United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
EPA-eOO/2-78-004p
June 1978
Research and Development
Source Assessment:
Chemical and
Fertilizer Mineral
Industry,
State  of the Art

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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~600/2-78-004p
                                            June 1978
             SOURCE ASSESSMENT:
  CHEMICAL AND FERTILIZER MINERAL INDUSTRY
              State of the Art
                     by

      J. C. Ochsner and T. R. Blackwood
        Monsanto Research Corporation
             Dayton, Ohio  45407
           Contract No.  68-02-1874
               Project Officer

   *         S. Jackson  Hubbard
  Resource Extraction and Handling Division
Industrial Environmental  Research Laboratory
           Cincinnati,  Ohio  45268
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 Environmental
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 constitute endorsement or
recommendation for use.
                               11

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                           FOREWORD
     When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our
environment and even on our health often require that new and
increasingly more efficient pollution control methods be used.
The Industrial Environmental Research Laboratory - Cincinnati
(IERL-Ci) assists in developing, and demonstrating new and
improved methodologies that will meet these needs both effi-
ciently and economically.

     This report contains an assessment of air emissions and
water pollutants from the chemical and fertilizer mineral indus-
try.  This study was conducted to provide a better understanding
of the distribution and characteristics of emissions and efflu-
ents from this source.  Further information on this subject may
be obtained from the Extraction Technology Branch, Resource
Extraction and Handling Division.
                                   David G- Stephan
                                       Director
                     Industrial Environmental Research Laboratory
                                      Cincinnati
                               111

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                             PREFACE


The Industrial Environmental Research Laboratory  (IERL) of the
U.S. Environmental Protection Agency  (EPA) has the responsibility
for insuring that pollution control technology is available for
stationary sources to meet the requirements of the Clean Air Act,
the Federal Water Pollution Control Act, and solid waste legisla-
tion.  If control technology is unavailable, inadequate, or
uneconomical, then financial support is provided for the develop-
ment of the needed control techniques for industrial and extrac-
tive process industries.  Approaches considered include process
modifications, feedstock modifications, add-on control devices,
and complete process substitution.  The scale of the control
technology programs ranges from bench- to full-scale demonstra-
tion plants.

IERL has the responsibility for developing control technology for
a large number of operations (more than 500) in the chemical and
related industries.  As in any technical program, the first step
is to identify the unsolved problems.  Each of the industries is
to be examined in detail to determine if there is sufficient
potential environmental risk to justify the development of con-
trol technology by IERL.

Monsanto Research Corporation (MRC) has contracted with EPA to
investigate the environmental impact of various industries that
represent sources of pollutants in accordance with EPA's respon-
sibility, as outlined above.  Dr. Robert C. Binning serves as MRC
Program Manager in this overall program, entitled "Source Assess-
ment," which includes the investigation of sources in each of
four categories:  combustion, organic materials, inorganic materi-
als, and open sources.  Dr. Dale A. Denny of the Industrial
Processes Division at Research Triangle Park serves as EPA Proj-
ect Officer for this series.  Reports prepared in this program
are of two types:  Source Assessment Documents and State-of-the-
Art Reports.

Source Assessment Documents contain data on pollutants from
specific industries.  Such data are gathered from the literature,
government agencies, and cooperating companies.  Sampling and
analyses are also performed by the contractor when the available
information does not adequately characterize the source pollut-
ants. These documents contain all of the information necessary
for IERL to decide whether a need exists to develop additional
control technology for specific industries.
                               IV

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State-of-the-Art Reports include data on pollutants from specific
industries which are also gathered from the literature, govern-
ment agencies, and cooperating companies.  However, no extensive
sampling is conducted by the contractor for such industries.
Sources in this category are considered by EPA to be of insuffi-
cient priority to warrant complete assessment for control technol-
ogy decision making.  Therefore, results from such studies are
published as State-of-the-Art Reports for potential utility by
the government, industry, and others having specific needs and
interests.

This study was undertaken to provide information on air emissions
and water pollutants from the chemical and fertilizer mineral
industry.  The work was performed for the Extraction Technology
Branch, Resource Extraction and Handling Division,  Industrial
Environmental Research Laboratory, Cincinnati.  Mr. S.  Jackson
Hubbard served as EPA Task Officer.

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                            ABSTRACT


This report describes a  study of air 'and water pollutants emitted
by the chemical and  fertilizer mineral industry.  The potential
environmental effect of  the source was evaluated using a hazard
ratio  (defined as the ratio of the maximum time-averaged ground
level concentration  to an ambient air quality standard for air
and the ratio of discharge rate to a water quality criteria for
water).

Air and water pollutants are generated during the conversion of
naturally occurring  minerals into suitable forms for use in
chemical and fertilizer  production.  These minerals are barite,
borates, fluorspar,  lithium minerals, mineral pigments, phosphate
rock, potash, salt,  sodium sulfate, sulfur, and trona ore.  The
representative plant size for each mineral, except borates, was
determined by dividing the total annual production by the number
of plants.  (In the  case of borates, one plant which accounts for
over 75% of annual production was considered representative.)

The emission factor  for  respirable particulates emitted from the
representative source ranges from 0.02 g/metric ton for sulfur to
110 g/metric ton for potash.  The hazard ratio for respirable
particulates emitted from the representative source ranges from
0.00005 for sulfur to 0.9 for potash.  Total particulate emis-
sions from the production of chemical and fertilizer minerals
contribute 0.2% of the national emissions burden.

Hazard ratios for water pollutants were developed only for the
phosphate rock industry as it was the only industry for which
complete information was available concerning river flow rate and
concentration.  For  a representative source, the hazard ratios of
elemental phosphorous, fluoride, and total suspended solids (TSS)
are 0.061, 0.051, and 0-0025,  respectively.

The four significant wastewater problem areas in the mining and
beneficiation of minerals in the chemical and fertilizer industry
are mine water drainage,  wastewater from the fluorspar industry,
phosphate rock slimes, and sulfur bleedwater brines.  The Florida
phosphate rock slimes problem may well be the most important of
all fertilizer production problems.  Suspended solids are the
principal pollutant in chemical and fertilizer wastewater dis-
charges.  While a variety of treatment technologies are available
for removing suspended solids, only a small number are widely
                               VI

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used.  The unlined settling pond is the most widely used form of
control technology.

This report was submitted in partial fulfillment of Contract
68-02-1874 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency.  This report covers
the period October 1976 to August 1977, and work was completed as
of March 1978.
                              Vll

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                            CONTENTS
Foreword	iii
Preface	iv
Abstract	vi
Figures	xi
Tables	xiii
Abbreviations and Symbols 	 xiv
Conversion Factors and Metric Prefixes. .... 	  , .xv

   1.  Introduction 	 1
   2.  Summary	3
   3.  Source Description 	 8
            Process description 	 8
            Source types	9
   4.  Emissions	39
            Selected pollutants	39
            Emission characteristics	 .40
            Definition of the representative source	50
            Hazard ratio	50
   5.  Control Technology	52
            State of the art—air pollution control
              technology	52
            State of the art—water pollution control
              technology	53
   6.  Growth and Nature of the Industry	57
            Barite	57
            Boron	«... 58
            Fluorspar	59
            Lithium minerals	60
            Phosphate rock	  . .60
            Potash	61
            Salt	,63
            Sodium sulfate	63
            Sulfur	 .66
            Trona ore	66

References	70
Appendices

   A.  Principal producers and their geographical distribution.74
   B.  Emission factor estimates for mining and beneficiation
         operation	85
   C.  State particulate emission burdens from the production
         of specific materials	92
                               IX

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                      CONTENTS (continued)


                                                               93
   D.  Major wastewater problem areas 	
   E.  Hazard ratio calculations	•	
   F.  Effluent concentrations for various minerals at
         various sites	,Qg
   G-  Sampling and analytical methodology	• • • •  •
   H.  Sampling mechanics and individual field test data. .  . J.J.U

Glossary	
                                 x

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                             FIGURES

Number                                                       Page
   1    Barite, fluorspar, phosphate rock, lithium minerals,
          and mineral pigments	8
   2    Brine minerals:  borax, natural soda ash, lithium
          salts, salt, and potash	8
   3    Rock salt and trona ore	9
   4    Sulfur  (the Frasch hot water process)	9
   5    Barite beneficiation (wet process)	12
   6    Barite beneficiation (dry grinding process) 	 13
   7    Barite benef iciation (flotation process)	14
   8    Borate benef iciation (Boron, California)	16
   9    Flowsheet for the production of anhydrous borax at
          Searles Lake, Trona,  California, by American
          Potash & Chemical Corp	17
  10    Fluorspar beneficiation (HMS process) 	 19
  11    Fluorspar beneficiation (froth flotation)  	 20
  12    Spodumene beneficiation (flotation process) 	 21
  13    Lithium salt recovery (natural brine, Silver Peak
          operations)	21
  14    Mineral pigment beneficiation 	 22
  15    Location of Florida phosphate deposits	25
  16    Phosphate rock beneficiation (eastern process).... 26
  17    Phosphate rock beneficiation (western process).... 26
  18    Potassium chloride beneficiation from sylvinite ore  . 29
  19    Langbeinite beneficiation 	 30
  20    Potash recovery by solution mining of sylvinite ore  . 30
  21    Minerals recovery at Great Salt Lake	31
  22    Rock salt mining and beneficiation	32
  23    Sodium sulfate from brine wells 	 33
  24    Cross section of a typical sulfur-bearing salt dome  . 35
                               XI

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                       FIGURES  (continued)

Number                                                       Pag<
  25    The Frasch process	35
  26    Sulfur mining and beneficiation 	 36
  27    Trona ore beneficiation (sodium sesquicarbonate
          process	.37
  28    Trona ore beneficiation (monohydrate process) .... 37
  29    Searles Lake minerals recovery	38
  30    Selected phosphate rock sources 	 42
  31    Particle size distribution of phosphate rock dryer
          dust	43
  32    Production trend of barite in the United States ... 58
  33    Production trend of boron in the United States. ... 59
  34    Production trend of fluorspar in the United States.  . 60
  35    Demand for phosphate rock in the United States. ... 62
  36    Production trend of phosphate rock in the United
          States	62
  37    Demand trend for potash in the United States	64
  38    Production trend for potash in the United States. .  . 64
  39    Demand trend for salt in the United States	65
  40    Production trend for salt in the United States. ... 65
  41    Demand trend for sodium sulfate in the United States. 67
  42    Production trend for sodium sulfate in the United
          States	67
  43    Consumption trend of Frasch sulfur in the United
          States. .	68
  44    Production trend for Frasch sulfur in the United
          States	68
  45    Demand for soda ash in the United States	69
  46    Production trend for soda ash in the United States.  . 69
                               XII

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                             TABLES

Number                                                       Pag(
   1    Salient Features of the Chemical and Fertilizer
          Mineral Industry	4
   2    Chemical and Fertilizer Minerals Production and
          Population Densities by State 	 10
   3    Chemical Analysis of Average Barite Ore 	 11
   4    Potash Minerals 	 28
   5    Typical Minerological Analysis of Potash Ore of
          Carlsbad, New Mexico	28
   6    Production and Particulate Emission Data for the
          Chemical and Fertilizer Mineral Industry	41
   7    Air Emission Sources of Phosphate Rock Mining and
          Beneficiation 	 41
   8    New Mexico Potash Particulate Emission Data 	 44
   9    Hazard Ratio Calculations 	 51
  10    Control Technology and Its Use for Removal of
          Suspended Solids	55
  11    Performance of Treatment Systems	56
                              Xlll

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                    ABBREVIATIONS AND SYMBOLS
CD         — concentration of the discharge
D          — representative distance from the source
Dsp        — distance from plant at which hazard ratio equals  0.1
F          — hazard factor  (ambient air quality standard)
HMS        — heavy media separation
LC50       — lethal concentration which causes 50% mortality in
              the test species
mi, m2     — slopes used in calculating distances to samplers
NIOSH      — National Institute of Occupational Safety and
              Health
NO         — nitrogen oxides
  X
Q          — representative mass emission rate
Sa         — hazard ratio for air
 A
Sp         -- hazard ratio for respirable particulates
SI7         — hazard ratio for water effluent
 w
so,i, 2,3,1* — high-volume sampler locations
TLV        — threshold limit value
u          — average wind speed
V          — volumetric flow rate of river discharge
¥„         — volumetric flow rate of the river
 I\
x., y.      — Cartesian coordinates used to relate position of
              ith sampler to the source
X., Y.      — downwind and lateral distance, respectively, from
 1            source along the dispersion centerline
0          -- angle of mean wind speed
IT          -- 3.1416
a          — standard deviation in the horizontal of the plume
 •^            concentration distribution
a          -- standard deviation in the vertical of the plume
              concentration distribution
Y          -- maximum time-averaged downwind concentration
 max
                               xiv

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             CONVERSION FACTORS AND METRIC PREFIXES3
                       CONVERSION FACTORS

  To convert from	To	Multiply by

Degree Celsius  (°C) Degree Fahrenheit          top = 1.8 toc + 32
Kilogram (kg)       Ton  (short, 2,000 Ib mass)       1.102 x 10~3
Kilogram (kg)       Pound-mass (avoirdupois)                2.204
Kilometer2  (km2)    Mile2                            3.860 x 10"1
Meter  (m)           Foot                                    3.281
Meter2 (m2)         Foot2                             1.076 x 101
Meter3 (m3)         Gallon (U.S.  liquid)              2.642 x 102
Meter3 (m3)         Foot3                             3.531 x 101
Metric ton          Pound-mass                        2.205 x 103
Radian (rad)        Degree                            5.730 x 10l


                            PREFIXES

 Prefix   Symbol   Multiplication factor   	Example	

  Kilo      k              103             1 kg = 1 x 103 grams
  Milli     m              10~3            1 mm = 1 x 10~3 meter
  Micro     y              10~6            1  g = 1 x 10~6 gram
 Metric Practice Guide.  ANSI/ASTM Designation:  E 380-76e,
 IEEE Std 268-1976, American Society for Testing and Materials,
 Philadelphia, Pennsylvania, February 1976.  37 pp.
                               xv

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                            SECTION 1

                          INTRODUCTION
The conversion of naturally occurring mineral deposits into chem-
icals and fertilizers involves surface and underground mining and
a variety of beneficiation steps.  Air and water pollution is
produced by individual sources (unit operations) during mining,
processing, and material transfer activities.

An investigation of the chemical and fertilizer mineral industry
was conducted to provide an understanding of the distribution and
characteristics of the air pollution emissions and wastewater
effluents.  Data collection emphasized the accumulation of suffi-
cient information to ascertain the need for developing control
technology.

Information came from the literature, federal and state environ-
mental agencies, and personal contacts with industry.

This document contains information on:

   • Emission sources and composition.

   • Geographical distribution and production figures
     for the minerals under study.

   • Air emission levels as obtained by direct sampling
     for the phoshate ro.ck and potash industries.

   • A method to estimate the air emission levels due to
     chemical and fertilizer mineral unit operations.

   • Wastewater effluent concentrations and characteristics.

   • Hazard ratios of air emissions and wastewater effluents.

   • Types of control technology used and proposed for air
     and water pollutants.

   • Trends in the demand and production of chemical and
     fertilizer minerals.

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Particular attention is paid to the phosphate rock industry due
to its predominant size in relation to other mineral productions,

Items of special interest to the reader may be Sections 4_and 5,
Emissions and Control Technology.  In addition,  a discussion of
major wastewater problem areas is given in Appendix D.

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                            SECTION 2

                             SUMMARY
The chemical and fertilizer mineral industry converts naturally
occurring minerals into forms suitable for use in chemical and
fertilizer production.  During this conversion, air and water
pollutants are generated.  The minerals are barite, borates,
fluorspar, lithium minerals, mineral pigments, phosphate rock,
potash, salt, sodium sulfate, sulfur, and trona ore.  The purpose
of this document is to aid the U.S. Environmental Protection
Agency in determining the need to develop new control technology
for the industry, with particular emphasis on the future.

The chemical and fertilizer mineral industry is necessary to our
national well-being, particularly with its basic tie-in to food
production.  J?or example, over 90% of the phosphate produced in
Florida is used in agriculture.

Table 1 presents some important features of the industry which
will be referred to in the subsequent discussion.

For each mineral, except borates, the representative plant size
given in Table 1 was determined by dividing the total annual
production by +-hg m11™^1" of plants^(In the case of borates, one
plant which accounts for over 75% of annual production was con-
sidered representative.)  Of course the actual size of plants in
an industry may vary considerably.  The representative plant size
is an average value used to determine a representative mass
emission rate.

Other important features to note:

   • Chemical and fertilizer mineral operations are typically
     conducted in relatively isolated regions where the popu-
     lation density is usually less than 50 persons/km2.

   • The combined annual production for 7 of 11 minerals
     accounts for only 7% of the total chemical and fertil-
     izer mineral industry.

   • The major air jpollutant of concern emitted during the
                  Ifl.b.e.miC.a-l and fe rjiilizer minerals is respir-
    ^ableTless than 7-um aepmetric mean aiameEer
     matter.

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       TABLE  1.   SALIENT FEATURES  OF  THE  CHEMICAL  AND  FERTILIZER  MINERAL INDUSTRY
Number of Annual Representative
principal production, plant size,
Mineral
Barite
Borates
Fluorspar
Lithium
Mineral pigments
(Iron oxide pigments)

Phosphate rock
Potash
Brine salt
Rock salt
Evaporated salt
Sodium sulfate
Sulfur
Trona ore
Total
sites
24
3
11
4

15

23
76
37
19
11
5
13
3
170
metric tons metric tons/yr
1,167,0008
1,063,000
111,000
12,000°
H
63,500
h
44,276,000
13,479,000
20,900,000
12,160,000°
4,940,000°
1,864,000
7,325,000
3,682,0003
112,683,500
50,000
800,000
10,000
3,000

4,000

2 , 000 , 000
2,000,000
600,000
600,000
450,000
400,000
600,000
1,000,000
Emission rate
of respirable
particulates ,
g/s
0
0
0
0

0

4
12
0
0
0
0
0
0
.05
.90 .
.02
.002

.004

.0
.0
.30
.04
.20
.20
.0006
.60
Contribution
to national
emission
burden
Hazard ratio of total
for respirable particulates,
particulates
0.004
0.07
0.002
0.0002

0.0003

0.3
0.9
0.02
0.003
0.02
0.02
0.00005
0.05

0.
' 0.
0.
0.

0.

0.
0.
0.
0.
0.
0.
0.
%
001
001
0002
000007

0001

10
10
01
0007
003
001
, 000009
0.002
Average
population
density of
major
producing
areas ,
persons/km2
10
10
80
120

100

50
3
50
60
20
10
30
1
Emission
factor for
respirable
particulates ,
g/metric ton
17
21
36
10

20

37
110
9
1
9
7
0
11










.2

.3
.02

0.2
— 	 • 	 i — — — — 	 V 	
1974 production.   1975 production.   1976 production.   1972 production.   Includes only New Mexico mines.   1973 production.

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 The hazard or pollution potential of  a  representative source may
 be assessed by the use of a hazard ratio.

 The hazard ratio for an air pollutant,  SA/  is  the  ratio of the
 maximum time-averaged ground level concentration to  an ambient
 air quality standard:
                           SA =
                                                                (1)
where
        Xmax = maximum time-averaged ground  level  concentration
           F = hazard factor  (ambient air ^quality  standard)
 For ground level sources, the hazard ratio  for respirable  partic-
 ulates, Sp, is':
                           s  =
                                Dl
 where  Q = representative mass emission rate, g/s
        D = representative distance from the source, m
             (for the purposes of Table 1, D = 400 m)

 As can be seen, hazard ratios for phosphate rock and potash  are
 .at_ least an order ^pf magnitude -larger than those for any other
 mxneraJLa.  Other minerals may produce air emissions more toxic
   lan respirable particulate matter, but the volume of emissions
 from the phosphate rock and potash industries is large enough tp
 overshadow them.

 Of the total particulate emission from the phosphate rock  indujj-
"Ifry, approximately 44%is ca,used bvt Igadinq^pf IraTTroaH hopper^
 cars.  The industry is aware of the problem, and companies are
 " individually devising schemes to handle the situation.  It is
 estimated that by 1980, application of the best available  control
 technology will reduce air emissions by 26%.

 Two items of interest which concern fluoride and radioactive pol-*-
 lution from phosphate mining are noted.  Fluoride compounds
 (reported as fluorine) account for about 5% of the emissions.
 The concentration in the emissions and the rock being mined  are
 not significantly different.  _UrahiuitL_concentrations , which  vary
 directly with the phosphat^ nnnr!e«J-ra-Mon of phosphate ^CQfik,.
 5sua3.lv are jTT'to 165 g/metric ton a of rock.  More study may be
^needed to better define radioactive pollution from phosphate
 mining.
 al metric ton equals 106 grams; conversion  factors  and metric
  system prefixes are presented in the prefatory material.

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At the time of this writing, the state of New Mexico  is  imple-
menting control regulations concerning the potash  industry.   It
is evident that further control will be necessary.  The  question
which remains for the industry is:   How much?

The emissions from Ozark submerged-combustion evaporators  are a
major problem for the two Carlsbad, New Mexico,  facilities which
process langbeinite ore.  Prior particle size measurements show
that all the particles in such emissions are less  than 7 ym.
A sturjy •» ° ^viT-rrm+i yi in pT-ngrp.H^ to assess the applj-catic-n of
Monsanto ' s BRINK® fine particle elimi^tors_to_ ' tHejorogLfiin.   Once
this problem area is solved, it i s^beTTevedT^iat^t'Re  necessary
control technology will exist for the  potash industry.

To summarize the state of control technology for the  chemical and
fertilizer industry, it appears that the necessary controls exist
and are being applied by the industry to control air  and water
pollution.  The trend in fugitive emission control _( a ^relatively
new area of^ environmental concern)
        JT
TicuTate "emissions from the productIoli~o~f"chemTc^T™^n3rfertilizer
minerals have been estimated to be 0.2% of the overall national
emission.

The hazard ratio for a water pollutant, S^, is the ratio of dis-
charge rate to a water quality criteria.  The river concentration
is taken into effect so that what is being considered is an
excess relative dose.

The hazard ratio is defined as

                        S  -    V°
                           "
(VR + VD)
                                      F
where  S  = hazard ratio for water effluent
       V  = volumetric flow rate of the discharge, m3/s

       C  = concentration of the discharge, mg/m3

       VR = volumetric flow rate of the river, m3/s

        F = hazard factor; EPA water quality criteria or  0.01  of
            the LC50a (96-hr)

The list of hazard ratios for water includes only those for  the
phosphate rock industry.  It was the only industry for which com-
plete information was available concerning river flow rate and
concentration.  For a representative source, discharging  into
Florida's Peace River, the hazard ratios of elemental phosphorus,
fluoride, and total suspended solids (TSS) are 0.061, 0.051, and
0.0025, respectively.
 LC50 is the lethal concentration which causes 50% mortality  in
 the test species.

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There are four significant wastewater problem areas in the mining
and beneficiation of minerals for the chemical and fertilizer
industry.  They are:

   • Mine water drainage
   • Wastewater from the fluorspar industry
   • Phosphate rock slimes
   • Sulfur bleedwater brines

Suspended solids are the principal pollutant in wastewater
discharges.  Treatment technologies available for removing sus-
pended solids are varied, but only a small number are widely
used.  The unlined settling pond is, by far, the most widely used
form of control technology.

The Florida phosphate rock slimes problem may well be the most
important of all fertilizer production problems.  The industry
has been active for a number of years to devise methods for
dewatering the slimes, but until available schemes become econ-
omically feasible, settling ponds will be widely used.

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                            SECTION 3

                       SOURCE DESCRIPTION
PROCESS DESCRIPTION

Materials used in the chemical'and fertilizer industries include
a number of different mineral compositions, so industry mining
practices involve a spectrum of conventional surface and under-
ground methods.  Processing also varies to some degree, being
dependent upon the particular mineral or product.

Typical unit operations, used by the industry as a whole, include:
     Drilling
     Blasting
     Quarrying
     Truck loading and unloading
     Dragline operation
     Conveying
     Crushing and grinding
     Screening
Flotation
Thickening
Filtering
Evaporation
Drying
Bagging
Storage
             «*

These minerals may be placed in four categories according to
their processing operations.  Block diagrams for each category
are given in Figures 1 through 4.
OPEN PIT
MINING
PREVALENT


CRUSHING,
GRINDING,
SCREENING


CLASSIFICATION,
FLOTATION,
FILTERING


DRYING,
BAGGING,
STORAGE
      Figure 1.  Barite, fluorspar, phospnare rock, lithium
                 minerals, and mineral pigments.
LAKE BRINE


EVAPORATION,
PRECIPITATION
*_.

