United States
Environmental Protection
Agency
Industrial Environmental
Research Laboratory
Cincinnati OH 45268
EPA-600/2-78-004b
March 1978
Research and Development
Source Assessment:
Major Barium Chemicals
Environmental Protection
Technology Series
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-78-004b
March 1978
SOURCE ASSESSMENT:
MAJOR BARIUM CHEMICALS
by
R. B. Reznik and H. D. Toy, Jr.
Monsanto Research Corporation
Dayton, Ohio 45407
Contract No. 68-02-1874
Project Officer
Mary Stinson
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
Edison, N. J. 08817
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
DISCLAIMER
This report has been reviewed by the Industrial Environ-
mental Research Laboratory - Cincinnati, U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products con-
stitute endorsement or recommendation for use.
-------
FOREWORD
When energy and material resources are extracted, processed, con-
verted, and used, the related pollutional impacts on our environ-
ment and even on our health often require that new and increasingly
more efficient pollution control methods be used. The Industrial
Environmental Research Laboratory - Cincinnati (lERL-Ci) assists in
developing and demonstrating new and improved methodologies that
will meet these needs both efficiently and economically.
This report contains an assessment of air emissions from the pro-
duction of major barium chemicals. This study was conducted to
provide EPA with sufficient information to decide whether additional
control technology needs to be developed for this emission source.
Further information on this subject may be obtained from the Metals
and Inorganic Chemicals Branch, Industrial Pollution Control Division.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
m
-------
PREFACE
The Industrial Environmental Research Laboratory (IERL) of
the U.S. Environmental Protection Agency (EPA) has the respon-
sibility for insuring that pollution control technology is
available for stationary sources to meet the requirements
of the Clean Air Act, the Water Act and solid waste legis-
lation. If control technology is unavailable, inadequate,
uneconomical, or socially unacceptable, then financial sup-
port is provided for the development of the needed control
techniques for industrial and extractive process industries.
Approaches considered include: process modifications, feed-
stock modifications, add-on control devices, and complete
process substitution. The scale of the control technology
programs ranges from bench- to full-scale demonstration
plants.
IERL has the responsibility for developing control technology
for a large number (>500) of operations in the chemical and
related industries. As in any technical program, the first
step is to identify the unsolved problems. Each of the in-
dustries is to be examined in detail to determine if there
is sufficient potential environmental risk to justify the
development of control technology by IERL. This report
contains the data necessary to make that decision for the
production of major barium chemicals.
Monsanto Research Corporation has contracted with EPA to
investigate the environmental impact of various industries
IV
-------
that represent-sources of emissions in accordance with EPA's
responsibility, as outlined above. Dr. Robert C. Binning
serves as Program Manager in this overall program, entitled
"Source Assessment," which includes the investigation of
sources in each of four categories: combustion, organic ma-
terials, inorganic materials, and open sources. Dr. Dale A.
Denny of the Industrial Processes Division at Research
Triangle Park serves as EPA Project Officer for this series.
This study of major barium chemicals was initiated by IERL-
Research Triangle Park in August 1974; Mr. Edward J.
Wooldridge served as EPA Project Leader. » The project was
transferred to the Industrial Pollution Control Division,
lERL-Cincinnati, in October 1975; Ms. Mary K. Stinson served
as EPA Project Officer from that time through completion of
the study.
-------
ABSTRACT
This report describes a study of air emissions from the manu-
facture of major barium chemicals. Compounds studied include
barium sulfide, barium carbonate, barium chloride, barium
hydroxide, and barium sulfate. Total production of all com-
pounds (except barium sulfide which is primarily an inter-
mediate) is approximately 100,000 metric tons per year.
Emissions released during the manufacturing process consist
of particulates, sulfur oxides, nitrogen oxides, carbon
monoxide, hydrocarbons, barium compounds, and polynuclear
organic materials. Major emission points are the black ash
rotary kiln where barite ore is reduced to barium sulfide,
the hydrogen sulfide incinerator where byproduct HaS is
burned, the exhaust from the barium hydroxide process, and
final product dryers and calciners.
In order to evaluate potential environmental effects the
source severity, S, was calculated for each emission from
each emission point. Severity is defined as the ratio of
the average maximum ground level concentration, Xmax, to the
ambient air quality standard (for criteria pollutants) or
to a reduced TLV (for noncriteria pollutants). The highest
values of S occurred for sulfur oxide emissions from the H2S
incinerator (1.89), the black ash rotary kiln (1.51), and
the barium hydroxide process exhaust (1.6), and for emissions
of soluble barium compounds from product dryers and calciners
(0.79 to 200).
-------
A variety of control devices is used to reduce emissions.
Scrubbers and baghouses are used on the black ash rotary
kiln and on product dryers and calciners. A scrubber and
an electrostatic precipitator are employed to control the
exhaust from the barium hydroxide process. Byproduct H2S
may be absorbed in caustic instead of being incinerated.
This report was submitted in partial fulfillment of Contract
No. 68-02-1874 by Monsanto Research Corporation under the
sponsorship of the U.S. Environmental Protection Agency.
This study began in August 1974 and was completed as of
August 1977.
Vii
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CONTENTS
Foreword iii
Preface iv
Abstract vi
Figures xi
Tables xii
Abbreviations and Symbols xiv
Conversion Factors and Metric Prefixes xvi
I Introduction 1
II Summary 2
III Source Description 10
A. Description of the Industry 10
B. Process Description 14
1. Barium Sulfide 16
2. Barium Carbonate 17
3. Barium Sulfate 19
4. Barium Chloride 20
5. Barium Hydroxide 21
IV Emissions 23
A. Selected Emissions 23
1. Emissions from Barite Preparation 24
2. Emissions from the Rotary Kiln 24
3. Emissions from the H2S Incinerator 31
4. Ba(OH)2 Production 32
5. Emissions from Dryers and Calciners 33
6. Emissions from Packaging and 36
Shipping
7. Summary 37
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CONTENTS (Continued)
IV (continued)
B. Emission Characteristics 37
1. Barite Preparation 37
2. Rotary Kiln and H2S Incinerator 39
3. Dryers and Calciners 40
C. Environmental Effects 41
1. Total Emissions 41
2. Source Severity 45
3. Affected Population 52
V Control Technology 56
A. Barite Preparation 55
B. Black Ash Rotary Kiln 56
C. H2S Incinerator 59
D. Dryers and Calciners 59
E. Barium Hydroxide Production 60
VI Growth and Nature of the Industry 61
A. Technology 61
B. Industry Production Trends 61
VII Appendices 64
A. Calculation of Production Data 65
B. Emissions Calculations 73
C. Sampling Program 79
D^ Polycyclic Organic Materials 97
E. Derivation of Source Severity Equations 105
F. Derivation of Average Distance From a 123
Source to a Rectangular Plant Boundary
G. Plume Rise Correlation ' 130
VIII Glossary 132
IX References 134
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FIGURES
Number Pa9e
1 Overall Flow Diagram for Production of " 3
Barium Chemicals
2 Locations of Plants Producing Barium 10
Chemicals
3 Barium Sulfide Production from Barite 16
4 Barium Carbonate from Barium Sulfide and 17
Sodium Carbonate
5 Barium Carbonate from Barium Sulfide and 18
Carbon Dioxide/Sodium Carbonate
6 Barium Sulfate Production 19
7 Barium Chloride Production 20
8 The Deguide Process for Ba(OH)2 Manufacture 22
9 Variation of "x with Distance 52
10 FMC Double Alkali Scrubber System 58
11 Production Level of Barium Chemicals, 61
1950-1973
A-l Barite Consumption 66
A-2 Production of BaS and BaCO3 67
A-3 Production of Ba(OH)2 and BaCl2 67
A-4 Production of BaSO^ and BaO 68
A-5 Production of Other Barium Chemicals 68
C-l Particulate and POM Sampling Train 80
C-2 GCA Sampling Locations 84
C-3 POM Sample Work-up 85
C-4 Mass Spectra for Solution of Standards 89
for Use in POM Analyses
F-l Rectangular Plant Boundary 123
F-2 Coordinate System for Calculating Average
Distance
XI
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TABLES
Number Page.
1 Barium Chemical Producers 2
2 Air Emissions From Barium Chemical Production 5
3 Total Emissions From Barium Chemicals Pro- 6
duction
4 Source Severity and Affected Population 8
5 List of Barium Chemical Plants 12
6 Estimated 1972 Barium Chemicals Production 13
7 Process Variations and Techniques for 15
Controlling Air Emissions
8 Emission Points and Emissions in the Pro- 23
duction of Barium Chemicals
9 Rotary Kilns Used in the Manufacture of 25
Barium Chemicals
10 S02 Emissions from Coal/Coke in Rotary Kilns 27
11 SO2 Emissions from Barite in Rotary Kilns 27
12 POM Emissions from Black Ash Rotary Kiln 30
13 POM Emissions from Coal-Fired Boilers 31
14 Particulate Emissions from a Dryer and 35
Calciner
15 Summary of Emission Factors 38
16 Characteristics of Emissions from Rotary 40
Kilns and H2S Incinerator
17 Barium Compounds Dried and Calcined Annually 44
18 Total Emissions from Barium Chemicals 44
Industry
19 Total Emissions of Criteria Pollutants by 45
State and Nation
20 Emission Severity Equations 48
21 Kiln Stack Heights for Black Ash Rotary Kiln 49
XII
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TABLES (Continued)
Number Page
22 Source Severities for Emissions from Black 50
Ash Rotary Kiln (Without Emission Controls)
23 Source Severities for Emissions from Black 50
Ash Rotary Kiln (With Alkaline Scrubber)
24 Stack Heights for Dryers and Calciners 51
25 Source Severities for Dryers and Calciners 52
26 Summary of Source Severities and Average 53
Maximum Ground Level Concentrations
27 Summary of Affected Population 55
A-l Estimated Consumption of Barite Raw Material 69
A-2 Production Data for Barium Carbonate 70
A-3 Estimated Production of Barium Carbonate 71
by Manufacturer
B-l Emissions from Gas Fired Burners 74
B-2 Emissions from BaCOa Dryer and Calciner 74
B-3 Fugitive Dust Emission Rates 76
C-l Particulate Data 91
C-2 POM Content of Samples 92
C-3 Emission Rates and Emission Factors 93
C-4 Total POM Emissions 96
D-l Structural Formulas and Carcinogenicity 98
of POM's
E-l Pollutant Severity Equations 105
E-2 Values of a for the Computation of a 107
E-3 Values of the Constants used to Estimate 108
Vertical Dispersion
E-4 Summary of National Ambient Air Quality 115
Standards
G-l Plume Rise for Dryers and Calciners 131
xm
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ABBREVIATIONS AND SYMBOLS
Ambient air quality standard
Atomic mass unit
Ap Area of affected population
A, B, C, D, E, F Atmospheric stability classes
a, b, c, d, e, f Constants in dispersion equations
a, b;x, y, 1-x, 1-y Sides of a rectangle (a, b) and
fractional distances to the sides
from a point in the center
(Appendix F)
AR The ratio Q/aciru
BR The ratio -H2/2c2
D Distance from a ground level source
D^ Inside stack diameter
D Affected population density
e Natural logarithm base
F Hazard factor
H Effective stack height
h Physical stack height
AH Plume rise
POM Polycyclic organic material
P Total affected population
p Atmospheric pressure
Q Mass emission rate
R Distance from a point in a
rectangle to the perimeter
S Source severity
T Ambient temperature
a
T Stack gas temperature
XIV
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ABBREVIATIONS AND SYMBOLS (Continued)
to Instantaneous averaging time of
3 minutes
t Averaging time
TLV Threshold Limit Value
u Wind speed
u, v Rectangular coordinates
(Appendix F)
V Stack gas exit velocity
x, Xi, x2 Downwind dispersion distances
from source of emission release
x Downwind distance where maximum
ground level concentration occurs
y Horizontal distance from center-
line of dispersion
•n 3.14
6 Polar coordinate angle
0 Standard deviation of horizontal
^ dispersion
a Standard deviation of vertical
dispersion
X Downwind ground level concentration
at reference coordinate x and y
with emission height of H
X Time average ground level concen-
tration of an emission
X Instantaneous maximum ground level
max concentration of a pollutant
x" Time average maximum ground level
concentration of a pollutant
xv
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CONVERSION FACTORS AND METRIC PREFIXES'
CONVERSION FACTORS
To convert from
to
Multiply by
degree Celsius (°c)
degree Kelvin (°K)
joule (J)
kilogram (kg)
kilogram (kg)
kilometer2 (km2)
meter (m)
meter (m)
meter2 (m2)
meter2 (m2)
meter3 (m3)
meter3 (m3)
metric ton
pascal (Pa)
pascal (Pa)
second (s)
degree Fahrenheit
degree Celsius
British thermal unit (Btu)
pound-mass (Ib mass
avoirdupois)
ton (short, 2,000 Ib mass)
mile2
foot
mile
foot2
inch2
foot3
liter
pound
inch of mercury (60°F)
millibars (mb)
minute
t° = 1.8 t° + 32
t° = t° - 273.15
C K
9.479 x I0~k
2.204
1.102 x 10~3
2.591
3.281
6.215 x IO-4
1.076 x 101
1.550 x 103
3.531 x 101
1.000 x 103
2.205 x 103
2.961 x I0~k
1.000 x 10~2
1.667 x 10~2
METRIC PREFIXES
Prefix
kilo
milli
micro
nano
Symbol
k
m
y
n
Multiplication
factor
103
10- 3
io-6
io-9
5 kg
6 mg
5 ym
5 ng
Example
= 5 x IO3 grams
= 5 x 10~ 3 gram
= 5 x 10~6 meter
= 5 x 10- 9 gram
9Metric Practice Guide. American Society for Testing and Materials.
Philadelphia. ASTM Designation: E 380-74. November 1974. 34 p.
XVI
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SECTION I
INTRODUCTION
Air emissions which have a potential effect on the environ-
ment are released during the manufacture of barium chemicals.
These emissions are characterized in this report as to type,
origin, and emission rate. Their potential environmental
impact and possible control measures are also discussed.
The following barium compounds, which are made in quantities
>4.5 x 103 metric tons/yr (5.0 x 103 tons/yr), are consid-
ered in this study: barium sulfide (BaS), barium carbonate
(BaCOa) , barium hydroxide [Ba(OH)2l, barium sulfate (BaSOit) ,
and barium chloride (BaCl2). Lower volume barium compounds
and barite ores which only undergo physical beneficiation
are not included.
The barium chemicals industry is dominated by the manufac-
ture of barium carbonate, which is used in glass and ceramics
and in the production of barium sulfate and barium hydroxide.
Manufacturing begins with barite ore that is reduced in a
rotary kiln to barium sulfide. The sulfide serves as an
intermediate in the production of other barium compounds.
al metric ton = 106 grams; conversion factors and metric
system prefixes are presented in the prefatory pages.
-------
SECTION II
SUMMARY
Barium chemicals constitute a small sector of the inorganic
chemicals industry, with total annual production (excluding
intermediates) on the order of 1 x 105 metric tons. Over
90% of all production occurs at four plant locations:
Chemical Products Corporation in Cartersville, Georgia;
FMC Corporation in Modesto, California; Great Western Sugar
Company in Johnstown, Colorado; and Sherwin-Williams Company
in Coffeyville, Kansas. A list of manufacturers is given
in Table 1 along with their representative products.
Table 1. BARIUM CHEMICAL PRODUCERS
Company
Product
Barium and Chemicals, Inc,
Chemical Products Corp.
FMC Corporation
Great Western Sugar Co.
Mallinckrodt, Inc.
Richardson-Merrell, Inc.
Sherwin-Williams Co.
(Produces barium
chemicals on demand)
BaS
BaCO3
BaCl2
BaS (captive)
BaC03
BaC03 (captive)
Ba(OH)2 (captive)
BaS (captive)
BaC03
Ba(OH) 2
-------
Those barium compounds produced in amounts over 4.5 x 103
metric tons/yr (5.0 x 103 tons/yr) include barium sulfide,
barium carbonate, barium hydroxide, barium chloride, and
barium sulfate. Production (Figure 1) begins with barite
ore which is ground, mixed with coal or petroleum coke, and
fed into a rotary kiln. In the kiln, BaSOi^ is reduced to
BaS, commonly known as black ash. The black ash leaves
the kiln and passes to a wet ball mill for grinding, after
which the soluble BaS is leached out.
BARITE (GROUND)
COAL OR
PETROLEUM COKE
C02AND/ORNa2C03-
Ba(OHL
t
CALCINING
BaCO
BARIUM SULFIDE
(BLACK ASH)
PRECIPI-
TATION
*• H2S AND / OR Na2S HCI — *•
I
r
PRECIPI-
TATION
BaCL
BaSO,
Figure 1. Overall flow diagram for production
^f barium chemicals
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Barium carbonate is produced by reacting BaS solution with
C02 and/or Na2C03. Barium chloride is prepared by reacting
the same solution with HC1. Barium sulfate is manufactured
by treating BaCO3 with H2SOt+. Barium hydroxide is produced
by the Great Western Sugar Company from barium carbonate via
a barium silicate intermediate. Sherwin-Williams Company
employs a different, proprietary process to make its Ba(OH)2.
The estimated 1972 production levels for the various barium
compounds are as follows: barite ore (consumption),
9.6 x 104 metric tons (11.6 x 10^ tons); BaS, 7.3 x 104
metric tons (8.0 x 104 tons); BaCOa, 4.2 x 101* metric tons
(4.6 x 101* tons); BaCl2, 9 x 103 metric tons (9.9 x 10k tons) ;
Ba(OH)2, 12 x 103 metric tons (13.2 x 103 tons); BaSO^,
5 x 103 metric tons (5.5 x 103 tons); and other barium chemi-
cals, <4.5 x 103 metric tons (<5.0 x 103 tons).
Barium compounds are prepared in solution and must be
precipitated or crystallized and then dried before shipment.
Barium carbonate for use by the glass industry is also
calcined. Where by-product H2S is formed, it is disposed
of either by incineration or by absorption in caustic.
Air emissions generated during barium chemical production
consist of the criteria pollutants (particulates, NO , SO ,
X X
CO, and hydrocarbons), soluble barium compounds, and poly-
nuclear organic materials (POM's). The emission points are
listed in Table 2 together with their associated emissions
and emission factors. Where applicable, emission factors
are shown for both controlled and uncontrolled conditions.
A range of emission factors is provided for dryers and
calciners because of their variability of operation.
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Table 2. AIR EMISSIONS FROM BARIUM CHEMICAL PRODUCTION
Emission point.
Barite preparation
Black ash rotary kiln
H2S Incinerator
Barium hydroxide production
Rotary kiln at Great
Western Sugar Co.
Sherwin-Williams pro-
prietary process
Barium chemical dryers
and calciners
Emissions
Particulate
Particulate
SO
X
NO
X
CO
Hydrocarbons
POM's
S0x
Particulate
SO
X
NO
X
CO
Hydrocarbons
Particulate
SO
X
NO
X
CO
Hydrocarbons
Soluble barium
compounds
Emission Factor, g/kg
Uncontrolled
10
25
0
5
0
0
1,882
0
5
0
410
0
0
0
0
_b
± 50%
± 20%
.6 ± 100%
,
± 100%
.8 ± 100%
.001 to 0.01
± 1%
_b
_b
.6 ± 100%f
± 100%f
.8 ± 100%
_b
± 10%
.8 ± 100%
.11 ± 55%
.07 ± 140%
.04 to 10
Controlled
1 ± 75%
*0.4C
H
0.2 to 0.5
0.66
5e
0.86
unknown
b
<0.4f
0.2 to 0.5f
0.66
5e
0.86
<0.59
_b
b
b
b
10.25
Emission factors for barite preparation, the black ash rotary kiln, and the kiln
at Great Western Sugar Co. are per kg of feed material into the kiln. Sulfur
oxide emissions from the incinerator are per kg of H2S burned. The other factors
are per kg of final product.
Not applicable.
CBased on two kilns equipped with scrubbers.
Based on one kiln with a scrubber.
£*
No data available; assumed to be the same as uncontrolled.
Kiln is equipped with scrubber; emission factor estimated to be the same as for
black ash kiln.
^Controlled with electrostatic precipitator; emission factor based on control
efficiency of electrostatic precipitator units.
-------
Sampling tests were conducted to identify POM emissions from
the black ash rotary kiln. Twenty-seven different compounds
were identified in the exhaust from a kiln using coal as the
reducing agent. Of these, the following are reported to be
carcinogenic: methylfluoranthene, benzo(c)phenanthrene,
benz(a)anthracene, methyl chrysene, 7,12-dimethylbenz(a)anthra-
cene, benzo(b)fluoranthene, benzo(a)pyrene, 3-methylcholanthrene,
indeno(l,2,3-cd)pyrene, dibenz(a,h)anthracene, dibenzo(c,g)-
carbazole, and dibenzo(a,h and a,i)pyrene. The POM emission
rate is similar to that found in coal-fired boilers. It is
expected that POM emissions will be less when coke is used
as the reducing agent.
Total national emissions from the barium chemicals industry
are presented in Table 3. When compared to total national
emissions from all stationary sources, they account for less
than 0.1% of the national emission burden. Over 95% of the
emissions from this industry occur in the states of Cali-
fornia, Georgia, Kansas, and Colorado, but the industry
contributes less than 1% of the total emissions from these
four states.
