EPA 440/1-75/032-a
 Group I, Phase II
   Development Document for Interim
  Final Effluent Limitations. Guidelines
                  and
   Proposed New Source Performance
            Standards for the


                  LEAD
             Segment of the
        NONFERROUS METALS
          MANUFACTURING
         Point Source Category
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

               FEBRUARY 1975

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                           ERRATA PAGE
              Primary Lead Development Document
1.   pp. 4, 5, 104 and 105 — change all pH ranges to read
     "pH ... Within the range 6.0 to 9.0" and delete Hg from
     tables

2.   pp 4 and 104—net monthly precipitation discharge
     table, change "Pb..1.0..0.5, Zn...l0...5" to
     "Pb...1.0...0.5, Zn...l0...5"

3.   p 51, 6th paragraph, last line delete "of the
     discharge" and replace with "during liming and
     settling".

4.   p 49—delete "Mercury" from table.

5.   p 106—-delete "Hg...0.005" from table.

6.   pp 53 and 54—delete last two paragraphs on p 53
     and first four paragraphs on p 54.

7.   p 67—delete "mercury" from fourth paragraph, and
     delete fifth paragraph.

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          DEVELOPMENT  DOCUMENT

                   for

PROPOSED EFFLUENT  LIMITATIONS GUIDELINES

                   and

    NEW SOURCE PERFORMANCE STANDARDS

                 for  the

              LEAD SEGMENT
                 Of  the
    NONFERROUS METALS  MANUFACTURING
         POINT SOURCE  CATEGORY
            Russell  E.  Train
             Administrator

             James L.  Agee
   Assistant Administrator for Water
        and Hazardous  Materials
              Allen Cywin
 Director, Effluent Guidelines Division

        George  S.  Thompson, Jr.
            Project Officer
              November 1974

      Effluent  Guidelines Division
Office of Water and Hazardous Materials
  U.S. Environmental Protection Agency
        Washington, D.C.    20460
                      -•L ' i
      t.nviroaraental Protection
      Region V, Library
      230 South Dearborn Stre«f
      Chicago, Illinois  60604

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ENVIRONMENTAL PROTECTION AGJ3ICY

-------
                           ABSTRACT
 This document presents the findings of an extensive study of
 the primary lead industry by  the  Environmental  Protection
                           307 of the
 Effluent  limitations  guidelines  contained herein  set   forth
 the  _ degree   of   effluent   reduction  attainable through  the
 application   of   the   best   practicable   control  technology
 currently   available,   and the  application   of thebelt
 available technology  economically  achievable, which must  be
 i  iol?   bY  exas*ln?  Pci«t  sources by  July  1, 1977, and July
 1, 1983,  respectively.   The standards  of  performance for  new
 sources   contained  herein   set  forth  the degree of effluent
 av^M? at*ainatle  throu9h the  application   of the  best
 available   demonstrated    control   technology,   processes
 operating methods, or  other alternatives.          processes,
refaSTiS?161* ¥ ^ ^ recomi"e«<3ations in this document
relates the  waste  water  generated  by  the  primary  lead
subcategory  to  the  production  of  primary  lead at those
facilities defined by this subcategcry.
n?SS!f!ng ^?ta  an?. rationale  for  development  of   the
proposed  effluent  limitations  guidelines and standards of
performance are contained in this report.        ^naaras or
                          111

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                           CONTENTS
 Section
 I

 II

 III
 IV
 V
VI
VII
VIII
 CONCLUSIONS

 RECOMMENDATIONS

 INTRODUCTION
   Purpose and Authority
   Methods Used for Development of Effluent
     Limitations Guidelines and Standards of
     Performance
   General Description of Primary Lead Industry

 INDUSTRY CATEGORIZATION
   Introduction
   Objectives of Categorization
   Factors Considered

 WASTE CHARACTERIZATION
   Introduction
   Sources of Waste  Water
   Summary

 SELECTION OF POLLUTANT PARAMETERS
   Introduction
   Rationale  for the  Selection  of Pollutant
    Parameters
   Rationale  for the  Rejection  of Other Waste Water
    Constituents as  Pollutant  Parameters