DRYING,
BAGGING,
STORAGE
         Figure 2.   Brine minerals:  borax, natural soda
                    ash, lithium salts, salt, and potash.

-------
          UNDERGROUND
            MINING
CRUSHING,
 SIZING,
PACKAGING
                    IMPURITY REMOVAL,
                      EVAPORATION,
                    CRYSTALLIZATION
•»- SALT PRODUCT
              DRYER,
             STORAGE
              Figure 3.  Rock  salt and trona ore.
           PUMP HOT
           WATER TO
           FORMATION
  MOLTEN MATERIAL
    REMOVED TO
    THE SURFACE
                                       85%   _
                     SHIPPED IN
                    LIQUID FORM
        Figure  4.   Sulfur (the Frasch hot water process).

Each mineral  is described below in terms of annual production,
composition,  and unit operations to provide a broad perspective
of the chemical and fertilizer mineral industry.  A breakdown of
population density  and mineral production by state is presented
in Table 2.

SOURCE TYPES

Barite  (1-3)

Production—
Q.S. production of  barite in 1975 totaled 1,167,000 metric  tons,
a 16% increase  over 1974 levels.  Based on production figures  for
 (1) Fulkerson,  F.  B.   Barium.  In:  Mineral Facts  and Problems.
    1975  Edition.   Preprint from-Bureau of Mines Bulletin 667.
    U.S.  Department of the Interior, Washington, D.C.   13 pp.
 (2) Stevens,  R.  M.  Barite.  Mining Engineering, 29(3):53-54, 1977

 (3) Development Document for Effluent Limitations  Guidelines and
    Standards of Performance, Mineral Mining and Processing
    Industry, Volume  II/ Minerals for the Chemical and Fertilizer
    Industries.  Contract 68-01-2633, U.S. Environmental Protec-
    tion  Agency, Washington, D.C., January 1975.   310 pp.

-------
TABLE 2.   CHEMICAL AND  FERTILIZER MINERALS  PRODUCTION
            AND POPULATION DENSITIES  BY STATE
State
Alabama
Alaska
Arkansas

California





Colorado
Florida
Georgia

Hawaii
Idaho
Illinois


Kansas
Kentucky
Lpuisiana


Michigan

Missouri
Montana

Nevada



New Jersey
New Mexico

New York
North Carolina

North Dakota
Ohio
Oklahoma
Pennsylvania
Tennessee

Texas




Utah




Virginia
West Virginia
Wisconsin
Wyoming

	 . — •
	 Mineral 	
Srine salt
Barite
Barite
Iron Oxide pigments
Barite
Borates
Lithium
Potassium salts
Evaporated salt
Sodium Bulfate
Fluorspar
Phosphate rock
Barite
Iron oxide pigments
Evaporated salt
Phosphate rock
Barite
Fluorspar
Iron oxide pigments
Brine and rock salt
Fluorspar
Barite
Brine and rock salt
Sulfur
Iron oxide pigments
Brine and rock salt
Barite
Fluorspar
Phosphate rock
Barite
Fluorspar
Lithium
Evaporated salt
Iron oxide pigments
Potash
Evaporated and rock salt
Brine and rock salt
Lithium
Phosphate rock
Brine salt
Brine and rock salt
Evaporated salt
Iron oxide pigments
Barite
phosphate rock
Barite
Fluorspar
Brine and rock salt
Sodium sulfate
Sulfur
Fluorspar
phosphate rook
Potash
Brine salt
Sodium sulfate
Iron oxide pigments
Rock salt
Iron oxide pigments
Phosphate rock
Trona ore
Production
10 3 metric tons
_a
122
152
_b
10
1,063
—
159
1,367
1,118
-
34,535
-
—
-
1,328
-
60
-
1,267
-
-
11,929
3,019
-
4,370
178
-
1,328
498
-
3
-
-
1,837
132
4,718
9
2,214
-
4,224
4.5
-
19
2,214
_
-
9,391
373
3,727
1
1,328
272
650
373
-
1,104
-
1,328
3,682
Population
density,
persons/km2
30
0.2
10

10





10
50
30

50
3
80


10
30
30


60

30
2

2



370
3

150
120

3
100
15
100
40

20




5




130
80
30
1

    Dashes indicate data not available.  Estimated from current capacity.
                              10

-------
the first 10 months, it appears that U.S. barite production  in
1976 will increase by 5% over 1975.  Nevada produced more  than
70% of the 1975 output, followed by Missouri, Arkansas, Georgia,
Alaska, California, Illinois, and Tennessee.  A list of the  prin-
cipal producers and their geographical distribution is provided
in Appendix A.

Source Composition—
Barite  (BaSOiJ is the only source of barium and barium compounds.
Theoretically, barite contains 65.7% barium monoxide (BaO) and
34.3% sulfur trioxide (S03).  The chemical analysis of average
barite ores is presented in Table 3  (4).

                 TABLE 3.  CHEMICAL ANALYSIS OF
                           AVERAGE BARITE ORE (4)
                 	Component	Percent

                 Barium sulfate          94 to 96
                 Iron  (III) oxide       0.8 to 2.0
                 Strontium sulfate      0.1 to 2.0
                 Barium carbonate          1.0
                 Silicon dioxide        3.0 to 6.0
                 Water                  0.5 to 2.0
                 Fluorine                  nil
                 Lead                      nil
                 Zinc                      nil
Most commercial sources are bedded deposits and vein deposits in
limestone, dolomitic sandstone, and shale, or residual deposits
in which chunks of barite are enclosed in clay.   Barite some-
times occurs as a gangue mineral in metallic ores such as lead,
zinc, and silver, and it is frequently associated with fluorspar.

Examples of replacement-type deposits occur in Arkansas, Nevada,
and California.  Residual deposits are found in Georgia, Missouri,
Tennessee, and several eastern states.

Mining—
The barite industry uses a variety of mining methods depending on
the size and type of deposit.

Bedded and vein deposits are mined by open pit or underground
methods.  In Nevada, barite in bedded deposits is blasted from
open quarries with little or no subsequent sorting or
beneficiation.
(4) Kirk-Othmer Encyclopedia of Chemical Technology, Second
    Edition, Vol. 3.  John Wiley & Sons, Inc., New York,
    New York, 1967.  927 pp.
                               11

-------
 Residual deposits of barite are usually mined by power shovels  or
 dragline in open pits after removal  of  overburden.  Overburden  in
 Missouri is rarely over 0.6 m or  0.9 m,  but in Georgia it may
 range from 3 m to 15 m.  In most  cases,  the clay strata is hauled
 to the washing plant by dump trucks.

 Beneficiation—
 The methods used in the beneficiation of barite depend on the
 nature of the ore and the type of product to be made.

 Of the significant U.S. locations producing either barite ore or
 ground barite, approximately 50%  use log washing and jigging
 methods to prepare the ore for grinding.   About 30% are dry
 grinding operations, and the remainder  utilize froth flotation
 techniques for the beneficiation  of  the  washed and/or jigged ore.

 Wet process—Wet processing plants use washers or jigs to remove
 clay from the barite ore.  The soft  mined ore is passed through a
 breaker and fed to the log washer.   The  washed ore is then
 screened in a trommel circuit, dewatered,  and finally jigged to
 separate gravel from the product.  A flow diagram for wet process-
 ing is given in Figure 5.

               MAKEUP WATER AND RECYCLED WATER
                  FROM THE TAILINGS POND
  ORE
                     •KDEWATER)

                         f WRODUCT
                       WATER TO
                     SETTLING POND
               I LOG WASHER
 ROTARY
 BREAKER    ^     WASTE TO
       SOLID  SETTLING POND
       WASTE
 WASTE TO
SETTLING POND
                                                      -»
-------
transferred into  the  product silos.   The barite is removed  from
these silos either  to bulk hopper cars or to the bagging plant.
A flow diagram  for  dry processing of barite is given in Figure  6
              ORE
           ROLL
          CRUSHER"1
                                  t _ _  SCREW
                                 IAA/VI CONVEYOR
                                             »- BULK PRODUCT
                                             *• BULK PRODUCT
                                                 BAGGER
      Figure  6.   Barite beneficiation (dry grinding process).

Flotation  Process—This process consists of crushing the ore to
free  it  from gangue material,  washing it to remove the clay,
jigging  the  washed ore to separate the gravel, and grinding and
beneficiating it by froth flotation to recover barite concen-
trates.  The concentrates are  filtered, dried, and bagged for
shipment.  A process flow diagram is given in Figure 7.

Borates  (3,  5)

Production—
All U.S. boron  production and  about three-fifths of the world
production comes from bedded deposits and lake brines in Califor-
nia.  In 1975,  U.S.  production was recorded as 1,063,000 metric
tons.  A list of the principal producers and their geographical
distribution is provided in Appendix A.

Source Composition—
The principal boron minerals (those of commercial value) are
tincal (Na2B£fOy-10H2O) ,  kernite (Na2Bii07 -4H2O) , colemanite (boro-
calcite, Ca2B6Oii•5H2O),  ulexite (boronatrocalcite, CaNaB5Og•8H2O)
priceite (pandermite,  5CaO-6B2O3•9H20), boracite (stassfurite,
        6^3 o) '  an<^ sassolite (natural boric acid, £[3603) .
(5) Wang, K. P.  Boron.   In:   Mineral Facts and Problems, 1975
    Edition.  Preprint  from Bureau of Mines Bulletin 667, U.S.
    Department of the Interior,  Washington, D.C.  12 pp.
                                13

-------
                                           ORE
           JIG
          [DEWATER)
            T
    BALL MILL
    GRINDER
                         LOG WASHER
                                           ROTARY
                                           BREAKER
              AIR
           CLASSIFIER
                       CONVEYOR
                                           OOOO
                                             FLOTATION CELLS
         ^^m\^u^L
         ^^Tfr^^^^n
  THICKENER T
                  FILTER
                              DRYER
                                            STORAGE
                                              SILO
                                                        BAGGER
Figure  7.   Barite  beneficiation  (flotation process)
                                14

-------
Virtually all the domestic reserve of boron minerals  is  in
California.  The primary deposit is at.Boron; other deposits
occur at Searles Lake and in the Furnace Creek district  of  Inyo
County.

The large Kramer deposit at Boron is a high-grade, predominately
crystalline tincal ore body overlying kernite.  The overburden
consists mainly of layers of shale, sandstone, conglomerate, and
tufts of vegetation.

Mining and Beneficiation—
U.S. Borax and Chemical Corp., which accounts for over 75% of
total U..S. borate production, mines its Kramer ore body  at Boron
by open pit methods.   The pit is 305 m deep, and the ore is
brought up by inclined conveyor.  The crushed ore is shipped to a
refining plant near the mine site for dissolving at about the
boiling point of water, thickening, washing to remove impurities,
and vacuum crystallization.  A process flowsheet is provided in
Figure 8.

Kerr-McGee employs the evaporative or "trona" process at its Trona
Plant.   (This plant was operated by American Potash and  Chemical
Corp. before the company was acquired by Kerr-McGee.)   It has a
daily boric anhydride  (B2O3) capacity of 270 to 360 metric tons,
including 136 metric tons of anhydrous borax and 72 metric tons
of boric acid.  It processes 0.63 m3/s of brine pumped from a
series of wells.  A process flowsheet is provided in Figure 9 (4).

The Furnace Creek deposits contain both ulexite and colemanite.
Tenneco Oil Co. owns the colemanite-ulexite open pits near Ryan
which supply colemanite ore to a calcining plant near Death
Valley Junction and ulexite to a mill at Dunn.  After processing,
the ores contain 26% to 28% B203.

Fluorspar (3, 6-8)

Production—
Domestic production of fluorspar in 1975 amounted to 111,000
metric tons.  Most domestic fluorspar comes from Kentucky and
Illinois, where four companies  produced 85% of the acid and
ceramic-grade fluorspar output.  A list of the principal pro-
ducers and their geographical distribution is presented  in
Appendix A.
(6) MacMillan, R. T. Fluorine.  In:  Mineral Facts and Problems,
    1970 Edition.  U.S. Department of the Interior, Washington,
    D.C., 1973.
(7) Singleton, R. H.  Fluorspar in 1975.  Mineral Industry
    Surveys, U.S. Department of the Interior, Washington, D.C.,
    November 17, 1976-  8 pp.
(8) Weisman, W. K. Fluorspar.  Mining Engineering, 29(3):59-61,
    1977.

                               15

-------
  CRUSHED ORE BIN
                        6VRATORY
                        CRUSHER
                                             GYRATORY
                                             CRUSHER
                                                     STORAGE SILOS
Figure 8.   Borate  beneficiation  (Boron,  California).
                             16

-------
            BORAX
                                              r* WATER
                                                BLEED TO BORAX REFINING
                   CALCINERS
                             NATURAL GAS .
                                BURNER    CALCINE HOPPER
                  REFRACTORY-LINED
                     FURNACE'
                  HOT AIR
SLAG CLEAN-OUT
                  CRUSHER
                                       TRAVELING FEED HOPPER
                                       CALCINE BED
                                     WATER- COOLED JACKETS

                                     ANHYDROUS BORAX FURNACES
                       MOLDING MACHINE
{
V
ROC
ROD MILL FEED
1 "
*,jf
'11
\ MTI 1 ^

BIN

lib*
UP* .
> *
MAGNETIC
SEPARATOR

r1
REJECT L,

-------
Fluorspar veins vary in width from film thickness to more than
9 m wide.

In the western states, fluorspar occurs under a wide variety of
donditions:  as fillings forming more or less well-defined veins,
in fractures and shear zones, and as replacements in the country
rock.

Mining—

Mining is done by shafts, drifts, and open cuts.  Mines range in
size from small operations using mostly hand-operated equipment
to large, fully mechanized mines.

B6neficiation—
The two main processes used to beneficiate fluorspar ore are wet
heavy media separation (HMS) and froth flotation.

Heavy media separation—An HMS plant may not only upgrade and
preconcentrate the ore to yield an enriched flotation feed, but
it can also produce metallurgical grade gravel as a finished
product.

The ore is first crushed to proper size, then washed and drained
on vibrating screens to eliminate as much fines as possible.
Oversize material is recycled back to the screen; undersize
matter is sent to a spiral classifier for recovery as flotation
plant feed.  Middlings from the screening operation are fed to an
HMS separatory cone which contains a suspension of finely ground
ferro-silicon and/or magnetite in water, maintained at a pre-
determined specific gravity.  The light fractions, or tailings,
float and overflow a weir.  The heavy particles  (which are flota-
tion feed) sink and are removed by an airlift.

The float and sink discharges go to drainage screens where 95% of
the media are drained through the "screens, magnetically separated
from the slimes, and returned to.the circuit.

The float and sink products pass over dewatering screens, and the
water is pumped back to the plant.  A flow diagram is provided in
Figure 10.                                          '

Froth flotation—In froth flotation plants, fluorspar and other
valuable minerals—barite, lead sulfide, and zinc sulfide—are
recovered from the gangue material -which is left as mill tailings.
For the average small mill treating up to 90 metric tons of ore a
day,  primary crushing is adequate. Fluorspar ores usually require
grinding to 48 mesha or 65 mesh to liberate calcium fluoride from'
the gangue.
3Mesh equivalents are given in standard engineering texts

                               18

-------
    CRUDE ORE
         GYRATORY
          CRUSHER
       *J N/^l
SCREEN
         t
    FLOTATION
      FEED
         TO CRUSHING
         AND RECYCLE

           SPIRAL
          CLASSIFIER
                   WATER FOR
                    RECYCLE


                  | Trrrr^T^M |
                THICKENER
                     FLOTATION
                       FEED
   SEPARATORY
     CONE
WATER FOR RECYCLE
            I

        SCREEN
                                                  GANQUE MATERIAL
                                WATER FOR RECYCLE


                                        SCREEN
                                                     TO
                                                  THICKENER
                              'MEDIA
                              RECYCLED
                              TO CONE
        Figure 10.  Fluorspar beneficiation (HMS process).
Flotation of fluorspar must be extremely selective,  especially
when  producing acid  grade concentrate.   The various  grades of
concentrates produced  are stored in  thickners until  filtered.

The barite^. lead sulfide,  and zinc sulfide concentrates  are sold
in filter cake form.   The fluorspar  concentrates are  dried in
rotary  kilns and then  shipped.  A flowsheet diagram  for  the froth
flotation process is presented in Figure 11.

Lithium Minerals (9, 10)

Production—
In 1976,  lithium chemicals were produced domestically by Foote

 (9)  Cummings,  A. M.   Lithium.  In:  Mineral  Facts and Problems,
     1970  Edition.   U.S.  Department  of the Interior,  Washington,
     D.C.,  1973.
                                                                  «• *
(10)  Alexander,  J.  H.   Lithium.   Mining  Engineering,  29(3) :66,
     1977.
                                 •19

-------
          ORE
                                          FINEOREBIN
                                         B.ALLMILL
                                         GRINDER
                             -lolololo
                                                CLASSIFIER
                              FLOTATION cais
                   lf//*j\\y
               THICKENERY
                         FILTER PRESS
                              ROTARY
                              DRYER
STORAGE
 SILOS
     Figure  11.   Fluorspar beneficiation (froth flotation).

Mineral Co.,  Lithium Corp. of America, and Kerr-McGee Corp.  A
list of principal producers and their geographical distribution
is presented in  Appendix A.

Mining—
Foote Mineral produces  lithium chemicals from spodumene ore mined
at Kings Mountain,  North Carolina,  and from lithium-containing
brines at Silver Peak,  Nevada.

Lithium Corp.  of America has concentrated all of its lithium pro-
duction at Bessemer City,  North Carolina, where it mines  spodu-
mene from the pegmatite dikes.

Kerr-McGee continues to extract small quantities of lithium car-
bonate from  the  brines  at Searles Lake, California.

Beneficiation—
In North Carolina,  spodumene is recovered from the pegmatite ore
by crushing,  screening, grinding, and flotation.  Lithium com-
pounds are recovered from spodumene concentrates by acid  or
alkali treatment.    See Figure 12 for a process flow diagram.

At the Searles Lake,  California site, brine with a 0.033% lithium
chloride  (LiCl)  content is concentrated in evaportors, causing
several salts to precipitate.  Through a combined leach-flotation
process, the  lithium compound is recovered as crystals.    A
                                20

-------
/^~\ BALL MILL
Wy) GRINDER
i
1
SLIMES
REMOVAL
SLI
(OVER
ALTERNATE OR
MES-TAILI
FLOW RECY
OPTIONAL
ROTATION
t
CELLS
IOIOIOIOI
1
T
NGS TO Si
CLED TO P
PROCESS

BYPRODUCT
FLOTATION AND
CLASSIFICATKM
* t
TTLING 50LI
ROCESS ) WAST
FILTER
PRESS s
	 "pUHll — ""CO
1 — X — '
1
1 ROTARY
LDRYER
^Zf-


' MAGNETIC
SEPARATION
i
LOW IRON
PROCESSING
'OOUMENE
NCENTRATE
'RODUCT
SPODUMENE
CONCENTRATE
	 ». PRODUCT
	 ^ BYPRODUCT
CERAMIC GRADE
" SPODUMENE PRODUCT
LOW IRON
SPODUMENE PRODUCT
                Figure 12.
Spodumene beneficiation
(flotation process).
process flowsheet  is  given in Figure 29  (Section  3).   At Silver
Peak, Nevada,  brines  containing 0-244% LiCl are concentrated to a
6% LiCl content  by solar evaporation.  A process  flowsheet is
presented in Figure 13.
                                     LIQUOR

BRINE PRELIMIW
FROM-^- SOLAR
WELLS EVAPORATI

LIME
pv
REACTION
ON POND


btCUNDAKY
SOLAR
EVAPORATION
MAGNESIUM SODIUM CHLORIDE
HYDROXIDE AND
SOLID WASTE POTASSIUM CHLORIDE
SOLIDS TO
STORAGE
LIME SODA ASH
-^ II
4


REACTOR
FILTER FILTER
-3111111111111; jiiiiniiiyi -
                                              MAGNESIUM
                                              HYDROXIDE
                                              SOLID WASTE
           Figure 13.   Lithium salt recovery  (natural
                        brine,  Silver Peak operations).
                                21

-------
Mineral Pigments  (3)

Production—
Mineral pigments might better be called iron oxide pigments,
since they are the only natural pigments currently being mined
and processed.  The quantity of natural iron oxide pigments sold
by processors in the United States in 1972 was about 63,500
metric tons.  A list of principal producers and their geograph-
ical distribution is presented in Appendix A.

Source Composition—
Hematite and limonite are minerals which consist mostly of iron
oxides.  Their occurrence is closely linked to that of iron ore.
Pigment materials and iron ores are often mined in the same
localities, and iron ores are used at times for red and brown
mineral pigments.

Mining—
Iron oxide pigments are mined from open pits using power shovels
or other earth removing equipment.  At some locations, pigments
are a minor byproduct of iron ore mining.

Beneficiation—
Two processes are used; the choice of process depends on the
source and purity of the ore.  For relatively pure ores, process-
ing consists of crushing, grinding, and air classification.  A
drying step may also be included.

On the other hand, less pure ores require a washing step to ^
remove sand and gravel, followed by dewatering and drying.  These
processes are presented in Figure 14.
                                          PRODUCT
                           RECYCLE
           Figure 14.  Mineral pigment beneficiation,
                               22

-------
 Phosphate Rock (11,  12)

 Production—
 Production of phosphate  rock in 1975 totaled 44,276,000 metric
 tons.   Based upon U.S. Bureau of Mines figures, production for
 the  first 10 months  of 1976 was at a pace equal to 1975 figures.
 Phosphate is distributed in three major producing areas:  Florida
 and  North Carolina;  the  western states of Idaho, Montana, Utah
 and  Wyoming; and Tennessee.  Florida, by far the largest producer,
 provided over three  quarters of the domestic production in 1975.
 A list of the principal  producers and their geographical distri-
 bution is presented  in Appendix A.

 Source Composition—
 Phosphate rock does  not  have an explicit chemical composition.
 The  major phosphorus minerals of most phosphate rock are in the
 apatite group and may be-represented by the formula
 Ca5(P04)3(F, Cl, OH). The (F, Cl, OH)  radical can be any combina-
 tion of the fluoride, chloride, or hydroxyl ions, while the
 phosphate (PO^)  radical  can be partly replaced by the vanadate,
 silicate, sulfate, or carbonate ions.  Rare earths, chromium,
 cadmium,  and uranium are otfier regular impurities.  Uranium
 concentrations,  which vary directly with the phosphate concentra-
 tion of phosphate rock,  usually are 40 to 165 g/metric ton of
 rock (13) .

 The  Bone Vallev For-mai-inn r  an alluvial deposit east of Tampa,
"jlorida,  has become  the  most important phosphate resource in ~the_
 Unite_d__States^  The  Bone Valley material occurs in a matrix coiti^"
 posed of clay, pebble phosphate, and sand in proportions of about
 one-third each.    The matrix, ranging from 0.3 m to 15 m in
 thickness, averages  about 5 m.

 Research and development may convert the phosphate-bearing,
 Hawthorne Limestone  Formation in Florida to an important phos-
 phate reserve.  The  Hawthorne Limestone Formation is a dolomitic
 deposit underlying the land pebble deposits which has been
 exposed by present mining.   The extent of the formation has not
 been fully determined, but it is estimated to contain several
 hundred billion metric tons of phosphate rock with an average
 grade of about 5% phosphorus pentoxide (P205), compared to the
 (11)  Emigh,  G.  D.   Phosphate Rock.   Mining Engineering,
      29(3):6870,  1977.
 (12)  Stowasser, W.  F.   Phosphate Rock.   In:   Mineral Facts and
      Problems,  1975 Edition.   Preprint  from Bureau of Mines
      Bulletin 667,  U.S.  Department  of the Interior, Washington,
      B.C.   16 pp.
 (13)  Reconnaissance Study of Radiochemical Pollution from Phos-
      phate  Rock Mining  and Milling.   PB 241 242,  U.S. Environ-
      mental  Protection  Agency,  Denver,  Colorado,  December 1973.
      106 pp.

                                23

-------
11% to 14% of P205 ore now mined.  The location of Florida  phos-
phate deposits is provided in Figure 15  (14).

Mining—
Phosphate rock mining procedures are somewhat different  in  each
of the major producing areas.