Table 3. TOTAL EMISSIONS FROM BARIUM CHEMICALS PRODUCTION
Emission
Particulates
SO
X
NO
X
CO
Hydrocarbons
Quantity emitted,
metric tons
1,100
7,200
132
625
105
Percent of
national
emissions
<0.01
0.024
<0.01
<0.01
<0.01
Percent of
combined
emissions for
California,
Colorado,
Georgia,
and Kansas
0.056
0.72
<0.01
<0.01
<0.01
-------
In order to evaluate potential environmental effects,
dispersion equations were used to calculate the average
maximum ground level concentration, x" , of emissions from
in 9.x
the various processing operations (Table 4) . For criteria
pollutants, X-,.,,, was compared to the corresponding ambient
Xllcl,?C
air quality standard, AAQS, as a measure of source severity,
S:
AAQS
For noncriteria emissions, a reduced TLV® was substituted
for the AAQS (values for S appear in Table 4) :
" ~ TLV x 8/24 x 1/100 ^'
The affected population is defined as the number of persons
around an emission source who are exposed to an average
ground level concentration of an emission greater than the
appropriate AAQS or reduced TLV. These values also appear
in Table 4 for the various process operations.
Standard control techniques are used in the barium chemicals
industry to reduce air emissions. Barite preparation opera-
tions are partially enclosed and include spraying with water.
One plant has a baghouse on the grinding process. Two of
the five black ash rotary kilns in the industry are equipped
with alkaline scrubbers and baghouses are being installed on
two others.
Emissions of particulates and SO during barium hydroxide
.X,
production are controlled with an alkaline scrubber at Great
Western Sugar Company. Particulates are controlled with an
electrostatic precipitator at Sherwin-Williams Company.
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Table 4. SOURCE SEVERITY AND AFFECTED POPULATION
Emission point
Barite preparation
Black ash rotary kiln
H2S Incinerator
Barium hydroxide
Great Western
Sugar Co.
Sherwin-Williams
Dryers and calciners
Emission
Particulates
Particulates
S°x
NO
X
CO
Hydrocarbons
POM'S
so
Particulates
SO
X
NO
X
CO
Hydrocarbons
Particulates
SO
X
NO
X
CO
Hydrocarbons
Soluble barium
"max' wg/m3
Uncontrolled
a
220
550
16
190
25
0.022 to 0.22
690
a
a
18
200
27
a
570
1.3
0.13
0.14
1.3 to 330
Controlled
62
17
8.5 to 21
32
360
48
unknown
a
9.4
12
a
a
a
0.69
a
a
a
a
£9.8
Source severity
Uncontrolled
a
0.85
1.51
0.16
0.0047
0.16
0.033 to 0.33
1.89
a
a
0.18
<0.01
0.17
a
1.6
0.013
<0.01
<0.01
0.79 to 200
Controlled
0.24
0.066
0.023 to 0.058
0.32
0.0091
0.30
unknown
a
0.036
0.032
a
a
a
<0.01
a
a
a
a
<5,9
Affected population,
persons
Uncontrolled
a
0
35
0
0
0
0
67
a
a
0
0
0
a
68
0
0
0
0 to 886
Controlled
0
0
0
0
0
0
unknown
a
0
0
a
a
a
0
a
a
a
-a
18
CO
Not applicable.
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The evolution of by-product H2S during the production of
BaC03 is avoided at one facility by precipitating ex-
clusively with Na2C03. Other producers incinerate H2S or
absorb it in caustic; however, only absorption does not
generate additional air pollution in the form of S02-
Production levels in the barium chemicals industry are not
expected to increase in the future, and may decline. Conse-
quently, air emissions by the industry will remain the same
or decrease. The installation of baghouses on the two black
ash rotary kilns at one plant will decrease its particulate
emissions. Plans are also being made for controlling the
one remaining uncontrolled black ash kiln.
-------
SECTION III
SOURCE DESCRIPTION
A. DESCRIPTION OF THE INDUSTRY
The five major barium chemicals [BaS, BaCO3/ BaCl2f
Ba(OH)2l are manufactured at seven locations in the United
States (Figure 2) . Major chemicals are defined as those
produced in excess of 4.5 x 10 3 metric tons/yr by a series
of chemical reactions. They do not include lower volume
barium compounds or barite ores which only undergo physical
benef iciation .
Figure 2. Locations of plants producing barium chemicals
10
-------
The plant sites shown in Figure 2 are so scattered that there
is no concentration of the industry. Production is carried
on in areas of low population density (<100 persons/km2,
Table 5). The only exception, St. Louis County where
Mallinckrodt, Inc., is located, has a population density of
743 persons/km2. The average population density of the four
counties where >90% of all production occurs is 27 persons/
km2.
The companies listed in Table 5 are quite diverse in that
they generally produce different types of chemicals and
cover a 10-fold range of capacities. Production is dominated
by barium carbonate and its precursor, barium sulfide. A
brief description of each company is provided below for
comparison:
Chemical Products purchases barite ore and manu-
factures BaCOa an^ BaCl2 via BaS. Barium sulfide
is also sold as a final product.l
FMC purchases barite and makes BaC03 from BaS.
They also make Ba(NO3)2 (<4.0 x 103 metric tons/yr)
from BaC03.2
Sherwin-Williams purchases barite and makes
BaCC-3 via BaS and Ba(OH)2 by a proprietary pro-
cess. Another of their products is lithopone
(<4.0 x 103 metric tons/yr), a pigment composed
of ZnS (28% to 30%) and BaSO^ (70% to 72%) which
is made by reacting BaS with
Personal communications. J. L. Gray and R. E. Kotteman,
Jr. Chemical Products Corp., Cartersville, Georgia.
2Personal communications. R. Brown. FMC Corporation,
Modesto, California.
3Personal communications. J. J. Nilles and R. W. Hellon.
Sherwin-Williams Co., Coffeyville, Kansas.
11
-------
Table 5. LIST OF BARIUM CHEMICAL PLANTS
to
Company
Barium and Chemicals,
Inc.
Chemical Products
Corp.
FMC Corporation
Great Western
Sugar Co.
Mallinckrodt, Inc.
Richardson-Merrell,
Inc.
Sherwin-Williams
Co.
Location
(city, county, state)
Steubenville,
Jefferson, Ohio
Cartersville, Barstow,
Georgia
Modesto, Stanislaus,
California
Johnstown, Weld,
Colorado
St. Louis, St. Louis,
Missouri
Phillipsburg,
Hunterdon, New Jersey
Coffeyville,
Montgomery, Kansas
County
population
density,
persons/km2
89
27
49
8
743
62
24
Product
Variety of
barium chemi-
cals made on
demand
BaS
BaCO3
Bad 2
BaS
BaC03
Ba(N03) 2
Ba(OH)2
BaC03
BaSOu
BaS
BaC03
Ba(OH)2
Only companies making major barium chemicals are listed. Buckman Laboratories
in Memphis, Tennessee, produces barium sulfate from purchased BaCO3 as an
intermediate in the production of barium metaborate.
-------
Great Western Sugar purchases makeup barite
and produces Ba(OH)2 from recycled BaC03. The
hydroxide is for captive use in sugar refining
3
and is converted to BaCO- k
Richardson-Merrell and Mallinckrodt purchase
BaCO3 to make BaS04.l'3
Barium and Chemicals purchases BaCO3 to make
other barium chemicals on demand. This company
is not considered further in this report since
production is on a batch basis.1
Production data for barium chemicals are difficult to obtain
because government statistics cover only barium carbonate,
and individual plants do not disclose such information. The
yearly production level is also dependent on the economy.
Estimated 1972 production is calculated in Appendix A and
summarized in Table 6. Over 90% of all production occurs at
Chemical Products Corp., FMC Corp., Great Western Sugar Co.,
and Sherwin-Williams Co.
Table 6. ESTIMATED 1972 BARIUM CHEMICALS PRODUCTION
Compound
Barite ore (consumption)
BaS (intermediate)
BaCO 3
BaCl2
Ba(OH)2
BaSOij
Other barium compounds
1972 Production,
103 metric tons
96
73
42
9
12
5
<4.5
^Personal communications. D. Muller. Great Western Sugar Co.,
Johnstown, Colorado.
13
-------
The barium chemicals industry employs many process varia-
tions and control techniques which influence the types and
amounts of air emissions released during production. The
important ones are listed in Table 7.1~tf As a result, there
is no representative plant or process in the industry.
B. PROCESS DESCRIPTION
The starting point in the manufacture of barium chemicals
is barite (baryte) ore, which is primarily barium sulfate.
Barite is mined in seven states (Alaska, Arkansas, Cali-
fornia, Georgia, Missouri, Nevada, Tennessee) and serves
not only as the raw material for barium chemicals but also
as an ingredient in oil well drilling muds.5 The average
analysis of chemical grade barite is BaSO4, 94% to 96%;
Fe2O3, 0.8% to 2.0%; SrS04, 0.1% to 2.0%; BaCO3, 1%; Si02,
3.0% to 6.0%; H20, 0.5% to 2.0%; F, Pb, and Zn, nil.6 Before
shipment to consumers, the ore is washed with hot water to
remove impurities. It is then crushed and agitated with
water in a jig for further purification. The barite may
then be shipped or it may be further processed by milling
and magnetic separation.
After it arrives at a plant site, the partially purified
barite is milled (if necessary), mixed with coal or petro-
leum coke, and reduced in a rotary kiln to barium sulfide,
which is an intermediate in the production of barium
chloride and barium carbonate. A flow diagram of the over-
all process was shown earlier in Figure 1.
5Fulkerson, F. B. Barite. In: Minerals Yearbook 1972,
Volume I: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1974. p. 181-187.
6Preisman, L. Barium Compounds. In: Kirk-Othmer Encyclo-
pedia of Chemical Technology, Second Edition. Vol. 3,
Standen, A. (ed.). New York, Interscience Publishers, Divi-
sion of John Wiley & Sons, Inc., 1964. p. 80-99.
14
-------
Table 7. PROCESS VARIATIONS AND TECHNIQUES FOR CONTROLLING
AIR EMISSIONS1"14
Process
Variation/control
technique
Emissions affected
Barite ore
preparation
Rotary kiln to
reduce barite
to BaS
Barium carbonate
production
Barium hydroxide
production
Product dryers
and calciners
Ore may be milled
before or after it
arrives at plant
site
Water spray at
grinding operation
Operations partially
enclosed; exhausted
through baghouse
Coal or petroleum
coke may be used
as a reducing agent
Different types of
ore and degree of
milling
Variable sulfur con-
tent of coal/coke
Add-on scrubber
Precipitation with
Na2CO3 or CO2/
latter generates
H2S which must be
absorbed or incin-
erated
Two completely dif-
ferent processes
with different
controls
At least five dif-
ferent types of
dryers and calcin-
ers are used
Add-on baghouse
Add-on scrubber
Fugitive dust
Fugitive dust
Fugitive dust
POM; hydrocarbons
Particulate
SO
Particulate; SO
SO
x
Particulate; SO ;
NOX; CO; hydro-
carbons
Soluble barium
compounds
Soluble barium
compounds
Soluble barium
compounds
15
-------
1. Barium Sulfide
Barium sulfide or black ash is made by reducing barite
(BaSO^) in a rotary kiln with coal or petroleum coke
(Figure 3) . Unmilled barite ore is first ground, then
mixed with coal or coke in a ratio of 3 to 4 parts barite
per 1 part coal or coke. One of the black ash manufacturers
uses coal as a reducing agent while the others use petro-
leum coke.1"4 The mixture is fed into a rotary kiln where
the temperature is raised to between 900°C and 1,200°C by
gas heating.
PARTICIPATE PARTICULATE .
EMISSIONS EMISSIONS S02 , COMBUSTION PRODUCTS
HOT WATER
BARITE
I
MILLING
(DRY)
(OPTIONAL)
1
I
MIXER
I
ROTARY
KILN
\
LEACHING
FILTER
1
BARIUM
SULFIDE
LIQUOR
COAL
INSOLUBLE MATTER
Figure 3. Barium sulfide production from barite
Inside the kiln barium sulfate is reduced by carbon to
barium sulfide. The reaction shown below is thought to
occur:
+ 4C + BaS + 4CO
(3)
since a blue flame typical of CO combustion can be observed
above the bed of materials in the kiln.1
The conversion reaction is approximately 90% efficient (the
general range is 85% to 95%). The variation in percent BaS
formed is due to the presence of iron and silica impurities
which cause side reactions producing complex water-insoluble,
16
-------
but acid-soluble, barium silicate, ferrate, and carbonate.
The water-soluble barium sulfide is leached from the black
ash with hot water and filtered to remove any remaining
insoluble matter. The resulting solution, containing 17%
to 18% BaS, is then ready to feed into the barium carbonate
or barium chloride process.6
Exhaust gases from the rotary kiln pass through cyclones
before going to the atmosphere. Stack emissions include
particulates, SO , NO , CO, hydrocarbons, and POM's (poly-
X X
nuclear organic materials). The remaining process emissions
are fugitive dust emissions from grinding (milling) and
mixing.
2.
Barium Carbonate
Barium carbonate is manufactured from barium sulfide by
two precipitation processes: precipitation with Na2C03/ or
precipitation with CO2 followed by precipitation with Na2C03.
In the first process the following reaction occurs:
BaS
(aq)
60-70°C
Na2c°3(aq) + BaC03
Na2S
(ag)
(4)
The resulting slurry is washed, filtered, and dried (Figure 4)
The dried barium carbonate is then ground to the desired size
and packaged. This process is used by about 50% of the
industry; actual production data are unavailable. 1-lt
PARTICULATE
H20
BaS i *
»
Na2C03 REACTOR
WASH WATER
1
HI i/if A**I irn »
BaC03
n i TTI? in •»<
-—i
rAKIIUULftlt
EMISSIONS
DRYER
Na2S SOLUTION
EMIS
GRINDER
1
PACKAGING
SION
i
Figure 4. Barium carbonate from barium sulfide
and sodium carbonate
17
-------
In the second process (Figure 5), carbon dioxide, obtained
from the stack gas of the rotary kiln, is bubbled through a
barium sulfide solution and causes the following reaction:
40-90°C
BaS
(a .
C02(g) + H20
BaC0
H2S
(g)
(5)
This reaction removes 95% of the BaS in a series of concen-
tration steps. In the repulper, Na2C03 is added and reacts
with the remaining BaS as shown in Equation 4. The product
is thickened, filtered, and dried at 50°C to 100°C.1'3
Barium carbonate for use in the glass industry (about 30% of
production) is further processed in a calciner (at 400°C to
450°C). This produces a densified product which can be
mixed with other glass raw materials without segregation.1'3
SO,
BaS
cbT
REACTOR
BaC03 SOLUTION
CONCEN-
TRATOR
prpm PCD
KtrULr tK
ci i n
FILl
fER
f 1
Na2C03 Na2S SOLUTION
PARTICULATES
' T '
,co_
PACKAGING
OR
SHIPPING
GRINDING,
MILLING,
AND
SCREENING
•K-
*l
- DRYER
BaC03
CALCINER
Figure 5. Barium carbonate from barium sulfide and
carbon dioxide/sodium carbonate
18
-------
By-product H2S is either absorbed in caustic to produce
Na2S or incinerated to give SO2- One company uses incin-
eration while another practices both techniques. Two
carbonate producers do not generate H2S.1~'t
The dry barium carbonate is ground and screened to the
desired size range, then packaged for shipment. Large
volumes are bulk shipped in railroad hopper cars.
Particulate emissions in the production of barium carbonate
arise from drying, calcining, grinding, screening, and
packaging. Combustion products are emitted from the dryers
and calciner. If H2S is incinerated, S02 is also released.
3.
Barium Sulfate
Synthetic barium sulfate is produced by the reaction of
BaCO3 with H2S04 (Figure 6) . 1 The reaction is:
BaCO3(s) + H2S04(aq)
H2O + CO2
(6)
H2S04
co2
t
REACTOR
BaS04
H20
1
WASHER
PARTICULATES
M
DRYER
PACKAGING
BaSO.
H20
Figure 6. Barium sulfate production
The product is washed, dried, and packaged. The last two
steps are sources of particulate emissions.
19
-------
4. Barium Chloride
Barium chloride is manufactured by reacting barium sulfide
solution with hydrochloric acid (Figure 7) as follows:
BaS(aq) + 2HC1(aq)
H2S
(g)
(7)
SOLUTION
CAUSTIC
ABSORBER
|
t
REACTOR
—
S02
INCIN-
ERATOR
SETTLER
.MUD
FILTER
8aClz
LIQUOR
T
PROPRIETARY
*• PURIFICATION •>
PROCESS
CRYSTAl-
" LIZATION
—•-LIQUIDS
LIQUID
SOLIDS-
ICULATES
BaCI2OR Bad,- 2H?0
Figure 7. Barium chloride production1
A rubber-lined, agitated reaction vessel is used with a gas
outlet pipe. Standard hydrochloric acid (20° Be, 31.45% HCl)
is used to form the barium chloride.1'6 The resulting solu-
tion is filtered of solids and then purified by a proprietary
process. The barium chloride liquor is concentrated, then
evaporated and crystallized in the same step. The crystals
are dewatered in a pan filter and dried. Barium chloride
is packaged in moisture-proof steel or fiber drums.
By-product £[28 is either absorbed in a caustic solution or
incinerated to S02- The exact amount incinerated is unknown,
but the manufacturer indicated that H2S is generally absorbed
20
-------
in caustic. In addition to S02, the manufacturing process
causes emissions of particulates from drying and packaging.
5. Barium Hydroxide
Barium hydroxide is manufactured by two companies using
different processes. The Sherwin-Williams Co. uses a pro-
prietary process to make the monohydrate. Emissions of
particulates, SO2, and combustion products (gas heating) are
given off in their process. Particulates from the operation
are controlled by an electrostatic precipitator.3 The pro-
duct dryer also causes particulate emissions.
The Great Western Sugar Co. uses the Deguide process to make
barium hydroxide for use in sugar purification. It is based
on the reaction between barium carbonate and monobarium
silicate to form tribarium silicate:7
2BaCO3 + BaSi03 -* Ba3Si05 + 2CO2 (8)
The silicate is hydrolyzed to form barium hydroxide and mono-
barium silicate which is recycled:
Ba3Si05 + 2H2O ->• 2Ba(OH)2 + BaSi03 (9)
The hydroxide is used in sugar purification and is finally
converted to BaCO3 which is also recycled.7 Recycle of the
barium compounds is the key to the economic success of this
7Dahlberg, H. W., and R. J. Brown; revised by .W. Newton, II,
and M. G. Auth. The Barium Saccharate Process. In: Beet-
Sugar Technology, Second Edition, McGinnis, R. A. (ed.).
Fort Collins, Colorado, Beet Sugar Development Foundation,
1970. p. 573-578.
21
-------
process. A flow diagram of the overall process appears in
Figure 8.
ATM.
i,
ALKALINE .PARTI CULATES
SCRUBBER ^COMBUSTION
'PRODUCTS
t
Ba,<
„ ROTARY *
KILN
FILTER ...„„ .,
CAKE nLTCR
1
H20
,so2,
T
JiOc Ba
_L HYDRO-
LYSIS
BaSi03 SLURRY
1
MIYFP -*
IMPURE
{ '
(OH), SUGAR
*• PURIFI
CATION
1
BaC03
SUGAR
* O
- — i
MAKEUP BaS04 ,SAND,
AND COKE
• PURE SUGA
Figure 8. The Deguide process for Ba(OH)2 manufacture7
Barium sulfide and H2S are not formed as products in the
Deguide process although they may exist as reaction inter-
mediates in the kiln. Instead, makeup barite, sand, and
coke are added to the recycled BaSi03 and BaCOs before the
mixture is fed into the rotary kiln. The overall reaction
that occurs is then:
2SiO + 3C
2Ba3Si05 + 6S02 + 3C02 (10)
No information is available on the amount of makeup
that is added.
Exhaust gases from the rotary kiln are controlled by an alka-
line scrubber.1* The only other air emission is fugitive dust
from the preparation and handling of makeup barite, sand, and
coke.
22
-------
SECTION IV
EMISSIONS
A. SELECTED EMISSIONS
The various emission points in the production of barium
chemicals are listed in Table 8 along with their respective
emissions. Combustion products from dryers and calciners
were not studied in detail because calculations (Appendix B)
showed them to be negligible (<100 metric tons/yr for the
entire industry).
Table 8. EMISSION POINTS AND EMISSIONS IN THE PRODUCTION
OF BARIUM CHEMICALS
Process or operation
Emission
Grinding and milling of
barite; mixing with coal
or coke
Barium sulfide rotary kiln
H2S incinerator
Barium hydroxide production
Product dryers and calciners
Packaging and shipping
Particulates (fugitive)
Particulates, SOX, NOX, CO,
hydrocarbons, POM's (stack)
SO2 (stack)
Particulates, SOX, NOX, CO,
hydrocarbons (stack)
Particulates, combustion
products (stack)
Particulates (fugitive)
23
-------
1. Emissions from Barite Preparation
Barite ore must be ground and mixed with coal or coke before
it is fed into the rotary kiln. This processing is a source
of fugitive dust emissions whose magnitude depends on the
extent to which the operations are enclosed. Water sprays
are also employed to control emissions. (At one site, the
ore is milled before it arrives at the plant.) No data could
be found in the literature on emissions from barite prepara-
tion nor have they been measured by any of the manufacturing
companies.