CONTROL AND TREATMENT TECHNOLOGY
   Introduction
   Process Waste Water Effluents and Present
    Control and Treatment Practices
  Additional Treatment Technology

COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
  Introduction
  Basis for Cost Estimation
  Economics of Present Control and Treatment
    Practices
  Economics of Additional Control and Treatment
    Practices
  Nonwater Quality Aspects
   1

   3

   7
   7
  8
  9

 15
 15
 15
 15

 37
 37
 37
 47

 49
 49

 50

 57

 65
 65

 65
 73

 77
 77
 77

78

94
97
                           v

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                    CONTENTS (continued)
Section
IX       BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
         AVAILABLE- -EFFLUENT LIMITATIONS GUIDELINES          101
           Introduction                                      ]JJ
           Industry Category and Process Waste Waters        1U2
           Effluent Limitations Based on the Application
             of the Best Practicable Control Technology
             Currently Available                             102

X        BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE-
         EFFLUENT LIMITATIONS GUIDELINES                     1°9

XI       NEW SOURCE PERFORMANCE STANDARDS                    I11

XII      ACKNOWLEDGMENTS                                     113

XIII     REFERENCES                                           115

XIV      GLOSSARY                                             117
                             VI

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10       Flow Sheet of Water Circuit at Plant A
                           FIGURES




                          Title


 1         Geographic Locations of Domestic Primary Lead
          Smelters and Refineries                                n


 2         Generalized Flow Sheet of a Lead Smelter and
          Refinery                                               17



 3         cross  Section of a Typical Updraft Sintering
          Machine
                                                                 19
         Generalized  Diagram  of  Water  Uses  and Waste Water
         Sources  in Primary Lead Plants                          38



                      Sclubilities of ^tal  ions as  a Function
                                                                 68


7        Experimental Solubilities of zinc                       70


8        Experimental Solubilities of Cadmium                    71



9
                       Solubilities  of  zinc.  Cadmium,  Copper,
                       fT r^i -4-;a4-^e-  •= .->  -. T>..	j^-i _    ^  _    /a*


                                                                 72



                                                                 80


11       Flow Sheet of water Circuit at Plant B                  33



12       Flow Sheet of Water Circuit at Plant c                  86


13       Flow Sheet of Water Circuit at Plant D                  89



14       Flow Sheet of water Circuit at Plant E                  93
                          vn

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                           TABLES
Number                   Title
1        Lead Smelters and Refineries                        12

2        Mine Production of Recoverable Lead in the
         United States, by State                             13

3        Lead Consumption in the United States, by Product   14

4        Salient Characteristics of U.S. Lead Smelters       16

5        Ore Minerals of Lead                                28

6        Ranges of Composition of Lead Concentrates
         Produced by Gravity and Flotation Procedures        29

7        Chemical Requirements                               30

8        Typical Southeastern Missouri Lead Concentrate
         Analysis                                            31

9        Intermediate Products of a Western Smelter          33

10       Climatic Characteristics at U.S. Lead Smelters
         Locations                                           35

11       Waste Effluents from Plant A (Outfall No. 001)       40

12       Waste Effluents from Plant A (Outfall No. 002)       41

13       Waste Effluents from Plant A (Effluent from
         Projected Treatment Plant with Revised
         Water Circuits)                                     42

14       Waste Effluents from Plant E (Outfall No. 001)       43

15       Waste Effluents from Plant C (Outfall from
         Settling Pond)                                      44

16       Present Control and Treatment Methods and
         Discharges for Process Waste Water in Primary
         Lead Industry                                       45

17       Concentrations of Selected Constituents of Acid
         Plant Slowdown After Liming From Primary
         Nonferrous Smelters                                 46
                           Vlll

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                     TABLES  (continued)


Number                      Title

18       Solubility of Metal Sulfides                        7a

19       Capital and Operating Costs of Current Waste Water
         Treatment Practices in Primary Lead Industry        79

20       Additional Control And Treatment Costs              98

21       Conversion Table                                   12a

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                           SECTION I