In Florida, the overburden covering the matrix is a quartz  sand
and clay averaging about 6 m in thickness.  Electric-powered
draglines strip the overburden and mine the matrix.  The drag-
lines work in cuts that may be 45 m to 80 m wide and range  from
approximately 300 m to 1000 m long.  Overburden is stacked  on
natural ground level adjacent to the cut.  The draglines deposit
the matrix in previously prepared sluice pits.  Hydraulic guns
slurry the matrix, and it is pumped to the washing plant.

Mining procedure in North Carolina is similar to that in Florida.

In the western states, all phosphate ore is stripmined except
that obtained from two underground mines in Montana.  Ore mined
in the western states is either truck-hauled or moved by rail to
processing plants.

Ore in Tennessee is stripped and mined with small draglines and .
trucked directly to the plants or transferred to railroad cars
for daily movement into the plants.

Beneficiation—
Beneficiation of eastern phosphate ore varies somewhat from plant
to plant as grade, screen analysis, and ratio of pebble concen-
trate in the feed change.  The matrix slurry (20% to 50% solids)
is pumped through pipelines to the washing plant.  Through a
series of screens in closed circuit with hammer mills and log
washers, the matrix is broken down to permit separation of the
nonphosphate-bearing sand and clay from phosphate-bearing pebbles
and sands.  The separation is made at 14 mesh or 16 mesh to
obtain a washed screen oversize pebble or coarse fraction.

The next step is the cyclonic removal of the -150 mesh material
(slimes, colloidal clays, and very fine sands)  which are pumped
to settling ponds.  The oversize phosphatic material is trans-
ferred to the flotation section, where it undergoes first stage
flotation.  The floated material may be stored or conditioned for
a second stage flotation.  The phosphate rock product is dried,
sometimes ground, and stored in silos from which it is transfer-
red to railroad hopper cars for transport.  A process flowsheet
is presented in Figure 16.
(14)  Bromwell, L. G.  Dewatering and Stabilization of Waste
     Clays,  Slimes,  and Sludges.   Florida Phosphatic Clays
     Research Project,  Lakeland,  Florida, June 1976.  43 pp.
                               24

-------
10
            LEGEND
        jNorthern land-pebble district
        j Hardrock district
        (Central land-pebble district
                    20    40    60
                         Scale, miles
 Figure 15.   Location of Florida  phosphate  deposits  (14)
                                    25

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                                                   WATER
                                                       SECONDARY
                                                      FLOTATION CELLS
          SCREEN
           ALTERNATE ROUTE
SLIMES TO   TAILINGS TO
SETTLING   DISPOSAL POND
 POND
                                                 TAILINGS TO
                                                DISPOSAL POND
                                                           ROTARY
                                                            DRYER
                                                            PRODUCT
   Figure 16.  Phosphate rock  benef iciation (eastern  process).

Western phosphate  ore is transported from  the mine to the plant
by truck or rail.   When it is  benef iciated,  it enters the first
stage  of benef iciation, which  consists of  crushing and/or scrub-
bing.   Subsequent  sizing is obtained by  further crushing, grind-
ing, and classification, with  the sized  feed being directed to
the desliming section for removal of the -325 mesh material.  The
slimes are discharged either directly to a tailings pond or
through a thickener.   The underflow product from the  desliming
step is filtered,  and it may be  further processed through a
drying and/or calcining step prior to shipment. , A process flow
diagram for western ore is given in Figure 17.
                          - RECYCLE WATER

°/ROLL
/CRUSHER
MINE



— 1
1
SCRUBBER
                                    FLOTATION CELLS
                                    AND CONDITIONER
                                                           -PRODUCT
       	ALTERNATE ROUTE
                                                  r A nv ^/**
                       ROTARY
                        DRYER
                                                          PRODUCT
                         SLIMES AND
                         TAILINGS TO
                        SETTLING POND
   Figure  17.   Phosphate rock beneficiation  (western  process).
                                  26

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Potash (3, 15, 16)

Production—
In 1975,  domestic production of potash totaled 2,268,000 metric
tons of potassium oxide  (K2O).  Preliminary estimates for 1976
production are 2,168,000 metric tons of K2O.

The^U.S.  potash industry now comprises 10 firms which operate 11
facilities:  7 underground mines in New Mexico, 1 underground
solution mine in Utah, 2 brine treatment plants in Utah, and 1
brine treatment plant in California.  A list of the principal
producers and their geographical distribution is presented in
Appendix A.

Source Composition—
Potash is the common term for compounds of the element potassium,
and it is often used to mean the equivalent K20 content of sub-
stances,  even though no oxide is actually present.  Sylvinite, a
mineralogical mixture of sylvite (KCl) and halite (NaCl), is the
major ore for producing potash.  A list of potash minerals is
provided in Table 4 (17).

Currently 84% of domestic production comes from the bedded
deposits in southeastern New Mexico near Carlsbad.  A typical
mineralogical analysis of New Mexico potash ore is presented in
Table 5  (18). Average K20 content of the New Mexico ore is 15%.

Mining—
Mining methods and equipment have been adapted from coal and salt
mining.  Shaft depths in New Mexico range from 233 m to 575 m.

Most of the mines in New Mexico use "conventional" mining methods:
a cycle of undercutting, drilling,  and blasting with an ammonium
nitrate-fuel oil mixture, and a system of loaders, shuttle cars,
and belt haulage.
 (15) Keyes, W. F. Potash.  In:  Mineral Facts and Problems,
     Bureau of Mines, 1975 Edition.  Preprint from Bulletin 667,
     U.S. Department of the Interior, Washington, B.C.  15 pp.

 (16) Rampacek, C.  The Impact of R&D on the Utilization of Low-
     Grade Resources.  Chemical Engineering Progress, 73(2) :57-
     68, 1977.
 (17) Katari, Va. , I. Gerald, and T. Devitt.  Trace Pollutant Emis-
     sions from the Processing of Nonmetallic Ores.  EPA-650/2-
     74-122, U.S. Environmental Protection Agency, Research
     Triangle Park, North Carolina, November 1974.  277 pp.

 (18) Klingman, C. L. Salt.  In:  Mineral Facts and Problems, 1975
     Edition.  Preprint from Bureau of Mines Bulletin 667, U.S.
     Department of the Interior, Washington, D.C.  12 pp.

                               27

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          TABLE  4.   POTASH MINERALS  (17)
Type of ore
Chlorides

Chloride-sulfates
Sulfates








Nitrates
Silicates

'

Micas








Minerological
name
Sylvite
Carnallite
Kainite
Alunite
Polyhalite
Langbeinite
Leonite
Syngenite
Krugite
Apthitalite
Picromerite
Kalinite
Niter
Leucite
Feldspars :
Orthoclase
Anorthoclase
Muscovite
Biotite
Phogopite
Lepidolite
Zinnwaldite
Roscoelite
Glauconite
Carnotite
Nephelite
Composition
KC1
KCl-MgCl2-6H2O
MgS04'KCl-3H20
K2 [Al(OH) 2 ('6)80414
K2S04 -MgSO4 -2CaSO4 =2H20
K2S04-2MgS04
K2SO4-MgSO4-4H2O
K2SO4 -CaSO4 -H2O
K2S04 «MgSO4 «4CaSO4 '2H20
(K,Na)2SO4
K2S04-MgSOi+-6H2O
K2S04 -A12 (804) 3 =24H20
KNO3
KAl(Si03)2

KA18i3O8
(Na,KJ"AlSi3d8
H2KA13 (SiO4) 3
(H,K) 2 (Mg,Fe) 2A12 (8104) 3
(H,K,Mg,F) 3Mg3Al(SiO4) 3
H,Li(Al,OH,F2)Al(Si03) 3
H2K4Li4Fe3Al8F8Si14042
H8K(Mg,Fe) (A1,V) 4 (SiO3) 12
KFeSi2O6 «nH20
K2O-2U203-V2O5-3H2O
K2Na6Al8Si9034
Equivalent
K2O
content, %
63.1
17.0
18.9
11.4
15.5
22.6
25.5
28.8
10.7
42.5
23.3
9.9
46.5
21.4

16.8
2.4 to 12.0
11.8
6.2 to 10.1
7.8 to 10.3
10.7 to 12.3
10.6
7.6 to 10.3
2.3 to 8.5
10.3 to 11.2
0.8 to 7.1

TABLE 5.  TYPICAL MINEROLOGICAL  ANALYSIS OF POTASH
          ORE  OF CARLSBAD, NEW MEXICO (17)
          Component
Percentage
 (range)
         Sylvite
         Halite
         Langbeinite
         Kainite
         Leonite
         Kieserite
         Carnallite
         Polyhalite
         Anhydrite
         Insolubles
   23 to 28
      71
Trace to 2
  0.1 to 0.5
Trace to 0.1
Trace to 1.0
    Trace
     0.15
    Trace
  0.5 to 1.5
                          28

-------
Potash plants  treating natural brines collect  the brines by .pump-
ing from wells or collecting canals.

Beneficiation—
In New Mexico, the potash ore is usually processed in refineries
adjacent to  the mines.  Two processes are employed:   one for the
recovery of  potassium chloride (KC1) from sylvinite  and the other
for processing langbeinite ores.

Most of the  KC1 is recovered from sylvinite ore  by flotation
methods.   The  first step of this process is to treat the ore with
a hydrophobic  material (e.g., an aliphatic amine)  which will
selectively  coat one of the ore constituents  (KC1).   Air is then
bubbled through the slurry, and the air bubbles  attach themselves
to the coated  particles and float them to the  surface, while the
uncoated particles sink.   A process flowsheet  is given in Fig-
ure 18.  On  a  large scale and particularly with  high-analysis
ores, the  flotation process is much cheaper than one involving
dissolution  and crystallization.  However, available resources of
the high-grade low-clay ores that have been mined and concen-
trated during  the past 40 yr are declining in  grade.  The ore to
be mined in  the future is more difficult to beneficiate because
its increased  clay content interferes with flotation.
               BRINE
                         BRINE RECYCLE
                         —-j	
                      WATER
              BALL MILL
              GRINDER
FLOTATION
CHEMICALS
DESLIME AND
SEPARATE
1


                            MOIOIOIO
                               FLOTATION CELLS
              DEWATER
                    BRINES TO  SLIMES
                    WASTE OR TO WASTE
                    RECYCLE
                   	ALTERNATE ROUTE
                DRYER
                                              SCREEN
                                            TAILINGS
                                          WASTE AND BRINE
                                                      PRODUCT
Figure 18.   Potassium chloride beneficiation  from sylvinite ore.

For several  years,  industry and government  researchers have, been
working to fashion  systems involving flotation  and leach-
crystallization  processes for treatment of  the  low-grade
resources.   One  of  the sylvinite ore processing plants currently
uses a leach-crystallization process; the remaining plants use
flotation.
                                 29

-------
Langbeinite  is a natural potassium  magnesium sulfate  (K2Mg2[SO^]3)
usually  intermixed with sodium chloride.   Two facilities  at
Carlsbad process langbeinite ore.   The ore is mixed, crushed,  and
dissolved  in water to which KCl  is  added.   Partial evaporation of
the solution produces selective  precipitation of potassium
sulfate  (K2S04), which is recovered by centrifugation or  filtra-
tion from  the brine liquor, dried,  and sold.  A simplified proc-
ess flowsheet is given in Figure 19.
     POTASSIUM
 WATER CHLORIDE
                LANGBEINITE ORE
                                                            MAGNESIUM
                                                            • CHLORIDE
                                                            COPRODUCT
                           FILTER
                                                            POTASSIUM
                                                          »- SULFATE
                                                            PRODUCT
              Figure 19.  Langbeinite  beneficiation.
    i
In Utah,  two facilities practice  solution mining of sylvinite.   A
saturated brine is drawn to the surface and evaporated to  dryness
in large  surface ponds.  The dried  material is then harvested
from the  ponds and separated by flotation into sodium and  potas-
sium chlorides.  The sodium chloride  tailings are discarded  as
waste;  the potassium chloride is  dried and packaged.  A process
flow diagram is provided in Figure  20.
             WATER
1
SYLVINITE
DEPOSIT




EVAPORATION
PONDS

WATEf
1
» c^lr^i
* L->|U
?
o

o
FLOTATION
SEPARATION
                                             DRYER
                                                   POTASSIUM
                                                   •CHLORIDE
                                                    PRODUCT
                                   SODIUM CHLORIDE
                                    SOLID WASTE
Figure 20.
Potash recovery by solution mining  of sylvinite ore,

                     30

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The processes employed at Searles Lake  and at the Great Salt Lake
are similar  in that the brine is evaporated in steps to selec-
tively recover sodium chloride, sodium  sulfate,  and potassium
sulfate.   Process flowsheets for mineral  recovery from the Great
Salt Lake  and Searles Lake are provided in Figure 21 below and in
Figure 29  in Section 3, respectively.
         GREAT
         SALT
         LAKE WASHOUT
         BRINE  WATER
WATER •
            PARTIAL
          EVAPORATION
                                             FILTER
LIQUOR TO
 LAKE
                                                    DRYER
             POTASSIUM
             SULFATE
             PRODUCT
                                     .BITTERN SOLIDS
                                       PRODUCT
                                 SODIUM SULFATE
           WASTE WATER TO LAKE

         Figure  21.   Minerals recovery  at  Great Salt Lake.

Salt  from Brine,  Rock Salt, and Evaporated  Salt (3, 18)

Production—
Total  salt production for the United States in 1976 was
38 million metric  tons.  Of the U.S. salt production,  55% was
produced as salt  in brine, 32% as rock salt,  and 13% as  evapor-
ated  salt.  A list of the principal producers,  types of  operation,
and geographical distribution of salt  production is presented in
Appendix A.

Source Composition—
Sodium chloride, or salt, is the chief source of all forms of
sodium.   Salt is produced on a large scale  by mining bedded and
dome^type underground deposits and by  evaporating lake and sea
brines.

Bedded deposits containing hundreds of feet of salt have been
formed from ancient seas.  Salt domes,  such as those along the
Texas-Louisiana coastline, are formed  by  geologic pressures which
force bedded  salt  deposits to be extruded into vertical  pipelike
intrusions similar  to volcanic necks.   Salt domes have been
drilled  to a  depth of 6,000 m without  reaching the bottom of the
salt.
                                31

-------
Mining—
Over one-half of the U.S. salt output is produced by  introducing
water into a cavity in the salt deposits and removing the  brine.
Holes are drilled through the overburden into the deposit  through
a smaller pipe inside a casing.  About 1 yr of pumping fresh
water into a well is required to enlarge the cavity sufficiently
to obtain full production of the saturated brine which forms in
the cavity at the foot of the pipe.  The brine is pumped or  air-
lifted through the annular space between the pipes.

Rock salt is mined on a large scale in Michigan, Texas, New  York,
Louisiana, Ohio, Utah, New Mexico, and Kansas.  Room-and-pillar
is the prinicpal mining method.  Rock salt mining, like coal
mining, uses conventional techniques such as undercutting, drill-
ing, blasting, loading, transporting, and hoisting.

Beneficiation—
In most cases, the only treatment applied to mined rock salt is
size reduction and classification by screening.  One  or more of
the three stages of crushing occurs underground with  the rest
above ground.  A process flowsheet for rock salt is provided in
Figure 22.
              - ALTERNATE OR
               OPTIONAL PROCESS
                                                  • PRODUCT
         Figure 22.  Rock salt mining and beneficiation,
(19)  Klingman, C. L.  Soda Ash  (Sodium Carbonate), Sodium Sulfate,
     and Sodium.  In:  Mineral Facts and Problems, 1975 Edition.
     Preprint from Bureau of Mines Bulletin 667, U.S. Department
     of the Interior, Washington, D.C.  13 pp.
                                32

-------
Sodium Sulfate  (3, 19)

Production—
U.S. production of sodium  sulfate  (Na2SOtt) ,  or  salt  cake,
amounted to 1,184,000 metric  tons  in  1973.   A list of  the  princi-
pal producers and their geographical  distribution is presented in
Appendix A.

Mining and Beneficiation—
Sodium sulfate  is recovered from Great  Salt  Lake and Searles  Lake
brines by a step-wise evaporation  process  and from West  Texas
brines by a selective crystallization process.  Process  flow  dia-
grams are shown in Figure  23  below and  in  Figure 29  in Section 3.
                                          STEAM VENT
SODIUM
SULFATE
BRINE WELL



SETTLING


1 	 1 '
_ COOLING AND H
i

SETTLING ~J
LIC
EVAF
SALT CAVERN
                                    FILTER
                                                   DRYER
                                   LIQUOR TO
                                    'ORATION
                                    POND
          Figure  23.   Sodium  sulfate  from  brine wells.

Sulfur  (3, 20, 21)

Production—
In 1975, the U.S. production  of  sulfur  from  Frasch mines was
7,325,000 metric  tons.  Frasch sulfur accounted for  64% of  the
domestic production of sulfur in all  forms in  1975,  as compared
to 69% in 1974.   Frasch sulfur was produced  at 13 mines in  Texas
and Louisiana.  A list of principal producers  and their geograph-
ical distribution is provided in Appendix  A.

Source Composition—
Native sulfur is  sulfur that  occurs in  its elemental form in
nature.  Frasch sulfur is native sulfur mined  by the Frasch hot-
water process.  Minable deposits of native sulfur are of three
types:  sulfur combined with  anhydrite  cap rock lying on salt
domes, sulfur associated with bedded  anhydrite, and  sulfur  at
volcanic origin.

The major domestic sources of sulfur  (85%  of plant production)
are associated with the Gulf  Coast salt domes.  The  sulfur-
(20) Shelton, J. E.  Sulfur  in  1975.  Mineral  Industry  Surveys,
     U.S. Department of the  Interior, Washington,  D.C.,  July 10,
     1976.  17 pp.
(21) Lewis, R. W.  Sulfur.   In:  Mineral Facts and Problems, 1970
     Edition.  U.S. Department  of  the Interior,  Washington,  D.C.,
     1973.

                                33

-------
bearing cap rock occurs at depths of less than 900 m as  shown  in
Figure 24  (22).  Most of the elemental sulfur is found in  the
limestone or carbonate zone of the cap rock, and it may  vary from
nearly 0 m to  100 m in thickness, having sulfur content  which  may
range from traces to more than 40%.

Mining—
Mining of sulfur is accomplished by the Frasch, or hot water
process, illustrated in Figure 25.  In this process, sulfur is
melted underground by pumping hot water to the formation.  Molten
sulfur is then raised to the surface through the drill pipe and
stored as a liquid in steam-heated tanks.  In most installations,
the liquid sulfur is pumped directly into heated and insulated
ships or barges which transport the sulfur in liquid form.  Less
than 15% of the total sulfur produced in the United States is
metered and pumped to storage vats for cooling and solidifying
before it is sold in dry form.

In addition to producing wells, "bleed-off" wells must be drilled
in appropriate locations to control dome pressure and allow for
continuous introduction of hot water (see Figure 24).  A process
flow diagram is provided in Figure 26.

Trona Ore  (19)

Production—
In 1974, U.S.  trona ore production was 3,682,000 metric tons.
Most of the world's supply of natural soda ash comes from a small
region in southwest Wyoming called the Green River Basin.  A list
of the principal producers and their geographical distribution is
presented in Appendix A.

Source Composition—
The terms soda ash and sodium carbonate are used interchangeably.
The material of commerce—trona—obtained from Wyoming normally
contains more  than 99.8% sodium carbonate, and the sodium chlo-
ride content is less than 0.05%.  The presently mined deposits
average 93% trona (Na2CC>3 'NaHC03 -2H20) , with small  (less than
0.10%)  quantities of sodium chloride and sodium sulfate.

Mining—
Underground mining of trona is similar to coal mining.  Both
room-and-pillar and longwall methods are used.  The material is
undercut, drilled, blasted, crushed, and transported to  the
surface by established methods.

Beneficiation—
The refining process for trona ore consists of its conversion  to
pure sodium carbonate.   The process includes the removal of
(22) Kirk-Othmer Encyclopedia of Chemical Technology, Second
     Edition, Vol. 19.  John Wiley & Sons, Inc., New York,
     New York, 1967.  839 pp.

                               34

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                                         SULPHUR WELLS 9UCOWATER WELL
           Figure 24.   Cross  section of a  typical
                         sulfur-bearing salt dome.
Kirk-Othmer  Encyclopedia of Chemical Technology,  Copyright  (c)  1967.
         Reprinted by permission  of John Wiley &  Sons,  Inc.
                Figure  25.  The Frasch process.

Kirk-Othmer  Encyclopedia of Chemical Technology, Copyright  (c) 1967,
         Reprinted by permission of John Wiley S Sons,  Inc.
                               35

-------
                TREATMENT
                CHEMICALS
        RAW WATER

i SLOWDOWN
-i* ^*-
BOILERS


HttPY
EXCHANGERS f
1


HEATER

SULFUR
DEPOSIT

1
«^J
1



                                                    •MOLTEN SULFUR
                                                     PRODUCT
                SLOWDOWN
               	ANHYDRITE DEPOSITS
               	CONVENTIONAL SALT DOME OPERATIONS
 BLEED WATER
TO TREATMENT
AND DISPOSAL
           Figure 26.  Sulfur mining and beneficiation.

insoluble  impurities through crushing, dissolving  and separation;
removal of organic impurities  through carbon absorption;  and
removal of excess carbon dioxide  and water by calcining and
drying to  soda ash.  Two variations of the process are  used:  the
"sesquicarbonate" process and  the "monohydrate" process.   General
process flowsheets for both processes are shown in Figures 27 and
28, respectively.

Searles Lake in California is  the only U.S. source of natural
soda ash other than the Green  River Basin.  The brines  are
obtained by drilling wells into the aquifer and installing pumps
and pipelines to transfer the  liquid to the processing  plant.  A
process flowsheet is provided  in  Figure 29.
                                 36

-------
CO
   Figure 27.  Trona ore beneficiation
               (sodium sesquicarbonate process)
Figure 28.  Trona ore beneficiation
            (monohydrate process).

-------
u>
00
                                                                                           *- BORAX PRODUCT
                                                                                               POTASSIUM
                                                                                             CHLORIDE PRODUCT
                                                                                          •-LITHIUM SALTS PRODUCT
                                                                                          •-SODA ASH PRODUCT
                                                                                          ^^---7$—*-BORAX PRODUCT
                                                                                            DRYER
                                                                                                     MELT,
                                                                                                    CALCINE
                                                                                                 SODIUM SULFATE
                                                                                                    PRODUCT
                               Figure  29.   Searles Lake minerals  recovery.

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                             SECTION  4

                             EMISSIONS


SELECTED POLLUTANTS

The major air pollutant of  concern emitted  from  the  production  of
chemical and fertilizer minerals  is  respirable  (less than  7-ym
geometric mean diameter) particulate matter.  This particulate
contains free silica, the crystalline  silicon dioxide which  is
mostly quartz, tridymite, and cristobalite.

The American Conference of  Governmental Industrial Hygienists
(ACGIH) has suggested a TLV® (threshold limit value)  (23)  for
respirable particulates as  shown  in  Equation 1:


              TLV = % quartz + 2  (for  % ^artz ±1%)            (4)

where       TLV = threshold limit value, mg/m3
       % quartz = percent of quartz  in respirable dust

Respirable particulates with less than 1% quartz are termed
"inert" and a TLV of 10 mg/m3 is  suggested  for these (23) .   The
criteria document on crystalline  silica published by the National
Institute of Occupational Safety  and Health  (NIOSH)  states that
occupational exposure shall be controlled so that no worker  is
exposed to a time-weighted  average concentration of  free silica
greater than 50 yg/m3 as determined  by a full shift  sample for up
to a 10-hr workday, 40-hr workweek (23) .  In addition, parti-
culate matter is one of the air quality criteria pollutants  and
has a 24-hr primary ambient air quality standard of  260 yg/m3.

Nitrous oxides (NOV) and cajcJjcjijggonQaida-J^^              from
                      rTTe^epollutants have threshold limit
                      55 mg/m3, respectively.  Both  of these are
criteria pollutants with primary air quality standards of 100 g/m3
(0.05 ppm) for the annual arithmetic mean for nitrogen dioxide
(NO2) and 10 mg/m3 (9 ppm) for an 8-hr average concentration for
CO.  There is also a 1-hr average concentration standard for CO
(35 ppm) .
(23)  Documentation of Threshold Limit Values for Substances  in
     Workroom Air.  American Conference of Governmental Indus-
     trial Hygienists, Cincinnati, Ohio, 1972.  97 pp.
                               39

-------
 EMISSION CHARACTERISTICS

 Air  Emissions

 Air  emission factors  derived  from direct  sampling data are not
 available for  most  of the  mineral producing  industries in this
 study.   In fact,  the  only  direct  information available concerns
 production of  potash  and phosphate rock.