One of the four major barium chemical plants was sampled in
order to assess the severity of fugitive dust emissions from
barite preparation. The sampling procedure and analytical
results are given in Appendix C. The emission factor was
'found to be 1 g/kg ± 75% (Appendix B.2).
2. Emissions from the Rotary Kiln
Rotary kilns are used in the manufacture of barium chemi-
cals at the four plants shown in Table 9. The kilns are
exhausted through cyclones to reduce process loss (^5% loss
without cyclones; ^0.5% loss with cyclones).1 Table 9
identifies the additional control devices on the kilns.
The rotary kiln at Great Western Sugar produces tribarium
silicate instead of barium sulfide (Section III.B.5). Con-
sequently, the emission factors developed in this section of
the report cannot be directly applied to that kiln. Although
emissions data are not available on the kiln, state emission
standards for S0x and particulates are met using an alkaline
scrubber.
24
-------
Table 9. ROTARY KILNS USED IN THE MANUFACTURE OF
BARIUM CHEMICALS 1~'*
Company
Chemical Products
FMC
Sherwin-Williams
Great Western
Product
from kiln
BaS
BaS
BaS
Ba3Si05
Number
of kilns
2
1
2
1
Controls
(after cyclones)
Baghouses are
being installed
Double alkali
scrubber
None on large
kiln; scrubber
on small kiln
Alkaline scrubber
a. Particulates - Particulate emissions in rotary kilns
are caused by the entrainment of dust particles in the feed
material. Emission level is a function of the type of '
barite ore used, how finely it is ground, and the air flow
rate through the kiln. All kilns are equipped with cyclones
which reduce process loss from ^5% to ^0.5%. Additional
control measures are employed at some plants (Table 9).
Uncontrolled dust emissions from the kiln range from 5 to
15 g/kg of feed material because of the variations in
operation mentioned above.1-3
Sampling measurements taken on one kiln during the course of
this study (Appendix C) yielded an emission factor of
6.25 g/kg ± 15% of feed material. An average value of
10 g/kg ± 50% is used in this report.
One company reported data on a kiln equipped with a scrubber.
Emissions varied from 150 g/hr to 180 g/hr while the ore
feed rate ranged from 29 kg/min to 33 kg/min. The equivalent
emission factor is 0.07 g/kg + 14% of feed material, which
corresponds to approximately 99% efficiency.
25
-------
Another scrubber had an emission factor of 0.4 g/kg/
equivalent to a 96% 'efficiency. This scrubber was designed
for SO rather than particulate removal.
X
b. SO - Sulfur oxides are produced in the rotary kiln by
2v
the oxidation of sulfur present in the coal or petroleum
coke used as a reducing agent, and by side reactions in which
reacts with impurities in the ore to give insoluble
barium compounds and SO . Hence, SO emissions depend on
X X
the sulfur content of the coal/coke and the level of
impurities in the ore.1'2 These parameters vary from pro-
ducer to producer, as well as from one time period to another
for the same producer.
One manufacturer reported average SO emissions of 22.4 g/kg
X
of feed material, with maximum emissions of 25.6 g/kg. Another
producer had an average uncontrolled emission factor of
27.5 g/kg. The second producer was using a higher silica
ore, although neither company disclosed its exact ore compo-
sition.
In order to verify the SO emission factors, material balance
calculations were performed for the two SO formation mechan-
X
isms described above as summarized below:
For coal/coke having a sulfur content of 1% to
7%, S02 emission factors appear in Table 10.
These are based on the stoichiometric conversion
of sulfur to sulfur dioxide, and a feed ratio
of 4 parts barite to 1 part coal/coke.
26
-------
Table 10. S02 EMISSIONS FROM COAL/COKE IN ROTARY KILNS
Sulfur content of
coal/coke,
S02 emission
factor, g/kg
of feed material
1
2
3
4
5
6
7
4
8
12
16
20
24
28
For barite ore composed of 95% BaSO^, with a
conversion ratio to BaS of 90% to 95%, the SO2
emission factors are given in Table 11. The
feed material is 4 parts barite to 1 part
coal/coke, and all of the BaSO^ lost is assumed
to yield SO2.
Table 11. S02 EMISSIONS FROM BARITE IN ROTARY KILNS
Conversion of
BaSO4 to BaS,
%
90
91
92
93
94
95
S02 emission
factor, g/kg
of feed material
21
19
16.5
14.5
12.5
10.5
Tables 10 and 11 agree with the reported SO emission
x.
factors. The combined emissions are higher than expected,
but the assumed stoichiometric conversion is a worst case
situation. An average uncontrolled emission factor for SO
of 25 g/kg ± 20% of feed material is used in this report.
27
x
-------
One company, which had installed a scrubber system specifical y
to control SO emissions, reduced them to 0.2 g/kg to 0.5 g/kg/
X
corresponding to a control efficiency of 98% to 99%. The sys-
tem has reduced the stack gas concentration of SOx'from 5,000
ppm to as low as 52 ppm.
c. NO - No measurements have been made, for NO emissions,
ry ^±
which result from the combination of atmospheric nitrogen
and oxygen in the combustion zone of the kiln. An emission
factor was estimated based on the rate of fuel consumption,
3
which was reported to be 150 m3/metric ton of BaS produced.
The emission factor is 0.6 g/kg ± 100% of feed material
(Appendix B.3).
d. CO and Hydrocarbons - No data have been reported for
emissions of carbon monoxide and hydrocarbons from the
rotary kiln. One company stated that none were detected
in the stack gases by an Orsat analysis, which has a detec-
tion limit on the order of 0-1%, or 1,000 ppm. However,
since coal is used as a reducing agent, these emissions were
expected to be present. Therefore, a sampling test was
performed for CO and hydrocarbons as described in Appendix C.
The emission factor for CO is 5 g/kg ± 100%, and that for
hydrocarbons is 0.1 g/kg ± 100% (Appendix B.4).
e. POM's - Polynuclear organic materials (POM's) are
known to be emitted from combustion processes. Their for-
mation is favored under poor combustion conditions (insuffi-
cient oxygen) and when coal or wood is used as a fuel instead
of gas or oil. POM's are of importance because some of
them are known to be carcinogenic [e.g., benzo(a)pyrene]8
(Appendix D).
8Particulate Polycyclic Organic Matter. Washington, National
Academy of Sciences, 1972. 361 p.
28
-------
Although no measurements had been made for POM's from the
black ash kiln, their presence was assumed since coal/coke
was used as a reducing agent. Consequently, sampling tests
were conducted to determine the level of POM emissions
from the rotary kiln (Appendix C). The results given in
Table 12 indicate that 27 compounds were detected, of which
14 have shown carcinogenic activity in animals.
The kiln that was tested used coal as a reducing agent. It
is believed that petroleum coke would yield lower POM emis-
sions since coke is prepared by heating petroleum to drive
off all volatile compounds. For confirmation, a petroleum
coke sample was extracted with pentane and the extract
analyzed by gas chromatograph-mass spectrometry. No POM's
were detected.
To compare the magnitude of POM emissions, Table 13 lists the
results of a series of tests on coal-fired boilers.9 Emis-
sion factors for each compound are given in pg/kg of fuel
burned. The data show that rotary kiln emissions are in the
same range as those from coal-fired boilers.
In subsequent calculations, a range of 0.01 g/kg to 0.001
g/kg of feed material is used for the POM emission factor.
Kilns equipped with scrubbers or using coke as a reducing
agent are expected to exhibit lower emissions.
9Hangebrauck, R. P., D. J. Von Lehmden, and J. E. Meeker.
Emissions of Polynuclear Hydrocarbons and other Pollutants
from Heat-Generation and Incinerator Processes. Journal
of the Air Pollution Control Association. 14;267-278,
July 1964.
29
-------
TABLE 12. POM EMISSIONS FROM BLACK ASH ROTARY KILN
Compound
Dibenzothiophene
Anthracene
Phenanthrene
Methylanthracenes
Me thy Iphenanthr ene s
Fluoranthene
Pyrene
Methylpyrenes
Methylfluoranthenes
Benzo ( c ) phenanthrene
Naphthobenzothiophene9
Chrysene
flenz (a) anthracene
Methylehrysenesc
7 , 12-Dimethylbenz (a) anthracene
Benzo (b) f luoranthene1
Benzo (k) f luoranthene
Benzo (a) pyrene
Benzo (e) pyrene
Perylene
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo ( g , h , i ) pery lene
Dibenz (a , h) anthracene
7H-Dibenzo (c , g) carbazole
Dibenzo (a, i) pyrenei
Dibenzo(a,h)pyrenek
Total POM's
Hazardous
rating3
_
-
~
None
None
-
-
Nonef
•H-+
± \
+ J
±
+-H-+
++ 1
+++ )
'
j
++++
+
-
H-++
+++
t£ }
Emission
factor,
yg/kg
520 to 2,400
320 to 4,500
100 to 670b
45 to 470
20 to 210
19 to 70b
0 to u42
unknown
1 9fl 4-ri ciQrt
i. £, U to ( D j U
29 to 110
0 to 13
b
8 2 to 435
K
30 to 83
0 to 36
0 to 61
0 to 13
0 to 63
0 to 23
0 to 45b
,100 to 8,700
aHazardous rating scale is:8
- not carcinogenic
* uncertain or weakly carcinogenic
+ carcinogenic
++' +++i ++++ strongly carcinogenic
These compounds were not resolved on the gas chromatograph -
mass spectrometer.
°The different methyl isomers were not resolved on the gas
chromatograph - mass spectrometer.
dNo rating given in Reference 8; 9-methyl isomer is listed
as a neoplastic agent in the 1974 Toxic Substances List.1"
eNo rating given in Reference 8.
fNo rating given in Reference 8; 2-methyl isomer is listed
as a carcinogenic agent and 3-methyl isomer as a neoplastic
agent in the 1974 Toxic Substances List.1"
9 indexed in Chemical Abstracts as benzonaphthothiophenes of
o i/!*;r?r\are three' namely, benzo(b)naphtho(l,2-d 2, 1-d
thefnaii?? ?e; ^x* isomers co«ld "<* be resolved with
tne analytical method used.
hThe mass ion for this compound was detected but no
standard was available.
11ndexed in Chemical Abstracts as benz(e)acephenanthrylene.
JIndexed in Chemical Abstracts as benzo(rst)pentaphene.
kIndexed^in Chemical Abstracts as dibenzo(b,defJchrysene.
T ,' Christensen, H.E.,
T. T. Luginbyhl (ed.). Rockville, Maryland, U S
Department of Health, Education and Welfare, June if74.
30
-------
Table 13. POM EMISSIONS FROM COAL-FIRED BOILERS*
(Vig/kg fuel)
Compound
Anthracene
Phenanthrene
Fluor an thene
Pyrene
Benz (a) anthracene
Benzo (a) pyrene
Benzo ( e ) pyrene
Perylene
Benzo (g , h , i , ) pery lene
Anthanthrene
Coronene
Test unit
1
4.6
3.8
0.49
0.49
2
11
16
7.1
0.95
2.7
3
18
10
0.97
3.3
4
10
17
0.77
10
0.77
5
26
309
1,170
494
120
309
245
48
139
9.0
10
6
29
95
51
3.5
6.9
7
875
1,420
231
17
115
163
17
35
Note: Blanks indicate no POM emissions detected.
3. Emissions from the H2S Incinerators
Only two companies operate H2S incinerators. Another plant
precipitates barium carbonate with Na2CO3, while Great
Western Sugar does not make BaCOs" via BaS. l~k No sampling
measurements were performed on the incinerators. Instead,
the emission factor for S02 was calculated from a material
balance, based on the reaction:
HS
S02 + H20
(11)
The emission factor is 1.882 kg S02 per kg of H2S burned.
The accuracy is estimated to be within 1% since the oxida-
tion reaction proceeds to completion.
31
-------
4. Ba(OH)2 Production
Stack emissions from the production of barium hydroxide are
difficult to assess since two different processes are used,
one of which is proprietary. At Great Western Sugar, a
rotary kiln is used to make tribarium silicate from recycled
monobarium silicate and barium carbonate. There are no
other sources of stack emissions since the barium compounds
are not dried.4 (Fugitive emissions for all barium chemi-
cals are discussed in Section IV.A.I.)
Emissions from the rotary kiln consist of particulates, SOx
from makeup barite ore and coke, and combustion products,
NO , CO, and hydrocarbons. An alkaline scrubber is used to
control particulates and SOx emissions in order to meet
state standards. It is believed that the emission factors
developed for the black ash rotary kiln would apply to this
kiln also, as a first approximation, because the kiln design
is the same.
The amount of sulfur oxide emissions should be the same
because of two opposing factors. The sulfur in the feed
material should be less because only makeup barite and coke
are used, but the SO released should be greater since no
BaS is made. All of the BaSO^. is converted to tribarium
silicate and SO2. Therefore, SO emissions are estimated
to be comparable to those from the BaS rotary kiln.
Information on the Sherwin-Williams process for manufacturing
Ba(OH)2 is proprietary. Emissions from raw material prepara-
tion and product drying are considered in Sections IV.A.I
and IV.A.5, respectively. Emissions from the rest of the
process are exhausted through stacks equipped with electro-
static precipitators for particulate control.3 No data are
available, but particulate emissions are judged to be <0.5 g/kg.
32
-------
Emissions of S02 were reported to be equimolar to Ba(OH)2
production, plus a small additional quantity for process
loss (estimated at ^10%).3 The emission factor is then
410 g SO2/kg of Ba(OH)2 produced (±10%).
Emissions of combustion products were estimated based on
reported fuel usage rate and the emission factors derived
in Appendix B.I. Fuel used for drying was estimated and
subtracted from total fuel burned. The following emission
factors were calculated: NO , 0.8 g/kg; CO, 0.11 g/kg; and
X
hydrocarbons, 0.07 g/kg.
5. Emissions from Dryers and Calciners
Particulate emissions from dryers and calciners are impor-
tant because BaC03, BaCl2, and Ba(OH)2 are considered to be
hazardous compounds (Section IV.B). Barium sulfate is inert
and nonhazardous.
Various types of dryers are used in the industry. Those in
use at the major companies are listed below:1"3
Type of dryer Number in use
Rotary 4 (one is a predryer)
Drum 1
Flash 1
Spray 1
Calciners (three) are all of the rotary design (i.e., an in-
clined cylinder which rotates on its axis). Dryers and
calciners are heated with gas and have a dust trap before
the exhaust stack. In addition, three of the dryers and one
of the three calciners are equipped with baghouses to further
control particulate emissions. Another dryer is controlled
with a wet scrubber.1"3
33
-------
The parameters that determine the amount of uncontrolled
particulates emitted by dryers and calciners include the
specific equipment design, the size of particles being pro-
cessed, the moisture content of the final product, and the
air flow rate through the kiln. Variations in these para-
meters may change the emission factor more than 200-fold
(from ^0.04 g/kg to 10 g/kg). Plume opacities may vary from
0% to 30%.1-3
Because the industry is small and diversified, there is no
representative dryer. Moreover, emissions data are too
limited to establish a quantitative relationship between
dryer parameters and emission factors. The following
qualitative comments can be made.
Finer sized particles produce dust more readily.
As an example, BaCl2 crystals are larger than
those of BaCOa, and calcined BaC03 is of a
larger grain size than uncalcined material.
Other things being equal, BaCl2 will dust less
than BaC03, and calcined BaC03 less than un-
calcined
A higher moisture content in the final product
will reduce emissions. As an example, barium
chloride is often prepared as the dihydrate,
and stack opacity is near 0% . l
A higher air flow rate through the kiln causes
increased dusting. This occurs, for instance,
when the production rate is increased.
Only limited testing has been performed on dryers and
calciners. Test data for one rotary dryer and one calciner
are presented in Table 14. Measurements were not performed
according to EPA Method 5, and the results are of unknown
accuracy.
34
-------
Table 14. PARTICULATE EMISSIONS FROM A
DRYER AND CALCINER
Parameter
Emission, mg/sec Run 1
Run 2
Run 3
Average
Allowable emission, mg/sec
Process flow rate, metric
tons/hr (taken from state
regulations for emission
standards)
Emission factor, g/kg
Rotary dryer
7.49
36.82
26.95
23.75
955-8
2.3
0.037
Rotary calciner
27.22
40.73
33.98
678.4
1.4
0.087
Note: Blank indicates particulate emissions not reported.
Emissions from a drum dryer were reported in the National
Emission Data System (NEDS).11 Annual emissions were given
as 5.4 metric tons and the production rate was 0.9 metric
tons/hr. The emission factor, assuming continuous operation,
is 0.7 g/kg.
One company reported that uncontrolled emissions from a
rotary dryer ranged from 5 g/kg to 10 g/kg before installa-
tion of a baghouse. Opacity ranged from 20% to 30%. The
emission factor with the baghouse was 0.25 g/kg (>95% effi-
ciency) , and the opacity reading was 0%.
Because of the wide range in emission factors, the diversity
in dryers and calciners, the limited data, and the unknown
accuracy of the data, an average emission factor was not
determined for particulates. Instead, a range of emission
nPoint Source Listing for Inorganic Pigments, SSC 3-01-035,
National Emission Data System. Environmental Protection
Agency. Research Triangle Park. August 1974.
35
-------
factors for uncontrolled emissions, from 0.04 g/kg to
10 g/kg, is used to describe particulate emissions. Con-
trolled emissions are on the order of <0.25 g/kg. The
actual lower limit is unknown since only one baghouse
effluent has been tested.
Barium sulfate dryers were not studied because the compound
is not hazardous and the amount of material processed is only
•^5.0 x 103 metric tons/yr. Based on a worst case emission
factor of 10 g/kg, total particulate emissions would be 50
metric tons/yr.
6. Emissions from Packaging and Shipping
After barium compounds have been dried, they may be screened
and milled before packaging. All of these steps in final
product preparation occur within the plant building and are
not sources of fugitive emissions.
The loading of bulk product into railroad hopper cars may
cause dusting. However, observation of a loading operation
showed that the dust cloud was visible only at the top of
the railroad car. No dust could be seen drifting away from
the operation and it was concluded that emissions from this
process were also zero.
Any other possible fugitive emissions were measured in
the sampling tests discussed in Appendix C.- They appear
in the aggregate emission factor of 1 g/kg reported for
barite preparation.
36
-------
7. Summary
Emission factors and their associated accuracies are
summarized in Table 15 for the entire production process.
Both controlled and uncontrolled emission factors are pre-
sented where appropriate. Uncontrolled emissions from
the black ash rotary kiln are controlled with cyclones, and
uncontrolled dryers and calciners are equipped with cyclones
or dust traps.
B. EMISSION CHARACTERISTICS
1. Barite Preparation
Barite ore is primarily (95%) barium sulfate, a nonhazardous
chemical. The pure compound is used in taking x-ray photo-
graphs of the stomach and intestines. No Threshold Limit
Value (TLV®) has been specifically assigned to BaSO^ or
barite.12
Inhalation of barite dust causes the lungs to appear dark
on an x-ray photograph, a condition known as baritosis.
12TLV's® Threshold Limit Values for Chemical Substances
and Physical Agents in the Workroom Environment with
Intended Changes for 1975. American Conference of
Governmental Industrial Hygienists. Cincinnati. 1975.
97 p.
37
-------
Table 15. SUMMARY OF EMISSION FACTORS
Process
Barite preparation
Black ash (BaS)
rotary kiln
H2S incinerator
Ba (OH) 2 production
Great Western
Sugar rotary
kiln
Sherwin-Williams
proprietary
Product dryers and
calciners
Emission
Particulates
Particulates
SO
NOX
cox
Hydrocarbons
POM'S
SO
X
Particulates
SO
NOX
cox
Hydrocarbons
Particulates
SO
X
NO
cox
Hydrocarbons
Particulates
(soluble
barium com-
pounds )
Emission factor, g/kg
Uncontrolled
_a
10 ± 50%
25 ± 20%
0.6 ± 100%
5 ± 100%
0.8 ± 100%
0.001 to 0.01
1,882 ± 1%
a
u
a
a
410 ± 10%
0.8 ± 113%
0.11 ± 55%
0.07 ± 144%
0.04 to 10
Controlled
1 ± 75%
<0.4
<0.5,
0.6b
sb .
0.8
unknown
a
Assumed to
be the
same as
black ash
rotary
kiln
<0.5
~a
a
<0.25
Type control
Water spray
Scrubber
(only par-
ticulates
and SOX are
known to be
controlled)
a
Scrubber
(only par-
ticulates
and SOX are
known to be
controlled)
Electrostatic
precipita-
tor (only
particu-
lates are
controlled)
Baghouse
Basis for
emission factor
Feed material into
the rotary kiln
Feed material into
the rotary kiln
H2S burned
Feed material into
the rotary kiln
Ba (OH) 2 produced
Product dryed or
calcined
GO
CXI
Not applicable.
Assumed to be the same as uncontrolled.
-------
This condition has no specific symptoms and does not seem
to reduce lung capacity or cause emphysema or bronchitis.13"16
2. Rotary Kiln and H2S Incinerator
Emissions from the rotary kiln and H2S incinerator consist
of particulates, SO , NO. CO, hydrocarbons, and POM's. The
A X
emission characteristics are summarized in Table 16.