                          CONCLUSIONS
  The nonferrous metals manufacturing  point  source  cateaorv
  has been divided into the following subcategoriesT  °ateg°ry
      (1)   Bauxite refining subcategory
      (2)   Primary aluminum subcategory
      'qi   Secondary  aluminum subcategory
           Primary copper  smelting  subcategory
           Primary copper  refining  subcategory
      x~,   Secondary  copper subcatagory
      (7)   Primary lead subcategory
      (8)   Primary zinc subcategory
 fr~om  f£bcat^°ry  .has been found to be distinctly different
 SSLS   standPomts  of  processes   employed/  prodSc?s
 produced,  and  process  waste  waters generated  as well as
 other less significant factors.   Effluent  lim^JfJ!!    *

                                             lt
 forthefi


 lubcategory    Standards of Performance for the primary lead





                                                         i




locked y ?n   «Ias9 P^"''^"t* """ are S-^aphL,^
metaUurgicSl suWaric  fold  cla^f lp"a*lon  an
-------
cascading of process waste water  is  practiced  to  varying
extents.

For  primary lead facilities geographically located in areas
of net evaporation, the effluent limitation and standard  of
performance,  based  upon  current industry practices, is no
discharge of process waste  water  pollutants  to  navigable
waters.    A  storm  water  runoff  discharge  provision _is
proposed  for  these  facilities  to   alleviate   potential
problems  associated  with  this source of waste water.  For
primary lead facilities geographically located in  areas  of
net  precipitation,  a  discharge  of process waste water is
permitted.  The amount of pollutant discharge, as a function
of lead production, was derived  as  a  product  of   process
waste water flow volume per unit of production and pollu-cant
concentration, after application of liming and settling.

Since   control  routes  for   the  minimization of acid  plant
blowdown  by means  of reuse and  recycle,   producing   smaller
values  than  indicated   by the best practicable technology,
are  questionable  and since  additional  sulfur oxide permanent
control may be required   of   primary   lead  smelters,  which
SSSlf  increase   ?he   magnitude   of  the   blowdown,  the best
available technology economically achievable  is  considered
to  be identical  to the  recommended best  practicable control
technology  currently   available.    New  source   performance
 standards  for  air pollution will probably require permanent
 sulfur oxide  control of  the entire  sinter machine offgas  by
 means  of  weak-strand  gas recirculation.  For  this reason,
 the best demonstrated control technology is considered to be
 identical  to  the   proposed   best   practicable   control
 technology currently available.

 It  has  been  estimated  that  for  the  existing plants to
 achieve  the  levels  cf  control  of  process  waste  water
 pollutants  recommended  for  July 1, 1977 and July  1.  1983,
 the required capital cost and annual  operating  cost  would
 total  $1,275,000  and $570,700, respectively.

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                    SECTION II


                 RECOMMENDATIONS
  n  arof^    facillties geographically  located

 i«r«ter|o^tt.nSaPSrt^igSledl'2|t'SI °* ^«~
 provisions to this regulation follow-  Waters'   sPecial

SsEL'L-F"

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                       	lEffluent_limitation§
   Effluent
characteristic
Maximum for
 any 1 day
Average of daily
 values for 30
consecutive days
shall not exceed
                             Metric units__(mg/ll
TSS
Cd
Pb
Zn
pH
   50
     1.0
     1.0
   10
       25
         0.5
         0.5
         5
Within  the  range  7.0  to  10.5
                                 English units  (ppm)
 TSS
 Cd
 Pb
 Zn
 ES.
50
1
1
10


.0
.0

in the r
25
0.5
0.5
5
ange 7.0 to 10.5 	
      For primary lead facilities geographically located
 in areas of net precipitation:
                            lEfJ[lu.ent_limitation£
    Effluent
 characteristic
 Maximum for
  any 1 day
 Average of daily
  values for 30
 consecutive days
 shall not exceed
                          Metric units  (kilograms  per  1000  kg
                                              of  product)	
 TSS
 Cd
 Pb
 Hg
 Zn
 pH
      0.042
      0.0008
      0.0008
      8.0x10~6
      0.008
          0.021
          0.0004
          0.0004
          4.0x10~6
          0.004
  Within the range 7.0 to 10.0