 Emission factors  for  respirable and total particulate  emissions
 from the various  mineral operations are presented in Table 6.

 The  major pollutant of each mineral industry in  the study is
 respirable particulate matter.  Because of this  and the  relative
 production figures, actual sampling was not  deemed necessary  for
 every mineral.

 As can  be observed  from Table 6,  phosphate rock  alone  accounts
 for  39% of the chemical and fertilizer mineral tonnage.   Because
 phosphate rock production  is  so high in relation  to the  other
 minerals,  additional  air-sampling studies would  have little util-
 ity  in  identifying  potential problems of any proportion.   Addi-
 tional  sampling would not be representative  of the chemical and
 fertilizer mineral  industry unless  every mineral  cited in  this
 report  was sampled.

 In the  absence of direct sampling data, estimates  were determined
 by an indirect method (Appendix B).

 Phosphate Rock—
 Phosphate rock production accounts  for an estimated 44%  of the
 total particulate emission from chemical and  fertilizer  industry
 mining  and beneficiation.  The high percentage is  caused by the
 large volume of phosphate rock production and the  kinds  of opera-
 tions necessary to  run an industry  of its size.  For example, the
 loading of railroad hopper cars,  a  major source of particulates,
 is an operation used  only by industries with  large amounts of
 material  to handle.

 The  source of  air emission during phosphate  rock mining  and pro-
 cessing are pictured  in Figure 30.   The emission  factor  which
 corresponds to each source and the  following discussion  are
 summarized in  Table 7.

 No sampling for the dragline source  in Florida has been  done.
 However,  some  estimates have been made on fugitive emission from
 other source assessment studies on  mining.   Dust emissions from
 surface mining of coal were measured by MRC  as 0.085 g/kg  of
 overburden removed.   Battelle indicated that overburden  removal
was the  largest emission source at  strip mines and estimated
 0.05  g/kg.  Engineering Research  and Technology, when providing
 input on  the air  quality aspects  of  coal.development in  northwest


                               40

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        TABLE  6.   PRODUCTION  AND PARTICULATE EMISSION  DATA FOR
                     THE CHEMICAL AND  FERTILIZER  MINERAL  INDUSTRY
Mineral
Barite
Borates
Fluorspar
Lithium minerals
Mineral pigments
Phosphate rock
Potash
Brine salt
Rock salt
Evaporated salt
Sodium sulfate
Sulfur
Trona ore
Total
Respirable Total Total particulate
particulate, particulate, due to production, to
g/metric ton g/metric ton metric tons/yr
17
21
36
10
20
37-
110
9
1.
9
7.
0.
11
Estimated. Assumes 80%
TABLE 7.


AIR


Emission factor/
Control
devices:
170a
203a
350a
iooa
190a
362C 16
1,110° 16
86a 1
2 103
86a
3 73a
02 0.2a
iioa
36
198
216
39
1.2
12
,028
,783
,797
122
425
136
1.5
405
,164
Contributioi
from product:
overall nat:
emission, '
0.001
0.001
0.0002
0.000007
0.0001
0.10
0.10
0.01
0.0007
0.003
0.001
0.000009
0.002
0.2
of current capacity. ""Determined from sampling results.
EMISSION SOURCES OF
Dragline
Stripping Mining
of of the
overburden ore
g/kg 0.025 0.0004

Existing types None None
Effectiveness /
Future
trends
% None None
None None
PHOSPHATE

Drying
0.071

Cyclone and
wet scrubbers
>95
None
a
ion Production
ional Tonnage,
i metric tons
1,167,000
1,063,000
111,000
12,000b
63,500
44,276,000
15,120,000d
20,900,000
12,160,000
4,940,000
1,864,000
7,325,000
3,682,000
112,683,500
Year
1974
1975
1975
1976
1972
1975
1975
1976
1976
1976
1973
1975
1974
Production for underground
Percent
of total
1.04
0.94
0.10
0.01
0.06
39.29
13.42
18.55
10.79
4.38
1.65
6.50
3.27
100
mines only
ROCK MINING AND BENEFICIATION3
Silo
storage
0.105

Scrubbers
>95
None

Loading
0.161

Enclosure
_c
Exhaust fugitive
dust to
control device

Total
0.362

_b
_b
_b






aNumbers were derived from six sample runs made at one site.  See Appendix H.  "Not applicable.
CNot available.

-------
                                         BENEFICIATION
                                           PLANT
                           DRAGLINE
             BENEFICIATED
           PHOSPHATE ROCK ORE
                        OPEN STORAGE *            LOADING OF RAILROAD CARS

           Figure 30.   Selected  phosphate rock sources.

Colorado,  proposed an emission  factor of 0.024 g/kg of overburden
removal,  including a  correction for climatic conditions and
control measures (watering)  at  the mines (24) .
Overburden,
                                       mining is believed to be
rtm'cTTTess  overburden material is handled; the average" overBurden
depths  in  Florida are about 6 m versus up to 60 m for coal mining.
Also, phosphate  rock deposits in Florida are generally mined  in
areas where  the  water_jtabjLe is near the surface.  Because the
moisture content of  thlT over Jour den is nlgri^ TesFs dust is
produced.

An emission  factor for the overburden removal of phosphate rock
lies toward  the  bottom of the range offered by PEDCo — 0.024 g/kg
to 0.05 g/kg of  overburden (24).  PEDCo estimated particulate
emissions  from dragline operations at an open pit copper mine in
Butte, Montana.   The emission rate of ore mined was 0.0004 g/kg.
This excavation  area was noted to be moist and nondusting.
Although actual  measurements were not taken at phosphate rock
mines, an  emission factor of this order of magnitude was felt to
be representative for the mining of the ore.

After the  overburden is removed, the ore is placed into sluice
pits, broken up  by hydraulic monitors, and subsequently pumped to
the beneficiation plant.   Each company's benef iciation methods
differ slightly  and  are dependent on the characteristics of the
(24) Evaluation of Fugitive  Dust Emissions from Mining, Task  1,
     Report:  Identification of Fugitive Dust Sources Associated
     with Mining.  Contract  68-02-1221, Task 36, U.S. Environmen-
     tal Protection Agency,  Cincinnati, Ohio, April 1976.   78  pp.
                                42

-------
matrix.  In each  case,  however,  the beneficiation is a wet proc-
ess and therefore not  a source of air emissions.
The beneficiated  rock  is  transferred to open storage piles.  As
this material  is  often moist,  no controls are used or expected in
the future although some  emissions do result from the operations.
The moist material  is  usually  conveyed to a rotary dryer.  A
particle size  distribution of  phosphate rock dryer dust from orie
location is presented  in  Figure 31 (personal communication with
H. Robert Trew, Agrico Chemical Co.,  Mulberry, Florida,
February 17, 1977).  An analysis of the particle emissions from
phosphate rock processing and  the results of MRC sampling and
methodology are presented in Appendices G and H.
                                        AFTER CYCLONE
                                        BUT PRIOR TO
                                        SCRUBBER
                                         NO. 1 DRYER STACK
                                                    100 150 200
                              PARTICLE DIAMETER. \im (Log Scale)
            Figure  31.
Particle size distribution of
phosphate rock dryer dust.
Emission factors  for  phosphate mining that are presented in this
report are based  on Florida phosphate operations.   Western phos-
      mining oppT-af-inns  arp. recognized as haying greater air emig-
sions
                                         wet/-sluiced to benef icia-
tion and dust may  occur  in transport from pit to processing plant.
In addition, the overburden removal for western phosphate mining
averages more than 6  m and is  drier than the Florida overburden.
For western mines,  a  more  realistic overburden emission factor
would be near the  high end of  the range or 0.05 g/kg of over-
burden  (24) .  Thus for western mines,  the overall emission factor
could be about  7%  greater  than the factor for Florida mines.

Potash —
The air emission data for  potash refinery activity near Carlsbad,
New Mexico, is  presented in Table 8 (15, 25) .  The seven
 (25) Nicholson, B.  R.  Air  Quality Estimates of the New Mexico
     Potash Industry.  State  of New Mexico Environmental Protec-
     tion Agency, Santa  Fe, New Mexico,  August 1976.  59 pp.
                                43

-------
      TABLE 8.  NEW MEXICO POTASH PARTICULATE EMISSION  DATA

                  Time basis:   31,536,000  s/yr




Company
A
B

C
D
E

p
G

Annual
emission
rate (25) ,
g/s
22.58
318.66

10.86
62.82
26.8

87.51
91.97


Snission
Ore processed, factor
Average
K2O
content, %
40
8

16
18
14

11
23
1975
production,
kg/yr
1.655 x 109
3.625 x 109

1.932 x 109
1.944 x 109
0.468 x 109

1.653 x 109
2.202 XvlO9
based on
production,
g/kg
0.430
2.772

0.177
1.019
1.806

1.670
1.318

Ore processed.
current
capacity (15) ,
kg/yr
2.121 x 109
4.318 x 109

1.989 x 109
2.778 x 109
1.753 x 109

2.149 x 109
2.273 x 109
Emission
factor
based on
capacity.
gAg
0.336
2.327

0.172
0.713
0.482

1.284
1.334




Comments
Dryer emissions only -
Includes a separate salt
operation .
Uses a leaching operation .
_a
Dryer emissions only .
Cutback due to construction
_a
_a
  Not applicable.
companies  (A-G), which operate in the vicinity of Carlsbad, New
Mexico, are listed.  The two sets of emission factors, based on
production and capacity, are presented to equalize any production
irregulatities  (such as E's cutback on production due to construc-
tion) .  A comments column is provided to explain the deviation
among the numbers.  Except where designated, the emission factors
represent the total particulate emission of the refineries.
These emission factors account for operations such as rock trans-
fer, grinding, screening, drying, bagging, loading, and  (in B and
F's case) evaporation.

The major source of emissions is the drying operation, which is
employed at all locations.  The emission factors for A and E give
a rough indication of the amount of emission caused by drying.

Another major source of particulate emission appears at the
locations where langbeinite ore is processed by an evaporation
step, using Ozark submerged-combustion evaporators.  An Ozark
evaporator consists of a tank to hold the liquid, a burner and
gas distributor that can be lowered into the liquid, and a com-
bustion-control system.  Submerged-combustion evaporators often
have a high entrainment loss.  Prior particle size measurements
of the particulate matter emitted from a plant's Ozark evaporator
showed 100% of the particles to be less than 7 ym.  These would
all remain suspended.  A study is currently in progress to assess
the application of Monsanto's BRINK® fine particle eliminators to
the problem.

State and National Emissions Burden—
Emission factors for total particulates were used to calculate
each state's emission rate as the product of its emission factor
and its mineral processing rate.  The state emission burden is
thus calculated as the percent contribution of the state's
                                44

-------
particulate emission rate for chemical and fertilizer mineral
processing to its overall particulate emission rate.  Appendix C
displays the state emission burdens.

Water Effluents  (3)

Most of the chemical and fertilizer mineral operations use large
amounts of water and generate wastes in the form of overburden,
slimes, and tailings.

Water used in the mineral mining and processing industry can be
characterized as:

   • Noncontact cooling water.

   • Process water (wash water, transport water, scrubber
     water, process- and product-consumed water, and
     miscellaneous water).

   • Auxiliary process water.

Noncontact cooling water is cooling water which does not come
into direct contact with any raw material or product used in or
resulting from the process.

Process water comes into direct contact with raw materials or
products of the process.

Auxiliary process water is water which is used for process
necessary in the manufacture of a product without contacting the
process materials directly.

The amount of water used by facilities in the chemical and
fertilizer mineral industry ranges from 0 to 726,400 m3/day.
Typically, the plants which utilize very large quantities of
water use it for heavy media separation and flotation processes,
wet scrubbing  and noncontact cooling, or as the process medium
in sulfur mining.

The following is a discussion of water uses and effluent charac-
teristics for each mineral in the chemical and fertilizer mineral
industry.  Tables of effluent concentrations or mineral categor-
ies which have discharges are given in Appendix F%

Barite—

Mine water discharges—
     Water use—Underground mine workings intercept numerous
ground water sources.  At one location, the water is directed
from sumps in the mine to an upper level sump.  The mine water
is then neutralized with lime  (CaO) for pH adjustment during
pumping and sent to a pond for gravity settling prior to
discharge into a nearby creek.

                               45

-------
     Effluent characteristics—The total annual effluent dis-
charge to the creek is estimated to be 760,000 m3/yr.

Wet process—
     Water use—The quantity of water consumed, which ranges from
7.3 to 290 md per metric ton of product at different sites,
depends upon the quality of the ore and the type of waste mater-
ial associated with the ore.  Process water is recycled in all
the plants; makeup water may be required at some.

     Effluent characteristics—Under normal conditions, no
effluent discharges from any of these plants.  However, heavy
rainfall, overflow from ponds can occur.  The amount of such
intermittent discharges is unknown.

Dry process—No water is used in barite dry grinding plants, nor
is there any pumping of mine water.

Flotation process—
     Water use—The plants in this category consume, on the aver-
age about 30-0 m3 per metric ton of product.  A large portion of
the process water has been recycled from thickening operations.
Well water and river water are used at some plants as additional
process water.

     Effluent characteristics—Barite plants have no or only
intermittent discharges which occur during heavy rainfall or to
maintain a constant pond elevation.

Borates--

Water use—The mined borax ore processing plant in the United
States consumes 2.8 m3/metric ton.   An additional 0.8 m3/metric
ton enters with the ore.   Most of the cooling water is recycled,
and all the process wastewater is sent to evaporation ponds.

Effluent characteristics—There is no plant effluent.

Fluorspar—

Mine water discharge—Of the seven currently productive mines in .
the United States, six are underground and one is a dry open-pit
mine.  In addition, there are three underground mines being
developed and five nonproducing mines which are active for mine
dewatering purposes.   At two of the productive mines, up to 40%
and 62% of the mine discharge water is used at the mills.  The
remaining effluent is then discharged.

Heavy media separation—
     Water use—In these plants, water consumption ranges from
2.7 to 9.6 m^/metric ton of feed.
                              46

-------
     Effluent characteristics—Five of the six plants in this
category have no effluent.  The water is recycled back through
closed circuit impoundments.

Froth flotation—
     Water use—Ores with different physical characteristics
require different quantities of process water.  A maximum 20% of
the process water is recycled from the thickeners, while the rest
discharges into a ponding system.  An average process hydraulic
load for these plants is 2,070 m3/day.

     Effluent characteristics—Plant wastewater is treated in
settling ponds.  At most, 20% of the water from the clarification
pond is recycled and the remainder is discharged.  Total recycle
attempts have failed because the numerous reagents used in vari-
ous flotation circuits caused chemical buildups.

Lithium Minerals—

Natural brine  (Silver Peak operations)—
     Water use—Process water consists of brine from an under-
ground source and fresh water used for wash purposes.

     Effluent characteristics—All process water is evaporated.
and there is no discharge.

Flotation process—
     Water use—At both plants in this category, the process
water recycle is 90% or greater.  Total water usage is in the
range of 13.0 to 28.0 m3/metric ton of ore.

     Effluent characteristics—Each plant has one effluent stream.
The discharge consists primarily of settling pond overflow with
minor contributions from mine pumpout and miscellaneous surface
runoff.

Mineral Pigments—

Water use—At one plant, process water use is approximately
28.0 mVmetric ton of product.  The water is obtained untreated
from a large settling pond.  Approximately 95% of the process
water overflows from the thickener and drains to the settling
pond.  The remaining 5% is evaporated on a drum dryer.

Effluent characteristics—The water effluent is sent to a set-
tling pond from which there is no significant discharge.

Phosphate Rock—

Eastern process—
     Water use—Nearly all water used in the beneficiation of
phosphate ore is for processing purposes.  Only small amounts are


                                47

-------
 used  for  noncontact  cooling  and  sanitary  purposes.  A typical
 hydraulic load  is  in the  range of  41.0  m3/metric  ton  of  product.

      Effluent characteristics—Effluents  are periodically  or con-
 tinuously discharged from one or more settling areas  by  all of
 the beneficiation  plants.  The volume of  effluent is  related to:

    •  Percent recycle        • Surface runoff
    •  Amount of  rainfall      • Available settling pond acreage

 Western process—
      Water use—The  water used is  almost  totally for  processing
 (greater  than 95%) with only a small volume for other areas of
 the plant.  An  average water usage is 7.0 m3 per metric  ton of
 product.

      Effluent characteristics—Most of  the plants have no
 discharge.

 Potash—

 Water use—The  average fresh water use  at sylvinite and  lang-
 beinite ore plants is"4.0 and 7.0  m3 per metric ton of product,
 respectively.

 Fresh water use at the Utah  operations  amounts to 10,600 m3/day.
 This  water is used first  on  the  flotation circuit and then in
 solution  mining.

 Effluent  characteristics—There  are no  effluents from sylvinite
 or langbeinite  plants.  All  wastewater  streams are fed to  evapora-
 tion  ponds from which there  are  no discharges.

 In Utah,  the brine resulting from  the operations is evaporated to
 recover solids  for the flotation unit;  there is no wastewater for
 discharge.

 Salt  from Brine, and  Rock Salt—

 Salt  from brine (Great Salt  Lake)—
     Water use—Most  wastewater  comes from the washing of
 recovered  sodium chloride.

     Effluent characteristics—There are no effluents; discharged
waste brines are returned to the lake source.

Rock salt—
     Water use—In the mining and  processing of rock  salt, water
consumption varies due to"its miscellaneous uses. Water  is rou-
tinely used for cooling,  heating,  and sanitation, with a small
volume used to dissolve anti-caking reagents.  Variable  amounts
are also used in dust collection and washdown of waste salt.  The


                               48

-------
volume of intake water per unit of production can range from 0.01
to 1.3 m3 per metric ton of product.

     Effluent characteristics—Plant effluents consist primarily
of mine seepage and wastewater from dust collectors and miscellan-
eous washdown of operating areas.

Sodium Sulfate—

Water use—Process water consists entirely of brine, all of which
goes to the process and then to waste with no recycle.

Effluent characteristics—There is no discharge at these loca-
tions; in the arid climate, effluents evaporate.

Sulfur—

Anhydrite deposits—
     Water use—Plants located on anhydrite deposits consume
about 8.0 m3 of water per metric ton of product.  Approximately
50% of the water is recycled back to the system, and the remain-
der is lost in the sulfur-bearing formation.

     Effluent characteristics—There is no process water effluent
from these plants.

Salt dome operations—
     Water use—The average amount of process water consumed by
each of the plants is about 30,000 m3/day.  These plants are all
designed for a given hot water load.  The sulfur-to-water ratio
varies a great deal from formation to formation, and the quantity
of water used by the industry is not determined solely by the
quantity of product.

     Effluent characteristics—The major waste from salt dome
mines is the bleedwater from the formation.

Trona Ore—

Water use—Water use at mines with attached refineries is deter-
mined principally by the refining process.  The only kinds of
water intrinsically associated with the mines are mine pumpout
water, dust control water, and sanitary water, the latter two
being rather small.

Most plant water intake comes from the Green River  (fresh water)
and from mine pumpout  (salt water).  In some instances, mine
pumpout is used as part of the process water; in others, it is
discharged to the treatment ponds.  The average river intake for
three refiners is 8,700 m3/day; average pumpout for all four
trona ore mining facilities is 640 mVday.

There are three major routes of consumption:

                               49

-------
   • Evaporation by drying operations and cooling water
     recycling.

   • Discharge of wastewater to evaporation ponds.

   • Discharge of wastes to waterways.

Effluent characteristics—Only one facility discharges process
wastewater, and plans are under way to eliminate this.

One mining plant discharges its mine water; another plant dis-
charges ground and runoff waters.

DEFINITION OF THE REPRESENTATIVE SOURCE

A Florida phosphate rock-producing facility was chosen as repre-
sentative of the chemical and fertilizer mineral industry because:

   • Phosphate rock constitutes 40% of the chemical and
     fertilizer mineral output.

   • The bulk of the industry is concentrated in a relatively
     small area  (about 3 1/2% of Florida's land area, and the
     plants have large capacities.

   • The unit operations used by the phosphate rock industry are
     representative of the whole chemical and fertilizer mineral
     industry.

The representative source is defined as one with average emission
parameters; i.e., average emission factor and average production
rate.  Florida phosphate rock plants have production rates of
from 450,000 metric tons/yr to 4,500,000 metric tons/yr with an
average of 2,000,000 metric tons/yr.

The average emission factor was determined by making six sample
runs at one site (Appendix H).  Thus the representative source
has an emission factor of 0.037 g/kg for respirable particulates.

The sampled plant had an average area of 0.51 km2.  The repre-
sentative distance to plant boundaries, taken as the radius of a
circle whose area is equal to the area of the plant, was 400 m.
The representative population density was taken as the population
density of Polk County, Florida, the major producing area, and
was determined to be 50 persons/km2.

HAZARD RATIO

Air

The maximum hazard ratio due to respirable particulate emissions
from the representative plants of each mineral category is


                               50

-------
provided  in  Table 9.  An example of  hazard ratio calculations  is
provided  in  Appendix E, together with  the equations utilized.

                TABLE 9.  HAZARD RATIO  CALCULATIONS


Mineral
Barite
Borates
Fluorspar
Lithium
Mineral pigments
(Iron oxide pigments)
Phosphate rock
Potash
Brine salt
Rock salt
Evaporated salt
Sodium sulfate
Sulfur
Trona ore
Total
Number of
principal
sites
24
3
11
4

15
23
7C
37
19
11
5
13
	 3
170
Representative
Emission Representative
rate of distance to Hazard
respirable plant ratio for
plant size, particulate,
metric tons/yr
50,000
800,000
10,000
3,000

4,000
2,000,000
2,000,000
600,000
600,000
450,000
400,000
600,000
1,000,000

g/s
o.osa
0.903
0.02a
0.0028

0.0048
4.0b
12.0b
a
0.30
a
0.04
a
0.20
a
0.20
0.00068
0.60a

boundary ,
m
400
400
400
400

400
400
400
400
400
400
400
400
400

respirable
particulates
0.004
0.07
0.002
0.0002

0.003
0.3
0.9
0.02
0.003
0.02
0.02
0.00005
0.05

Average
population
density
of major
producing
areas ,
persons/km2
10
10
80
120

100
50
3
50
10
20
10
30
1

Affected
population.
O.KSp<1.0
persons
0
0
0
0

0
15
15
0
0
0
0
0
0

 Estimated.  Determined from sampling results.  Includes only New Mexico mines.

Water

The  phosphate rock industry was  the  only one  for which complete
information was available concerning river flow rate and concen-
tration.   For a representative source  discharging into Florida's
Peace  River, the hazard ratios of  elemental phosphorus, fluoride,
and  total suspended solids are 0.061,  0.051,  and 0.0025, respect-
ively.   Hazard ratio calculations  are  provided in Appendix E,
together with the equations utilized.
                                 51

-------
                             SECTION 5

                        CONTROL TECHNOLOGY


 STATE  OF  THE ART — AIR POLLUTION CONTROL TECHNOLOGY

 Phosphate rock

 Since  the stripping of overburden and mining of the Florida
 phosphate matrix is carried out under somewhat "wet" conditions,
 industry  does not consider this a source of air emissions.
 Therefore,  they have no controls on this operation and do not
 expect a  future need.   Since this condition is naturally differ-
 ent  for the western operations, controls may be needed.

 The  beneficiated rock in open storage piles is moist.  No con-
 trols  are used or expected in the (future, although some emissions
 do result.

