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

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                         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.

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                             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

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                           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

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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.

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                          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).

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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.

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                         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

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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.

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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

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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.

-------
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

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        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

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                                       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

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                          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

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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

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                    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

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                         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

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           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

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                 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

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            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

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 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

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      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

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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

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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

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                         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

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        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

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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

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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

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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

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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

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                         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

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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

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          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

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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

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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

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                         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 - «§^                    ,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

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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

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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

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                         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

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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

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                        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

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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

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                        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

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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

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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

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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

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                               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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