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                              English units (pounds per 1000 Ib
                                              of product] ____


                                 °-OZ42                 0.021
                                 0.0008                0.0004
                                 0.0008                0.0004
                                 8.0x10-6              4.0x10-6

                                                      0.004
                                              7 . 0 _tg_10 . 0
?{!*  h!SJ  availabif  technology economically achievable and
the  best   available   demonstrated   control   technology

identical' to^f^  T^5'  °r  °ther  alternatives 1^4
identical  to  the  best  practicable   control   technoloav

andrestan^ilab^  ?6 CO^S^^^ effluent lirJtSons
and  standards  of performance are identical to the effluent

thS1^ i°nS ^lde^nes established after the application  of
the best practicable control techr.clcgy currently available.
The  rationale  for these effluent limitations and standards
of performance are contained in Sections IX, X,  and  XI  of
this development document.

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                        SECTION III



                        INTRODUCTION
             ft  tha?. Publi=ly <**>ea treatmen  workf,
          " s^sariStSLS' -r -ssssr -,«
 Administrator pursuant to Section 304 (b)  of thS Act.
         301Jb)  .S80  re^uires ^e achievement by not later
 technology  economically  achievable  which  will  rlsui? i
 reasonable further progress toward the goal  of eliminati


attainable  through  the  appliation  of





salting subcategory of 'tL^onfer^oaa  etals ca'tegorf.

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          Methods Used for Development^o£_gffluent
    Limitations Guidelines and Standards of Performance


The   guidelines  and  standards  of  performance  that  are
recommended in this document for the primary  lead  industry
were  developed by analyzing information on the industry and
its  current  water  management  practices,   as   well   as
information   on   the   practices  in  related  industries.
Initially, a  literature  search  was  made  of  statistical
abstracts,  monographs,  and  journal  articles  in order to
assemble data on the companies in the primary lead industry.
From this information, an inventory was  compiled  for  each
facility,   covering   location,  age,  climate,  number  of
employees, operations  conducted,  production  figures,  air
pollution  control systems employed, and future plans.  This
inventory  provided  an  overview  upon  which  later   data
acquisitions  could  be  built  and  from which the need for
industry subcategorization could be assessed.

There are seven plants or properties in  the  United  States
presently  engaged  in  lead  smelting  and/or  refining.  A
representative of each of these was contacted  by  telephone
or  letter  to  acquire information on production operations
and waste water treatment methods.  Assistance was  provided
by  members  of  the Water Pollution Control Subcommittee of
the American Mining Congress  in  obtaining  data  from  the
firms  they  represented.   Several  state  water  pollution
control  offices  and  EPA  regional   offices   contributed
information  on  the  primary  lead  facilities  under their
jurisdiction.

General information from firms  was  obtained  by  telephone
conversations  with  each  company.   Information  regarding
process  equipment,  water  usage,  waste  water   outfalls,
treatment  practices,  treatment  costs, water analyses, and
storm water runoff was requested during these conversations.

Plant visits were made to six sites.  The sites selected for
visits  represented  a   variety   of   climates,   industry
processing   practices,  ore  types,  and  water  management
methods.

Additional data for four plant sites were obtained from  the
Corps of Engineers Permits to Discharge under the Refuse Act
Permit  Program,  (RAPP).  These included (in varying degrees
of detail) composition, temperature, and  volume  of  intake
and  effluent  water,  plus  a  general description of waste
water treatment.  Some analysis data was  also  provided  on
the questionnaire completed by several companies.