 Typically,  the moist material is conveyed by an underground belt
 operation to a rotary dryer.  ^The^dust f rom the_dryers__ is_handled
 by eye lon_e-_wet_ ^scrubber c omb i na t i o nsT  THne^peraFion us es~li    -
 rotary dryer which^Ealf"~a eye lone"™ s"cr\ibber followed by twin wet
 scrubbers.)   In this way, the emission becomes a stack emission.
point, the material  may  be  ground,  sometimes under wet conditions;
the procedure varies from plant to  plant.   One plant which was
visited does not  use a grinding operation  at all.
The material  is  trjmsJ:errj2d_jEL^
Control devices ^o^rTo^cTr'tFansferjunctions are typically jscrub-
      with -aja—avacage, collection ^efficiency greater than 9JLjLt-
From the storage  silos  the  rock is  dropped into railroad hopper
cars for transportation to  fertilizer manufacturing centers.  In
loading facilities  typical  of  the phosphate industry, loading is
accomplished manually from  overhead storage by an operator stand-
ing at the roof level of the railroad car.  Usually the drop
areas have flexible rubber  couplings which deliver the rock to
within about 0.610  m (2 ft) of the  top of the loading door; this
helps direct the  rock.   However,  t he^J^adJng ^probl em_ jJLjiot,
dusting., caused by ..the drop , ^jaJ^jtKe^p i ckujelof<>dus t^n^h£_^di.s-
pT££Qa^£.i-£j^                      The industry is workTng^to
control the dust  in this operation.
                                52

-------
Companies have installed extensive ductwork systems to capture
the dust and exhaust it to a scrubber.  However, as noted by one
industry representative, operators do not always use the equip-
ment properly.  Dust-catching enclosures must be clamped onto the
railcar doors tight enough to capture the dust.  One plant uses a
mechanized system in which the ends of eight loading ducts fit
over the tops of the eight railcar doors and exhaust the dis-
placed air to a scrubber.  In older facilities, this may not be
possible.  At one location, for example, the available headroom
between the bottom of the storage silo and the top of the rail-
cars is limited, and cars are typically not of uniform height or
door configuration.  This situation required the design of a
system to load the cars from an outside hopper adjacent to the
silos, allowing for more working space.  In either case, it
appears that the future trend is first to contain the fugitive
emission and then to treat it as a stack emission.

Potash

The most obvious form of current control technology is the use of
dry cyclones, not only at drying locations, but at milling,
screening, and bagging points as well.  According to the New
Mexico Environmental Improvement Agency, nearly all the existing
potash refineries will need to control their present emissions.
At this point, the agency is investigating different types of
control technology and their costs (25).

STATE OF THE ART—WATER POLLUTION CONTROL TECHNOLOGY (3)

Four significant wastewater problem areas have been found in the
mining and beneficiation of minerals for the chemical and fertil-
izer industries:

   • Mine water drainage which contains acid, heavy metals,
     fluorides, and phosphates occurs frequently in this
     segment of the mineral mining industry.

   • Wastewater from the fluorspar industry contains soluble
     fluoride in addition to suspended solids.

   • Phosphate rock beneficiation produces very large quanti-
     ties of slimes that have exceptionally high water retention.

   • Sulfur production from onshore salt domes creates quanti-
     ties of bleedwater brine containing up to 106 mg/mj of
     sulfides.  Both the sulfides and brine cause treatment
     and/or disposal problems for the sulfur industry.

A detailed discussion of each problem and the control technology
used is presented in Appendix D.

Control practices such as judicious selection of raw materials,
good housekeeping, and minimizing leaks and spills are of limited

                               53

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 importance  in  the  chemical  and  fertilizer mineral  industries.
 Raw materials  are  fixed by  the  composition of  the  ore;  good
 housekeeping,  leaks,  and  spills have  little  impact on waste
 loads;  and  noncontact water  is  rarely used in  these processes.

 The areas where control is  important  include:

    • Wastewater containment.

    • Separation and control  of  mine water, process water, and
     rain water.

 Containment

 Most wastewater treatment and control facilities in the chemical
 and fertilizer minerals industry use  one or more settling ponds.
 Often the "pond" is actually a  swamp, gully, or other low spot
 which will  collect water.  During periods of heavy rainfall,
 these "ponds" are often washed  out, and the settled solids  may be
 swept along as well.  In many other cases, the pond may remain
 intact  during rainfall, but  its function as a  settling pond is
 significantly impaired by the large amount of water flowing
 through it.  In addition to problems  caused by rainfall and
 flooding, waste containment  in  ponds  can be troubled with ground
 seepage around and beneath the  pond,  escape through pot holes,
 faults  and  fissures below the water surface, and the physical
 failure of  pond dams  and dikes.

 In most cases, satisfactory pond performance can be achieved by
 proper  design.  When  this is not possible, alternative treatment
 methods—thickeners,  clarifiers, tube and lamella  separators,
 filters, hydrocyclones, and centrifuges—can be utilized.

 Separation  and Control of Wastewater

 In these industries,  wastewater may be separated into three cate-
 gories;  mine water drainage, process water,  and rain water  runoff.

The relative amounts  and compositions and applicable control
 techniques  of the above wastewater streams differ  from one
mineral category to another.

Process water and mine drainage are typically controlled and con-
tained  by pumped or gravity flow through pipes, channels, ditches
and ponds.  Rain water, though, is often uncontrolled; it may
either  contaminate process and mine drainage water, or flow off
the land independently as nonpoint-source discharges.  Rain water
runoff  increases suspended solid matter in rivers,  streams,
creeks  or other surface water used for process water supply.

Suspended solids are  the principal pollutant in the wastewater
discharges  of the chemical and  fertilizer mineral  industry.  The
treatment technology  available  for removing suspended solids from

                               54

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wastewater are numerous and varied, but only a relatively small
number are used widely.  Table 10 shows the approximate breakdown
of usage for the various techniques.

          TABLE 10.  CONTROL TECHNOLOGY AND ITS USE FOR
                     REMOVAL OF SUSPENDED SOLIDS  (3)


                                                   Percent of
                                                   facilities
 	Removal technique	using technology

 Settling ponds  (unlined)                           95 to 97
 Settling ponds  (lined)                                <1
 Chemical flocculation  (usually with ponds)          2 to 5
 Thickeners and clarifiers                           2 to 5
 Hydrocyclones                                         <1
 Tube and lamella  settlers                             <1
 Screens                                               <1
 Filters                                               <1
 Centrifuges                                           <1
Generally, the current  industry experience with settling ponds
shows effluents with TSS concentrations ranging from 14,000 mg/m3
to 703,000 mg/m3.  Performance data for some treatment systems
are presented in Table  11.

Chemical and fertilizer mineral operations are typically con-
ducted in relatively isolated regions where there is no access to
publicly owned wastewater treatment plants.  In areas where
publicly owned facilities could be used, pretreatment to reduce
the load of suspended solids would be required.
                                55

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          TABLE 11.   PERFORMANCE OF TREATMENT  SYSTEMS  (3)
Total suspended
solids, g/m3
Plant
Sulfur:
A


B
C



D
E


F
Fluorspar :
A
B
Phosphate rock:
A
B
C
D
E
F

Lithium minerals :
A

B

Rock salt :
A
B
Salines from lake brines :
A
Influent

120


-
100



148
271


324

8,633
25,356

5,620
329
1,684
2,036
6,500
2,985


17,150

4,720


-
194

1,945
Effluent

65


33
14



290
50


76

235
316

193
50
21
39
17
645


41

14


180
216

703
Percent
reduction

45.83


-
86.0



-
81.55


76.55

97.28
98.75

96.56
84.80
95.45
96.26
99.36
78.39


99,76

99.70


-
-

63.86
Treatment

Flash strip hydrogen
sulf ide , oxidation
with seawater.
None .
Spray aeration to
reduce hydrogen
sulf ide , oxidation
with seawater .
Oxidation, ponds.
Flue gas to strip
hydrogen sulf ide ,
ponds .
Oxidation , ponds .

Pond.
Thickener, ponds.

Pond .
Ponds .
Ponds .

Ponds -
Flocculating agent.
thickener -

Flocculating agent,
pond-
Flocculating agent,
pond .

None .
None .

None .
NOTE.—Dashes indicate data not available.
                                   56

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                            SECTION 6

                GROWTH AND NATURE OF THE INDUSTRY


A 1975 study conducted at a number of selected mines  (not limited
to the chemical and fertilizer industry) showed the various mine
operating expenses as a percentage of overall expenses  (26).  In
the period 1966 to 1974, administration costs rose slightly from
16.8% to 17%.  Crusher expenses dropped from 15% to 12%, while
drilling and blasting costs fell from 11.2% to 10%.  Loading
expenses dropped from 18% to 16%, but haulage costs rose from 39%
to 45%.  Many mines are looking at mobile crushers and belt
conveyors to reduce haulage costs.

The chemical and fertilizer mineral industry, being of a diverse
nature, will be considered by mineral.

BARITE

Emerging Technology

New discoveries of barium throughout the world can be expected
due to technological advances in exploration and prospecting.
Improvements in mining and beneficiation will help to maintain
high quality.

Demand and Production Trends

No new large-scale markets for barium are on the horizon; yet in
order to assume a continuing supply, most major barite producers
are conducting extensive exploration and development programs.

The U.S. oil-well-drilling industry is the major consumer of out-
put (90%), and Nevada will continue to be the largest U.S. sup-
plier of barite.  For the next 20 yr to 25 yr, imports of barite
should provide one-third of the U.S. supply.  A comparison of
past and present domestic barite .production is presented in
Figure 32.
(26)  Steidle, E.  Evaluating the Role of Draglines and Shovels
     in Mining.  Mining Congress Journal, 63(4):30-33, 1977.
                               57

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             1,200
             1,100
           •ffi
           - 1,000
              900
              800-
              700l_
              1971
1972
1973
1974
                        1975
                        1976
                                  YEAR
              Figure 32.
   Production trend of barite
   in the United States.
BORON
Emerging  Technology                         \
                                               \
The processes  used  to  recover boron compounds from bedded depos-
its or  from underground  brines or brine lakes are not expected to
change  significantly by  the  year  2000.   The solution phase is an
important segment of boron recovery technique, and some improve-
ments in  evaporation of  the  solutions may be expected as the
chemistry of various brine systems becomes better known.  It
would appear that additional air  pollution control technology
will not be needed  in  the U.S.  Borax and Chemical Corp. plant at*
Boron, California.  A  3-yr,  $10 million program to cut dust
emissions drastically  was successfully  concluded in 1972.

Demand and Production  Trends

Present markets for boron compounds are relatively secure in
terms of competition with substitutes,  and the pattern may not
alter radically in  the future.  The average annual growth rate
for domestic consumption of  borates is  expected to be between
3.5% and 5% during  the 1975  to 1980 period;  this is a decrease
from recent years,  predicted as a consequence to the record 1973
consumption.  A comparison of past and  present domestic boron
production is presented  in Figure 33.
                                58

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                1,100
                1,000
                900
                 1972
               Figure  33.
                         1973
                                  1974
                                  YEAR
               1975
                       1976
Production trend of boron
in the United States.
FLUORSPAR
Emerging Technology

No emerging technology  of  significant important was found in this
study.

Demand and Production Trends

The demand for  fluorspar in 1976  was  very  sluggish.  The drastic
decrease in acid-grade  fluorspar- consumption  for the past two
years was at least partially  caused by the plans of the U.S.
Consumer Product Safety Commission  and the U.S.  Food and Drug
Administration  to ban the  use of  fluorocarbon propellants F-ll
and F-12 in nonessential items.   A  further decrease in demand may
occur in 1977.

In the aluminum industry,  the demand  for fluorspar was not as
great due to pollution  control measures which have made it possi-
ble to recover  more of  the fluorine.   Byproduct fluoride recovery
has become an important source.   In 1976,  the fluorspar equiva-
lent recovered  from phosphate rock  is estimated at 72,600 metric
tons, equal to  14.5% of the estimated acid-grade consumption.  A
comparison of past and  present domestic fluorspar production is
provided in Figure 34.
                               59

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                  300
                  250
                2 '200
               o
               o
               o:
                  150
                  100
                       I
                               I
                  1969   1970   1971  1972  1973  1974  1975  1976
                                 YEAR

            Figure 34.  Production trend of  fluorspar
                        in the United  States.

LITHIUM MINERALS

Emerging Technology

No emerging technology  in the mining or  beneficiation of these
minerals was noted in this study.

Demand Trends

The aluminum industry is the largest consumer  of lithium, which
as lithium carborate increases production/  lowers costs, and
reduces fluoride emissions.  Predictions are:

   • The use of lithium in the aluminum  industry will continue
     to expand.

   • 1977 will show a 10% growth in demand  over 1976.

   • There will be little buildup of lithium inventories.

With the return of more favorable worldwide  economic conditions,
it may be concluded that the growth rate for lithium chemicals
will increase  10% per year over  the next 3-yr  to 4-yr period.

PHOSPHATE ROCK

Emerging Technology

New methods to collect  dust  emissions  from  beneficiation plants,
particularly in the railcar  loading area, are  coming into view.
                                60

-------
The development of hydrometallurgical processes to recover phos-
phorus from matrix or concentrates by direct acidulation may make
it possible to improve recovery rates and reduce waste disposal
problems.  New mining and processing techniques may be developed
to utilize the potential resources of the Florida Hawthorn Forma-
tion or the Phosphoria Formation in the Western United States.

Demand and Production Trends

The past 30 yr have seen an average growth of about 6% per year
in phosphate rock production.  Although production will probably
increase in the future, growth rates are not likely to be as con-
sistent or as high as in the past; one authority forecasts 4.7%.
Future growth will be influenced by the following emerging fac-
tors that can have serious effects:

   • The current buildup of mines and fertilizer plants in
     countries whose objective is export.

   • The increasing reliance of many western rock-producing
     countries on rock and fertilizer exports.  Except for the
     United States and Australia, the plants are owned or con-
     trolled by governments and therefore are not subject to
     regular free business restraints.

   • Most European fertilizer plants, second only to the
     United States in capacity, are subject to prices imposed
     by rock exporting countries, and these have been very
     high over the past 3 yr.

   • Prices received by the farmer for his products may not
     be high enough to strengthen his continued increase in
     fertilizer use.

Comparisons of past and present phosphate rock demand and produc-
tion are provided in Figures 35 and 36, respectively.

Florida production is expected to peak in the next 5 yr and
decline thereafter.  If the demand for phosphate continues to
grow, then a substantial increase in production will come from
the western phosphate fields.  Southeastern Idaho contains about
80% of the western field reserves.

POTASH

Emerging Technology

Dust from potash plants in New Mexico may have to be controlled
even more.  Vegetation is sometimes affected by the emissions.

Potash mines are relatively safe and clean.  Mining bedded veins
is less hazardous than recovery from nonbedded deposits because
of the thickness and uniformity of the potash beds.

                               61

-------
   60,000
   50,000
"
   40,000
  1 30,000
    20,000
    10,000
      1950
1960
1970
1980
1990
                                YEAR
        Figure  35,
      Demand for  phosphate  rock
      in the United States.
2000
          60
          50
      £
      u
          40
      §   3°
      o
      en
          20
          10
          1950
      Figure 36,
                               j_
    I960
    1970

    YEAR
    1980
   1990
    Production  trend  of phosphate
    rock  in the United States.
                             62

-------
Demand and Production Trends

The United States demand for potash in the year 2000 is expected
to be between 9 x 106 and 14 x 106 metric tons equivalent of K2O,
representing average growth rates of 2.2% and 3.8%, respectively.

These growth rates are below those of recent past years.  From
1964 to 1973, the average increase in demand was 6.3%.  It is
believed that this growth rate cannot be maintained because of
physical limitations on consumption.  Restraints on domestic fer-
tilizer use, such as land availability, more efficient fertilizer
application, new fertilizer technology, and a shift by developing
nations away from importing U.S. food, should hold U.S. demand
for potash to a modest growth level.

Consumption of potash by the chemical industry, which amounts to
only 5% of the total, should expand at about the same rate as
agricultural use.

Comparisons of past and present demand and production are pro-
vided in Figures 37 and 38, respectively.

SALT

Emerging Technology

It is likely that future improvements in salt processing will
come in the form of minor changes to reduce costs or improve
quality rather than as major technological breakthroughs.

Demand and Production Trends

In those countries where the industrial base is still developing,
growth in demand for salt is expected to be faster than it is in
the United States.  Growth rates are projected to 4.0% per year
for the United States and 6.3% annually for the rest of the
world.

Total salt production in 1976 was up 2% over 1975, and consump-
tion increased 5%.  The principal reason for the increased con-
sumption was greater activity in the many areas of the chemical
industry which consume the bulk of the salt production.  Compari-
sons of past and present salt demand and production are provided
in Figures 39 and 40, respectively.

SODIUM SULFATE

Emerging Technology

No emerging technology of significant importance was found in
this study.
                                63

-------
       6,000
      5,000
    °  4,000
    a"
    z
     "? 3,000
      2,000 —
      1,500
        1950
                  1960
             1970
         1980
                       YEAR
  Figure  37.   Demand trend for  potash
                 in the United States.
      3,000
      2,500
    o
    OL
      2,0001—
        1950
Figure 38,
    I960
1970
1980
                       YEAR
Production trend for potash
in  the United  States.
                      64

-------
   70,000
   60,000
   50,000
   40,000
   30,000
   20,000
     1950
                1960
                          1970
                          YEAR
                                   1980
                                             1990
    Figure  39.
                  Demand  trend for salt
                  in  the  United States.
•z.
o
   70,000.
   60,000
   50,000
   40,000
  30,000 -
  20,000
     1950
                           I
              1960
 1970
YEAR
1980
1990
Figure  40
                Production trend  for  salt
                in  the  United  States.
                      65

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Demand and Production Trends

Consumption figures for sodium sulfate are not easily obtained,
and those appearing in the literature are often unreliable.  No
attempt is usually made to forecast cumulative demand or growth
rate for this commodity.  Comparisons of past and present sodium
sulfate demand and production are provided in Figures 41 and 42,
respectively.

SULFUR

Emerging Technology

If the results of preliminary testing are favorable, the use of
sulfur as a substitute for asphalt in road paving could open a
major new volume sulfur market before the end of the decade.

Demand and Production Trends

At the end of 1976, demand for sulfur began to strengthen.  These
improved levels of demand should carry into the year 1977.

Voluntary sulfur production (particularly Frasch process produc-
tion in the United States) has been faced with rapidly rising
production costs and prices which are not high enough to attract
the capital necessary for exploration and development of new
sulfur sources.

In the longer term, demand for sulfur from the rapidly growing
world fertilizer market will continue to increase while the out-
look for additional supplies of sulfur remains uncertain.

Comparisons of past and present consumption and production of
Frasch sulfur in the United States are presented in Figures 43
and 44, respectively.

TRONA ORE (SODA ASH)

Emerging Technology

Solution mining of trona is technically possible, but no success-
ful attempts have been made.  A new process or innovation in the
direction of solution mining might reduce the cost of mining
considerably.

Demand and Production Trends

U.S. demand for soda ash is predicted to reach 14.2 million
metric tons/yr by 2000, indicating a growth rate of 3.0% per year.

U.S. production of natural soda ash from trona or alkaline brines
is increasing rapidly.  Between 1961 and 1974, average annual
natural soda ash output increased more than 13% per year.

                               66

-------
  1,900
   /

  1,800


  1,700


 g 1,600
 s

 I 1500
 E

"2 1,400
 o

 S 1.300
 g
 ^ 1,200


  1,100


  1,000

   900
     1950
1955
                         1960
                    1965
                   1970
1975
                             YEAR
  Figure 41.   Demand  trend for sodium  sulfate
                 in the  United States.
   1,400
   1,300
  •s
   1,200
  o
  I—f
  E3
   1,100
   1,000
    900
     1950
 1955
I960
                                   1965
                              1970
1975
                            YEAR
    Figure 42.    Production trend  for  sodium
                   sulfate in the United  States.
                           67

-------
  5,900
 :5,500
 !5,000
  4,800
    1971
1972
 1973
                                1974
                             1975
                            1976
                          YEAR
    Figure 43.
     Consumption trend  of Frasch
     sulfur in  the United States.
  .000
  7,500
o
o
a:
a.
  7,100
    1971
1972
1973
1974
1975
1976
                           YEAR
    Figure 44.
     Production  trend  for Frasch
     sulfur in the United States.
                          68

-------
Capacity  is expected to  reach 7.85 million metric tons/yr  by
1978.  Comparisons of  past and present U.S. demand and production
of soda ash (natural and synthetic) are  provided in Figures 45
and 46, respectively.
              14,000
            -g 10,000
            •fe
              5,000
              4,000
                1950
                        1960
                Figure 45.   Demand  for  soda ash
                             in the  United States.
                     7,000
                   •c 6,000
                   ft
                   E
                     5,000 —
                     4,500
                       1950
I960      1970
    YEAR
                                              1980
                               1970      1980      1990      2000

                                  YEAR
              Figure  46.   Production  trend for soda.
                           ash in the  United States.'
 aincludes synthetic  and natural soda  ash from Searles  Lake,
 California, and  trona ore from Wyoming.
                                  69

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                           REFERENCES


 1.  Fulkerson, F. B.  Barium.  In:  Mineral Facts and Problems,
     1975 Edition.  Preprint from Bureau of Mines Bulletin 667.
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 2.  Stevens, R. M.  Barite.  Mining Engineering, 29(3):53-54,
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 3.  Development Document for Effluent Limitations Guidelines
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12.   Stowasser, W. F.  Phosphate Rock.  In:  Mineral Facts and
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16.   Rampacek, C.  The Impact of R&D on the Utilization of Low-
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19.   Klingman, C. L.  Soda Ash  (Sodium Carbonate), Sodium Sulfate,
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                                71

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24.  Evaluation of Fugitive Dust Emissions from Mining, Task 1,
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25.  Nicholson, B. R.  Air Quality Estimates of the New Mexico
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26.  Steidle, E.  Evaluating the Role of Draglines and Shovels
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28.  Minerals Yearbook 1973; Volume II:  Area Reports:  Domestic.
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29.  Blackwood, T. R., P. K. Chalekode, and R.  A. Wachter.
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30.  Lament, W. E., J. T. McLendon, L. W- Clements, Jr.,  and I.
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31.  Blackwood, T. R., and R.  A. Wachter.  Source Assessment:
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32.  Eimutis, E. C., T. J. Hoogheem, and T. W.  Hughes.  Briefing
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33.  Specht, R. C.  Phosphate Waste Studies.   Bulletin Series
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34.  Eimutis, E. C., J. L. Delaney, T. J. Hoogheem, S. R. Archer,
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     December 1977.  132  pp.


                               72

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35.   Turner, B. D.  Workbook of Atmospheric Dispersion Estimates.
     Public Health Service Publication No. 999-AP-26, U.S.  Depart-
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     May 1970.  84 pp.
                                73

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                           APPENDIX A

                     PRINCIPAL PRODUCERS AND
            THEIR GEOGRAPHICAL DISTRIBUTION (27,  28)
(27)  Minerals Yearbook 1973;  Volume I:   Metals,  Minerals,  and
     Fuels.   U.S.  Department  of the Interior,  Washington,  D.C.,
     1975.   1383 pp.

(28)  Minerals Yearbook 1973;  Volume II:   Area  Reports:   Domestic.
     U.S. Department  of the Interior, Washington,  D.C.,  1975.
     800  pp.
                                74

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                       TABLE A-l.   PRINCIPAL  PRODUCERS OF BARITE

Company
Alaska Barite Co.
Dresser Minerals
NL Industries, Inc.
Industrial Minerals Co.
New Riverside Ochre Co.
Paga Mining Co., Div.
Thompson-Weinman & Co.
Pfizer, Inc., Minerals,
Pigments & Metals Div.
Dresser Minerals Division,
Dresser Industries, Inc.


Milchem, Inc.
NL Industries Inc., Baroid Div.
<_n Dresser Minerals Div.
Milchem, Inc.
NL Industries, Inc., Baroid Div.
NL Industries, Inc., Delore Div.
Pfizer s Co.
NL Industries, Inc., Baroid Div.
Dresser Minerals Division,
Dresser Industries, Inc.
FMC Corp.
Milchem, Inc., Mineral Div.
NL Industries, Inc., Baroid Div.
B. C. Wood
Dresser Industries, Inc.
The Milwhite Co., Inc.
National Lead Co.
Type of activity
Open pit
Mine and plant
Mine and plant
Mine and plant
Open pit mine

Open pit mine and grinding mill

Grinding plant

Grinding plant


Grinding plant
Grinding plant
Mine
Mine and mill
Mine and mill
Mill
Mine and mill
Open pit mine

Open pit mine
Open pit mine
Open pit mine
Two open pit mines and plant
Open pit mine and plant
Grinding plant
Grinding plant
Grinding plant
County
Southeastern Alaska
Hot Spring
Hot Spring
Shasta
Bartow

Bar tow

St. Clair

Orleans and
Calcasieu

Orleans
Orleans
Washington
Washington
Washington
St. Louis
Washington
Elko

Lander
Lander
Lander
Monroe
Loudon
Cameron
Harris
Nueces
State
Alaska
Arkansas
Arkansas
California
Georgia

Georgia

Illinois

a
Louisiana,
a
Louisiana
Louisiana
Missouri
Missouri
Missouri
Missouri
Missouri
Nevada

Nevada
Nevada
Nevada
Tennessee
Tennessee
Texasa
Texasa
Texas
Grinds imported ore.