The health effects of airborne POM's have been the subject
of much study, and it is suspected that these materials
contribute to the higher incidence of disease in urban areas.
Several of the POM's are known carcinogens when injected into
/
experimental animals. However, because of the complex nature
of the atmosphere, it is impossible to delineate the actual
effects of airborne species.8
13Pendergrass, E. P., and R. R. Greening. Baritosis.
Archives of Industrial Hygiene and Occupational Medicine.
7^:44-48, 1953.
lifWillson, J. K. V., P. S. Rubin, and T. M. McGee. The
Effects of Barium Sulfate on the Lungs. American Journal
of Roentgenology, Radium Therapy and Nuclear Medicine.
8_2:84-94, July 1959.
15Gleason, M. N., R. E. Gosselin, and H. C. Hodge. Clinical
Toxicology of Commercial Products. Baltimore, The Williams
& Wilkins Co., 1957. p. 28-29, 120-121.
16Barium and Its Inorganic Compounds. American Industrial
Hygiene Association Journal. 23_: 517-518, November-
December 1962.
39
-------
Table 16. CHARACTERISTICS OF EMISSIONS FROM ROTARY
KILNS AND H2S INCINERATOR
Emission
Particu-
late
S0x
N0x
CO
Hydro-
carbons
POM's
TLV,
mg/m3
10
13 (S02)
9 (N02)
55
(1,000
ppra,
CHiJ
0.2
Ambient
air
quality
standard,
mg/m3
0.26
0.365
0.1
40
0.16
None
Atmospheric
reactivity
Stable
Forms sulfates;
contributes to
photochemical
smog
Forms nitrates;
contributes to
photochemical
smog
Stable
Reacts with aci-
dic gases in
the formation
of photochem-
ical smog
Oxidize readily
in the atmos-
phere
Health
effects
Irritating
to lungs
Irritating
to lungs
Asphyxiant
Methane is
an as-
phyxiant
Some POM's
are car-
cinogenic
3. Dryers and Calciners
Particulates composed of soluble barium compounds are
emitted during the drying and calcining of BaC03, BaCl2 and
Ba(OH)2. These compounds are all considered hazardous on
ingestion^and have a TLV of 0.5 mg/m3.12'15
The effects of barium poisoning are acute rather than
chronic since barium compounds are not accumulated by the
body. The first symptoms on ingestion are usually great
weakness, salivation, and nausea, followed by vomiting,
diarrhea, and severe abdominal pain. Later symptoms include
40
-------
paralysis of the extremities, breathing difficulty, and
rapid pulse. Eventually cyanosis sets in and then death.6'15
Effects on inhalation are a matter of speculation since no
controlled studies have been performed. Occupational
poisoning is practically unknown, and the few reported cases
are ambiguous in terms of the actual cause of symptoms.
Because these compounds are toxic on ingestion, it is recom-
mended that exposure to airborne dusts be reduced to 0.5
mg/m3,i2,i6,i7
C. ENVIRONMENTAL EFFECTS
1. Total Emissions
In order to assess the environmental impact of barium
chemical production, total national emissions of criteria
pollutants from the industry were calculated. Each process
causing emissions was treated separately by considering the
material processed at each of the four major plant sites
and the control techniques employed in each case.
a. Barite Preparation - Approximately 98% of raw material
consumption occurs at three locations (Appendix A.I). One
of these plants receives milled barite ore; the other two
plants grind the ore on site. Fugitive dust from grinding
is partially controlled at one site with water sprays and
at the other site by partial enclosure of the operation and
by use of a baghouse on the exhaust. The emission factor of
1 g/kg applies to grinding operations at both sites, and
total particulate emissions are estimated at 78 metric tons/yr,
17Effect of Barium Carbonate Fumes on Respiratory Tract.
Journal of the American Medical Association. 117:1221,
1941.
41
-------
There are fewer fugitive dust emissions from the two other
large barium chemical plants because one does no grinding
while the other (Great Western Sugar) consumes only 2.7 x 10
metric tons/yr of raw materials. Estimated emissions are
<9 metric tons/yr. Total emissions of fugitive dust from
the whole industry are ^90 metric tons/yr.
b. Rotary Kiln -
(1) Particulates - Uncontrolled kilns process about two-
thirds of the barite ore consumed in the industry. (This
will be reduced to about one-third after baghouses are in-
stalled at Chemical Products.) Total particulate emissions
from these kilns are 7.8 x 102 metric tons/yr. Controlled
emissions (based on a 95% efficiency) are estimated at
39 metric tons/yr and total industry emissions are ^820
metric tons/yr.
(2) SO - Uncontrolled SO emissions amount to 1.86 x 103
X X
metric tons/yr, whereas controlled emissions (based on an
emission factor of 0.5 g/kg) equal 20 metric tons/yr for a
total of 1.88 x 103 metric tons/yr.
(3) NO - No data are available on how well NO emissions
X X
are controlled by scrubbers. Therefore, based on an un-
controlled emission factor of 0.625 g/kg, total industry
emissions amount to 73 metric tons/yr.
(4) CO and hydrocarbons - Carbon monoxide emissions total
550 metric tons/yr while hydrocarbons emissions amount to
90 metric tons/yr. Both figures are for uncontrolled
emissions.
c. H2S Incinerator - Two barium chemical plants operate
H2S incinerators. Total SO emissions from the two inciner-
-
-------
ators were found by using NEDS data for one plant (SO calcu-
X
lated by a material balance), and using the average hourly
S0x emission rate for the other plant (as supplied by plant
personnel). Total emissions are 3.3 x 103 metric tons/yr.
d. Ba(OH)2 Production - Total emissions at Great Western
Sugar are based on the controlled emission factors given
in Table 15 for the black ash rotary kiln. The material
fed into the kiln is greater than the estimated Ba(OH)2 pro-
duction (Appendix A.4) of 7 x 103 metric tons because of
coproduction of BaSiOa and stack losses (S02 and C02)• The
feed is estimated at 1.4 x 101* metric tons/yr, and annual
emissions are therefore: particulates, 5 metric tons/yr;
SO , 7 metric tons/yr; NO , 8 metric tons/yr; CO, 68 metric
X X
tons/yr; and hydrocarbons, 10 metric tons/yr.
Total emissions at Sherwin-Williams, based on the emission
factors in Table 15 and production of 5.5 x 103 metric tons/yr
of Ba(OH)2 (Appendix A.4), are: particulates, 3 metric
tons/yr; SO , 2.045 x 103 metric tons/yr; NO , 4 metric
x x
tons/yr; CO, <1 metric ton/yr, and hydrocarbons, <0.4
metric tons/yr.
e. Dryers and Calciners - The compounds BaCOs, BaCl2, and
Ba(OH)2 are dried except for the,Ba(OH)2 produced by Great
Western Sugar Co., and about one-third of the BaC03 made is
calcined for use in glass manufacturing. The industry
utilizes seven dryers and three calciners, of which three
dryers and one calciner are controlled with baghouses, and
one dryer is controlled with a wet scrubber. The amounts
of products dried and calcined are shown in Table 17.
43
-------
Table 17. BARIUM COMPOUNDS DRIED AND CALCINED ANNUALLY
Products
dried and
calcined
BaC03
Bad 2
Ba(OH) 2
Total
Controlled,
metric tons
31,900
0
5,000
36,900
Uncontrolled,
metric tons
21,300°
9,000
0
30,300
Total,
metric tons
53,200
9,000
5,000
67,200
3These are equipped with cyclones or settling chambers.
See Appendix A.
Q
Includes one predryer.
Total particulate emissions were calculated, based on an
uncontrolled emission factor of 5 g/kg and a controlled
emission factor of 0.25 g/kg, to be 160 metric tons/yr.
This value may be high because the industry has installed
controls preferentially on the dustiest dryers.
f. Summary - Total emissions from the barium chemicals
industry are summarized in Table 18.
Table 18. TOTAL EMISSIONS FROM BARIUM CHEMICALS INDUSTRY
Source
Barite prep.
Rotary kiln
H2S incin-
erator
Ba(OH)2 prod.
Dryers and
calciners
Total
Particulates
90
820
0
8
160
1,100
S0x
0
1,880
3,200
2,050
0
7,200
NO
X
0
73
0
12
47a
130
CO
0
550
0
69
63
625
1
Hydrocarbons
0
90
0
11
4a
105
l
From Appendix B.I.
44
-------
The magnitude of these emissions can be compared to the
total emissions from all stationary sources in the states of
California, Colorado, Georgia, and Kansas18 (Table 19). It
can be seen that the barium chemicals industry contributes
less than 1% of the emission burden from these four states
for each criteria pollutant, and less than 0.1% of the
national emission burden.
2. Source Severity
In addition to the total national emissions of criteria
pollutants, another measure of the potential environmental
effect of barium chemicals production is the ratio of the
average maximum ground level concentration, x" , of a plant
IB 9.X
emission to the corresponding ambient air quality standard,
AAQS. This ratio has been termed the source severity, S, as
defined earlier in Equation 1:
_ xmax
= AAQS
In the case of noncriteria pollutants a "reduced" TLV, called
the hazard factor (F) , replaces the AAQS, and source severity
is defined as:
S = (12)
where F = TLV x 8/24 x 1/100 (13)
8/24 corrects the TLV to a 24-hour exposure, and 1/100 is
a safety factor.
45
-------
Table 19. TOTAL EMISSIONS OF CRITERIA POLLUTANTS BY STATE AND NATION18
Location
California
Colorado
Georgia
Kansas
All four states
Total emissions
from barium
chemicals
industry
Industry con-
tribution to
state total
United States
Industry con-
tribution to
national total
Particulates,
metric tons/yr
1,006,452
201,166
404,574
348,351
1,960,543
1,100
0.056%
17,872,000
<0.01%
sox,
metric tons/yr
393,326
49,188
472,418
86,974
1,001,906
7,200
0.72%
29,949,000
0.024%
N0x,
metric tons/yr
1,663,139
147,496
379,817
233,987
2,424,439
130
<0.01%
. 22,258,000
<0.10%
Hydrocarbons ,
metric tons/yr
2,160,710
193,456
458,010
309,633
3,121,809
625
<0.01%
22,045,000
<0.10%
CO
metric tons/yr
8,237,667
875,781
2,036,010
1,002,375
12,151,833
105
<0.01%
96,868,000
<0.10%
-------
Values for xmax can be predicted from plume dispersion
equations. Under C class air stability the following rela
tions apply:19
xmax
Y = ^r n z,)
Amax ir^nii* \j-->i
where Xmax = instantaneous (i.e., 3-min. average) maximum
ground level concentration
t0 = 3 min.
t = averaging time of interest for 7
^ Amax
Q = emission rate, g/s
H = effective stack height, m
u = wind speed, m/s (the national average of
4.5 m/s was used)
TT = 3.14
e = 2.12
A 24-hour averaging time was used for non-criteria pollutants,
For ground level sources (H=0) the maximum ground level con-
centration occurs by definition at the plant boundary. In
this case S is related to the average distance, D, from the
emission point to the plant perimeter. Equations for S in
terms of Q, H, and D are summarized in Table 20. Detailed
derivations are presented in Appendix E.
19Turner, D. B. Workbook of Atmospheric Dispersion Esti-
mates, 1970 Revision. U.S. Department of Health, Education
and Welfare. Cincinnati. Public Health Service Publication
No. 999-AP-26. May 1970. 84 p.
47
-------
Table 20. EMISSION SEVERITY EQUATIONS
Emission
Severity equation
For elevated sources:
Particulate
SO
NO
x
Hydrocarbon
CO
Other
For ground level sources;
Particulate
s = 70 Q
S =
S =
S =
S =
S =
50 Q
H
315 Q
H2.1
162 Q
H2
0.78 Q
H2
5.5 Q
TLV-H2
S = 4'020 Q
D1.81
48
-------
a. Barite Preparation - Barite preparation is a ground
level source of emissions and the relevant parameters are
Q and D. The emission rate is equal to the product of the
emission factor, shown in Table 15, and the amount of raw
material processed at a plant site. As shown in Appendix
A.I., three plants each process ^39 x 103 metric tons/yr
of raw material (barite ore plus coal/coke) and account for
'v98% of raw material consumption. Therefore, Q = 1 g/kg •
3.9 x 107 kg/yr • 1 yr/3.15 x 107 s = 1.24 g/s.
The value for D, calculated in Appendix F for the barium
chemicals plant that was sampled, is 244 m. The corresponding
source severity, S, is 0.238.
b. Black Ash Rotary Kiln - Kiln stack heights are listed
in Table 21 and emission factors are shown in Table 15.
Table 22 lists source severities based on a feed rate of
^39 x 103 metric tons/yr, an average stack height of 32 m,
and no emission controls. (Effect of plume rise is con-
sidered in Appendix G.)
Table 21. KILN STACK HEIGHTS FOR BLACK ASH ROTARY KILN1"3
(meters)
Uncontrolled
38
28
29
Controlled
10 (small kiln)
23
Average 32 Average 23
The emission rate is lower when an alkaline scrubber is
used as a control device. Severities for this case are
shown in Table 23.
49
-------
Table 22. SOURCE SEVERITIES FOR EMISSIONS FROM BLACK ASH
ROTARY KILN (WITHOUT EMISSION CONTROLS),
Emission
Particulate
S0x
CO
Hydrocarbon
POM
Q,
g/s
12.37
30.92
0.742
6.18
0.989
0.00124 to 0-0124
S
0.846
1.51
0.161
0.00471
0.156
0.0333 to 0.333
Table 23. SOURCE SEVERITIES FOR EMISSIONS FROM BLACK ASH
ROTARY KILN (WITH ALKALINE SCRUBBER)
Emission
Particulate
S0x
NO
X
CO
Hydrocarbon
POM
Q,
g/s
0-495
0.247 to 0.618
0.742
6.18
0.989
unknown
S
0.0655
0.0234 to 0.0585
0.323
0.00911
0.303
unknown
A stack height of 23 m was used in calculating S. The
capacity of the smaller controlled kiln was about half that
of the large one, and the severities (with a stack height
of 10 m) would be about twice as great.
c. H2S Incinerator - The two H2S incinerators have stack
heights of 38 m and 36 m.1"3 The emission rate was calcu-
lated by assuming that the total national S02 emission of
50
-------
3.265 x 103 metric tons was emitted continuously and in an
equal amount by both stacks. On this basis Q = 51.8 g/s and
the source severity is 1.89.
d. Dryers and Calciners - Stack heights for dryers and
calciners are shown in Table 24. An average process weight
was found by dividing the total material dryed and calcined
(67.2 x 103 metric tons) by the total number of dryers and
calciners (10). This yields an annual capacity of 6.7 x 103
metric tons. The source severity of particulate emissions
was found from the equation
Q
TLV-H2
(16)
using the TLV for soluble barium compounds (0.5 mg/m3). The
results, given in Table 25 show the range of severities for
uncontrolled and controlled emissions for an average stack
height. (See Appendix G for the effect of plume rise.)
Table 24. STACK HEIGHTS FOR DRYERS AND CALCINERS1"3
(meters)
Uncontrolled
•*
Average
12.2
12.2
7.9
11.0
11.0
10.9
Controlled
6.1
9.1
13.7
13.7
7.6
Average 10.0
51
-------
Table 25. SOURCE SEVERITIES FOR DRYERS AND CALCINERS
Type of
dryer/
calciner
Uncontrolled
Controlled
Emission
factor,
g/kg
0.4 to 10
<0.25
Q,
g/s
0.00854 to 2.13
<0.0534
Stack
height,
m
10.9
10.0
Source
severity
0.791 to 197
<5.87
e. Barium Hydroxide Production - Source severities for the
two processes were calculated from the emission factors and
annual capacities presented in Section IV.A.4 and IV.C.l.d.
The stack height for the rotary kiln equipped with an alkaline
scrubber at Great Western Sugar is ^18.3 m.4 The stack
height at Sherwin-Williams is 45.7 m. 3 Source severity values
are included in Table 26.
f.
Summary - S and x values for emissions from all the
~ ~~" max
process operations are summarized in Table 26.
3. Affected Population
The average ground level concentration, x", of an emission
will vary with the distance, x, from the emission point, as
shown in Figure 9.
DISTANCE FROM SOURCE
Figure 9. Variation of x with distance
52
-------
Table 26. SUMMARY OF SOURCE SEVERITIES AND AVERAGE MAXIMUM GROUND LEVEL CONCENTRATIONS
Emission point
Barite preparation
Black ash rotary kiln
(uncontrolled)
Black ash rotary kiln
(controlled)
H2S Incinerator
Dryers and calciners
(uncontrolled)
Dryers and calciners
(controlled)
Barium hydroxide
production
Sherwin-Williams
Great Western
Sugar
Emission
Particulate
Particulate
so
NO
COX
Hydrocarbons
POM's
Particulates
so
NO
COX
Hydrocarbons
POM's
S0x
Soluble
barium
compounds
Soluble
barium
compounds
Particulate
so
NO*
COX
Hydrocarbons
Particulates
S0x
NOX
COX
Hydrocarbons
Stack height,
m
0
(D = 244 m)
32
32
32
32
32
32
23
23
23
23
23
23
37
10.9
10.0
45.7
45.7
45.7
45.7
45.7
18.3
18.3
18.3
18.3
18.3
Q,
g/s
1.24
12.37
30.92
0.742
6.18
0.989
0.00124 to 0.0124
0.495
0.247 to 0.618
0.742
6.18
0.989
unknown
51.8
0.00854 to 2.13
50.0534
0.0791
64.87
0.127
0.0087
0.0111
0.173
0.216
0.259
2.16
0.345
xmax'
yg/m3
61.9
220
551
16.1
188
25.0
0.022 to 0.22
17.0
8.5 to 21.4
32.3
364
48.5
unknown
690
1.32 to 328
<9.78
0.69
567
1.30
0.13
0.14
9.38
11.8
18.2
201
26.7
AAQS,
rag/m3
0.260
0.260
0.365
0.100
40
0.160
0.000667
0.260
0.365
0.100
40
0.160
0.000667
0.365
0. 001673
0.001678
0.260
0.365
0.100
40
0.160
0.260
0.365
0.100
40
0.160
Source severity
0.238
0.846
1.51
0.16L-
0.00471
0.156
0.0333 to 0.333
0.0655
0.0234 to 0.0585
0.323
0.00911
0.303
unknown
1.89
0.791 to 197
55.87
<0.01
1.55
0.013
<0.01
<0.01
0.036
0.032
0.182
<0.01
0.167
tn
U)
Reduced TLV.
-------
As a result, the population around a source site will be
exposed to differing emission levels. The affected popula-
tion is defined as the population around a site exposed to
a x/AAQS ratio greater than 1.0. (For noncriteria pollutants
the ratio 7/F is used.) The mathematical derivation of the
affected population is presented in Appendix E.
The affected population was calculated for the various emis-
sion points in the barium chemicals industry (Table 21). An
average population density of 21 persons/km2 was used (based
on the four largest manufacturing sites), except for barium
hydroxide production in which case the actual population
densities at the two plant sites were used. Other input
data (Q, h) were identical to those employed in the source
severity calculations.
Since barite preparation is a ground level source (h = 0) , the
severity equation for particulates was solved to find the
distance at which S = 1.0.
For particulates, S = 4/02° Q
D1.81
Using Q = 1.24 g/s for barite preparation, and letting
S = 1.0, then D = 110 m. Since the distance to the plant
boundary is 244 m, the affected area is zero; i.e., no
population is exposed to S >_ 1.0.
-------
Table 27 / SUMMARY OF AFFECTED POPULATION
Emission point
Barite preparation
Black ash rotary kiln
(uncontrolled)
Black ash rotary kiln
(controlled)
H2S incinerator
Dryers and calciners
(uncontrolled)
Dryers and calciners
(controlled)
Barium hydroxide
production
Sherwin-Williams
Barium hydroxide
production
Great Western
Sugar
Emission
Particulates
Particulate
SO
NOX
COX
Hydrocarbons
POM's
Particulate
so,
NO
COX
Hydrocarbons
POM's
SO
X
Soluble
barium
compounds
Soluble
barium
compounds
Particulate
sov
NOX
COX
Hydrocarbons
Particulate
so
NO;;
cox
Hydrocarbons
Stack height,
m
0
(D = 244 m)
32
32
32
32
32
32
23
23
23
23
23
23
37
10.9
10.0
45.7
45.7
45.7
45.7
45.7
18.3
18.3
18.3
18.3
18.3
Q,
g/s
1.24
12.37
30.92
0.742
6.18
0.989
0.00124 to 0.0124
0.495
0.247 to 0.618
0.742
6.18
0.989
unknown
51.8
0.00854 to 2.13
£0.0534
0.0791
64.87
0.127
0.0087
0.0111
0.173
0.216
0.259
2.16
0.345
Population density,
persons/km2
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
24
24
24
24
24
8
8
8
8
8
Affected
area, km2
0
0
1.3
0
0
0
0
0
0
0
0
0
unknown
2.5
0 to 32.8
0.6
0
2.8
0
0
0
0
0
0
0
0
Affected
population ,
persons
0
0
35
0
0
0
0
0
0
0
0
0
unknown
67
0 to 886
18
0
68
0
0
0
0
0
0
0
0
Ul
Ul
-------
SECTION V
CONTROL TECHNOLOGY
The production of barium chemicals involves a number of
process steps that are potential sources of air pollution,
and the industry employs a variety of techniques to reduce
air emissions.