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  Two   plant sites  were  visited in  order to sample  and   navz^
  Sf^  lnter"al  and  °»ttall   streams.    The  sJtes  werl
  selected  in order to obtain  the widest variety of streams  J?
  unitaoStal^ti0n'  /°  deVel°P 8P«"ic information regarding
  unit  operations and waste  characterization,  to  verify  the
  treatment.   **'   ^   "° dete™ine  ^e effect  of  wastewater
 The data obtained from the literature  and  the  field  were
 prod^d  and^hfa^ J^.80"?68 ™* -lames of wLle wltJr
 ?£*   f •   u       quantities of  constituents  contained  in
 the   discharge.    on  the  basis  of  this  analysis   the
 constituents of waste water considered to  be  pollutfonally
 significant were identified.                   p^-tj-uxionaiiy
                   On  ^COntro1. and  treatment  technologies
 ifo             °r Un  r considerati°n were supplemented by
 information  covering  control   technologies   from   other
 industries,  which  might be applicable to the treatmen^and
 control of waste  water  from  the  primary  lead  industry
 Consideration  was  given to both inplant and end-*of-procel;
 technologies and to applications of the  effluent  from  ?he
 various  production  operations.  For each of the control or
 treatment technology candidates, the resultant  was?e  Sater
 constituents   were   determined  and  the  limitations  and
                                            were

                                  ^^^
 All   of   the  information  developed  was  evaluated  in  order  to
 ^^Hi*1^  leV6lS   °f  tech«clogy   constitute the   bes?
 liable ^T^1 technolo5Y currently  available,  the  best
 J  !^i S   technology   economically achievable, and  the  best
 available demonstrated  control technology.
classified  under  SIC  3356,  and  are  not  subjec? to Ihe
1031 UeaSVS d.Standards set f°^h by this  document.   si?
1031 (Lead and ^mc Ores)  describes establishments which are

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primarily  engaged  in  the  mining,  milling,  or otherwise
preparing lead ores, zinc ores, or  lead-zinc  ores.    These
establishments   are   also  not  subject  to  the  proposed
regulations derived from this document.

The primary lead industry, consisting of six  domestic  lead
smelters  and  five  refineries  ranks  fifth  in tonnage of
United States metals produced, after iron, aluminum,   copper
and  zinc.   The geographic distribution of these facilities
is shown in Figure  1 and tabulated  in Table 1.  Four of  the
six smelters have on-site refineries, while two produce lead
bullion, which is shipped to a lead refinery.

Primary lead in the United States is recovered entirely from
sulfide  ores,  which  are  associated  with other minerals,
chiefly zinc, copper, and silver.   In addition to  zinc  and
copper,  associated  byproducts  in seme of the more complex
ores  include  economically   significant  amounts  of  gold,
silver, cadmium, bismuth, indium, and antimony.

There   are  approximately  48  mines that mine ore containing
important   percentages   of    lead   and  31   concentrating
facilities,  which   supply  lead  concentrates  to  the  six
smelters.   Some  lead concentrates are  imported from  as  far
as Australia.   In  1971,  the  leading mines,  all in Missouri,
produced  72 percent of total  domestic  mine   production,  the
 10 leading  mines   produced   85  percent, and the  25 leading
mines contributed  98 percent.   In this same  year,  mines west
of the Mississippi  produced  almost  99  percent of  the lead
ores,   with  the  most   important lead producing  areas being
southeastern  Missouri,  Shoshone County  in   Northern   Idaho,
the area  just south of  Salt  Lake City  in north  central Utah,
and  the   Upper   San Miguel  region  in  southwestern Colorado.
 The 1971  lead mine production by states is  given  in Table  2.

 Lead consumption in the United States, by product,   in  1970
 and 1971, is  shown in Table  3.
                             10

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(S)  = Smelter only.
(R)  = Refinery only.
(S 4- R)  = Smelter and refinery.
          Figure 1.   Geographic locations of domestic primary lead smelters and refineries.

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                                                                                    (1-5)
                                             TABLE 1 •   LEAD SMELTERS AND REFINERIES



Company Location
American Smelting and Glover,
Refining Company Missouri
Ditto East Helena,
Montana


_, " El Paso,
^ Texas
" Omaha,
Nebraska
Annual Tons
of Lead
Containing
Material
Treated 1972
159,600
192,000


not reported

136,000


First
Year Of
Operation
1968
1888


1887

1870


Raw Materials
Used
Lead Cone.
Waela Residue
Lead Residues
Lead Cone.
Siliceous Ores
Zinc Residue