-------
                           TABLE A-2.   PRINCIPAL  PRODUCERS  OF BORON
            Company
       Type of activity
                                                                          County
                          State
Kerr-McGee Chemical Corp.
Tenneco, Inc.
United States Borax &
  Chemical Corp.
Dry lake brines
Open pit mine

Open pit mine
San Bernadino
Inyo

Inyo and Kern
California
California

California
 Boron minerals and compounds produced.
                         TABLE  A-3.   PRINCIPAL PRODUCERS OF  FLUORSPAR

Company
Ozark-Mahoning Co.
Type of activity
Underground mine and plant
County
Jackson
State
Colorado
Minerva Company,  mining division
  of Minerva Oil  Co.
    Crystal Group
    Minerva No. 1
Ozark-Mahoning Co.
Calvert City Chemical Co.

Roberts Mining Co.
J. Irving Crowell,  Jr.
D & F Minerals Co.
Spor Bros.
U.S. Energy Corp.
Willden Fluorspar Co.
Underground mines  and mill
Underground mines  and mill
Underground mines  and mill
Underground mine and mill

Mine and plant
Underground mine
Mine
Open pit and underground mines
Open pit mine
Underground mine
Hardin
Hardin
Hardin
Crittenden and
  Livingston
Ravalli
Nye
Brewster
Juab
Juab
Juab
Illinois
Illinois
Illinois

Kentucky
Montana
Nevada
Texas
Utah
Utah
Utah

-------
                     TABLE A-4.   PRINCIPAL PRODUCERS  OF LITHIUM  MINERALS
            Company
       Type of activity
      County
    State
Kerr-McGee Chemical Corp.
Foote Mineral Co.
Foote Mineral Co.
Lithium Corp. of America,  Inc.
Dry lake brines
Dry lake brines
Open pit mine and  plant
Open pit mine and  plant
San Bernardino
Esmeralda .
Cleveland
Gaston
California
Nevada
N. Carolina
N. Carolina
        TABLE A-5.   PRINCIPAL PRODUCERS  OF MINERAL PIGMENTS (IRON OXIDE PIGMENTS)

Company
a
Leber Mining Co. .
New Riverside Ochre Co.
Pfizer, Inc., Minerals, Pigments
and Metals Div.a
Prince Manufacturing Co .
George B. Smith Chemical Works
Cleveland-Cliffs Iron Co.
Cities Service Co.&
E. I. du Pont de Nemours
& Co . , Inc . "
Allegheny Ludlum Steel Corp.9
Lanzendorfer Minerals Co.
Minerals, Pigments & Metals
Div. , Chas. Pfizer & Co. , Inc.
The Prince Manufacturi g Co.
Reichard-Coulston, Inc.
Hoover Color Corp.9
Delta Oil Co.c
Type of activity

Mine
Mine and plant

Plant
Plant
Plant
Mine
Plant

Plant
Plant
Pit

Plant
Plant
Plant
Strip mine
Plant
County

Nevada
Bartow

St. Clair
Adams
Kane
Marquette
Mercer and Middlesex

Essex
Allegheny
Cambria

Northampton
Carbon
Northampton
Pulaski
Milwaukee
State

Arkansas
Georgia

Illinois
Illinois
Illinois
Michigan
New Jersey

New Jersey
Pennsylvania
Pennsylvania

Pennsylvania
Pennsylvania
Pennsylvania
Virginia
Wisconsin
 Iron oxide pigments (crude)  produced.   Iron oxide pigment materials produced.
Clron oxide pigments (finished)  produced.   Iron oxide pigments (manufactured) produced.

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                          TABLS  A-6.   PRINCIPAL PRODUCERS  OF PHOSPHATE ROCK
               Company
                                          Type of activity
                                        County
                                                   State
oo
Agrico Chemical Co.
Borden, Inc.
Brewster Phosphates
Gardinier, Inc.
W. R. Grace & Co.
International Minerals &
  Chemical Corp.
Mobil Oil Corp., Chemical Div.
Occidental Petroleum Corp.,
  Suwannee River Phosphate Div.
Swift Chemical Co.
U.S.S. Agri-Chemicals, Inc.
Beker Industries
Monsanto Co.
J. R. Simplot Co.
Stauffer Chemical Co.
Stauffer Chemical Co.
Cominco American, Inc.
Stauffer Chemical Co.
Texasgulf, Inc.
Hooker Chemical Corp.
Monsanto Co.

Stauffer Chemical Co.
Tennessee Valley Authority
Stauffer Chemical Co.
Stauffer Chemical Co.

Stauffer Chemical Co. of Wyoming
                                      Three open pit mines
                                      Open pit mine
                                      Open pit mine
                                      Open pit mine
                                      Open pit mine

                                      Three open pit mines
                                      Two open pit mines
Open pit
Two open
Open pit
Mine and
Mine and
Mine
Mine and
Mine
Mine and
Plant
Open pit
Open pit
Open pit
mine
pit mines
mine
plant
plant

plant

plant

mine and plant
mines and plant
mines and plant
                                      Open pit mines and plant
                                      Open pit mines and plant
                                      Open pit-underground mine
                                      Open pit mine and beneficiation
                                        plant
                                      Open pit mine and beneficiation
                                        plant
Polk
Polk
Polk
Polk
Polk

Polk
Polk

Hamilton
Polk
Polk
Caribou
Caribou
Bingham
Caribou
Caribou
Powell
Silver Bow
Beaufort
Hickman and Maury
Giles, Maury,
  Williamson
Giles and Maury
Maury and Williamson
Rich

Unitah

Lincoln
Florida
Florida
Florida
Florida
Florida

Florida
Florida

Florida
Florida
Florida
Idaho
Idaho
Idaho
Idaho
Idaho
Montana
Montana
North Carolina
Tennessee

Tennessee
Tennessee
Tennessee
Utah

Utah

Wyoming

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                       TABLE A-7.  PRINCIPAL POTASH PRODUCERS

Company
Kerr-McGee Chemical Corp.3
AMAX Chemical Corp.
Duval Corp. , Potash Division

International Minerals &
Chemical Corp.
Kerr-McGee Corp.
National Potash Co.
Potash Co. of America, a di-
vision of Ideal Basic
Industries , Inc .
Mississippi Co.
Kaiser Aluminum and Chemical
Corp.3
Texas Gulf Sulfur Co.a
Type of activity
Dry lake brines
Underground mine and refinery
Two underground mines and
refinery

Underground mine
Underground mine
Underground mine


Underground mine
Underground mine
Brine treatment

Brine treatment
County
San Bernardino
Eddy

Eddy

Eddy
Lea
Eddy


Eddy
Eddy
Tooele

Grand
State
California
New Mexico

New Mexico

New Mexico
New Mexico
New Mexico


New Mexico
New Mexico
Utah

Utah

Potassium salts produced.

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      TABLE A-8.   PRINCIPAL PRODUCERS  OF ROCK SALT, SALT FROM BRINE, AND EVAPORATED SALT
                Company
                                         Type of activity
                                        County
                          State
oo
o
    Olin Corp.
    Leslie Salt Co.
Metropolitan Water Dist.  of
  Southern California
Pacific Salt & Chemical Co.
Southwest Salt Co.
Western Salt Co.
Tanaka Hawaiian Salt
American Salt Corp.
Carey Salt Co.
Independent Salt Co.
Morton Salt Co.
Vulcan Materials Co.,
  Chemicals Div.
Allied Chemical Corp.,
  Industrial Chemicals Div.
Cargill, Inc.
Diamond Crystal Salt Co.,
  Jefferson Island Div.
The Dow Chemical Co.
International Salt Co.
  Avery Mine & Refinery
Morton Salt Co.
PPG Industries, Inc., Industrial
  Chemical Division
Diamond Crystal Salt Co.
                                   Brine wells
                                   Solar evaporation;and open pit
                                     mine
 Solar evaporation
 Solar evaporation
 Solar evaporation
 Solar evaporation
 Solar evaporation
 Wells and  underground
 Wells and  underground
.Underground
 Wells

 Brine wells

 Brine wells
 Underground mine

 Underground mine
 Brine wells

 Underground mine
 Underground mine

 Underground mine
 Brine wells and processing
   plant:   salt
Washington

Alameda,  Napa,
  San Bernardino,
  San Mateo

San Bernardino
San Bernardino
San Bernardino
Kern and  San Diego
Oahu
Rice
Reno
Ellsworth
Reno

Sedgwick

Iberville
St. Mary

Iberia
Iberville

Iberia
Iberia

Calcasieu

St. Clair
                                                        Alabama
California

California
California
California
California
Hawaii
Kansas
Kansas
Kansas
Kansas

Kansas

Louisiana
Louisiana

Louisiana
Louisiana

Louisiana
Louisiana

Louisiana

Michigan

   (continued)

-------
                                            TABLE A-8  (continued)
            Company
       Type of activity
County
State
The Dow Chemical Co.:
  Ludington plant
  Midland plant
Hooker Chemical Corp.

International Salt Co., Inc.
Martin Marietta Chemicals,
  Refractories Div.
Michigan Chemical Corp.
  St. Louis Plant
Morton Chemical Co., div.
  Morton-Norwich Products, Inc.

Morton Salt Co., div. of
  Morton-Norwich Products, Inc.
    Manistee plant

    Port Hurton plant

Pennwalt Corp.

Wilkinson Chemical Corp.


BASF Wyandotte Corp.
Brine wells and processing.
  plant:  bromine, calcium-
  magnesium compounds,
  magnesium compounds             Mason
Brine wells and processing
  plant:  bromine, calcium-
  magnesium compounds,  iodine,
  magnesium compounds,  salt       Midland
Brine wells and processing
  plant:  salt                    Muskegon
Underground salt mine             Wayne
Brine wells and processing
  plant:  magnesium compounds     Manistee
Brine wells and processing
  plant:  bromine, calcium
  magnesium compounds,  mag-
  nesium compounds, salt          Gratiot
Brine wells and processing
  plant:  bromine, magnesium
  compounds                       Manistee


Brine wells and processing
  plant:  salt                    Manistee
Brine wells and processing
  plant:  salt                    St.  Clair
Brine wells and processing
  plant:  salt                    Wayne
Brine wells and processing
  plant:  calcium-magnesium
  compounds                       Lapeer
Brine wells and processing
  plant:  salt                    Wayne
                                                                                           Michigan
                Michigan

                Michigan
                Michigan

                Michigan
                Michigan


                Michigan



                Michigan

                Michigan

                Michigan


                Michigan

                Michigan

                   (continued)

-------
                           TABLE  A-8  (continued)
Company
Type of activity
County
                                                                                                  State
    Huck Salt Co.
    Teledyne Potash Co.

    Morton Salt Co.
    Watkins Salt Co.,  Inc.
    Cargill, Inc.
    International Salt Co.
    Industrial Chemicals Div.,
      Allied Chemical  Corp.
    Hardy Salt Co.
    Diamond Shamrock Chemical Co.,
      unit of Diamond  Shamrock Corp.
    PPG Industries, Inc.
    Diamond Crystal Salt Co.
oo   Excelsior Salt Works, Inc.
    Morton Salt Co., a division of
      Morton International,  Inc.
    International Salt Co.
    Morton Salt Co., a division of
      Morton International,  Inc.
    Blackmon Salt Co.
    Western Salt Co.
    Diamond Shamrock Corp.
    The Dow Chemical Co.
    Montex Chemical Co.
    Morton Salt Co.
    PPG Industries
    Phillips Petroleum Co.
    Texas Brine Corp.

    United Salt Corp.
    Vulcan Materials Co.
                       Solar evaporation
                       Solar evaporation and rock
                         salt
                       Well
                       Well
                       Underground
                       Underground

                       Well
                       Well and plant

                       Well
                       Well
                       Well
                       Well

                       Well
                       Underground

                       Underground
                       Solar evaporation
                       Solar evaporation
                       Brine wells
                       Brine wells
                       Brine wells
                       Underground mine and brine wells
                       Brine wells
                       Brine wells
                       Brine wells

                       Underground mine and brine wells
                       Brine wells
                           Churchill

                           Eddy
                           Wyoming
                           SchuyJLer
                           Tompkins
                           Livingston

                           Onondaga
                           Williams

                           Lake
                           Summit
                           Summit
                           Meigs

                           Wayne
                           Cuyahoga

                           Lake
                           Woods
                           Harman
                           Chambers
                           Brazoria
                           Ward
                           Van Zandt
                           Duval
                           Hutchinson
                           Harris, Jefferson,
                             Matagorda
                           Fort  Bend and Harris
                           Yoakum
                Nevada

                New Mexico
                New York
                New York
                New York
                New York

                New York
                North Dakota

                Ohio
                Ohio
                Ohio
                Ohio

                Ohio
                Ohio

                Ohio
                Oklahoma
                Oklahoma
                Texas
                Texas
                Texas
                Texas
                Texas
                Texas

                Texas
                Texas
                Texas
                                                                                  (continued)

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                                     TABLE A-8 (continued)
00

Company
American Salt Co.
Great Salt Lake Minerals &
Chemicals Corp .
Morton Salt Co., a division of
Morton International , Inc .
Industrial Chemicals Div. Allied
Chemical Corp.
Inorganic Chemical Div.
FMC Corp.
PPG Industries, Inc., Chemical
Div.
Type of activity
Lake brine processing plant

Solar evaporation

Lake brine processing plant

Plant

Mine

Plant
County
Tooele

Weber

Salt Lake

Marshall

Tyler

Marshall
State
Utah

Utah

Utah

West Virginia

West Virginia

West Virginia

TABLE A- 9.
PRINCIPAL PRODUCERS OF
SODIUM SULFATE


Company
Kerr-McGee Chemical Corp.
Stauffer Chemical Co.
United States Borax &
Chemical Corp.
Ozark-Mahoning Co.
Great Salt Lake Minerals
& Chemicals Corp.
Type of activity
Dry lake brines
Dry lake brines

Open pit mine
Open pit mine

Salt lake brine
County
San Bernardino
San Bernardino

Kern
Gaines and Terry

Weber
State
California
California

California
Texas

Utah

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                         TABLE A-10.  PRINCIPAL PRODUCERS OF SULFUR
oo

Company
Freeport Minerals Co.


Texas Gulf, Inc.
Atlantic Richfield Co.
Duval Corp,
Texasgulf, Inc.

Type of activity
Prasch process


Frasch process
Frasch process
Frasch process
Frasch process

County
Jefferson,
Plaquemines ,
Terrebonne <
Lafourche
Pecos
Culberson
Jefferson, Liberty
Wharton
State


Louisiana
Louisiana
Texas
Texas

Texas

                        TABLE A-ll.  PRINCIPAL PRODUCERS OF TRONA ORE

Company
Type of activity
County
State
Allied Chemical Corp . , Industrial
Chemicals Division
FMC Corp. , Inorganic Chemicals
Division
Stauffer Chemical Co.
of Wyoming
Underground mine and refinery

Underground mine and refinery

Underground mine and refinery
Sweetwater

Sweetwater

Sweetwater
Wyoming

Wyoming

Wyoming

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                           APPENDIX B

                  EMISSION FACTOR ESTIMATES FOR
               MINING AND BENEFICIATING OPERATION
An emission factor estimate for the mineral of interest is
obtained by coupling the process information presented in the
source description section with actual emission factors for
related industries.

A list of typical mining and beneficiation operations and their
corresponding emission factors is presented in Table B-l (24, 25,
29).  Following the table, specific emission factors for each
mineral have been totaled; the results are shown in Tables 6-^2
through B-12.

The method helps to relate emission potentials for the minerals;
it does not give the definitive answers which can be obtained
only by actual sampling.
 (29) Blackwood, T. R., P. K. Chalekode,  and  R. A. Wachter.
     Source Assessment:  Crushed  Stone.  Contract 68-02-1874,
     U.S. Environmental Protection Agency, Cincinnati,  Ohio,
     July 1977.   91 pp.
                                85

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             TABLE B-l.
LIST OF  UNIT OPERATIONS AND
CORRESPONDING EMISSION FACTORS

Unit operation
Blasting
Drilling (wet)
Quarrying
Primary crushing
and unloading
Secondary crushing
and screening
Tertiary crushing
and screening
Fines crushing and
screening
Conveying
Loading trucks
Unloading trucks
Transport (wet)
Dragline (overburden
removal)
Dragline (ore
removal)
Bagging
Drying
Silo storage
Railcar loading
Respirable
particulates,
g/kg
0.0000088
0.000016
0.0011

0.0013

0.00034

0.000067

0.000015
0.000011
0.000045
0.000054
0.00020
a
0.0085
a
0.00004
0.00023
0.0071a
0.0113
0.016a
Total
particulates ,
g/kg
0.000052
0.00016
0.011

0.013

0.00062

0.00036

0.000092
0.0017
0.00017
0.00013
0.0012

0.085

0.0004
0.002
0.071
0.105
0.161
Type of
industry
Crushed stone
Crushed stone
Crushed stone

Crushed stone

Crushed stone

Crushed stone

Crushed stone
Crushed stone
Crushed stone
Crushed stone
Crushed stone

Coal

Coal
Potash
Phosphate rock
Phosphate rock
Phosphate rock
Reference
29
29
29

29

29

29

29
29
29
29
29

29

24
25
b
"b
"b

Assuming respirable particulates = total particulates x 0.1.

Values  as reported in Section 4, Table 7.
                                  86

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                TABLE B-2.  BARITE
  Unit operation
    typical to
   the industry
 Respirable
participates,
    g/kg
    Total
particulates,
    g/kg
Quarrying
Loading trucks
Unloading trucks
Conveying
Primary crushing
and unloading
Fines crushing
and screening
Drying
Bagging
Total :
g/kg
g/metric ton
0.0011
0.000045
0.000054
0.00011

0.0013

0.000015
0.014a
0.0002

0.017
17
0.011
0.00017
0.00013
0.0017

0.013

0.000092
0.140
0.002

0.17
170

 Assuming respirable particulates = total particu-
 lates x 0.1.
                TABLE B-3.  BORATES
  Unit operation
    typical to
   the 'industry
 Respirable
particulates,
    g/kg
    Total
particulates,
    g/kg
Quarrying
Conveying
Primary crushing
and unloading
Secondary crushing
and screening
Drying
Storage silo
Drilling (wet)
Blasting
Total :
g/kg
g/metric ton
0.0011
0.000011

0.0013

0.00034
0.0071a
0.0113
0.000016
0.0000088

0.021
21
0.011
0.0017

0.013

0.00062
0.071
0.105
0.00016
0.000052

0.203
203

a.
 Assuming respirable particulates = total particu-
 lates x 0.1.
                        87

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             TABLE B-4.  FLUORSPAR

Unit operation
typical to
the industry
Primary crushing
and unloading
Secondary crushing
and screening
Tertiary crushing
and screening
Fines crushing
and screening
Conveying
Drying
Silo storage
Railcar loading
Total :
g/kg
g/metric ton
Respirable
particulates ,
g/kg

0.0013

0.00034

0.000067

0.000015
0.000011
0.00719
O.Olia
0.016

0.036
36
Total
particulates,
g/kg

0-013

0.00062

0.00036

0.000092
0.0017
0.071
0.105
0.161

0.35
350

Assuming respirable particulates = total particu-
lates x 0.1.
          TABLE B-5.  LITHIUM MINERALS
 Unit operation
   typical to
  the industry
 Respirable
particulates,
    g/kg
    Total
particulates,
    g/kg
Quarrying
Loading trucks
Unloading trucks
Primary crushing
and unloading
Conveying
Drying
Bagging
Total :
g/kg
g/metric ton
0.0011
0.000045
0.000054

0.0013
0.000011
0.0071!*
0.0002

0.010
10
0-011
0.00017
0-00013

0.013
0.0017
0.071
0.002

0.10
100

Assuming respirable particulates = total particu-
lates x 0.1.
                       88

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          TABLE B-6.  MINERAL PIGMENTS
 Unit operation       Respirable          Total
   typical to        particulates,    particulates,
  the industry	g/kg	g/kg
Loading trucks
Unloading trucks
Primary crushing
and unloading
Conveying
Drying
Silo storage
Bagging
Total:
g/kg
g/metric ton
0.000045
0.000054

0.0013
0.000011
0.00713
0-011
0.0002

0.020
20
0.00017
0.00013

0.013
0.0017
0.071
0.105
0.002

0.19
190

Assuming respirable particulates = total particu-
lates x 0.1.


             TABLE B-7.  BRINE SALT
 Unit operation       Respirable          Total
   typical to        particulates,    particulates,
  the industry   	g/kg
Drilling (wet)
Drying
Primary crushing
and unloading
Bagging
Total :
g/kg
g/metric ton
0.000016
0-00713

0-0013,
0.0002

0.009
9
0.00016
0.071

0.013
0.002

0.086
86
Assuming respirable particulates = total particu-
lates x 0.1.
                        89

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               TABLE B-8.  ROCK SALT
  Unit operation
    typical to
   the industry
 Respirable
particulates,
    g/kg
    Total
particulates,
    g/kg
Underground
  drilling (wet)        0.000016
Underground blasting    0.0000088
Underground con-
  veying                0.000011
Underground primary
  crushing and
 * unloading             0.0013
                    0.00016
                    0.000052

                    0.0017
                    0.013
Total (underground)
0.5 x Total
(underground)
Surface secondary
crushing and
screening
Surface bagging
Total :
g/kg
g/metric ton
0.00134

0.00067


0.00034
0.0002a

0.0012
1.2
0.0149

0.0075


0.00062
0.002

0.010
10

 Assuming respirable particulates = total particu-
 lates x 0.1.
         TABLE B-9.  SOLAR EVAPORATED SALT

Unit operation
typical to
the industry
Drying
Primary crushing
and unloading
Bagging
Total :
g/kg
g/metric ton
Respirable
particulates ,
g/kg
0.00713
0.0013
0.0002d
0-009
9
Total
particulates ,
g/kg
0.071
0.013
0.002
0.086
86

 Assuming respirable particulates = total particu-
 lates x 0.1.
                        90

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            TABLE B-10.   SODIUM  SULFATE
  Unit operation
    typical to
   the industry
                       Respirable
                      particulates,
                          g/kg	
    Total
particulates,
  	g/kg 	
Drying
Bagging
  Total:
    g/kg
    g/metric ton
                        0.0071'
                        0.0002'


                        0.0073
                        7.3
   0.071
   0.002


   0.073
  73
 Assuming respirable particulates = total particu-
 lates x 0.1.