A. BARITE PREPARATION
The two companies that prepare barite on site use different
particulate control techniques. One company has enclosed
part of their operations and filters the exhaust air through
a baghouse. The other company sprays the grinding opera-
tions with water. The emission factor in Section IV
represents a controlled emission, and no data are available
on control efficiencies. The discussion in the previous
section showed that this process has a low environmental
impact (S = 0.24).
B. BLACK ASH ROTARY KILN
Two of the five kilns in the industry are presently controlled
with alkaline scrubbers and two are having baghouses in-
stalled. Plans are underway for placing a control device on
the fifth kiln.1-3 (The rotary kiln at Great Western Sugar,
which produces tribarium silicate, is controlled with an
alkaline scrubber.4) The scrubbers reduce both SO and
56
-------
particulate emissions, while the baghouses control only
particulates. The scrubbers may also lower the NO and hydro-
carbon emissions, but no data are available.
Very little is known about the effect of control devices on
POM emissions. Particulate POM's should be removed by the
same devices (scrubbers, baghouses, electrostatic precipi-
tators) that control other particulates.
The scrubber used by FMC Corporation has a double alkali
scrubbing system (Figure 10). The unit consists of a
vertical column packed with 9 feet of Intalox saddles and a
wire mesh entrainment separator used in series. The absorb-
ent liquor contains a high concentration of active alkali
(Na2S03/NaHS03) and sodium sulfate. Sulfate is formed by
oxidation and dissolved in the liquor. Final separation is
accomplished by a rotary vacuum filter which produces a waste
product containing 50% moisture, CaSO3, dissolved Na^Oi+X
Na2S03, and kiln ash. SO2 removal efficiency is up to 95%
with simultaneous removal of kiln ash.20
The other scrubber system utilizes a packed tower with
countercurrent flow. Control efficiencies have not been
measured, but packed bed scrubbers typically achieve >90%
control of SO and particulates.
20Kaplan, N. An EPA Overview of Sodium-Based Double Alkali
Processes - Part II - Status of Technology and Description
of Attractive Schemes. In: Proceedings: Flue Gas
Desulfurization Symposium-1973. Environmental Protection
Agency. Research Triangle Park. Publication No. EPA-
650/2-73-038. December 1973. p. 1019-1060.
57
-------
en
oo
FILTER VACUUM PUMP
THICKENER
f
--"
THICKENER
y_^i
THICKENER
RECIRCULATION
PUMP
SOLIDS TO LANDFILL
REGENERATION CIRCUIT
PUMP
FILTRATE RETURN
PUMP
Figure 10. FMC double alkali scrutoBer system
1 9
-------
C. H2S INCINERATOR
Hydrogen sulfide is generated when barium sulfide is reacted
with C02 to make barium carbonate or with HCl to make barium
chloride. One manufacturer uses Na2CO3 alone as a precipi-
tating agent and so produces BaCO3 and Na2S instead of H2S.
This process modification eliminates any air pollution
problem, and appears attractive as long as there is a market
for the byproduct Na2S.
In another process modification, the H2S stream is absorbed
in a bath of caustic instead of being incinerated. As in
the previous process, Na2S is a byproduct.
If hydrogen sulfide is not absorbed, it is incinerated to
form S02. This is done to control the foul odor of H2S since
S02 actually has a lower TLV than H2S (13 mg/m3 vs 15 mg/m3).
No control devices are used to lower S02 emissions from the
incinerator.
D. DRYERS AND CALCINERS
Dryers and calciners are equipped with settling chambers or
cyclones to reduce particulate losses. A number of them
(4 out of 10) are also equipped with baghouses, and one is
controlled with a wet scrubber. Producers have installed
baghouses preferentially on the dustiest stacks (i.e., those
exceeding 20% opacity limits), so that all of the stacks are
now reported to meet state standards.
One baghouse showed a collection efficiency of ^95%, which
is below the 99% efficiency generally reported for fabric
filters. It is possible that a small particulate size (
-------
produced as a powder with a range in particle size from
0.1 ym to 10 ym. Efficiencies of other baghouses in the
industry have not been reported.
E. BARIUM HYDROXIDE PRODUCTION
Great Western Sugar Company uses an alkaline scrubber on
their rotary kiln to control particulate and SO emissions,
4&
enabling them to meet state emission standards. The control
efficiencies have not been reported. The scrubber is a
moving-bed type in which mobile plastic spheres are retained
between fixed trays.
Sherwin-Williams Company employs an electrostatic precipitator
to control particulate emissions from their Ba(OH)2 process.
The efficiency is not known, but precipitators can operate
at efficiencies of >99%. This unit does not control SO
X
emissions.
60
-------
SECTION VI
GROWTH AND NATURE OF THE INDUSTRY
A.
TECHNOLOGY
Technology in the barium chemicals industry is stable, the
only recent major development being the production of barium
hydroxide by Sherwin-Williams by a new proprietary process.
Other activity has centered on process refinements to increase
product yield and purity. No new processes are foreseen,
partly because the barium chemicals market has declined over
the past 10 years.
B. INDUSTRY PRODUCTION TRENDS
The production of barium chemicals has suffered an overall
decline since the mid sixties as indicated in Figure 11.5'21~30
160
120
100
BARITE CONSUMPTION
FOR CHEMICALS
OTHER BARIUM
CHEMICALS PRODUCTION\
1940 1945 1950 1955 1960 1965 1970 1975
YEAR
Figure 11. Production level of barium chemicals, 1950-197321~30
61
-------
21Arundale, J. C., and F. M. Barsigian. Barite. In:
Minerals Yearbook 1951. Washington, Bureau of Mines,
1954. p. 186-195.
22Schreck, A. E., and J. M. Foley. Barite. In: Minerals
Yearbook 1956, Volume I: Metals and Minerals. Washington,
Bureau of Mines, 1958. p. 219-229.
23Skow, M. L., and V. R. Schreck. Barite. In: Minerals
Yearbook 1961, Volume I: Metals and Minerals. Washington,
Bureau of Mines, 1962. p. 295-308.
21+Barite. In: Minerals Yearbook 1966, Volume I-II: Metals
Minerals, and Fuels. Washington, Bureau of Mines, 1967.
p. 428-433.
25Eilersten, D. E. Barite. In: Minerals Yearbook 1967,
Volume I-II: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1968. p. 209-215.
26Diamond, W. G- Barite. In: Minerals Yearbook 196,8,
Volume I-II: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1969. p. 189-194.
27Diamond, W. G. Barite. In: Minerals Yearbook 1969,
Volume I-II: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1971. p. 193-198.
28Fulkerson, F. B. Barite. In: Minerals Yearbook 1970,
Volume I: Metals, Minerals, and Fuels. Washington,
Bureau of Mines, 1972. p. 205-210.
29Fulkerson, F. B. Barite. In: Minerals Yearbook 1971,
Volume I: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1973. p. 191-197.
30Current Industrial Report, Inorganic Chemicals 1973.
Washington, U.S. Bureau of the Census, 1975. 28 p.
Data for 1974 and 1975 are not available, but production
apparently continued to fall due to the economic slump. The
decline in production is attributed to the replacement of
barium compounds with materials of superior performance, and
no improvement is forecast in the future.31/32 As a result
3 Chemical Profile: Barium Carbonate. Chemical Marketing
Reporter. 207(13);9, March 31, 1975.
32Barium Chemical Producers See Future Demand Weakness.
Chemical Marketing Reporter. 207(13):21, March 31, 1975,
62
-------
air emissions in the industry are not expected to increase
above current levels.
The major uses (>10% of the total, each) of barium carbonate
are as a chemical intermediate in the production of other
barium compounds, as an ingredient in glass making to increase
optical density and radiation resistance, and as an additive
in brick and ceramic manufacture that removes troublesome
calcium and magnesium sulfates by coprecipitation.6»311 32
Barium chloride serves as a raw material in forming other
barium pigments and as an ingredient in baths used to heat
treat and case harden metals.6
As mentioned earlier, barium hydroxide is used in the re-
fining of sugar from sugar beets. Great Western Sugar
devotes their entire production to this purpose. The hydrox-
ide also acts as a neutralizer in the manufacture of lubri-
cating oil detergents composed of long-chain sulfonated
hydrocarbons. The market in this area has decreased because
the detergents for automobile use have changed to calcium
hydroxide as a neutralizer. However, Ba(OH)2 is still used
in making compounds for trucks and heavy equipment.3'6
Although barium sulfate was once a common white pigment, it
could not compete with titanium oxide and zinc oxide. It
functions now as a pigment extender except for some special
applications such as in photographic paper. In the area of
medicine, barium sulfate plays a role as an x-ray contrast
medium because its insolubility renders it nontoxic.6 In
this case, the compound must be purified to remove any traces
of soluble barium or strontium salts.
Barium chemicals also have a variety of miscellaneous appli-
cations. However, at present there are no new uses which
could spark an increase in production.
,63
-------
SECTION VII
APPENDIXES
A. Calculation of Production Data
B. Emission Calculations
C. Sampling Program
D. Polycyclic Organic Materials
E. Derivation of Source Severity Equations
F. Derivation of Average Distance from a Source
to a Rectangular Plant Boundary
G. Plume Rise Correlation
64
-------
APPENDIX A
CALCULATION OF PRODUCTION DATA3
It was necessary to estimate production data for barium
chemicals because individual companies do not disclose such
information and government reports supply only part of it.
Calculations described in subsequent sections of this Appendix
correspond to the year of 1972.
Historical production statistics, as reported by the Bureau
of Mines, are summarized in Figures A-l to A-5.5r2i-29,33
Only barite consumption, barium carbonate production, and
production of all other barium chemicals are given for
recent years.
1. RAW MATERIAL CONSUMPTION
The Bureau of Mines reports the amount of barite sold for
use in the manufacture of barium chemicals as 105,589 tons
in 1972. Since barite is mixed with coal or coke in a 4:1
ratio in the production of barium chemicals, total raw
material consumption is ^132,000 tons. Consumption is
estimated to be distributed as follows:
Non-metric units are used in this Appendix since that is
the form in which data and information were reported, and
the form in which most of the calculations were made during
this study.
33Harness, C. L., and F. M. Barsigian. Barite. In:
Minerals Yearbook 1946. Washington, Bureau of Mines,
1948. p. 161-173.
65
-------
o
o
o
o
BARITE CONSUMPTION
BARITE CONSUMPTION
50 -
1945 1950 1955 1960 1965 1970 1975
YEAR
Figure A-l. Barite consumption
Consumption for chemicals and lithopone is combined from
1957 to 1972.
66
-------
1945 1950 1955 1960 1965 1970 1975
YEAR
Figure A-2. Production of BaS and BaC03
l/l
o
30
25
20
o 15
§ 10
5
0
Q
O
Qi
Q_
1945 1950 1955 1960 1965 1970
YEAR
Figure A-3. Production of Ba(OH)2 and BaCl2
67
-------
CO
z
O
O
O
Q
O
35
30
25
20
15
10
5
1945 1950
1955 1960 1965
YEAR
1970
Figure A-4. Production of BaSO^ and BaO
LO
O
O
£3
=D
O
O
C£
Q.
20 -
10 -
1945 1950 1955 1960 1965
YEAR
1970 1975
Figure A-5. Production of other barium chemicals'
Data for 1942 to 1948 include pigments made of BaSO^ and
Ti02. Barium sulfate is included from 1959 to 1972; barium
oxide from 1958 to 1972; barium chloride from 1968 to 1972,
and in 1959, and barium hydroxide from 1968 to 1972.
68
-------
Table A-l. ESTIMATED CONSUMPTION OP BARITE RAW MATERIAL
Company
FMC
Chemical Products
Sherwin-Williams
Great Western Sugar
1972 Consumption,
tons
43,000
43,000
43,000
3,000
Great Western Sugar recycles barium carbonate and uses only
enough barite to make up process losses. The other three
companies are estimated to make approximately (±25%) equal
quantities of barium compounds, and estimated consumption
has been apportioned equally among them.
2. BARIUM SULFIDE
The production of BaS from barite at individual plants has
not been calculated in this report since emissions from the
rotary kiln are based on the raw material input. One company
reported that 1.3 Ib of barite yields 1 Ib of BaS; this gives
a total estimated production of ^80,000 tons in 1972.
3. BARIUM CARBONATE
Production data for barium carbonate are published by the
Bureau of Mines and the Department of Commerce (Table A-2).
The 1972 data disagree by 7% and an average figure of
46,000 tons has been chosen.
The quantity actually shipped is only 37,000 tons, or 9,000
tons less than the average figure. A comparison with figures
for other years indicates that this is a consistent difference,
and it is assumed that it reflects captive use by Great Western
Sugar in the production of barium hydroxide.
69
-------
Table A-2. PRODUCTION DATA FOR BARIUM CARBONATE
From Bureau of Mines5'
Chemical
Barium carbonate
Other barium
chemicals
Year
1972
1971
1970
1972
1971
1970
Produced,
tons
44,600
59,600
61,800
38,900
48,400
57,000
28,29
Sold by producers
Quantity,
tons
35,600
46,200
52,500
30,600
36,700
52,500
Value,
$1,000
5,250
5,870
5,960
8,620
9,620
11,000
From Department of Commerce30
Chemical
Barium carbonate
Other barium
chemicals
Year
1973
1972
1971
1970
1973
1972
1971
1970
Total
production,
tons
48,000
47,600
60,500
61,500
Total shipments
Quantity,
tons
35,200
38,700
47,200
44,000
Value,
$1,000
5,750
5,450
5,790
5,060
8,360
8,100
8,450
8,750
Note: Blanks indicate data not reported.
70
-------
The remaining 37,000 tons is apportioned below among PMC,
Sherwin-Williams, and Chemical Products according to their
reported barium carbonate capacity:31
Table A-3. ESTIMATED PRODUCTION OF BARIUM CARBONATE
BY MANUFACTURER
Company
FMC
Sherwin-Williams
Chemical Products
Total
Capacity,
tons/yr
30,000
12,000
15,000
57,000
Estimated 1972
production, tons
19,500
7,800
9,700
37,000
4.
BARIUM CHLORIDE
Barium chloride production is no longer reported separately
by the Bureau of Mines since the compound is only made at
one plant (Chemical Products Corp.). Instead, the production
of all other barium chemicals is reported at 38,900 tons.
Production of BaCl2 was reported by the Bureau of Mines for
1942 through 1967 and it averaged 10,000 tons/yr (±25%). It
was assumed that this level has remained constant, and that
1972 production was also 10,000 tons.
5.
BARIUM HYDROXIDE
Production of barium hydroxide form 1960 to 1967 averaged
20,000 tons/yr (±50%). However, these figures are calculated
on an octahydrate basis. In terms of Ba(OH)2, the production
would be 11,000 tons/yr. Production has declined since 1967
and the estimate for 1972 is 5,500 tons. Great Western Sugar
does not sell its hydroxide; consequently this figure
71
-------
refers solely to Sherwin-Williams. (Reported production and
sales of the hydroxide are identical.)
Production by Great Western Sugar has been calculated from
their use of barium carbonate (9,000 tons/yr). Assuming a
90% yield, the production level of Ba(OH)2 is 8,000 tons/yr.
This is consistent with data from the Bureau of Mines that
show production of other barium chemicals at 38,900 tons but
sales at 30,600 tons, a difference of 8,300 tons.
6. BARIUM SULFATE
Production of barium sulfate averaged 19,000 tons (±80%) from
1942 to 1958, the last year for which figures are available.
However, production declined from 1950 to 1958, and a value
of 6,000 tons was estimated for 1972 production. This has
been apportioned equally between Mallinckrodt and Richardson-
Merrell.
7. OTHER BARIUM CHEMICALS
During the years 1949 to 1957, production data for BaCOa,
BaCl2, Ba(OH)2, BaSO^, and BaO were all reported individually.
(BaO is no longer manufactured in the U.S.) The annual pro-
duction of all other barium chemicals averaged 5,000 tons
(±80%). It has been assumed that this level has declined
since then and that the 1972 production of miscellaneous
barium compounds was under 5,000 tons.
72
-------
APPENDIX B
EMISSIONS CALCULATIONS
1. . COMBUSTION PRODUCTS FROM DRYERS AND CALCINERS
Dryers and calciners are gas fired and emit participates
(barium compounds) and combustion products. Emissions of
combustion products from these units have not been measured;
hence, their magnitude was estimated.
One manufacturer reported that a dryer and calciner manu-
facturing barium carbonate consumed 6,500 ft3 of gas per
ton of product. Emissions data from four gas fired burners
were given in another report (Table B-l) .9 Since no
chemical reactions take place in either case, the same emis-
sion factors should apply to dryers, calciners and burners.
(Because NO formation is temperature dependent, its emis-
X
sion factor may be lower for dryers and calciners.)
Table B-2 lists estimated emissions from the drying and
calcining of BaCOs based on the emission factors in Table
B-l, a fuel usage rate of 6,500 ft3/ton, and the assumption
that 1,000 ft3 of gas have a heating value of one million
Btu.
With the assumption that fuel usage rates are the same for
all barium chemical dryers and calciners, the results show
that total annual emissions from dryers and calciners are
<100 tons.
As a check, the source severity and affected population were
calculated for NO for a plant drying 20,000 tons/yr of
iri.
barium chemicals, with a dryer stack height of 10 m. Source
severity is found to be 0.75 and the affected population (based
on 27 persons/km2) equals 16.
73
-------
Table B-l. EMISSIONS FROM GAS FIRED BURNERS"
Test
15
17
18
19
Average and 95%
confidence
limits
Standard
deviation
Emissions, Ib per million Btu
N0x
0.14
0.35
0.09
0.06
0.16 ± 113%
±0.11
S0x
_a
0
0
a
0
0
CO
0.013
0.020
0.026
0.030
0.022 ± 55%
±0.0064
Hydrocarbon
0.003
a
0.022
0.016
0.014 ± 144
±0.0079
Not reported.
Table B-2. EMISSIONS FROM BaC03 DRYER AND CALCINER
Emission
N0x
S0x
CO
Hydrocarbons
Emission factor,
Ib/ton
1.04 ± 113%
0
0.143 ± 55%
0.091 ± 144%
Total annual emissions
(based on annual production
of 100,000 tons), tons
52
0
7
5
2.
FUGITIVE DUST
The emission rate for fugitive dust emissions was calcu-
lated from the Gifford-Pasquill plume dispersion equation
for a ground level source:19
74
-------
where Q = emission rate, g/s
X = emission concentration, g/m3
u = wind speed, m/s
IT = 3.14
0y' °z = Plume concentration distribution functions
in the y and z directions, respectively
In the coordinate system considered here, the origin is
defined at ground level at the point of emission, with the
x-axis extending horizontally in the direction of the mean
wind. The y-axis is in the horizontal plane perpendicular
to the x-axis, and the z-axis extends vertically. The plume
travels along or parallel to the x-axis.
The values of both a and a are evaluated in terms of the
y z
downwind distance, x, conventionally by graphical methods.
Systems analysts at MRC have fitted curves to these graphs
which give excellent agreement. These continuous functions,
used to calculate values for o and a , are presented in
y z
Tables E-2 and E-3 in Appendix E.
In the case where ground level concentrations (z = 0) are
to be calculated, Equation B-l can be simplified to:
X(x,y,0, = _2__ exp [- i (^ J] (B-2)
And, when the concentration is to be calculated along the
centerline of the plume (y = 0), the equation reduces to:
y z
During the sampling measurements at Plant A, y could not be
determined because the wind direction was variable. In
addition, fugitive emissions were being caused at the plant
75
-------
site by activities other than grinding and mixing, such as
handling and conveying of ore by machinery, equipment in
motion, and the wind blowing dust from ore piles. Therefore,
Equation B-3 (y = 0, z = 0) was used to calculate Q from the
measured values of x- The distance x was measured from the
grinding operation to the sampling site. The results are
given in Table B-3.
Table B-3. FUGITIVE DUST EMISSION RATES
Test
1
2
3
4
5
6
7
8
u,
m/s
10
10
10
10
15
10
15
15
x,
m
490
770
1,050
1,575
2,250
1,950
1,800
660
AX,
pg/m3
440
220
100
0
100
50
90
230
Q, g/s
0.557
0.623
Q.486
0
2.660
0.697
1.644
0.745
The value of AX is the measured concentration minus the up-
wind concentration of 50 yg/m3. Test 4 was dropped because
of its low reading. It is thought that the wind may have
shifted while Test 4 was being run.
The average value of Q is 1.06 g/s and the standard devia-
tion is ±75%. These figures are used as the estimate of
the true emission rate, which could not be computed because
of wind variability and the multiple emission points. Since
the material flow into the kiln was 4.5 tons/hr, the emis-
sion factor for fugitive dust emissions is 1.87 Ib/ton or
2 Ib/ton (±75%).
76
-------
3. N0v FROM THE ROTARY KILN
X
Fuel consumption for the rotary kiln is 4,800 ft3 per ton
of BaS product. From Table B-l, the NO emission factor for
X
gas fired burners is 0.16 Ib/million Btu (±113%). Based on
a heating value of one million Btu per 1,000 ft3, the esti-
mated emission factor is then 0.77 Ib/ton of BaS product
(±113%) .