Lead Bullion
Secondary 'Lead


Slag Acid
Treatment Plant
None None
Slag None
Fuming
Furnace


Slag None
Fuming

None None


Products
Refined Lead
Copper Dross
Retort Bullion
Lead Bullion
Soda Ash Matte
Soda Ash Speiss
Lead Baghouse Dust
Zinc Fume
Lead Bullion
Zinc Fume

Refined Lead
Antimonal Lead
Solder
Bunker Hill Co.
St. Joe Minerals
Missouri Lead
  Operating Co.
Kellogg,
Idaho
                                         550,000
Herculaneum,    336,000
Missouri
Boss,
Missouri
192,500
                                1918
                                                        1892
                                                         1968
                                                                   Lead Cone.
                                                                   Lead Cone.
                                                                   Lead Cone.
                                              Slag
                                             Fuming
                                                                                       None
                                                                                       None
          Misc.  Lead Alloys
          Bismuth
          Copper Matte
          Sodium Telluride
            Slag,

300 TPD   Refined Lead,
          Gold,  Silver,
          Antimony

300 TPD   Refined Lead,
          Silver Bullion,
          Copper Matte

225 TPD   Refined Lead
          Copper Matte
          Dross
          Silver Bullion

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              TABLE 2.    MINE PRODUCTION OF RECOVERABLE LEAD
                          IN THE UNITED STATES, BY STATED
                                    (Short Tons)
State
Alaska
Arizona
California
Colorado
Idaho
Illinois
Kansas
Kentucky
Missouri
Montana
Nevada
New Mexico
New York
Oklahoma
Oregon
Soiuth Dakota
Utah
Virginia
Washington
Wisconsin
Other States
Total
1967
__
4,771
1,735
21,923
61,387
2,384
1,031
845
152,549
898
1,500
1,827
1,653
2,727
—
53,813
3,430
2,762
1,596
--
316,931
1968
W
1,704
4,001
19,778
54,790
1,467
1,227
W
212,611
1,870
863
1,363
1,396
2,387
W
45,205
3,573
5,655
1,126
140
359,156
1969
2
217
2,518
21,767
65,597
791
395
—
355,452
1,753
1,420
2,368
1,686
605
(1)
1
41,332
3,358
8,649
1,102
—
509,013
1970
__
285
1,772
21,855
61,211
1,532
80
--
421,764
996
364
3,550
1,280
797
(1)
3
45,377
3,356
6,784
761
__
571,767
1971
....
859
2,284
25,746
66,610
1,238
--
—
429,634
615
111
2,971
877
--
—
38,270
3,386
5,177
752
20
578,550
W   Withheld to avoid disclosing individual company confidential data;
    included in "Other States".

(1) Less than 1/2 unit.
                                     13

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      TABLE 3.    LEAD CONSUMPTION  IN  THE UNITED STATES,  BY  PRODUCT
Product
Metal products:
Ammunition
Bearing metals
Brass and bronze
Cable covering
Calking lead
Casting metals
Collapsible tubes
Foil
Pipes, traps, and bends
Sheet lead
Solder
Storage batteries:
Battery grids, posts, etc.
Battery oxides
Terne metal
Type metal
Total
Pigments:
White Lead
Red Lead and litharge
Pigment colors
Other^1'
Total
Chemicals :
Gasoline antiknock additives
Miscellaneous chemicals
Total
Miscellaneous uses:
Annealing
Galvanizing
Lead plating
Weights and ballast
Total
Other, unclassified uses
(2)
Grand Totalv '
1970

72,726
16,328
18,927
50,772
34,608
7,498
10,913
5,521
17,888
21,050
69,707

283,451
310,002
1,038
24,476
944,905

5,936
77,215
14,407
1,178
98,736

278,505
623
279,128

4,161
1,792
400
16,184
22,537
15 T 246

1,360,552
1971

87,567
16,285
20,044
52,920
29,993
7,281
10,041
4,417
18,174
27,607
70,013

322,236
357,567
1,409
20,812
1,046,366

4,731
61,838
13,916
773
81,258

264,240
401
264,641

4,068
1,395
582
17,453
23,498
15T751

1,431,514
(1)   Includes  lead content of leaded zinc  oxide and other pigments.
(2)   Includes  lead that went  directly from scrap to fabricated products.
                                   14

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                         SECTION IV


                  INDUSTRY CATEGORIZATION

                        Introduction

This  section  describes  the  scope  of  the  primary  lead
industry.  Included are technical  discussions  of  the  raw
materials   used,   methods   of  production,  and  products
produced.  Possible methods of subcategorizing this industry
into  discrete  units  for  separate  waste  treatment   and
effluent limitations guidelines are also discussed.