                TABLE B-ll.  SULFUR
  Unit operation
    typical to
   the industry
                       Respirable
                      particulates,
                          g/kg
    Total
particulates,
    g/kg
Drilling  (wet)
  Total:
    g/kg
    g/metric ton
                        0.000016


                        0.000016
                        0.016
   0.00016


   0.00016
   0.16
              TABLE  B-12.  TRONA ORE
  Unit operation
    typical to
   the industry
                       Respirable
                      particulates,
                          g/kg	
    Total
particulates,
    g/kg
Drilling (wet)
Blasting
Primary crushing
  and unloading
Conveying
                        0.000016
                        0.0000088

                        0.0013
                        0.000011'
  Total (underground)   0.0013

0.5 x Total
  underground)          0.0007
Secondary crushing
  and screening         0.00034
Drying                  0.0071a

  Total:
    g/kg                0.011
    g/metric ton       11
   0-00016
   0.000052

   0.013
   0.0017

   0.015
                                          0.008

                                          0.00062
                                          0.071


                                          0.110
                                        110
a
 Assuming respirable particulates = total particu-
 lates x 0.1.
                          91

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                          APPENDIX C

         STATE  PARTICULATE EMISSION BURDENS FROM
           THE PRODUCTION OF  SPECIFIC  MATERIALS
  TABLE C-l.
STATE PARTICULATE EMISSION BURDENS  FROM
THE  PRODUCTION OF SPECIFIC MATERIALS
Material produced
Barite





Borates
b
Fluorspar
Phosphate rock






Potash
Brine saltb






Rock salt




Solar evaporated salt



Sodium sulfate


Sulfur

Trona ore
State
Alaska
Arkansas
California
Missouri
Nevada
Tennessee
California
Utah
Florida
Idaho
Montana
North Carolina
Tennessee
Utah
Wyoming
New Mexico
Kansas
Louisiana
Michigan
New York
Ohio
Texas
Utah
Kansas
Louisiana
Michigan
New York
Ohio
California
New Mexico
Oklahoma
Utah
California
Texas
Utah
Louisiana
Texas
Wyoming
Overall
particulate
emissions,
10 3 metric
tons/yr
13.9
138
1,010
1,150
305
410
1,010
71.7
226.5
55.5
872
481
410
71.7
75.4
103
348
380380
706
160
1,770
549
71.7
348
380
706
160
1,770
1,010
103
93.6
71.7
1,010
549
71.7
380
549
75.4
Particulate
emissions
due to
production ,
metric
tons/yr
20.7
25.8
1.7
30.3
84.6
3.2
203
1.5
16,030
480
480
801
801
480
480
16,783
54
293
347
243
259
808
37
12.7
79.5
3.4
18.9
121
118
6
0.4
19
81
27
27
0.48
0.60
405
Contribution
from
production
to overall
state
emission, %
0.15
0.02
_c
-
0.03
-
0.02
-
7.1
0.87
0.06
0.17
0.20
0.67
0.64
16
0.02
0.08
0.05
1.15
0.01
0.15
0.05
_
0.02
-
0.01
-
0.01
_
_
0.03
_
-
-
_
-
0.54
 Total particulate emissions =  (total metric tons of emission/metric tons of pro-
 duction) [metric tons of production  (per state)/year].
 Production data for all producing states are not available.
GDashes indicate negligible emission, <0.01%.
                                92

-------
                           APPENDIX D

                 MAJOR WASTEWATER PROBLEM AREAS


MINE WATER DRAINAGE  (3)

Most chemical and fertilizer mineral mining operations have small
amounts of drainage which need little or no treatment.  The
exceptions are described below:

   • When the ore in phosphate rock mines lies below the
     water table, the water table may be lowered by massive
     pumping to drain the mine and surrounding area.  An
     alternate method is to mine below the water level.

   • Salt mines frequently have seepage and drainage problems
     which may be handled by pumping the water to the surface
     for subsequent treatment and disposal, or pumping the
     drainage directly to a nearby aquifer.

   • Fluorspar mine drainage varies to a great extent.  The
     quality of the water in terms of suspended solids and
     dissolved fluoride is better than the quality of waste-
     water from associated processing plants.

   • Barite mines normally have small amounts of mine drain-
     age, but at least one plant has a large drainage flow
     of acidic water which contains dissolved heavy metal
     salts.

FLUORSPAR WASTEWATER (3)

Process wastewater from fluorspar operations has a high content
of suspended solids and fluoride.  Fluorides are currently being
discharged without treatment.

PHOSPHATE ROCK SLIMES

Disposal problems associated with the slime from Florida land-
pebble water plants are by far the most serious environmental
problems facing the Florida phosphate rock industry.  The slimes
problem, in fact, may well be the most significant of all fertil-
izer production problems.
                               93

-------
Phosphate slime, which constitutes about one-third of  the  total
matrix mined, has been a disposal problem to the phosphate indus-
try ever since mining began  in Polk County, Florida, about 1890.
The disposal problem increased significantly in the late 1920"s
with the introduction of the flotation process.  This  is because
the matrix mined for flotation has a higher clay content than ore
mined before the use of flotation.

The treatment of slimes consists of gravity settling through an
extensive use of ponds.  At  3% to 5% solids, the slimes either
flow by gravity through open ditches with necessary lift stations
or are pumped directly to the settling ponds.

After an initial settling and clarification period, some of the
water containing the slimes  is reclaimed and can be recycled to
the plant.  However, subsequent settling of the slimes to  release
more water is very slow.  The slow settling characteristic, or
inability to dewater, is a common property of Florida phosphate
slimes.  At present, over 202.5 x 106 m2 of active and inactive
settling areas exist, surrounded by more than 480 km of earth
dams.  About 16.2 x 106 m2 of new settling areas are being con-
structed each year.  The magnitude of the disposal problem is
readily appreciated when it  is realized that the industry  pro-
duces some 36 million metric tons of these waste clays (dry
basis) annually.  A chemical analysis of slimes solids is  pre-
sented in Table D-l  (30).

Current dewatering concepts  are briefly presented in Figure D-l.
Other processes which have been proposed include freeze-thawing,
electro-osmosis, chemical coagulation, spherical agglomeration,
and drainage systems.

These potential solutions to the problem are being evaluated, and
the likelihood of finding feasible alternatives to above-ground
impoundments appears very good.

SULFUR PRODUCTION  (3)

Salt dome sulfur producers have to treat and dispose of large
amounts of bleedwater.  Two  problems are presented; the removal
of sulfides and the disposal of the remaining brine.  Currently,
there is no economical way to desalt brine.  Waste brine must be
disposed of immediately in brackish or salt water, or held to be
discharged intermittently at specified times.

The industry has two types of bleedwater treatment plants  for the
removal of sulfides prior to discharge.  Examples of each  are
presented in Figures D-2 and D-3.

(30)  Lamont,  W.  E., J.  T.  McLendon,  L. W. Clements, Jr.,  and
     I.  L.  Feld.   Characterization Studies of Florida Phosphate
     Slimes.   ROI 8089,  U.S.  Department of the Interior,  Washing-
     ton,  D.C.,  1975.  24  pp.

                               94

-------
                TABLE D-l.
Ul
CHEMICAL ANALYSES OF AS-RECEIVED  SLIMES SOLIDS  (30)
                 (percent)

Chemical analyses
Calcium oxide
Phosphorus pentoxide
Equivalent BPL3
Calcium oxide
Phorphorus pentoxide
Magnesium oxide
Aluminum oxide
iron (III) oxide
Silicon dioxide
Sodium monoxide
Potassium monoxide
Fluorine
Carbon
Carbon dioxide
Sulfur

1
8.3
5.1
11.1
1£-i

6.7
10.3
4.6
47.6
0.3
0.5
.1
1.1
2.2
0.22

2
12.8
8.2
17.9
ICfL

2.3
13.7
4.3
46.1
0.3
1.4
. 2
0.8
1.3
0.17

3
18.5
13.7
29.9
1-3C

4.0
12.2
2.5
30.4
0.2
0.6
.3
1.7
5.0
0.21

4
18.6
15.7
29.9
I-ac

1.5
13.5
1.9
33.4
0.3
0.8
1.0
1.5
0.31

5
18.4
16.2
35.4
1 Id

0.8
16.8
1.7
28.2
0.1
0.6
0.5
1.0
0.11

6
26.9
19.7
43.0
1-37

2.0
10.4
1.6
23.1
0.2
0.6
1.5
3.4
0.36

7
21.6
17.3
37.8
IOC

1.4
12.9
3.2
27.5
0.3
0.8
0.5
1.3
0.12

8
16.4
11.6
25.3
1 41

3.2
12.6
2.3
33.5
0.2
0.2
1.9
4.6
0.22

9
9.1
5.9
12.9
1 54

3.6
12.5
5.5
45.8
0.3
1.3
1.0
2.9
0.10
Sample
10
18.7
13.5
29.5
1-3Q

2.7
10.7
5.4
34.5
0.2
0.5
0.6
1.2
0.14

11
18.7
11.0
24.0
1 -jn

6.2
7.6
2.1
34.0
0.3
0.5
1.8
5.3
0.18

12
9.6
8.3
18.1
1 i ft

1.6
12.5
3.3
49.1
0.3
1.5
0.4
0.7
0.12

13
24.6
17.2
37. 6
1 A1

3.0
8.2
1.6
28.6
0.5
0.4
1.0
2.2
0.31

14
11.2
8.7
19.0
1OQ

2.2
13.0
8.3
39.5
0.4
1.1
0.6
1.1
0.21

15
10.1
9.7
21.2

'
1.6
12.1
2.8
46.6
1.2
0.8
0.7
1.0
0.17

Average
16.2
12.0
26.2
1-ae

2.9
11.9
3.4
36.5
0.3
0.8
.5
1.0
2.3
0.20

High
26.9
19.7
43.0


6.7
16.8
8.3
49.1
1.2
1.5
2.3
1.9
5.3
0.36

LOW
8.3
5.1
11.1
In A

0.8
7.6
1.6
23.1
0.1
0.2
0.7
0.4
0.7
0.10
    BPL = Bone phosphate of lime (% BPL • 0.4576 = %

-------
     SAND SPRAY
                   TAILS.  Sx,
                           CLAY
                                          /  y  / •/. /• y  /   .
                                   ^FLOCCULATED  CLAY AND,
    FLOCCULATED CLAY AND TAILINGS    \ /.TAILINGS MIX'/
                 -DILUTE =—S-S
                   CLAY    A  TAILINGS
                             DEWATERED TAILINGS
    PRETHICKENED CLAY/SAND MIX
 CLAY/SAND MIX.
    CLAY SANDWICH
                                  V / /  y / .CLAY / /  / //
                                    \: •.• -• _•.'••-••.: SAND ;.- •.•••VT7
                                    \ '  / / CLAY / /  //
                                      V. .•..'..•: SAND J•••.•.  /
   Figure D-l.   Current  dewatering concepts   (13)
            SULFUROUS       FLUE GAS
              ACID -        TO STACK
               I DEPOSITION    A
                 INHIBITOR     T
FLUE GAS
TO STACK
AIR LIFTED 	 fc SETT
BLEEDWATER ^ BAS

LING f T ^
IN MIXER PIPE
RAW WATER — »
BOILER
FLUE 	 *
PACKED __
TOWERS
1
PACKED
TOWERS
I
ECONOMIZER
GAS 1

	 » AERATORS 	 • SETTLING
» AC.IXAIUKO. • BASINS
WASTE WER
DISCHARGE
                                TO PROCESS
                               FOR MINE WATER
Figure D-2.   Bleedwater  treating  plant  type  1  (3).


                                 96

-------
                                         WATER
BLEEDWSTER-
                                                              SLU06E
                                                               TANK
                                                              SETTLING
                                                              BASINS
                                                             WASTE WATER
                                                              DISCHARGE
       Figure D-3.  Bleedwater treating  plant type 2  (3).


At one offshore salt dome facility, bleedwater is discharged
without  treatment due  to space restrictions.  Concentrations of
effluents  from bleedwater plants are  given in Appendix  F  in
Table F-6.
                                  97

-------
                           APPENDIX E

                    HAZARD RATIO CALCULATIONS
AIR

This appendix provides an example of the procedure used to calcu-
late the hazard ratio of maximum time-averaged downwind ground
level concentration to an ambient air quality standard and the
affected population for respirable particulates.  The effect of
growth factor and control technology on air emissions is also
briefly described.  In addition it discusses the hazard'ratio of
an effluent discharge to water quality criteria.

For ground level sources, the hazard ratio for respirable partic-
ulates is given as  (31):

                             = 4,020 Q                       (E_1}
                           P   Dl .81(4

where   Sp = hazard ratio for respirable particulates
         Q = representative mass emission rate, g/s
         D = representative distance from the source, m

For phosphate rock operations, the emission factor for respirable
particulates is 37 g/metric ton.  The emission rate from a repre-
sentative plant of 2 x 106 metric tons/yr is the product of the
emission factor and the production rate.  Assuming that one
operating year equals 260 operating days with each day 20 hr long:

  (385 metric tons/hr)(37 g/metric ton) = 14,230 g/hr =4.0 g/s

At the representative distance of 400 m, the hazard ratio is cal-
culated from Equation E-l as 0.30.

The distance at which the hazard ratio equals 0.1 for respirable
particulates is computed from Equation E-l, rearranged to:


                                                             (E 2)
(31)  Blackwood, T. R.,  and R. A. Wachter.  Source Assessment:
     Coal Storage Piles.  Contract 68-02-1874, U.S. Environmental
     Protection Agency, Cincinnati, Ohio, July 1977.  96 pp.
                               98

-------
             D       - r(4'°2°) (4.o)iii-8^
             Dsp=o.i - L - on — J        = 74° m


The area affected within the boundary of 400 m to 740 m is com-
puted by subtracting the area of a circle with a 400 m diameter
from the area of a circle with a 736 m diameter — 0.30 km2.  The
population affected is the product of the area affected and the
population density of 50 persons/km2 or 15 persons.        *

The growth factor is the ratio of the calculated 1980 emissions
levels to the 1974 levels.  Production for 1980 is calculated
assuming a 4.7% annual increase  (Section 6) from 1974 to 1980.
The 1980 production level is thus 54.58 x 106 metric tons.  The
1980 emissions are calculated by applying the efficiency of the
best available control technology to the emission factor for the
loading of railroad hopper cars, since this is the major area in
the phosphate rock industry where additional control technology
is being developed.  Assuming that new systems will be able to
attain efficiencies of 90% (by weight) , the respirable particu-
lates emission factor for railcar loading will be reduced from
161 g/metric ton (Section 6)  to 16 g/metric ton.

The new emission factor for total particulates , after applying
the best control technology available, is 217 g/metric ton.  This
represents a 60% reduction from the 362 g/metric  ton 1974 level.
Multiplying the 1980 production level of 54.58 x 106 metric tons
by this factor yields emissions of 11,848 metric  tons/yr of total
particulates in 1980.  The ratio of 1980 to 1974  emissions is
thus 0.74.

WATER

The concept of a hazard ratio applied to air emissions was con-
sidered an excess relative dose or relative environmental burden.
The same concept holds true for water discharges  (32) .
The hazard ratio is defined as:


                                 VDC
                         3W= (VR + VD)F
                         S,, = ,„    PT ^                    (E-3)
                                          1
where     S  = hazard ratio for water effluent

          V  = volumetric flow rate of the discharge
(32) Eimutis, E. C. , T. J. Hoogheem, and T. W. Hughes.  Briefing
     Document:  Water Source Severity and Initial Water Priori-
     tization Structures.  Draft prepared under EPA Contract 68-
     02-1874 by Monsanto Research Corporation, Dayton, Ohio, 21
     September 1976.  12 pp.
                                99

-------
          C  = concentration of the discharge

          V  = volumetric flow rate of the river
           Xx
           F = hazard factor

Table F-4 gives the discharge concentrations at 24 sites (person-
al communication with John C. Barnett, State of Florida, Depart-
ment of Environmental Regulation, January 26, 1977).  From the
table, the following average discharge concentrations were deter-
mined for a representative phosphate rock plant:  phosphorus as P,
1.08 x 103 mg/m3; fluoride, 1.72 x 103 mg/m3; TSS, 11.14 x 103
mg/m3.

An average discharge flow rate was determined to be 0.147 m3/s; a
case of direct discharge into the Peace River in central Florida
was assumed.  The average flow rate of the Peace River is
25.8 m3/s (33).  The hazard factors are developed in Reference 34
from EPA water quality criteria or similar data.  The hazard
factors for phosphorus, fluoride, and TSS are 0.1 g/m3,  0.19 g/m3,
and 25 g/m3, respectively (34).  Using Equation E-3, the hazard
ratios are 0.061 for phosphorus, 0.051 for fluoride, and 0.0025
for TSS.
(33)  Specht, R.  C.   Phosphate Waste Studies.   Bulletin Series
     No.  32, University of Florida Engineering and Industrial
     Experiment  Station, Gainesville,  Florida, February 1950.
     26 pp.
(34)  Eimutis, E. C., J. L. Delaney, T. J.  Hoogheem,  S. R.  Archer,
     J. C.  Ochsner,  W.  R.  McCurley, T. W.  Hughes,  and R.  P.  Quill.
     Source Assessment:  Prioritization of Stationary Water  Pollu-
     tion Sources.   EPA-600/2-77-107p, U.S.  Environmental  Protec-
     tion Agency, Research Triangle Park,  North Carolina,
     December 1977.   132 pp.

                              100

-------
           TABLE F-l.
              EFFLUENT  CONCENTRATION OF  POLLUTANTS
              FROM BARITE PROCESSING (3)
Daily average {maximum} , g/ra3
Effluent source Site
Underground mine 1

Dry process
Wet process 1

Flotation process:
Tailings pond 1

Clear water pond 1

Effluent
flow
760,000*

0
c


°f
(0.760)
°f
(0.380)
IDS
2,950
(6,900)

6.0 d
(8.0)

800
(1,271)
1,000
(1,815)
TSS
50
(100)

15
(32)

3
5
3
(6)
Ammonia
0.30
(1.0)

0.1
(0.5)

<0.1
I[<0.1)
5
(35)
Cadmium
0.01
(0.02)




0.004
(0.008)
_b

Chromium
_b





0.200
(0.400)
0.100
(0.120)
Iron,
total
0.10
(0.02)

0.04
(0.09)

0.030
(0.060)
0.030
(0.070)
Lead,
total
0.01
(0.02)

0.03
(0.10)

0.020
(0.080)
0.040
(0.090)
Manganese
0.02
(0.10)




0.002
(0.008)
0.004
(0.008)
Nickel,
total
0.02
(0.04)




0.030
(0.070)
0.030
(0.070)
Zinc,
total
0.01
(0.02)




0.005
(0.010)
0.030
(0.090)
    "m'/yr.
applicable.  CMot available.  pH. ETotal barium.  m3/min.
           TABLE  F-2.
              EFFLUENT CONCENTRATION OF  POLLUTANTS

              FROM FLUORSPAR PROCESSING  (3)
Effluent source
Mine water discharge





Average
Range

Heavy media separation
Froth flotation

Site
1
2
3
4
5
6



1
1
2
Effluent
flow,
JlVday
273
490
54
303
4,769
1,892
1,892
54
(4,769)
a
1,212^
2,608°

PH






7.5
7.0
(8.0)
7.8
7.2
8.2

Fluoride Sulfide






2.0 0.37
1.1 0.37
(3.2) 0.37
3.0
5.1
9.8
Daily average (maximum) , g/m3
Iron,
TDS TSS Cadmium Copper total






900 35 0.03 0.01 0.27
353 10 0.03 0.01 0.05
(2,998) (300) 0.03 0.01 (0.90)
10.0
500
1,800

Lead> Nickel, zinc,
total Manganese total total






0.08 0.12 0.20 0.31
Trace 0.10 0.29 0.02
(0.20) (0.15) 0.29 (1.00)
0.015 0.09


  G
  td
S 3
H i-3

M O
& °
IT" O
cn M
  
w pd
  H
  O
  G
  cn
                                                                                              M

                                                                                              a
                                                                                              H
                                                                                              X
Not available.  Assumes 80% of process waste as discharge.

-------
         TABLE F-3.   EFFLUENT  CONCENTRATION OF  POLLUTANTS
                       FROM LITHIUM MINERALS PROCESSING  (3)
   Effluent
    flow,
                                  Daily average (maximum), g/m3
                 Phosphorus,       Sulfate,
Site  m3/day  BOD TDS TSS  as P   Chloride  as S Aluminum Iron Manganese Silicon Sodium Potassium Fluoride  Lithium  pa
1    830   6   -  -
2   7,900   1.6 515 14
                  0.05
                  0.32
 a
28
_a
63
                                   4.2
 a
1.7
                                                 14.6
                                                     2929
                                                           6.0
 a
2.2
 _a
6.3
                                                                          7.0
                                                                          (7.5)
 Not available.
         TABLE F-4.   EFFLUENT  CONCENTRATION OF  POLLUTANTS
                       FROM PHOSPHATE  ROCK  PROCESSING  (3)
                Effluent  source:   Florida  operations

Site
1
2
3
4
5
6
7.
8b
9b
10°
11
12b
13b
14°
15b
16°
17
18
19
20
21
22
23
24
Effluent flow,
10~3 m3/min
Mean
15,872
9,259
12,893
2,267
12,450
11,606
10,043
12,867
5,841
a
47542
18,927
16,277
42,381
7,942
16,190
14,014
25,101
382
1,719
2,786
3,066
3,115
3,172
Max
56,781
41,640
49,210
13,461
46,791
42,828
35,303
43,381
32,831
_a
~a
~a
~a
7527672
63,216
126,702
89,506
70,216
2,146
_a
~a
~a
~a
~a
Daily average (maximum) , cf/m3
Mean pH
range '
6.2(7.9)
6.2(8.1)
6.8(7.9)
6.3(7.8)
6.4(8.3)
6.8(7.9)
6.0(7.5)
5.4(7.3)
6.4(7.7)
6.6(7.2)
6.9(7.5)
6.7(7.4)
6.0(7.4)
6.5(8.4)
6.3(9.3)
4.6(9.3)
6.0(8.0)
7.0(8.5)
7.1(8.1)
7.4
7.5
7.5
7.5
7.5
Fluoride
1.67
2.31
1.90
1.66
1.24
1.19
1.97
5.35
7.75
5.22
2.21
2.14
2.97
2.26
1.54
1.14
2.42
2.22
1.65

1.45


1.30
Phosphorus
0.69
0.39
0.78
1.71
2.24
2.54
1.42
5.57
9.83
6.76
1.07
0.86
21.73
18.44
1.71
10.08
1.41
1.02
0.36
1.94
1.07
0.96
1.22
0.38
TSS
7.46
6.01
3.67
5.21
11.20
4.93
9.21
10-83
8.23
6.86
3.14
2.32
8.34
26.44
18.28
34.00
7.86
21.65
19.01
1.24
13.10
0.18
0.35
16.96

 Not available.
3This data cannot be considered representative  of slime pond/
 settling area  mine effluent  due to mixing with gypsum stack/process
 water;  therefore, it  was not included  in averaging  calculations.
                                    102

-------
       TABLE  F-5.
EFFLUENT CONCENTRATION OF POLLUTANTS
FROM ROCK  SALT PROCESSING  (3)
Site
1
2
3
4
5a
5b
Effluent
flow,
10~3 mVmin
2,839
105
347
53
213
363
Daily average (maximum) , g/m3
TDS
4,660
30,900
a
30,200
53,000
(112,000)
319,000
(323,000)
Na
1,840
7,200
a
11,900
a
a
Cl
2,820
15,700
18,000
18,500
32,000
(69,000)
182,000
(190,000)
TSS
Trace
72
150
Trace
470
(4,050)
1,870
SOi,
Trace
1,400
370
a
208
260
PH
a
7.5
6.5
a
8.5
(9.0)
7.6

       Not available.
       TABLE F-6.
EFFLUENT  CONCENTRATION OF POLLUTANTS
FROM SULFUR PROCESSING (3)
         Effluent source:  Treated bleedwater effluents

Site
1
2
3
4
5
6
7


1
2
3
4
5
6
7



1
2
3
4
5
6
7

1
2
3
4
5
6
7
Effluent
flow.
mVday
4,600
27,000
19,000
38,000
17,000
23,000
11,500


4,600
27,000
19,000
38,000
17,000
23,000
11,500



4,600
27,000
19,000
38,000
17,000
23,000
11,500

4,600
27,000
19,000
38,000
17,000
23,000
11,500


Alkalinity Ammonia
149
145
104
130
50
110
76
Nitrogen-
Kjeldahl
0.95
0.84
5.64
1.3
0.9
0.8
2.0
Color
point
CO units
18
55
83
22
16
45
15
Manganese
0.014
0.011
0.095
0.300
0.600
0.700
0.120


g/n.3



BOD Chloride COD Fluoride Bromide Hardness
0.34 32 14,580 202 1.09
0,0 3.2 13,725 46 1.22
<0.2 89.5 5,895 292 0.23
0.5 5 25,000 42 0.5
0.4 2.1 15,500 32 0.4
0.4 350 13,732 490 0.5
0.35 6.4 18,250 70 0.2
Oil and
Total

grease pH phosphorus
1.2 7
0.9 7
2.4 7
4.0 7
2.0 7
11.0 6
2.0 8
Specific
conductance
pmhos
36,774
32,365
16,209
61,600
50,000
33,000
53,000
Mercury
0.0005
0.0003
0.0004
<0.001
<0.001
O.OOl

-------
TABLE F-7.  EFFLUENT CONCENTRATION OF POLLUTANTS
            FROM TRONA ORE PROCESSING  (3)

      Effluent source:  Process wastewater
             Effluent
               flow,      TS	TDS    TSS
      Site    m3/day    ~~     g/m3

        1       23      9,000   8,300   700
       Plans.are underway to eliminate this
       discharge, which is the only one in
       the industry.
                      104

-------
                           APPENDIX G

               SAMPLING AND ANALYTICAL METHODOLOGY


SAMPLING AND ANALYTICAL OBJECTIVES


A phosphate rock processing facility was sampled and analyzed for
the following:

   • Ground level concentration.

   • Meteorological data such as wind speed, direction, and
     atmospheric stability class.

   • Distance from sampler to source.