This value can be converted to Ib/ton of feed material based
on a feed ratio of 4 parts barite to 1 part coal and a
conversion factor of 1.3 Ib barite to 1 Ib BaS (see Appendix
A.I). The estimated emission factor is then 1.0 Ib/ton of
barite (±113%) or 1.25 Ib/ton of feed material (±113%).
4. CO AND HYDROCARBONS FROM THE ROTARY KILN
A stack gas sample from the barium sulfide rotary kiln was
analyzed for CO, total hydrocarbons (THC) , and CHi+ (see
Appendix C). The concentrations found were:
CO: 665 ppm
THC: 191 ppm (expressed as CHi* equivalent)
CH^: 161 ppm
THC less CH4: 30 ppm
Emission factors were calculated based on the average stack
gas flow rate of 13,572 ft3/min (see Table C-l in Appendix C)
and the kiln feed rate of 150 Ib/min.
CO flow rate = (13,572) (0.000665)
= 9.025 ft3/min
= 255.6 liters/min
77
-------
Since 1 g-mole occupies 22.4 liters, this is equivalent to
11.4 moles/min.
The CO mass flow rate is then 0.704 Ib/min, and the emission
factor is 9.4 Ib/ton. The accuracy of this number is not
known since it is only based on one measurement. However,
since CO is not detected by Orsat analysis, the concentra-
tion cannot exceed 1,000 ppm (14 Ib/ton).
The lower limit is unknown, but under good combustion condi-
tions (excess oxygen, good mixing of air and fuel) the CO
level is on the order of 10 ppm. This is equivalent to a
range of 0.1 to 14 Ib/ton in the emission factor. A worst
case error on the emission factor would then be 9.4 Ib/ton
(±100%) .
The emission factor for total hydrocarbons was calculated
in the same way as that for CO, using a molecular weight of
16 (i.e., the molecular weight of CH^). The emission rate
is 0.115 Ib/min and the emission factor 1.54 Ib/ton, of which
1.30 Ib/ton is methane. The error limits are assumed to be
the same as those for CO since they vary in the same way
under differing combustion conditions.
78
-------
APPENDIX C
SAMPLING PROGRAM
1. INTRODUCTION
In order to obtain quantitative data on stack emissions from
the black ash rotary kiln and on fugitive emissions from
barite preparation, a sampling program was undertaken at a
cooperating barium chemicals plant. Stack samples were taken
for polycyclic organic materials (POM's) and particulates
according to a modification of EPA Method 5. A grab sample
of the stack gas was analyzed for CO and hydrocarbon levels.
Finally, fugitive dust measurements were taken upwind and
downwind of the plant with a GCA respirable dust monitor.
2. SAMPLING METHODOLOGY
a. Particulate and POM Sampling
Particulates and POM's were sampled using the modification
of EPA Method 5 shown in Figure C-l. A glass-lined probe
was used with the regular sample train box. The standard
fiber glass filter was replaced with a quartz tissue filter.
A special 30-mm by 100-mm adapter, located in the heated
box along with the filter, contained approximately 6 g of
80- to 100-mesh Tenax GC resin. Quartz wool plugs were used
at both ends of the adapter to contain the resin. Prior to
use, the resin was purged for 24 hours at 500 ml/min with
prepurified helium at 325°C. The sample's flow direction
was marked on the glass so that the collected sample could be
back-flushed from the absorbent with helium prior to analysis.
79
-------
oo
o
FILTER-7 TENAXTRAP
/ /
THERMOMETER
HEATED GLASS
PROBE
CALIBRATED ORIFICE
THERMOMETERS \ ,/, TOLUJ
J^T T_ £^ CONTROL
" fI I VALVES
"^~^ rt>
-------
Three standard and one modified Greenburg-Smith impingers
were used in the system. The U-bend connecting the end of
the absorbent trap to the first impinger was wrapped with
asbestos to prevent premature condensation. The first
impinger contained 100 ml of 10% KOH; the second and third
each contained 100 ml of toluene; and the fourth, the modi-
fied Greenburg-Smith, contained 200 g of 6- to 16-mesh silica
gel.
There were absolutely no greases used on any of the ball
joints or other connections in the system. All ball joints
were covered with Teflon, and extreme care was exercised to
prevent loss of or damage to the Teflon.
The following steps were taken after sampling:
1. The Tenax trap was immediately removed from the
system, its ends were capped and clamped, and it
was placed in a plastic bag. (Parafilm "M" was
used in place of the caps and clamps for 3 runs.)
The bag was flattened to remove as much air as
possible, flushed out with nitrogen and sealed,
then placed under ice in an ice chest.
2. The filter was removed from its holder and care-
fully placed in the petri dish from which it came,
and the top of the dish was loosely taped in place.
The dish was placed in a plastic bag that was
flattened to remove the air, then flushed with
nitrogen, sealed, and placed under ice in an ice
chest.
3. The first impinger was emptied into a properly
labeled 250-ml amber bottle. The impinger was
washed with methylene chloride and the wash added
81
-------
to the impinger contents in the amber bottle. The
bottle was then flushed with nitrogen, sealed, and
placed under ice in an ice chest.
4. The contents of the other three impingers were
treated as described in item 3, each in a separate
bottle.
5. The entire train from the probe tip to the Tenax
trap was rinsed with three portions of methylene
chloride. The size of each portion was as small
as possible. These three rinsings were placed in
one amber bottle that was treated as described in
item 3.
6. The samples were kept in a light-free enclosure
at 0°C, under a nitrogen blanket.
The sampling site and number of traverse points were deter-
mined according to Method 1, Sample and Velocity Traverses
for Stationary Sources.34 The stack velocity, temperature
and pressure were determined by Method 2, Determination of
Stack Gas Velocity and Volumetric Flow Rate.34 Stack gas
composition was determined by Method 3, Gas Analysis for
Carbon Dioxide, Excess Air and Dry Molecular Weight.34
The moisture was assumed to be 4%, based on data obtained
during previous sampling by the company's sampling crew.
34Federal Register. 36 (247):24876-24895, December 23, 1971.
82
-------
The probe heater and oven heater were adjusted to provide a
gas temperature approximately 14°C above the point at which
moisture would condense out. Crushed ice was placed around
the impingers to a level well above that of the solutions in
the impingers. The oven temperature was held as close as
possible to 50°C ±2°C, the ideal working temperature for
Tenax.
Sampling runs were conducted according to Method 5, Deter-
mination of Particulate Emissions from Stationary Sources,34
and the sampling train was leak checked by plugging the inlet
to the filter holder and pulling a vacuum of 15 in. Hg, as
stipulated in Method 5. For the sampling undertaken at
this plant, runs 1 and 2 were done at a single point using
the quartz filter. Runs 3 and 4 were carried out using a
12-point traverse with a regular glass fiber filter so that
a particulate loading could also be obtained while POM's
were being collected.
b. CO and Hydrocarbons
Carbon monoxide and hydrocarbon samples were taken using
gas grab bottles. The grab bottles were evacuated and then
the samples were drawn into them from the stack gas stream.
c. Fugitive Dust Sampling
Fugitive emissions were sampled with a GCA respirable dust
monitor (Model RDM 101). The unit is a portable, self-
contained monitoring device with automatic and direct digital
readout of the mass concentration of airborne dust in mg/m3.
Eight samples were taken downwind of the source, and two
samples were taken upwind of the source for reference. Al-
though the testing was done specifically for the grinding
83
-------
operation, dust emissions from other process operations
may have increased the total amount of dust measured. Visual
observation indicated that grinding was the major (>90%)
source of fugitive dust at the plant.
Figure C-2 shows the approximate location of each sampling
point in relation to the source at plant boundaries, and
the predominant wind direction.
OS
BARITEOREPHf.
O SAMPLING POINT
SOURCE
04
O6
O3
02
O
100
O7 O8 v ^ . 9O.
o •
Figure C-2. GCA sampling locations
3. ANALYSIS OF SAMPLES
a. Particulate and POM Samples From the Rotary Kiln
(1) Preparative Procedure - Samples received from the field
were kept refrigerated until they were analyzed. The samples
consisted of several different impinger and wash solutions,
Tenax, and filters. The fractions were worked up separately
and then combined before final analysis. A flow diagram of
the preparative procedure is shown in Figure C-3.
84
-------
FRONT HALF
BACK HALF
TENAX
EXTRACT IN
SOXHLET
FILT|ERS PROBE WASH TOLUENE & RINSES KOH & RINSES
•PENTANE
EXTRACT ADD PENTANE
IN AND DECANT
SOXHLET
PENTANE
EVAPORATE TO
DRYNESS
i
DISSOLVE IN
PENTANE
SEPARATC
^>
KOH
1
EXTRACT c
PENTANE
SOLVENT
REDUCE TO 5-10 ml
REDUCE TO 5- 10ml
COLUMN CHROMATOGRAPHY
I SO-OCTANE
SAVE
100ml I SO-OCTANE
150 ml BENZENE
50 ml METHANOL /
CHLOROFORM
COLUMN CHROMATOGRAPHY
\
METHANOL /
I SO - OCTANE
BENZENE
DISCARD
SAVE
CHLOROFORM
BENZENE
DISCARD
REDUCET04mlONROTOVAP
PLACE IN VIAL-SUBMIT
TO ANALYTICAL LAB
PRECAUTIONS
REDUCET04mlONROTOVAP
PLACE IN VIAL-SUBMIT
TO ANALYTICAL LAB
EXPOSE SAMPLES TO ONLY YELLOW LIGHT.
EXPOSE SAMPLES TO AS LITTLE OXYGEN AS POSSIBLE.
FLUSH SAMPLES WITH NITROGEN WHENEVER NECESSARY.
KEEP SAMPLES REFRIGERATED UNTIL WORK UP.
WRAP VIAL IN ALUMINUM FOIL TO PROTECT FROM LIGHT.
USE CHEMICALS "DISTILLED IN GLASS" WHENEVER POSSIBLE.
AVOID PHYSICAL CONTACT OF SAMPLE, ESPECIALLY IN CONCENTRATED STATE.
DO NOT USE A TOTAL VACUUM WHEN SAMPLE IS IN THE ROTOVAP.
USE NITROGEN RATHER THAN AIR IN THE ROTOVAP.
Figure C-3. POM sample work-up
85
-------
The filters had been desiccated and weighed before the
sampling effort. To measure the particulate collected in
the four runs, they were again desiccated and weighed on
an analytical balance, and the difference between the weights
is the amount of particulate collected on the filters.
The solvent methylene chloride was used for the probe washes,
which also contained particulate. Each wash was evaporated
under nitrogen in a beaker that had been desiccated and
weighed. The samples were also placed in a desiccator and
then weighed, and the weight difference, again, is the
amount of particulate collected.
For the POM work-up, the filters were placed in a thimble and
extracted with 350 ml of pentane in a Soxhlet extraction
apparatus. The Tenax was also placed in an extraction thimble
and extracted with 350 ml of pentane. The particulate in the
beakers was washed with pentane and the pentane decanted off
to separate the soluble material from the insoluble particu-
late. These three pentane fractions were combined to make
the front half sample.
The toluene portion from the impingers was evaporated to
dryness in a rotovap. The residue was taken back up in
pentane. The KOH solution from the impingers was placed in
a separatory funnel and the aqueous portion was separated
from the solvent. The KOH was extracted with three portions
of pentane. The pentane with the toluene residue, the methylene
chloride from the KOH separation, and the pentane from the
extraction were combined and labeled as the back half sample.
(a) Runs 1 and 4 - The front and back half samples from
runs 1 and 4 were each divided quantitatively into two parts;
one of each was then sent to Battelle Memorial Institute's
(BMI) Columbus Laboratory for analysis. The remaining
86
-------
portions were retained and analyzed at Monsanto Research
Corporation.
Each of the four samples was reduced on a rotovap to
•v5 ml total volume and then processed by Rosen chromatography.
Each sample was put on a column of silica gel and eluted
with a 100-ml portion of isooctane and a 150-ml portion of
benzene. The benzene portion was again reduced to ^5 ml in
the rotovap. This fraction was transferred to a Kuderna-
Danish flask and evaporated to dryness using a stream of N2.
The POM's were then redissolved in 2 ml of methylene chloride
and transferred to a Viton-septum sealed vial. The vial was
covered with aluminum foil and refrigerated until required
for analysis. Just prior to analysis, the sample underwent
one more volume reduction via the Kuderna-Danish method.
The final volume was ^500 yl, the volume size that seems to
be optimum for detecting the POM peaks.
(b) Runs 2 and 3 - All four fractions of runs 2 and 3 were
combined and this sample was sent to Battelle Memorial Insti-
tute (BMI) for work-up and analysis. The concentrated solu-
tion was then returned and the gas chromatographic-mass
spectrometric analysis of this sample was also performed at
MRC. This procedure was followed because the analysis of
runs 1 and 4 indicated low POM levels in run 4. Since the
sampling time for run 1 was about twice that for the other
three runs, samples 2 and 3 were combined for better
resolution.
(2) Analysis - Analysis of the POM's was performed on the
Hewlett-Packard 598OA gas chromatograph-mass spectrometer
(GC-MS) with computer-data system. The gas chromatographic
separation was achieved using a 6-ft Dexil 300 glass column
with temperature programming from 180°C to 280°C at 8°C/min,
87
-------
becoming isothermal at 280°C. The carrier gas was helium at
a flow rate of 30 ml/min.
The mass spectrometer, operating in the electron impact mode,
was programmed to scan the 75-350 AMU range as the POM com-
ponents eluted from the gas chromatograph. The data system
was used to reconstruct the chromatogram using the total ion
mode, while the individual POM mass ions were displayed using
)
the selected ion mode. This provided the ability to identify
POM's by their mass spectra and retention times and to
quantitate the POM's by using the peak area of their mass
ions. Figure C-4 shows the computer printout for a solution
of standards.
Calibration curves were preprared for each POM of interest
using varying concentrations of the POM standards in methy-
lene chloride, plotting mass ion peak area vs. concentration,
and determining response factors if linear. POM peaks in
samples were compared with standard curves that had been
obtained under the same attenuation, injection volume (2 yl),
and tuning conditions.
BMI followed a similar analytical procedure with the samples
sent to them; however, they utilized internal standards
(methyl and phenyl anthracene derivatives) introduced into
the samples prior to processing via a modified Rosen chroma-
tographic separation. Quantitation was attained by relating
response factors to the internal standards compared with a
monthly calibration with POM standards. For runs 1 and 4,
the front and back half samples were combined before analysis.
b. Carbon Monoxide and Hydrocarbons from the Rotary Kiln
Gas samples were analyzed on an F&M Model 810 hydrocarbon
analyzer equipped with an Infrotronics Model CRS-101 inte-
-------
CO
10
DIBENZO'ta.i >& ( a,h ) PYRENES
S-
.DIBENZOTHIOPHENE
ANTHRACENE / PHENANTHRENE
-METHYL ANTHRACENES / METHY
PHENANTHRENE
-9-METHYLANTHRACENE
FLUORANTHENE
PYRENE
• 8EN20 ( o ) PHENANTHRENE
BENZ ( a ) ANTHRACENE / CHRYSENE
7,12 - DIMETHYLBENZ ( a ) ANTHRACENE
BENZO ( b ) FLUORANTHENE
-BENZO ( a ) PYRENE
—3 - METHYLCHOLANTHRENE
DIBENZO(a,h (ANTHRACENE
INDENOI l,2,3-cd)PYRENE
7H-DIBENZO(c,g)CARBAZOLE
O O
O **
i— "O
es P
oo
-------
grator, using helium carrier gas and flame ionization detector,
An unpacked 6 ft x 1/4 in. delay column was used with a
5 in. x 1/16 in. capillary restrictor. Concentrations were
calculated by comparing peak area to calibration standards.
4. CALCULATIONS AND RESULTS
a. Particulates from the Rotary Kiln
Data from the four sampling runs are presented in Table C-l.
The feed rate into the kiln was 150 Ib/min, giving an average
emission factor of 12.5 Ib/ton (±15%).
b. POM's from the Rotary Kiln
The polynuclear organic compounds detected by GC-MS are
listed in Table C-2. Structural formulas are given in
Appendix D. The MRC analysis of runs 1 and 4 showed that
over 95% of the POM's were in the front half of the sampling
train, and the table gives data only from these analyses.
The front and back halves of run 1 were later combined and
rerun.
Emission rates and emission factors for each run are pre-
sented in Table C-3. Rates were calculated from the particu-
late data in Table C-l. Thus, for anthracene/phenanthrene
in run 1, BMI measured 25,000 ng, or 25 yg. Since the
original sample had been split in two, the total weight would
be 50 yg. From Table C-l, a particulate weight of 976.75 nig
corresponded to an emission rate of 56.058 Ib/hr.
It follows that:
976.75 mg v 1 yg
56.058 Ib/hr ^ 26.0327 mg/hr
90
-------
Table C-l. PARTICULATE DATA
ABBR
DESCRIPTION
UNITS
TT
PB
DELH
VM
TM
VMSTD
VW
VWG
PCNTM
MD
C02
02
N2
MWD
MW
DELP
TS
PM
PS
vs
OS
AS
QS
QA
DN
PCTI
MF
MT
CAN
CAO
CAT
CAU
CAW
CAX
DURATION OF RUN
BAROMETRIC PRESSURE
AVG ORIFICE PRESS DROP
VOL DRY GAS(METER CON)
AVG GAS METER TEMP
VOL DRY GAS (STD COND)
TOTAL H20 COLLECTED"
VOL H20 VAPOR(STD CON)
PERCNT MOISTURE BY VOL
MOLE FRACTION DRY GAS
PERCENT C02
PERCENT 02
PERCENT N2
MOL WT OF DRY GAS
MOL WT OF STACK GAS
AVG STACK VELOCITY HEAD
STACK TEMPERATURE
STACK PRESSURE(STATIC)
STACK PRESSURE (ABS)
AVG STACK GAS VELOCITY
STACK DIAMETER
STACK AREA
STACK FLOW RT(DRY STD)
STACK FLOW RT(ACTUAL)
PROBE TIP DIAMETER
PERCENT ISOK1NETIC
PARTICULATE (FRONT)
PARTICULATE (TOTAL)
PARTICULATE (FRONT)
PARTICULATE (TOIAL)
PARTICULATE (FRONT)
PARTICULATE (TOTAL)
PARTICULATE (FRONT)
PARTICULATE (TOTAL)
1INUTES
IN HG
IN H20
DCF
DEG F
DSCF
ML
SCF
IN H20
DEG F
IN H20
IN HG
FPM
INCHES
SO IN
DSCFM
ACFM
INCHES
MG
MG
GR/DSCF
GR/DSCH
GR/ACF
GR/ACh
LB/HR
LB/HR
60.0
29.66
0.974
34.120
114.0
31.26
27.4
1.301
3,99
0.960
1.5
19.2
79.3
29,0
26.6
0.369
363.
-0.20
29.65
2611.
39.50
1225.4
13602.
22212,
0.245
99.7
976.70
976.75
0 «8
36.0
29.50
1.179
19,770
93.0
18,72
16.4
0.778
3.99
0.960
1,5
19,2
79,3
29.0
26.6
0.447
380.
-0.20
29,49
2912,
39,50
1225.4
14784.
24776.
0.245
91.5
616.90
616.90
0.5074
0.5074
0.3025
0.3025
64.292
64.292
30.0
29.50
0,913
15.797
100.7
14.74
12.9
0.613
3,99
0.960
1.5
19,2
79.3
29.0
28.6
0.344
343.
-0.20
29.49
2476.
39.50
1225.4
13157.
21066.
0.245
97,2
425.70
425.70
0,4447
0.4447
0,2775
0.2775
50,137
50,137
30.0
29.50
0.826
14,766
104.7
13.66
12.0
0.569
4.00
0.960
1.5
19.2
79.3
29.0
26.6
0.326
350.
-0.20
29.49
2420.
39.50
1225.4
12744.
20594,
0.245
93.1
439.30
439.30
0.4945
0.4945
0.3056
0.3058
54.010
54.010
-------
Table C-2.