                Objectives of Categorization

The  objective  of  industry  categorization is to establish
recommended   effluent   limitations   and   standards    of
performance,  which are specific and uniformly applicable to
a given category.  Categorization, therefore,  involves  the
identification   and  examination  of  the  factors  in  the
industry, which might affect categorization in terms of  the
recommendations to be developed.

                     Factors Considered

Manufacturing Process

As  explained in the previous section, there are six primary
lead smelters and five primary lead refineries in the United
States.   Salient   characteristics   of   each   of   these
operations,  including  data  on  the  number  of  years  in
operation, annual  tonnage  of  lead  concentrates  handled,
origin   of   concentrates,  method  of  handling  the  zinc
constituent in the  concentrates,  method  of  handling  SO2
offgas  from the sintering machine, location of the refinery
with respect  to  the  smelter,  and  annual  production  of
refined lead, are shown in Table 4.

The  sequence  of  lead  smelting  and  refining  processes,
illustrated in the generalized flowsheet in  Figure  2,  are
charge  preparation  (blending of the concentrate with flux,
return products, etc),  sintering,  blast  furnace  smelting,
and the subsequent refining operation to remove and, in some
cases,  recover metallic impurities.  The major steps in the
production of lead will be discussed in this sequence.

Charge Preparation.  In general practice, charge preparation
may involve the blending of lead  concentrates  with  fluxes
and  a  variety  of  recycle  products,  such  as  dust from
                           15

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              TABLE 4.   SALIENT CHARACTERISTICS OF U.S. LEAD SMELTERS



Plant
A



B




Year
First Origin of
Operated Concentrates
1891 U.S.A.
(S.E. Mo.
ores)

1968 U.S.A.
(S.E. Mo.
Ores)

Method of
Slag Handling S02
Fuming Gas From
Plant Sinter Mach.
None; Acid plant
zinc dis-
carded in
slag
None; Acid plant
zinc dis-
carded in
slag
Refined Lead
Refinery Production
Adjacent 1000 units/year
to Smelter kkg (tons)
yes 209 (230)



yes 121 (133)



1968
1917
1888
1887
   U.S.A.
   U.S.A.
Canada, Peru,
Australia

   U.S.A.
Canada, Peru,
Australia
   U.S.A.
Canada, Peru,
Mexico
None;      Spray chamber,
zinc dis-  baghouse,
carded "in  stack
slag

  yes      Acid plant
  yes      Spray chamber,
           baghouse,
  yes      Spray chamber,
           baghouse,
           stack
                                                           yes
                                                                        98
                                                           yes
               No; bullion
               refined at
               Asarco refin-
               ery in Omaha

               No; bullion
               refined at
               Asarco refin-
               ery in Omaha
                                                                       121
                                                                        58
                                                                        56
                                          (108)
                                          (133)
                       (64)
                       (62)
1870
   N.A.
  N.A.
N.A.
N.A.
                                                                      123
(136)

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SMI
Lead Concentrates

Flux 	 » Char
Prepar
[—
1
Recycle
Underslze
L ~

ation



^" Sinter Fume

SECTION
1



Coke 	 - BUgt
1 	 ». Furnace
t
Partial
Recycle of Sett
Refinery
Dross
Lead E

Slag
ler *

ullion
Solid!