   • Composition of emissions (emphasis on heavy metals) .

   • Fraction of respirable particulate (less than 7 ym) .

Dispersion equations were applied to reduce this data to the
following:

   • Mass emissions for selected site.
   • Respirable emissions  (less than 7 ym) for source type.
   • Emission factors for U.S. average conditions.
   • Composition of emissions.
   • Effects of wind speed on emissions.

ATMOSPHERIC DISPERSION MODELING

For the arrangement shown in Figure G-l, let the origin be
defined at the source and all remaining points in the usual
Cartesian coordinate system.  Let 0 be the angle of mean wind
speed.  Then to find the value of any point yi perpendicular to
the wind direction centerline, the following is computed:

                           m! = tan 9                        (G-l)

and for point S^ with coordinates x.^, y^^
                                  iT                          (G-2)
                                  xi
The angle a is found from


                               105

-------
                                   AZIMUTH
                                   METEOROLOGICAL STATION
               Figure  G-l.   Sampling arrangement.

                                    m2  - mi
                     a  =  arctan
                                1  +  [(mi) (ro2)J
The lateral distance Y.  is
Y. =  (sin a)
and the downward distance  X.  is
X. =  (cos a)
                                         (G-3)
                                                             (G-4)
                                                              (G-5)
Estimates of stability class were  determined using the procedure
described in Figure G-2.  The  dispersion coefficients Oy and az
can be found in Figures  3-2 and  3-3  of Turner's "Workbook of
Atmospheric Dispersion Estimates"  (35) .   The source strength Q
will be calculated as an average of  the N sampler readings from
the following:
(35) Turner, B. D.  Workbook of Atmospheric  Dispersion Estimates.
     Public Health Service Publication No. 999-AP-26,  U.S.  Depart-
     ment of Health, Education, and Welfare,  Cincinnati,  Ohio,
     May 1970.  84 pp.

                               106

-------
O
-J
,

TIME OF DAY
NOONTIME
LATE AM, EARLY PM
MID AM. MID PM
EARLY AM, LATE PM
INSOLATION
CLASS
4
3
2
1
                                   IFINDEX<1
                                     USE1
                                                                               •*-(!
1
WIND
SPEED
CALM
(0 to 2 MPH)
LIGHT
(2 to 5 MPH)
MODERATE
(5 to 10 MPH)
STRONG
O10MPH)

NET RADIATION INDEX
4
A
A
B
C
3
A
B
B
C
2
B
C
C
D
1
C
D
D
D
0
D
D
D
D
-1
F
E
D
D
-2
F
F
E
D
STABILITY CATEGORIES
             Figure G-2.   Flow chart of atmospheric stability class  determination.

-------
                         n
                    Q-  £
X • ira
Ai  y
                                     a u
                                      z
                        i=l N exp -
                                                             (G-6)
where  u = average wind speed

This process was computerized for efficient reduction  of  experi-
mental data.

FIELD SAMPLING AND ANALYTICAL METHODOLOGY

A Gaussian plume equation was used to estimate the  fugitive  dust
source strength from ground level ambient air samplers.   Since
the Gaussian plume equation gives a time-averaged description of
the concentration field, a number of receptors were used  as  shown
in Figure G-3.  The following rationale applies:  1) the  position
of the sampler determines ambient dust levels and 2) wind direc-
tion and velocity were not constant and affect time-averaging
results.  The positioning of samplers eliminated the need to
correct for concentration which varied with time.
                              V-/
                   ANGLE OF WIND/A  /
                                        SOURCE
                                           RESULTANT WIND
                                             DIRECTION
                 Figure G-3.  Sampler positions

                                108

-------
Sampler 1 is the primary source strength estimator and was
located as close to the source as possible.  This sampler was
placed from one to three obstruction heights from the source,
depending upon stability class.  Sampler 3 is required for corre-
lations with downwind power law decay.  Samplers 2 and 4 are
required for correlations with lateral dispersion estimates and
for estimating proximity to the plume centerline.  Sampler 0 was
used as a blank to compensate for other dust sources upwind of
the site under investigation.

A portable mechanical meteorological station gave the remaining
parameter, wind speed.  The azimuth was monitored throughout the
sampling period.  Figure G-4 is a pictoral overview of the inte-
grated sampling and analytical scheme.  The filter from Sampler 1
was analyzed by x-ray fluorescence techniques and compared to
source materials for composition.  A particle count was also made
via optical microscopy to check for fibers and to give a differ-
ent perspective to particle size distribution.

, \ RECORD L
\ WEIGHT / "
\ RECORD /
«•— \ TIME A*—
\ FLOWj
\ RECORD /
— \ TIME A"—
\ ROW /
\ RECORD L
^~\ WEIGHT y~

EQUILIBRATE
FILTER
1
WEIGH FILTER

LOAD FILTER
AND START
SAMPLER
1
TERMINATE
SAMPLING
AND UNLOAD
1
EQUILIBRATE
FILTER
i
.WEIGH FIITER

CALCULATE
AND DOCUMENT

/ SPECIFIED \
\ CONDITIONS /

„ / BALANCE \
"^"SPECIFICATIONS/

/ SAMPLER AND ^
•*-{ OPERATING
SPECIFICATIONS/

/ SPECIFIED \
"*\ CONDITIONS /




TO OTHER
ANALYSES
OR STORE

REPORT
RESULTS _
^^_
          Figure G-4.
Functional analysis of high-volume
suspended particulate sampling.

         109

-------
                           APPENDIX H

        SAMPLING MECHANICS AND INDIVIDUAL FIELD TEST DATA


The sampling procedure for fugitive dust may be broken  into  three
segments:  1) sampling preparations, 2) onsite sampling, and
3) data reduction.

SAMPLING PREPARATIONS

These preparations included a check of all equipment used for
onsite sampling.  The portable electric generators were test run
and adjusted to avoid onsite equipment failures.  All high-volume
air samplers were test run and calibrated, and the weather
station was set up and checked for proper operation.

In addition to the equipment check, the filters to be used in the
samplers were preweighed  (tared)  and coded to facilitate data
collection.  This same weighing and coding was also performed for
spare filters which were used to replace others damaged during
the trip to and through handling at the site.

Finally, maps and/or aerial photographs were loaned from plant
personnel at each sample site.  The photographs were used to help
plan a sampling strategy, to indicate possible obstructions, and
to acquaint the sampling team with the site.

ONSITE PROCEDURE

Sampling was done by a two-man crew with a van containing high-
volume samplers and a trailer containing gasoline-engine powered
electrical generators, gasoline,  weather station, and various
lengths of extension cords.

The crew checked with the U.S. Weather Bureau to determine the
forecasted cloud cover and the wind direction and velocity.  Once
onsite, actual wind direction was compared to that forecasted,
and then the hi-volume samplers were placed to include the
expected wind direction in the sampler matrix.  On the first day
at a sampling location, the filters were placed in the filter
holders while the samplers were still in the van.  On subsequent
days,  the new filters were placed in the samplers immediately
after the used ones were removed.
3Nonmetric units are used in this appendix since they correspond
 to those units utilized during sampling.

                               110

-------
 With the samplers ready to use, the two-man crew placed the hi-
 vol sampler with the synchronous motor and flow rate readout in a
 location on the upwind side of the fugitive emission source to
 gather the background data needed for the experiment.  The back-
 ground sampler was put into operation as soon as the small elec-
 trical generator was started since the concentration of dust on
 the filter was usually small.  A longer run time allowed the
 filter to collect more dust and made weighing the filter more
 accurate.

 Once the background sampler, So, was operating properly, the crew
 placed the next sampler, S]_, immediately downwind of the source.
 The distance from the source to the location of S± depended on
 atmospheric stability.  Sampler 83 was placed on a straight line
 with SQ and Si (along the wind direction).   Samplers 82 and 84 were
'were placed to the left and right of 83, spaced far enough apart
 to include expected wind fluctuations between 82 and 84.

 While the last four samplers were being positioned, the weather
 station was assembled.  The 10-ft telescopic pole used to support
 the instruments needed to record the wind speed and direction was
 anchored downwind of 83.  The sensors were  placed on top of the
 pole and electrically connected to gauges which give the wind
 speed in mph, the wind direction in degrees, the ambient tempera-
 ture, and the barometric pressure.  The wind indicator was set
 with 0° in the direction from which the wind was blowing.  Any
 plus or minus deviation meant that the wind was shifting.  Next
 the large electrical generator was placed downwind from 83 so
 that emissions from the generator could not affect the particu-
 late loadings in the hi-vols.  The system,  S^/ 82, 83,  84 and
 the weather station, were started, the time was recorded, and the
 first wind speed and direction were taken.   Each sampler was
 checked for proper operation; the filters were checked to make
 sure they were completely sealed; and the initial flowrate
 through the filter was recorded.

 Weather data was recorded every 15 min, and high-volume sampler
 flowrates were recorded every hour.  When the gasoline-powered
 electrical generators needed fuel, the system was turned off and
 refueling time was indicated on the data sheets.

 Once everything was running properly, the crew measured the dis-
 tances A, B, C, D, E, F, and G (see Figure  G-l)  and diagrammed
 the sampling area.  Any obvious source of emissions or any obsta-
 cle that may have interfered with the testing was noted on the
 diagram.

 After running for at least 4 hr, the equipment was shut down,
 loaded, and readied for the next set of sampling.
                               Ill

-------
DATA REDUCTION

The fugitive dust-sampling worksheet, Figure H-l, was completed
at the beginning of each sample run.  It shows the positions of
all samplers relative to the source, the atmospheric stability,
and which filters were used with which samplers.  A fugitive dust
sampler and meteorological data log, Figure H-2, was completed
during the sample runs at 15-min intervals.  It shows the condi-
tions under which sampling was conducted.

Figure H-3 is the worksheet used at the laboratory to determine
the ambient concentration of dust at each of the sampler posi-
tions during the sample run.  The input data for these calcula-
tions were taken from Figure H-l, Figure H-2, and the filter
weights determined prior to sampling.  The concentrations from'
the worksheet, the meteorological data, and the sampler position-
ing measurements were entered on a third table, Figure H-4.
Figure H-4 shows the collected data in a simplified form, includ-
ing the results of the particle size analysis (see Table H-l)
performed at the laboratory.  The data from Figure H-4 was then
input to the dispersion equation to calculate source strengths
and emission rates for each sample run.

Finally, the particles collected during each sample run were ana-
lyzed.  The chemical compositions were used to determine the
toxicity of the emissions and were compared with samples of
process materials.  These analyses and comparisons are presented
in Table H-3.

The concentration of fluoride compounds in the particulates,
reported as fluorine, averages about 5%.  The composition of a
sample of the rock being mined is not significantly different.

INDIVIDUAL FIELD TEST DATA

This section shows the field data and analytical results for the
plant sampled.  Table H-2 shows the meteorological conditions,
fugitive dust concentrations, and sampler positions (as related
to Figure H-l) for each test run.  Table H-3 gives the analytical
results for each sample run.

Six sample runs were made at one site from April 8 through 15,
1974.   The data collected during one of the tests was discarded
because of excessive change in the wind direction (66°).  The
reference point for the sampler setups was the storage and load-
ing area; however, because the sampler positions changed consider-
ably from one sample run to the next, emissions from different
parts of the process would dominate the results of different
sample runs.  This is shown in the wide range of calculated emis-
sion rates (56 Ib/hr to 250 Ib/hr).
                               112

-------
                                                            Run No.
                                                            DATE
                                             actual  barometric
                                                    pressure
                                                           _!lHg
                                           dry  bulb
                                           wet  bulb
                                             _op
                                             Op
                                          op
                                          Op
                                   ATMOSPHERIC  STABILITY DETERMINATION
                        reference
                          line
            sampler
         centerllne
 A
 B
 C
 D
 E
 .-?
 G
   ft. (measured)
   ft.      "
   ft.      "
   ft.      "
   ft.      "
   ft. (estimated)
   ft.      "
                 TIME
                  it
                  it
                  it
                                                                Stability Clt.gorleo
                              STABILITY
                                   COMMENTS:
 Sampler

   S
    0
Filter No.
Sampler No.
obtain sample of source before signing sheet
                                                   Sampling
                                                      crew
        Figure H-l.   Fugitive  dust  sampling worksheet,
                                  113

-------
                                                  Date
Run
Page

Time
(24 hr.
clock)








Totals
Average
Total el
Wind
Speed Direction
mph
avg.










apsed
range










Compass
degrees
avg.










range










time
Sl
Roto
cfm











Act
cfm











S2
Roto
cfm











Act
cfm











S3
Roto
cfm











Act
cfm











S4
Roto
cfm











Act
cfm











Other comments










r
Sampling crew
Figure H-2.  Fugitive  dust sampler and meteorological data log.

-------
        DATE
SOURCE
RUN NO..
Calculate



a - b =


d x e =
35310 x c _
f


a
b
c
Q
e
f
Q
^\^
Filter No.
FinalWt.
(mg)
Tare
(mg)
Net Wt.
(mg)
Flow Rate
(avg CFM)
Sample Time
(Minutes)
Total Volume
(Cubic Feet)
Concentration
(Mg/m3 )
So








s,








S2








S3








S4
-







tn
         PARTICLE SIZE ANALYSIS
                                                             Calculations By.
                        Figure H-3.  Fugitive dust  calculation  worksheet,

-------
                                    Run No.
Wind Speed
Wind Direction
Wind Direction range
Atm. Stability
Distance A
" B
" C
" D
" E
" p
" Q
Wet Bulb
Dry Bulb
Barometric Pressure
Concentration at SQ
Sl
s2
rr c
S3
tt q
S4
% Dust > 7u




































































































Figure H-4.
Summary of meteorological data, sampler
positions, and ambient concentrations.
                         116

-------
TABLE H-l.   PHOSPHATE ROCK

Sample 5
Loose particles
Size range,

0
2.3
4.6
9.2
18.4
36.8
73.6
l-i
to
to
to
to
to
to
to
Number of Weight,
Size
particles %
2.3
4.6
9.2
18.4
36.8
73.6
147
63
89
54
36
17
7
0
0.
0.
1.
5.
21.
71.
0
02
21
08
73
65
31

0
1.2
2.4
4.8
9.6


Filter
range ,
y
to
to
to
to
to


Fibers


0
2.3
4.6
9.2
18.4
36.8
73.6
147


to
to
to
to
to
to
to
to


2.3
4.6
9.2
18.4
36.8
73.6
147
294


51
77
54
43
10
8
4
0


0
0.
0.
1.
2.
19.
76.
0

Sample

04
25
60
98
07
06


6
0
1.2
2.4
4.8
9.6
19.2




to
to
to
to
to
to



1.2
2.4
4.8
9.6
19.2


: 0


1.2
2.4
4.8
9.6
19.2
38.4


particles
Number of
particles
84
103
49
8
0





104
81
33
7
2
0




Weight,
%
1.
10.
38.
50.
0





0.
4.
14.
24.
55.
0



41
08
38
13






97
41
39
42
81



                Fibers:  1
            117

-------
              TABLE H-2.   FIELD SAMPLING DATA FROM PHOSPHORUS ROCK PROCESSING


Wind speed, mph
Wind direction, °
Wind direction, range, °
Atmospheric stability
Distance, ft:
A
B
C
D
E,
Fa
G
Wet bulb, °F
Dry bulb, °F
b
Barometric pressure
Concentration, pg/m^:
S.
S?
s
s
s.
4 c
Source strength, Q
Elevation
Run No. 1
6.6
21.3
51.6
A

42
198
126
54
135
800
2,200
65
79

30.35

35.7
221
- 393
290
238
169.3 ± 67.6
30
Run No. 2
6.4
-57.7
65.7
A

0
159
144
-14
147
600
2,500
63
74

30.22

37
357
146
257
347
_d
30
Run No. 3
7.7
-3.0
35.8
B

-210
150
237
-210
228
579
4,500
62
80

30.42

85
1,407
668
1,028
690
82.16 ± 40.82
30
Run No. 4
14.0
-11.3
30.7
C

48
225
213
72
294
2,300
3,500
66
84

30.46

105
223
107
241
320
250.2 ± 166.6
30
Run No. 5
8.9
-7.9
42.0
C

108
90
129
129
267
500
2,000
73
88

30.35

63
1,276
1,052
1,009
870
55.63 ± 5.35
30
Run No. 6
6.25
15.1
42.5
A

72
223
135
90
144
350
2,500
75
88

30.29

70
1,623
1,834
1,433
829
126.6 ± 86.1
30

;j                                 D

 Estimated within 10% from transit.   Barometer pressure is for use in comparing different runs.

c                   d
 Q is  from computer.   No good.

-------
           TABLE H-3.  PHOSPHATE ROCK PROCESSING
      Material
          Sample
         sample, %
                              Run  3,   Run  5,   Run  6,
     Aluminum
     Calcium
     Chlorine
     Chromium
     Fluorine
     Iron
     Magnesium
     Manganese
     Phosphorus
     Potassium
     Silicon
     Sodium
     Sulfur
     Titanium
            2.11
           41.4
              a
             ~a
            3.82
            2.47
            0.09
            0.11
           32.6
            0.14
            5.45
            0.40
             _a
            1.10
             2.5
            60.0
              _a
              _a
             578
             1.6
             0.2
              _a
            2575
             0.08
             4.1
               a
              "a
             0.16
     2.93
    49.8
      _a
      _a
     57l
     1.46
     0.73
      _a
    2576
     0.07
    13.9
       a
      ~a
     0715
 3.19
59.5
   a
  ~a
 674
 2.13
 0.75
  _a
2274
 0.11
 5.3
   a
  "a
 0721
 Run
number
Minutes
  run
    Total
 particulate
emission rate,
    Ib/hr
 Standard
deviation,
  Ib/hr
Confidence
  limits
  1
  2
  3
  4
  5
  6
  232
  265
  350
  320
  245
  239
    169.3
      _b
     82.16
    250.2
     55.6
    126.6
  ±67.6
     b
  ±40.82
 ±166.6
   ±5.35
  ±86-1
 ±124.4
    _b
  ±75.0
 ±306.1
   ±9.83
 ±158.2
Run
number
Particle
size
distribution
Emission
factor,
Ib/ton
Comments on run
1
2
3
4
5
6
0

10.11% <7 y 0
0
0
.- — i
.434
b
.210
.639
.142
.322

Excessive
Storage.
Total.
Drying.

c
wind change .


_c
aNone detected.   No good.   Not applicable.
NOTE.—Compositions were calculated after drying.
                            119

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                            GLOSSARY


alluival:  Clay, silt, gravel, sand, or similar material deposited
     by running water.

apatite:  Any of a group of calcium phosphate minerals of the
     approximate general formula Ca5(F, Cl, OH, %CO3)(PO^)3.

azimuth:  Horizontal direction expressed as the angular distance
     between the direction of a fixed point (as the observer's
     heading) and the direction of the object.

bleedwater brine:  Water from bleedwater wells which are drilled
     by the sulfur industry to control dome pressure and allow
     for continuous introduction of hot water to the sulfur
     formation.

confidence level:  Range over which the true mean of a population
     is expected to lie at a specific level of confidence.

criteria pollutant:  Pollutant for which ambient air quality
     standards have been established.

dragline:  Type of excavating equipment which casts a rope-hung
     bucket a considerable distance, collects the dug material
     by pulling the bucket toward itself on the ground with a
     second rope, elevates the bucket, and dumps the material
     on a spoil bank, in a hopper, or on a pile.

dolomite:  Mineral consisting of a calcium magnesium carbonate
     (CaMg[CO3]2) found in crystals and in extensive beds as a
     compact limestone.

emission burden:  Ratio of the total annual emissions of a
     pollutant from a specific source to the total annual state
     or national emissions of that pollutant.

fibrosis:  Abnormal increase in the amount of fibrous connective
     tissue in an organ or tissue.

free silica:  Crystalline silica defined as silicon dioxide
     (SiO2)  arranged in a fixed pattern (as opposed to an
     amorphous arrangement).
                               120

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froth flotation:  Process used to  treat ore which produces one or
     more concentrates of valuable minerals and a tailings com-
     posed of waste or less valuable minerals.

fugitive emission:  Either gaseous or particulate emissions from
     industry-related operations that escape to the atmosphere
     without passing through a primary exhaust system.

gangue:  Waste material.

hazard factor:  Measure of the toxicity of prolonged exposure to
     a pollutant.

hazard ratio:  Hazard potential of a representative source
     defined as the ratio of a concentration to the hazard factor.

jig:  Mechanical device used for separating materials of differ-
     ent specific gravities by the pulsation of a stream of
     liquid flowing through a bed  of materials.

noncriteria pollutant:  Pollutant  for which ambient air quality
     standards have not been established.

quarrying:  Activity in an open or surface mine.

representative source:  Source that has the average emission
     parameters.

respirable particulates:  Those particles with a geometric mean'
     diameter less than or equal to 7 ym.

screen:  Mesh used to separate stone into various sizes.

silicosis:  Chronic disease of the lungs caused by the continued
     inhalation of silica dust.

slimes:  Fine clay slurry of about 3% to 5% solids content.

sluice pit:  Trough into which the phosphate matrix is slurried.

submerged-combustion evaporator:   Evaporation unit which consists
     of a tank to hold the liquid, a burner and gas distributor
     that can be lowered into the  liquid, and a combustion-
     control system.

sump:  Lowest part of a mine shaft into which water drains.

threshold limit value:  Concentration of an airborne contaminant
     to which workers may be exposed repeatedly, day after day,
     without adverse affect.

Trommel circuit:  Circuit of cylindrical or conical revolving
     screens used for sizing of rock.

                               121

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                                    TECHNICAL REPORT DATA
                             (Please read Instruction* on the revene before completing)
 . REPORT NO.
  EPA-600/2-78-004p
                 3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE
  Source Assessment:   Chemical and Fertilizer Mineral
  Industry, State of  the Art
                 6. REPORT DATE
                    June 1978  issuing date
                  . PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)

  J. C. Ochsner and  T.  R.  Blackwood
                 8. PERFORMING ORGANIZATION REPORT NO.

                    MRC-DA-773
 9. PERFORMING ORGANIZATION NAME AND ADDRESS

  Monsanto Research  Corporation
  1515 Nicholas Road
  Dayton, Ohio  45407
                 1O. PROGRAM ELEMENT NO.
                    1BB-610
                 li.CbNTHACf/GRANT NO.

                    68-02-1874
 12. SPONSORING AGENCY NAME AND ADDRESS
  Industrial Environmental Research Lab,, CINN, OH
  Office of Research and Development
  U.S. Environmental Protection Agency
  Cincinnati, Ohio  45268
                 13. TYPE OF REPORT AND PERIOD COVERED
                    Final      10/76 to 8/77	
                 14. SPONSORING AGENCY CODE

                     EPA/600/12
 15. SUPPLEMENTARY NOTES
  lERL-Ci task leader  for this report is S. Jackson  Hubbard, 513-684-4417
 16. ABSTRACT

       This report describes a study of air and water  pollutants emitted by the  chemical
  and fertilizes- mineral industry.  The potential  environmental effect of the  source was
  evaluated using a  hazard ratio  (defined as the ratio of the maximum time-averaged
  ground level concentration to an ambient air quality standard for air and the  ratio of
  discharge rate to  a  water quality criteria for water).

       Air and water pollutants are generated during the  conversion of naturally occurring
  minerals into suitable forms for use in chemical and fertilizer production.  These
  minerals are barite, borates, fluorspar, lithium minerals,  mineral pigments, phosphate
  rock, potash, salt,  sodium sulfate, sulfur, and  trona ore.

       The four significant wastewater problem areas in the mining and beneficiation of
  minerals in the chemical and fertilizer industry are mine water drainage, wastewater
  from the fluorspar industry, phosphate rock slimes,  and sulfur bleedwater brines.
 7.
                                 KEY WORDS AND DOCUMENT ANALYSIS
                   DESCRIPTORS
  Beneficiation
  Fertilizers
  Mining Engineering
  Emission
  Air Pollution
  Water Pollution
                                               b.IDENTIFIERS/OPEN ENDED TERMS
    Chemicals
    Phosphate
    Brine Minerals
                                 COSATI Field/Group
       68D
 8. DISTRIBUTION STATEMENT

  Release to the Public
    19. SECURITY CLASS (Thh Report)
     Unclassified
21. NO. OF PAGES
      138
                                               20 SECURITY CLASS (This pagt)
                                                 Unclassified
                               22. PRICE
EPA Form 222O-1 l»-73)
122
                                                                       BnweiFreiimiieomcE 1971-757-140/1360

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