POM CONTENT OF SAMPLES
(nanograms)
ro
Compound
Dibenzothiophene
Anthracene/phenanthrene
Methylanthracene/methylphenanthrene
Fluor anthene
Pyrene
Me thylpyrene/methylf luoranthene
Benzo (c) phenanthrene
Naphthobenzothiophene
Ehrysene/benz (a) anthracene
Methylchrysenes
7 , 12-Dimethylbenz (a) anthracene
Benzof luoranthene
Benzo (a) pyrene
Benzo ( e ) pyrene
Perylene
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo ( g , h , i ) perylene
Dibenz ( a, h) anthracene
7H-Dibenzo (c ,g) carbazole
Dibenzo (a,i) & (a,h).pyrene
Coronene
Barium run 1
MRC9
190,000
350,000
C
c
c
_c
<4,6006
C
42,550
C
<12,5006
C
h?°'i
L _f J
<2,1006
<3,2006
_d
<1,6006
<3,2006
<7,9006
_d
MRC rerun
170,700
310,100
52,400
31,400
12,800
_C
3,300
c
46,200
_c
1,000
34,100
[6,500r
~f J
1,900
4,800
_d
4,400
1,800
3,500
_d
BMI
_b
25,000
7,800
3,500
1,600
1,500
-------
Table C-3. EMISSION RATES AND EMISSION FACTORS
OJ
Compound
Dibenzothiophene
Anthracene/phenanthrene
Methylanthracene/methylphenanthrene
Fluoranthene
Pyrene
Methylpyrene/methylfluoranthene
Benzo (c) phenanthrene
Naphthobenzothiophene
Chrysene/benz (a) anthracene
Methylchrysenes
7 , 12-Dimethylbenz (a) anthracene
Benzof luoranthene
Benzo (a) pyrene
Benzo (e) pyrene
Perylene
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo (g,h,i)perylene
Dibenz (a,h) anthracene
7H-Dibenzo (c ,g) carbazole
Dibenzo (a,i) & (a,h) pyrene
Coronene
Totals
Run 1
Emission rate, mg/hr
MRC
9,892
18,223
a
a
_a
a
<240
a
2,215
_a
<651
_a
f 273bl
^
l-b J
<109
<167
a
<83.3
<167
<390
a
30,603
MRC
rerun
8,888
16,145
2,728
1,635
666
a
172
a
2,405
_a
52
1,775
f338b]
-'
L_b J
98.9
250
_a
229
93.7
182
a
35,658
BMI
a
1,302
406
182
83.3
78.1
<5
a
1,145
120
a
401
41.6
83.3
10.4
146
104
31.2
250
<5
78.1
<5
4,430
Emission factor, mg/kg
MRC
2.423
4.464
a
a
_a
a
<0.0587
a
0.543
_a
<0.159
_a
[0.0670b"|
i ]
<0.0268
<0.0408
_a
<0.0204
<0.0408
<0.0957
_a
7.497
MRC
rerun
2.177
3.955
0.668
0.400
0.163
a
0.0421
_a
0.589
_a
0.0127
0.435
[0.0829b~|
^
-b J
0.0242
0.0612
a
0.0561
0.0230
0.0446
_a
8.734
BMI
_a
0.319
0.0995
0.0446
0.0204
0.0191
<0.001
a
0.280
0.0293
a
0.0982
0.0102
0.0204
0.0026
0.0357
0.0255
0.0076
0.0612
<0.001
0.0191
<0.001
1.085
aNot determined; see Table C-2 for additional information
Total not resolved; combined value for benzo(a)pyrene, benzo(e)pyrene and perylene.
-------
Table C-3 (continued). EMISSION RATES AND EMISSION FACTORS
Compound
Dibenzothiophene
Anthracene/phenanthrene
Methylanthracene/methylphenanthrene
Fluor anthene
Pyrene
Methylpyrene/methy If luor anthene
Benzo (c) phenanthrene
Naphthobenzothiophene
Chrysene/benz (a) anthracene
Methylchrysenes
7,12-Dirnethylbenz (a) anthracene
Benzof luor anthene
Benzo (a) pyrene
Benzo (e) pyrene
Perylene
3-Methylcholanthrene
Indeno (1,2 , 3-cd) pyrene
Benzo (g,h,i) perylene
Dibenz (a,h) anthracene
7H-Dibenzo (c ,g) carbazole
Dibenzo(a,i) &( a, h) pyrene
Coronene
Totals
Run 4
Emission rate, mg/hr
MRC
2,119
4,182
a
a
a
a
<100
a
825
a
<279
a
r "sl
-
L -b J
<22
195
a
256
<33
<84
a
7,833
BMI
a
2,454
747
390
201
100
<11
_a
468
44.6
a
335
44.6
66.9
11.1
<11
<11
<11
<11
<11
<11
<11
4,863
Emission factor, mg/kg
MRC
0.519
1.024
a
a
_a
a
<0.025
_a
0.202
a
<0.068
a .
[O.0628b"|
^
-b J
<0.0055
0.0478
a
0.0628
<0.008
<0.020
a
1.919
BMI
a
0.601
0.183
0.0956
0.0492
0.0246
<0.003
_a
0.115
0.0109
_a
0.0820
0.0109
0.0164
0.0027
<0.003
<0.003
<0.003
<0.003
<0.003
<0.003
<0. 003
1.192
Not determined; see Table C-2 for additional information.
Total not resolved; combined value for benzo(a)pyrene, benzo(e)pyrene and perylene.
-------
Table C-3 (continued). EMISSION RATES AND EMISSION FACTORS
en
Compound
Dibenzothiophene
Anthracene/phenanthrene
Methylanthracene/methylphenanthrene
F luor anthene
Pyrene
Methylpyrene/me thy If luor anthene
Benzo (c) phenanthrene
Naphthobenzothiophene
Chrysene/benz (a) anthracene
Methylchrysenes
7 , 12-Dimethylbenz (a) anthracene
Benzof luoranthene
Benzo (a) pyrene
Benzo (e) pyrene
Perylene
3-Methylcholanthrene
Indeno (1,2, 3-cd) pyrene
Benzo ( g , h , i ) perylene
Dibenz (a,h) anthracene
7H-Dibenzo (c,g) carbazole
Dibenzo(a,i) & (a,h) pyrene
Coronene
Totals
Runs 2 and 3
Emission rate, mg/hr
MRC
2,477
5,800
1,048
1,192
545
a
<12.4
_a
1,078
a
<12.4
a
[ 246bl
-'
1 b 1
1- -^ J
<12.4
177
a
98.3
<12.4
<12.4
_a
12,661e
BMI
a
8,110
1,515
1,923
851
287
49.8
a
1,274
414
a
495
f251dl
L-d J
<50
127
51.0
53.5
<50
<50
<50
<50
15,348
Emission factor, mg/kg
MRC
0.607
1.421
0.257
0.292
0.134
a
<0.0030
a
0.264
a
<0.0030
_a
[O.0604bl
^
h 1
-D J
<0.0030
0.0434
a
0.0241
<0.0030
<0. 0030
a
3.1026
BMI
a
1.986
0.371
0.471
0.208
0.0704
0.0122
a
0.312
0.102
a
0.121
fo.0616d"|
L -d J
<0.012
0.0311
0.0125
0.013J
<0.012
<0.012
<0.012
<0. 012
3.758
Not determined; see Table C-2 for additional information.
Total not resolved; combined value for benzo(a)pyrene, benzo(e)pyrene and perylene.
Combined value for benzo(a)pyrene and benzo(e)pyrene.
p
Values about 20% too low because a portion of the sample was consumed in analysis at BMI.
-------
The emission rate for anthracene/phenanthrene is then
50 x 26.0327 = 1,300 mg/hr.
A comparison of results indicates major (order of magnitude)
differences between runs although duplicate analyses (the
two MRC tests on run 1 and the tests on runs 2 and 3) compare
favorably (within a factor of 2). It appears that the
preparative procedure is responsible for the differences in
the MRC and BMI results for runs 1 and 4. The differences
between the three tests may be caused by fluctuations in
the stack gas and/or variations in the preparative technique.
Total POM emissions for each test are presented in Table C-4.
Table C-4. TOTAL POM EMISSIONS
Run
1
4
2 & 3
Test
MRC (front)
MRC rerun (front
and back)
BMI (both)
MRC (front)
BMI (both)
MRC (front and
back)
BMI (both)
Emission rate,
g/hr
30.6
35.6
4.4
7.8
4.9
12. 7a
15.3
Emission factor,
mg/kg
7.5
8.7
1.1
1.9
1.2
3.1a
3.8
Values about 20% low; see footnote to Table C-3.
96
-------
APPENDIX D
POLYCYCLIC ORGANIC MATERIALS
The polycyclic organic materials (POM's) detected in samples
from the black ash rotary kiln are listed in Table D-l with
their structural formulas and carcinogenicity. The standard
nomenclature is used, but older synonymous names are also
given, in parentheses. Starred (*) compounds indicate dis-
agreement with standard numbering. The carcinogenicity of
each compound is indicated by a simple code:8
- not carcinogenic
± uncertain or weakly carcinogenic
+ carcinogenic
++, +++, ++++ strongly carcinogenic
97
-------
Table D-l. STRUCTURAL FORMULAS AND CARCINOGENICITY OF POM'S
Compound
Dibenzothiophene
Structure
Carcinogenicity
Anthracene
Phenanthrene
Fluoranthene
Pyrene
98
-------
Table D-l (continued). STRUCTURAL FORMULAS AND
CARCINOGENICITY OF POM's
Compound
Methylpyrene
Structure
Carcinogenicity
CH3
Benzo-dibenzothiophene
(Benzothionaphthene)
Benzo(c)phenanthrene
(3,4-Benzophenanthrene)
Benz(a)anthracene
(1,2-Benzanthracene)
Chrysene
(1, 2-Benzophenanthrene).
99
-------
Table D-l (continued). STRUCTURAL FORMULAS AND
CARCINOGENICITY OF POM's
Compound
4-Methylchrysene
Structure
5-Methylchrysene
Carcinogenicity
CH
6-Methylchrysene
7,12-Dimethylbenz(a)anthracene
(9,10-Dimethyl-l,2-benzanthracene)
Benzo(b)fluoranthene
(2,3-Benzofluoranthene)
100
-------
Table D-l (continued). STRUCTURAL FORMULAS AND
CARCINOGENICITY OF POM's
Compound
Structure
Carcinogenicity
Benzo(j)fluoranthene
(7,8-Benzof luoranthene i J^ JL .As.
L^^
Benzo(k)fluoranthene
(8,9-Benzofluoranthrene)
Benzo(ghi)fluoranthene
Benzo(a)pyrene
(1,2-Benzopyrene)
(3,4-Benzypyrene *)
101
-------
Table D-l (continued). STRUCTURAL FORMULAS AND
CARCINOGENICITY OF POM's
Compound
Benzo(e)pyrene
(4,5-Benzopyrene)
(1,2-Benzopyrene*)
Structure
Carcinogenicity
Perylene
3-Methylcholanthrene
CH
Indeno(1,2,3-cd)pyrene
(o-Phenylenepyrene)
102
-------
Table D-l (continued). STRUCTURAL FORMULAS AND
CARCINOGENICITY OF POM's
Compound
Benzo(ghi)perylene
Structure
Dibenz(a,h)anthracene
(1,2-5,6-Dibenzanthracene)
Carcinogenic!ty
Dibenzo(c,g)carbazole
(3,4-5,6-Dibencarbazole)
Anthanthrene
[Dibenzo (cd, jk) pyrene]
103
-------
Table D-l (continued). STRUCTURAL FORMULAS AND
CARCINOGENICITY OF POM's
Compound
Structure
Carcinogenicity
Dibenzo (a,h) pyrene f ^****f v^ ^i
(1,2-6,7-Dibenzopyrene)
(3,4-8,9-Dibenzopyrene*) II II .
CxkJkJ
Dibenzo(a,i)pyrene
(2,3-6,7-Dibenzopyrene)
(4,5-8,9-Dibenzopyrene*)
Coronene
104
-------
APPENDIX E
DERIVATION OF SOURCE SEVERITY EQUATIONS
(T. R. Blackwood and E. C. Eimutis)
1.
SUMMARY OF MAXIMUM SEVERITY EQUATIONS
The maximum severity of pollutants may be calculated using
the mass emission rate, Q, the height of the emissions, H,
or the distance from the source to the nearest plant boundary,
D, and the ambient air quality standard, AAQS, or the thresh-
old limit value, TLV. The equations summarized in Table E-l
are developed in detail in this appendix.
Table E-l. POLLUTANT SEVERITY EQUATIONS
Pollutant
Severity equation
For elevated sources:
Particulate
SO..
NO
x
Hydrocarbon
CO
Other
For ground level sources:
Particulate
70 Q
H2
162 Q
H2
0.78 Q
H2
5.5 Q
TLV-H2
4,020 Q
D1-81
105
-------
2. DERIVATION OF xmax FOR USE WITH U.S. AVERAGE CONDITIONS
The most widely accepted formula for predicting downwind
ground level concentrations from a point source is:18
where x = downwind ground level concentration at reference
coordinate x and y with emission height of H, g/m3
Q = mass emission rate, g/s
a = standard deviation of horizontal dispersion, m
a = standard deviation of vertical dispersion, m
z
u = wind speed, m/s
y = horizontal distance from centerline of dispersion, m
H = height of emission release, m
x = downwind dispersion distance from source of
emission release, m
TT = 3.1416
We assume that \ occurs when x»0 and y = 0. For a given
max
stability class, standard deviations of horizontal and verti-
cal dispersion have often been expressed as a function of
downwind distance by power law relationships as follows:35
ay = axb (E-2)
a = cxd + f (E-3)
Values for a, b, c, d and f are given in Tables E-2 and E-3.
Substituting these general equations into Equation E-l yields:
35Martin, D. 0-, and J. A. Tikvart. A General Atmospheric
Diffusion Model for Estimating the Effects on Air Quality
of One or More Sources. (Presented at 61st Annual Meeting
of the Air Pollution Control Association, for NAPCA,
St. Paul, 1968.) 18 p.
106
-------
x b+d ~ exP ~
ac-rrux + a
[—f 1
|_2(cxa + f)2 J
Assuming that xmax occurs at x<100 m or the stability class
is C, then f = 0 and Equation E-4 becomes:
For convenience, let:
A = Q and B
A and B
so that Equation E-5 reduces to:
-(b+d)
X = ARx ' exp —£| (E-6)
Table E-2. VALUES OF a FOR THE COMPUTATION OF o a'36
Stability class
A
B
C
D
E
F
0.3658
0.2751
0-2089
0.1471
0.1046
0.0722
For the equation
b
a = ax
y
where x = downwind distance
b = 0.9031
o /*
DTadmor, J. and Y. Gur. Analytical Expressions for the
Vertical and Lateral Dispersion Coefficients in Atmos-
pheric Diffusion. Atmospheric Environment. _3_: 688-689,
1969.
107
-------
Table E-3. VALUES OF THE CONSTANTS USED TO
ESTIMATE VERTICAL DISPERSION9'35
Usable range
>1,000 m
100-1,000 m
<100 m
Stability
class
A
B
C
D
E
F
A
B
C
D
E
F
A
B
C
D
E
F
Coefficient
0.00024
0.055
0.113
1.26
6.73
18.05
C2
0.0015
0.028
0.113
0.222
0.211
0.086
0.192
0.156
0.116
0.079
0.063
0.053
2.094
1.098
0.911
0.516
0.305
0.18
d2
1.941
1.149
0.911
0.725
0.678
0.74
0.936
0.922
0.905
0.881
0.871
0.814
-9.6
2.0
0.0
-13
-34
-48.6
f2
9.27
3.3
0.0
-1.7
-1.3
-0.35
0
0
0
0
0
0
For the equation;
a = ex
108
-------
Taking the first derivative of Equation E-6
3 = AP
dx R.
R
dl /
-b-d) x •-*{ (E-7)
and setting this equal to zero (to determine the roots which
give the minimum and maximum conditions of x with respect
to x) yields:
= 0 = AR
dx R
[-2dBRx-2d-b-d] (E-8)
Since we define that x-^0 or °° at x > the following ex-
ma x
pression must be equal to 0:
-2dB_,x~2d-d-b =0 (E-9)
S\
or (b+d)x2d = -2dB (E-10)
or x
X
R
2d ~2dBR 2d H2
b+d 2c2 (b+d)
2d ./LjLHi: \
\c2 (b+d)/
1
or x =i
yc2 (b+d) /
Thus Equation E-2 and E-3 become:
b_
= a H2 2d
/ d H2 \ Id _/d_Hi\2 (E-15)
a — c I - "I I I
z \c2 (b+d)/ \b+d /
109
-------
The maximum will be determined for U.S. average conditions
of stability. According to Slade,37 this is when a = az*
Since b = 0.9031, and upon inspection of Table E-236 under
U.S. average conditions, a = a , it can be seen that
0.881 ^ d -£ 0.905 (class C stability3). Thus, it can be
^
assumed that b is nearly equal to d or:
a = — (E-16)
Z
and
a = - (E-17)
Under U.S. average conditions, a = a and a - c if b = d
and f = 0 (between class C and D, but closer to belonging
in class C).
Then a = — (E-18)
Substituting for a and a into Equation E-l and letting
y = 0:
_ 7 1 /H/I
max
The values given in Table E-3 are mean values for stability
class. Class C stability describes these coefficients and
exponents, only within about a factor of two.
37Gifford, F. A., Jr. An Outline of Theories of Diffusion
in the Lower Layers of the Atmosphere. In: Meteorology
and Atomic Energy 1968, Chapter 3, Slade, D. A. (ed.).
Oak Ridge, Tennessee, U.S. Atomic Energy Commission
Technical Information Center. Publication No. TID-24190.
July 1968. p. 113.
110
-------
or
2 Q
xmax = - - (E-20)
For ground level sources (H = 0) , Xmav occurs by definition
IUQ.X.
at the nearest plant boundary or public access. Since this
occurs when y = 0, Equation E-l becomes:
y z
From the foregoing analysis of U.S. average conditions,
class C stability coefficients are the best first approxi-
mations to U.S. average conditions when a = a .
By letting D equal the distance to the occurrence of
X (see Tables E-2 and E-3) ,
in 3.x
a = 0.209 D°-9031 (E-22)
Y
a = 0.113 D°-911 (E-23)
z
Thus, x is determined as follows:
max
Y = ^2.36 Q (E_24)
max
It will be noted that Equations E-24 and E-20 are identical
with the algebraic substitution of
H2 = 0.01737 D1'814 (E-25)
For U.S. average conditions u = 4.47 m/s so that Equation
E-20 reduces to:
= 0.0524 Q (E-26)
xmax
111
-------
3. DEVELOPMENT OF SOURCE SEVERITY
The general source severity relationship has been defined
as follows:
S = Xmax (E-27)
X = average maximum ground level concentration
where S = source severity
= average maxim
ax ^
F = hazard factor
a. Noncriteria Emissions
The value of x maY t>e derived from x i an undefined
max max
"short term" concentration. An approximation for longer
term concentration may be made as follows:18
For a 24 hour time period,
xmax = xmax -l (E~28)
or
0.17
X = y ( 3 minutes \ (E-29>
*max xmax\1440 minutes/ ^ ^}
xmax = xmax ((K35)
Since the hazard factor is defined and derived from TLV
values as follows:
F = (TLV)
F = (3.33 x 10~3) TLV (E-32)
112
-------
then the source severity, S, is defined as:
X 0.35)
_ Amax _ '
S = -= (E-33)
(3.33 x 1(T3) TLV
105
(E_34>
If a weekly averaging period is used, then:
/ 3 \ 0.17
xmax ~ xmax\10080 ) (E-35)
or
and
F = (2.38 x 10~3)TLV (E-38)
and the source severity, S, is:
xmax _ max (E-39)
F (2.38 x 10~3) TLV
or
105X
TLV
max (E-40)
which is entirely consistent, since the TLV is being
corrected for a different exposure period.
113
-------
Therefore, the severity can be derived from xm=v directly
Hi 3.X
without regard to averaging time for non-criteria emissions.
Thus, combining Equations E-40 and E-26, for elevated source,
gives:
s = 5'5 Q (H-41)
TLV-H2
b. Criteria Emissions
For the criteria pollutants, established standards may be
used as F values in Equation E-27. These are given in
Table H-4. However, Equation E-28 must be used to give the
appropriate averaging period. These equations are developed
for elevated sources using Equation E-26.
i
(1) CO Severity - The primary standard for CO is reported
for a 1-hr averaging time. Therefore,
t = 60 min
t0 = 3 min
/ 3 \ °-17
xmax = xmax 60
? O / ^ \ 0 • 1 7
^-^-(— ) (E-43)
ireuH2 \ 60 /
2 Q
(3.14)(2.72)(4.5) H2
0.052 Q
(0.6) (E-44)
(0.6) (E-45)
114
-------
Table ,E'-4.
SUMMARY OF NATIONAL AMBIENT AIR
QUALITY STANDARDS 3 8
Pollutant
Particulate
matter
Sulfur oxides
Carbon
monoxide
Nitrogen
dioxide
Photochemical
oxidants
Hydrocarbons
(nonmethane)
Averaging
time
Annual (Geometric
mean)
2 4-hour b
Annual (arith-
metic mean)
2 4 -hour5
3-hour b
8-hour
1-hour b
Annual (arith-
metic mean)
l-hourb
3 -hour
(6 to 9 a.m.)
Primary
standards
75 ug/m3
260 yg/m3
80 pg/m3
(0.03 ppm)
365 yg/m3
(0.14 ppm)
-
10 mg/m3
(9 ppm)
40 mg/m3
(35 ppm)
100 yg/m3
(0.05 ppm)
160 yg/m3
(0.08 ppm)
160 yg/m3
(0.24 ppm)
Secondary
standards
60 yg/m3
150 yg/m3
60 yg/m3
(0.02 ppm)
260C yg/m3
(0.1 ppm)
1300 yg/m3
(0.5 ppm)
(Same as
primary)
(Same as
primary)
(Same as
primary)
(Same as
primary)
aThe secondary annual standard (60 yg/m3) is a guide for
assessing implementation plans to achieve the 24-hour
secondary standard.
Not to be exceeded more than once per year.
CThe secondary annual standard (260 yg/m3 ) is a guide for
assessing implementation plans to achieve the annual
standard.
