GAS AT STATION ~
-41-
-------
01
0<
0
7
8
8
2
4
5
8
6
8
5
8
2
9
4
2
7
3
8
6
5
4
6
TABLE 5-2
DISTRIBUTION OF ELEMENTS AMONG SLUlCE ASH,
PRECIPITATOR ASH, AND FLUE GAS AT STATION II
Coal in
lb/hr
Sluice Ash
(Average 22.27«)
Precipitator Ash
(Average 77.1%)
1950
20.5
78.8
0.044
2.7
93.4
o
o
0.8
99.1
127
16.0
83.9
0.080
16. 9
81.0
8.5
12. 1
83. 2
<0.028
<15.7
80.5
3000
18.5
80.7
2.6
16. 0
3.8
2.5
13.9
73.7
0.41
15. 6
82. 9
8.5
12. 7
86.5
18
1.1
91.3
578
27. 9
71.3
0. 63
10.3
82. 2
413
17. 2
82.0
6.6
17.3
81.5
0.037
2. 1
0
0.18
12.8
77.8
0.58
13. 6
68. 2
0.44
1.4
60.9
0.013
3.2
95.5
1350
3.4
8.8
155
21.1
78.3
0.24
18.0
80. 5
5.5
15.3
82.3
1.1
29.4
68.0
-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 Fluorine Nickel
Mercury Selenium Boron
Chlorine Lead Zinc
Antimony Molybdenum Cadmium
Chromium
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 Arsenic
Cobalt Silver
Uranium
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 recondense, 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-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 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-17
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 307o moisture, 570
ash, 0.57o 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
CBDSHED COAL
-------
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 scream. 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 period.
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 103 lb/hr (225 gpni) 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 2270 (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-
0
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 \
Sluice Solids v
—- )
Inlet Sluice Water
J
Outlet Sluice Water v
)
Refractory Cooling
Water (Not Samoled)
Refractory Cooling
Water (Not Samoled)
I
/
Precipitator Ash v
/
Fly Ash and Flue Gas N
/
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 the 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 8.57,.
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 nonrepresentative "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
-------
FIGURE 3-2 - VELOCITY PROFILE AT STATION II
FOR OCTOBER 21, 1974
AVERAGE VELOCITY - 61 fps
SAMPLE POINTS
R - 41 41/2"
1
R - 7' 7"
2
R - 9' 91/2"
3
R - II1 1/2"
4
A-12
-------
FIGURE 3-3 - GRAIN LOADING AT STATION II
AVERAGE - 0.018 qr/W
C
R - 7' 7"
2
R - 9' 91/2"
3
R - II' 1/2"
4
A -1-3
-------
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 period on
October 23rd. The wet electrostatic precipitator (WEP) sampl-
ing system used for sample collection is shown schematically in
Figure 3-4. 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 tub-
ing to prevent trace element contamination of the.sample. A
gas stream is isokinetically drawn from the stack by a vacuum
pump and metered by a dry gas meter. Approximately four hours
of sampling was required to obtain sufficient particulate matter
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 3% hydrogen peroxide solution, by
EPA Method 6. Orsat analysis of the flue gas for 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 held 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
7. Flue Gas Particulate
Loading
Flue Gas WEP
Particulate Collection
point sampling
continuous sampling
( )
(- -)
(- -)
Oct. 21 I Oct. 22 I 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 10s Ib/hr. From the moisture content of
the coal of 29.2"L, the dry coal flow rate was 2.75 x 103 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 78% precipitator
ash provided by plant personnel.
The average solids concentration in the sluice sample
described in Section 3.3 was determined to be 1.4870 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 lb/hr, the sluice solids flow rate was then 7.6 x
103 lb/hr by this method.
The coal burn rate was found to be 2.75 x 103 lb/hr on
a dry weight basis (Section 4.1) and the ash content 7.2370.
This predicts a total ash generation of 1.99 x 10" 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 102
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 1770-83% and 28%-7370,
the error in the sluice solids flow is ±257o.
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"
lb/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 48'1 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 lb/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 II
Stream Flow Rate
Coal
2.75
X
l/l
o
1—1
lb/hr
Inlet Sluice Water
5.02
X
10 s
lb/hr
Sluice Solids
4. 4
X
103
lb/hr
Outlet Sluice Water
5.02
X
10 s
lb/hr
Precipitator Ash
1. 53
X
10"
lb/hr
Flue Gas
5.46
X
107
scfh
Fly Ash
1.40
X
102
lb/hr
A-20
-------
APPENDIX 3
ANALYTICAL PROCEDURES
-------
APPENDIX B
TABLE OF CONTENTS
Page
1.0 SAMPLE PREPARATION B-I
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 Chloride2 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)
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 3-15
2.17 Sulfur Determination by Titrimetry B-16
2.18 Soectroohotometric 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 screams and filtrates
i 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
850r950°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 .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
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 fluoride4 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)/Cp
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
Mi
FIGURE 2-2
ANALYTICAL PROCEDURE FOR TRACE ELEMENT ANALYSIS
OF COAL ASH AND SLUDGE
B-5
-------
HN0,-H.S0,-HC10,
3 2 4 4
Reflux Digestion
Atomic Ahsoration Cr
HNO^ Digestion
Atomic Absorption
•Ag
Li-CO,-NaoB.0_ Fusion
2 3 2 4 7
X-Rav Fluorescence
Ba
Lime
Na^CO^ Fusion
Ion Selective Electrode
Fluorescence
Nar Fusion
¦CI, F
¦U
HNO^-HCIO^ Digestion
Fluorescence
•Se
HC1 Digestion
Tit rimetry
Gold Amalgamation
Atomic Absorption
•Hg
Primary Digestion
(HC1 Digestion)
Spectrophotometry
Atomic Absorption
Extraction/Atomic Absorption
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
Detection Limit (ppm)
Ash WEP
Element
Analytical Procedure
Coal
Sludge
Lime
Aqueoi
A1
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
. i
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°C
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 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 (J0-
012). An ammonium tartrate buffer is used to stabilize the
primary digestions. Nickel and cobalt are complexed with the
chelating agent sodium diethyldithiocarbaraate 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 (3U-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-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 fluoridq salts, uranyl
ions produce an intense specific fluorescence detectable at
levels of 10"13 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 Dlatinum 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-
lidinedithiocarbam&te (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
fluorometrieally. 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
j_ 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 Plameless 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 -r-2 oxidation-
state. The excess KMnOi* is removed with the addition of
-L.
hydroxylamine hydrochloride, and the Hg9' is reduced zo 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 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-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, 3ismuth, Le'ad and Tin in Aluminum,
Iron and Nickel-3ase 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. 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 Spectrophotometry Determination of
Boron Extracted From Radiofrequency Ashed Animal
Tissues Using 2-Ethyl-l, 3-Hexanediol", Anal.
Chem. 44(12), 3015 (1972).
0R-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(11),
1575 (1957).
TH-060 Thomas, Josephus, Jr. and Harold J. Gluskoter, "Deter-
mination of Fluoride in Coal with the Fluoride
Ion-Seleccive Electrode", Anal. Chem. 46(9),
1321 (1974).
TU-025 (G. K.) Turner Associates, "Uranium", Fluorometry
Reviews Series, Palo Alto, Ca. , Feb,. 1968.
B- 20
------- |