38code of Federal Regulations, Title 42 - Public Health,
Chapter IV - Environmental Protection Agency, Part 410
National Primary and Secondary Ambient Air Quality
Standards, April 28, 1971. 16 p.
115
-------
- = (3.12 x 10"2)Q
max
S = max (E-47)
Setting F equal to the primary standard for CO, i.e.,
0-04 g/m3 yields:
s = Xmax = (3.12 x 10"2)Q
F 0.04 .H*2
or
(EL49)
(2) Hydrocarbon Severity - The primary standard for hydro
carbon is reported for a 3-hr averaging time.
t = 180 min
t0 = 3 min
_ / 3 \ o.17
xmax = *max 180
= (0.5) (0.052)^0
,H2 l
116
-------
For hydrocarbons, F = 1.6 x lQ"k g/m3
and
_ Xmax _ 0.026 Q
« (E-54)
F 1.6 x lO-^H2
or
SHC - Ǥ^ ,K-55,
(3) Particulate Severity - The primary standard for
particulate is reported for a 24-hr averaging time.
- / 3 \ °-17
xmax = xmax T440 (E"56)
= (0.052) Q (0.35) (E-57)
H2
Amax
= (0-0182) Q (E_58)
~u 3
For particulates, F = 2.6 x 10~u g/m
s = _ 0.0182 Q (E-59)
F 2.6 x 10"1* H2
s = Z2_Q (E-60)
P H.2
(4) so Severity - The primary standard for SOx is
reported for a 24-hr averaging time.
117
-------
(0.0182) Q
max
(E-61)
The primary standard is 3.65 x 10-lf g/m3.
and
S =
max = (0.0182) Q
F 3.65 x I0~k H2
(E-62)
or
_n
S°
H2
(E-63)
(5) NO Severity - Since NO has a primary standard with a
...... '"" .............. X ' """"™ ....... ™" ..... " ........ X
1-yr averaging time, the x correction equation cannot be
ITlclX
used. As an alternative, the following equation was selected:
- 2.03 Q
x 0 ux
z
H
exp 2 a
(E-64)
A difficulty arises, however, because a distance x, from
emission point to receptor, is included and hence, the
following rationale is used:
The equation x
max
is valid for neutral conditions or when a -a . This
z y
maximum occurs when
H -
118
-------
and since, under these conditions,
o =
ax
then the distance x where the maximum concentration
ItlaX
occurs is:
max /2a
For class C conditions,
a = 0.113
b = 0.911
Simplifing Equation E-64
n i i T v 0.911
since oz = u.iu xmax
and u = 4 . 5 m/sec
Letting x = x in Equation IE-64,
max
X 1.911
max
JL_\1'098 (E-66)
xmax ~ \O.I6)
= 7.5 H1-098
119
-------
and ___ . - _ - (EL68)
X 1.911 (75 H1.098) 1.911
max \ i .o a. i
= (K085_Q 1Jl «E-69)
p 2
o = 0.113x°-911 (E-70)
z
a =0.113 (7.5 in1-1)0'911 (E-71)
z
oz = 0.71 H (El-72)
Therefore
- = 0.085 Q ^
xmax o i exp| ->••
H2.1
and
- _ 3.15 x 10~2 Q
= °-085 Q (0.371) (E-74)
Since the NO standard is 1.0 x 10 k g/m3, the NO severity
X X
equation is:
, (3.15 x 10-') Q
x 1 x 10-* iH2'1
= 315 Q
2ml
120
-------
4. AFFECTED POPULATION CALCULATION
Another form of the plume dispersion equation is needed to
calculate the affected population since the population is
assumed to be distributed uniformly around the source. If
the wind directions are taken to 16 points and it is assumed
that the wind directions within each sector are distributed
randomly over a period of a month or a season, it can be
assumed that the effluent is uniformly distributed in the
horizontal within the sector. The appropriate equation for
average concentration (x) is then:18
To find the distances at which x/AAQS or x/F = 1-°' roots
are determined for the following equation:
0 =J 2'03 Q exp|- I/—YH- 1.0 (E-79)
U JAAQSazux e p 2\az/ If
keeping in mind that:
a = a x b + c (E-80)
z
where a, b, and c are functions of atmospheric stability
and are assumed to be for stability Class C.
Since equation E-79 is a transcendental equation the roots
are found by an iterative technique using the computer.
For specified emission from a typical source, x/AAQS or x/F
as a function of distance might look as follows:
121
-------
DISTANCE FROM SOURCE
The affected population is then in the area
Ap = .
(E-80)
If the affected population density is D then the total
affected population P is
P = D A (persons)
P P
(E-81)
122
-------
APPENDIX F
DERIVATION OF AVERAGE DISTANCE FROM A SOURCE TO A
RECTANGULAR PLANT BOUNDARY
Consider a rectangular plant boundary of length "a" and
width "b". An emission point is located within it with
coordinates as shown in Figure F-l.
xa
(l-y)b
Figure F-l. Rectangular plant boundary
Here x, y, (1 - x) , and (1 - y) are fractional distances
to the sides.
0 < x, y, (1 - x) , (1 - y) < 1
x + (1 - x) = 1
y = (1 - y) = 1
The average distance from the point to the boundary can be
found from the integral
d6
where R is the distance from the point to the perimeter
of the rectangle.
123
-------
The coordinate system with R and 6 is shown in Figure F-2.
Notice that R is a different function along each side of
the rectangle. The line 6 = 0 is defined to be along the
line segment xa.
RECTANGULAR COORDINATES u AND v
Figure F-2.
Coordinate system for calculating
average distance
124
-------
The expression can then be written as:
2
D = 2>7 / (RI + R2 + RS + Kit) de (F-l)
0
This equation can be transformed into rectangular coordinates
u, v by the substitution:
de = udv - vdu (F-2)
U2 + V2
It becomes:
yb -d ^ x)a
D = I¥.(1^y)bRl x2a2+v2 ^ J *2 Y2b2 + u2
1 t
~ 2V / R
(1 r Y)b
(1 - x)a dv
3 (1 - x)2a2 + v2
yb
xa
" 1 - )b du
The R functions can be defined from Figure F-2 in terms of
u and v:
R = w^a- ->- v2 (F-4)
Kl
R = u2 (F-5)
Rg =N/(1 _ X)2a2 + v2 (F-6)
- y)2b2 + U2 (F-l)
125
-------
This yields:
yb -(1 - x)a
du
° 2^ / r 2TT /
J -^\ 2 2 _L 2
-(1 - y)b x xa
-(1 - y)b
(1 - x)a f dv
/
b V (1 - x)2a2 + v2
xa
, (1 - y)b f du_
2TT /
- y)2b2 + u2 (F-8!
This integral can be evaluated by using:
/du = loge (u + Vu2 + k2 ) (F-9
V u2 + k 2
which gives:
126
-------
D = I¥ loge (v +*
yb
-(1 - y)b
2ir xwye
loge (u + >/ u2 + y2b~2)
-(1 - x)b
xa
- x)a
v
- X)
-(1 - y)b
yb
log
(u WU2 +
xa
(F-10)
-(1 - x)a
This simplifies to:
D = ** log V x2a2 + y2b2 + yb
Vx2a2
- y)b
log
V x2a2 + y2b
+ xa
- x)2a2 + y2b2 - (1 - x)a
~ x)a
-L
- x)2a2 + y2b2 + yb
- x)2a2 + (1 - y)2b2 - (1 - y)b
y)b log V x^a2 + (1 - y)2b2 + xa
- X)a
(F-ll)
127
-------
Example A: Square with edge of 2(= a = b)
Case I - Point at center (x = y = 1/2); xa = yb = 1
= _
2ir
Case II - Point at corner (x = y = 0); xa = yb = 0
(1 - x)a = (1 - y)b = 2
D = -- log = -?- log — = 0.561
e~- 2 * ~
Example B: A rectangle with sides of 4(= a) and 1(= b)
Case I - Point in the center (x = y = 1/2);
xa = (1 - x)a = 2
yb = (1 - y)b = 1/2
D = 0 + 0 + i log V41/4 + 1/2 + 2 1<>g
w 47T e
V4 1/4 - 1/2 V4 1/4 - 2
D = 0.3151 + 0.6668 = 0.982
Case II - Point at corner (x = y = 0); xa = yb = 0
(1 - x)a = 4
(1 - y)b = 1
D = 0 + 0 + log +
77 e 2ir e
- 1 V3T"- 4
D = 0-1575 + 0.3334 = 0.491
128
-------
Example C: Barium plant
xa = 1,750 ft
(1 - x)a = 575 ft
yb = 1,135 ft
(1 - y)b = 175 ft
1/750 lorr 2,085.8 + 1,135 1,135 , 2,085.8 + 1,750
2 IT °9e 1,758.7 - 175 2ir iOge 1,272.3 - 575
, 575 1,272.3 + 1,135 175 , 1,758.7 + 1,750
2TT •Loge 601.0 - 175 2ir xoge 601.0 - 577
D = 197.7 + 308.0 + 158.5 + 136.6 = 800.8 ft (244 m)
129
-------
APPENDIX G
PLUME RISE CORRECTION
The Gaussian plume equation that is used to predict ground
level concentrations contains a factor called the effective
stack height, H. This is equal to the physical stack height
(h) plus the amount of plume rise (AH).
H = h + AH
An exhaust plume rises before dispersal due to its exit
velocity and temperature. In the case of barium chemicals
this is not a significant effect (AH/h <25%).
Plume rise can be estimated from the Holland formula19
V D. / T - T \
AH = -^-^ (1.5 + 2.68 x 10~3p -^= D.)
u \ ^ T i/
where V = stack gas exit velocity, m/sec
s
D. = inside stack diameter, m
u = wind speed, m/sec
p = atmospheric pressure, mb
T • = stack gas temperature, °K
S
T = ambient temperature, °K
3.
Under C class stability conditions AH is increased by a
correction factor of 1.10. The ambient temperature is
taken to be 294°K (70°F), the wind speed 4.5 m/sec, and the
pressure 1,013 mb.
For a black ash-kiln, AH can be determined from the stack
data in Table C-2. Here V =13.2 m/s, d = 1.0 m, and
S
130
-------
T
s
= 455°K. The plume rise is then 7.9 m, compared to the
actual stack height of 38.1 m. The ratio of AH/h is 21%.
Data for dryers and calciners appears in Table G-l.11 For
the rotary dryer and calciner, AH/h is only 2%. The drum
dryer (the only one in the industry) has a larger plume rise
(3.8 m) , but the effective stack height (11.4 m) is close
to the average stack height of 10 m used in calculating
severity, S.
Table G-l. PLUME RISE FOR DRYERS AND CALCINERS
11
Stack
height,
Unit m V , m/sec d, m T , °K AH AH/h
S S
Rotary dryer 11.0 0.31 0.91 497 0.18 0.02
Rotary calciner 11.0 0.79 0.52 443 0.20 0.02
Drum dryer 7.6 24.31 0.40 330 3.8 0.50
131
-------
SECTION VIII
GLOSSARY
BARITE - The ore from which barium chemicals are made; it
is 90% to 95%
BENEFICIATION - Processing of ore by physical means (e.g.,
grinding, washing) to remove impurities.
BLACK ASH - Barium sulfide produced by the reduction of
barite with coal/coke; so called because of its black color.
CALCINING - Heating of barium carbonate to increase its
bulk density; fine particles agglomerate to form larger ones,
CARCINOGEN - A chemical substance which causes cancer in
animals or man.
FUGITIVE DUST - Dust emissions from a process that are not
emitted from a stack or vent.
JIG - A mechanical device used for separating materials of
different specific gravities by the pulsation of a stream
of liquid through the bed of materials; employed in barite
ore benef iciation.
132
-------
LEACHING - Removal of a soluble component, in the form of
a solution, from an 'insoluble solid phase with which it is
associated.
LITHOPONE - A white pigment made of BaSO^ and ZnS.
ORSAT ANALYSIS - A technique for measuring the composition
of an exhaust gas by differential absorption of the com-
ponents.
PETROLEUM COKE - The solid residue remaining from the re-
fining of petroleum.
POLYNUCLEAR ORGANIC MATERIALS - Aromatic ring compounds
containing three or more rings; some POM's [e.g., benzo(a)-
pyrene] are known carcinogens.
ROTARY KILN - A high temperature process furnace lined with
refractory material; it is an inclined cylinder that rotates
on its axis.
133
-------
SECTION IX
REFERENCES
1. Personal communications. J. L. Gray and R. E.
Kotteman, Jr. Chemical Products Corp., Cartersville,
Georgia.
2. Personal communications. R. Brown. FMC Corp.,
Modesto, California.
3. Personal communications. J. J. Nilles and R. W.
Hellon. Sherwin-Williams Co., Coffeyville, Kansas.
4. Personal communications. D. Muller. Great Western
Sugar Co., Johnstown, Colorado.
5. Fulkerson, F. B. Barite. In: Minerals Yearbook 1972,
Volume I: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1974. p. 181-187.
6. Preisman, L. Barium Compounds. In: Kirk-Othmer
Encyclopedia of Chemical Technology, Second Edition.
Vol. 3, Standen, A. (ed.). New York, Interscience
Publishers, Division of John Wiley & Sons, Inc.,
1964. p. 80-99.
7. Dahlberg, H. W., and R. J. Brown; revised by W. Newton,
II, and M. G. Auth. The Barium Saccharate Process.
In: Beet-Sugar Technology, Second Edition, McGinnis,
R. A. (ed.). Fort Collins, Colorado, Beet Sugar
Development Foundation, 1970. p. 573-578.
8. Particulate Polycyclic Organic Matter. Washington,
National Academy of Sciences, 1972. 361 p.
9. Hangebrauch, R. P., D. J. Von Lehmden, and J. E. Meeker.
Emissions of Polynuclear Hydrocarbons and Other Pollu-
tants from Heat-Generation and Incinerator Processes.
Journal of the Air Pollution Control Association.
L4:267-278, July 1964.
134
-------
10. The Toxic Substances List 1974 Edition, Christensen,
H. E., and T. T. Luginbyhl (ed.). Rockville, Maryland,
U.S. Department of Health, Education and Welfare,
June 1974. 904 p.
11. Ppint Source Listing for Inorganic Pigments, SSC
3-01-035, National Emission Data System. Environ-
mental Protection Agency. Research Triangle Park.
August 1974.
12. TLV's® Threshold Limit Values for Chemical Substances
and Physical Agents in the Workroom Environment with
Intended Changes for 1975. American Conference of
Governmental Industrial Hygienists. Cincinnati. 1975.
97 p.
13. Pendergrass, E. P., and R. R. Greening. Baritosis.
Archives of Industrial Hygiene and Occupational
Medicine. 7_:44-48, 1953.
14. Willson, J. K. V., P. S. Rubin, and T. M. McGee.
The Effects of Barium Sulfate on the Lungs. American
Journal of Roentgenology, Radium Therapy and Nuclear
Medicine. £2:84-94, July 1959.
15. Gleason, M. N., R. E. Gosselin, and H. C. Hodge.
Clinical Toxicology of Commercial Products. Baltimore,
The Williams & Wilkins Co., 1957. p. 28-29, 120-121.
16. Barium and Its Inorganic Compounds. American Industrial
Hygiene Association Journal. 2_3_: 517-518, November-
December 1962.
17. Effect of Barium Carbonate Fumes on Respiratory Tract.
Journal of the American Medical Association. 117;1221,
1941.
18. 1972 National Emissions Report. Environmental Pro-
tection Agency. Research Triangle Park. Publication
No. EPA-450/2-74-012. June 1974. 422 p.
19. Turner, D- B. Workbook of Atmospheric Dispersion
Estimates, 1970 Revision. U.S. Department of Health.
Education, and Welfare. Cincinnati. Public Health
Service Publication No. 999-AP-26. May 1970. 84 p.
20 Kaplan, N. An EPA Overview of Sodium-Based Double
Alkali Processes - Part II - Status of Technology and
Description of Attractive Schemes. In: Proceedings:
Flue Gas Desulfurization Symposium-1973. Environmental
Protection Agency. Research Triangle Park. Publication
No. EPA-650/2-73-038. December 1973. p. 1019-1060.
135
-------
21. Arundale, J. C., and F. M. Barsigian. Barite. In:
Minerals Yearbook 1951. Washington, Bureau of Mines,
1954. p. 186-195.
22. Schreck, A. E., and J. M. Foley. Barite. In: Minerals
Yearbook 1956, Volume I: Metals and Minerals. Washing-
ton, Bureau of Mines, 1958. p. 219-229.
23. Skow, M. L., and V. R. Schreck. Barite. In: Minerals
Yearbook 1961, Volume I: Metals and Minerals. Washing-
ton, Bureau of Mines, 1962. p. 295-308.
24. Barite. In: Minerals Yearbook 1966, Volume I-II:
Metals, Minerals, and Fuels. Washington, Bureau of
Mines, 1967. p. 428-433.
25. Eilertsen, D. E. Barite. In: Minerals Yearbook 1967,
Volume I-II: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1968. p. 209-215.
26. Diamond, W. G- Barite. In: Minerals Yearbook 1968,
Volume I-II: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1969. p. 189-194.
27. Diamond, W. G. Barite. In: Minerals Yearbook 1969,
Volume I-II: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1971. p. 193-198.
28. Fulkerson, F. B. Barite. In: Minerals Yearbook 1970,
Volume I: Metals, Minerals, and Fuels. Washington,
Bureau of Mines, 1972. p.' 205-210.
29. Fulkerson, F. B. Barite. In: Minerals Yearbook 1971,
Volume I: Metals, Minerals and Fuels. Washington,
Bureau of Mines, 1973. p. 191-197.
30. Current Industrial Report, Inorganic Chemicals 1973.
Washington, U.S. Bureau of the Census, 1975. 28 p.
31. Chemical Profile: Barium Carbonate. Chemical Marketing
Reporter. 207(13);9, March 31, 1975.
32. Barium Chemical Producers See Future Demand Weakness.
Chemical Marketing Reporter. 207(13);21, March 31, 1975.
33. Harness, C. L. , and F. M. Barsigian. Barite. In:
Minerals Yearbook 1946. Washington, Bureau of Mines,
1948. p. 161-173.
34. Federal Register. 3^(247):24876-24895, December 23, 1971,
136
-------
35. Martin, D. 0., and J. A. Tikvart. A General Atmospheric
Diffustion Model for Estimating the Effects on Air
Quality of One or More Sources. (Presented at 61st
Annual Meeting of the Air Pollution Control Association,
for NAPCA, St. Paul, 1968.) 18 p.
36. Tadmor, J. and Y. Gur. Analytical Expressions for the
Vertical and Lateral Dispersion Coefficients in Atmos-
pheric Diffusion. Atmospheric Environment. 3:688-689,
1969.
37. Gifford, F. A., Jr. An Outline of Theories of Diffusion
in the Lower Layers of the Atmosphere. In: Meteorology
and Atomic Energy 1968, Chapter 3, Slade, D. A. (ed.).
Oak Ridge, Tennessee, U.S. Atomic Energy Commission
Technical Information Center. Publication No. TID-24190.
July 1968. p. 113.
38. Code of Federal Regulations, Title 42 - Public Health,
Chapter IV - Environmental Protection Agency, Part 410
National Primary and Secondary Ambient Air Quality
Standards, April 28, 1971. 16 p.
137
-------
TECHNICAL REPORT DATA
(Please read Instructions on the rtvene before completing)
1. REPORT NO.
EPA-60Q/2-78-004b
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
SOURCE ASSESSMENT:
6. REPORT DATE
March 1978 issuing date
MAJOR BARIUM CHEMICALS
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R. B. Reznik and H. D. Toy, Jr.
I. PERFORMING ORGANIZATION REPORT NO
10. PROGRAM ELEMENT NO.
1AB604
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
11. CONTRACT/GRANT NO.
68-02-1874
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory - Cin., OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/ 600/12
IS. SUPPLEMENTARY NOTES
19. ABSTRACT
This report summarizes data on air emissions from the production of major
barium chemicals. Compounds studied include barium sulfide, barium car-
bonate, barium chloride, barium hydroxide, and barium sulfate. In order
to evaluate potential environmental effects the source severity, S, was
calculated for each emission species from each emission point. Severity
is defined as the ratio of the average maximum ground level concentration,
Xjnax' to the ambient air quality standard (for criteria pollutants) or to
a reduced TLV (for noncriteria pollutants). The highest values of S
occurred for sulfur oxide emissions from the H2S incinerator (1.89), the
black ash rotary kiln (1.51), and the barium hydroxide process exhaust
(1.6), and for emissions of soluble barium compounds from product dryers
and calciners (0.79 to 200). Various control devices are used to reduce
emissions. Scrubbers and baghouses are used on the black ash rotary kiln
and on product dryers and calciners. A scrubber and an electrostatic
precipitator are employed to control the exhaust from the barium
hydroxide process. Byproduct H2S may be absorbed in caustic instead of
being incinerated.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Air Pollution
Assessments
b.lDENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
Source Assessment
Source Severity
c. COSATI Field/Group
68A
8. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (Thti Report)
Unclassified
21. NO. OF PAGES
153
20. SECURITY CLASS (Thttpage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
138
* U.S. GOVERNMENT PRINTING OFFICE: 1978—260-880/43
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