	 ' 	 S02 CM
Dust
System

Slag fc Slag
Granulation
J
Water
Slag ^ Zinc Fuming
""" Furnace
Stack
tt
1
_^ Acid
Plant


• _att cr
t

Recycle
to Sinter
t
- 1 g To
Waate

p Fume to Baghouse
„ Slag to Waste
Lead

"• 	 (ist and 2nd Co
Sulfur *|
f
[
i
ties B

t
pper By-Product
*" Reverberate
Furnace

f"*" Baghouse r *
	 J Softening Arsenl
cal & _, Hard Lead

	 ». Fume
ry 	 •• Copp
to C

to Baghouse
er Matte and Spelss
.opper Smelter
-CO , Silica 	 Lead Oxide
	 Refining
	 •» Antimonial
; ' 	 ; 	 Skims ' 	 1 	 '—— * 	
i *— f Slag to Charge Preparation (By-Product)
So£tfinsd Lead
Zinc to Desilverizing
Lead i AIr
til t . . T

Desilve
1

REFINERY
SECTION

Zinc 	 »— f. Desllver
'• 2

Si
rizlng (
^ Secondary
L<
i



Vaccum
^ Dezincinj?

Ca.MR 	 • Deblsmu
Ket



tie

NaOH 	 «• Refining 	
NaNO Kettle
Refined Lead

lver f llouard 1
klras Press
Sliver Skims
t
iros ^ Howard
Press
C12 Gas,
Oxidizing Flux,
Charcoal
1
Bismuth
^ Dross
	 sr Retort 1—
1
	 •» Cupel 1 	 •• D° re'
! 1
t
PbO(Lltharge)
Reclrculated
to B.F.
, Bismuth Metal
•y Removal, Traces of Zn, Sb , and As
(Caustic Dross to Charge Preparation)
Figure 2.   Generalized  flow sheet of a lead smelter and refinery.
                     17

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collection  systems,  fumes,  slags,  etc,   which   contain
recoverable  lead and other metals.  This blended mixture is
pelletized after addition of moisture  (up to 1C percent)  by
rolling  in  rotating  drums,  referred to as ball drums, to
form spherical pellets about 1/2 inch or more  in  diameter.
The pelletized concentrates are then sintered.
             Sintering  is  done  on  a  "sintering machine"
which, in essence,  is  a  traveling  grate  furnace.   Both
downdraft  and  updraft machines have been used in sintering
lead and zinc concentrates, but at present  the  latter  are
more commonly used for lead sintering.  Figure 3 illustrates
the  general structure and function of the updraft sintering
machine.  In U. S. sintering procedure, a positive  pressure
of  air  is  supplied  from below the traveling grate of the
sintering  machine  and   slightly   reduced   pressure   is
maintained  above  the  bed.   in  the operation, a layer of
pelletized charge is laid down on the bed of  the  sintering
machine  and  is ignited by downdraft burners above the bed.
The balance of the charge  (up to about 40 cm  (16  in)  total
depth)  is  spread  on  the burning layer, and the traveling
grate then enters the updraft windbox  section.   Under  the
effect of the applied updraft, the bed burns from the bottom
up.   The total charge is sintered in the front half, called
"strong gas strand", of the sinter machine, while  the  rear
half,  the  "weak  gas  strand"  is  used for cooling of the
sintered charge.

The objectives of the sintering operation are  not  only  to
remove  sulfur as SO2 and SO3 and to eliminate, by volatili-
zation, much of the undesirable impurities such as  arsenic,
antimony, and cadmium, but, equally as important, to produce
"sinter"  of  suitable  size  distribution  and strength for
subsequent treatment in the blast furnace process.

At the end of the sinter machine, the sinter is then  passed
through   a  sinter  breaker  (i.e.,  spiked  rolls).   This
operation breaks the sinter and  sizes  the  material.   The
oversize material (+ 2 inch)  is sent to blast furnace charge
preparation.   The  undersize  product  (-2  inch) is passed
through a set of roll crushers to further reduce the  sinter
in  size,  then  cooled  by water addition (usually recycled
water) and sent back to sinter  feed  preparation.   In  one
case,  the  sinter  temperature  is reduced by water sprayed
directly on the sinter strand.  The sinter sizing  operation
produces  a  considerable  amount  of dust, and this dust is
captured by wet scrubbers or baghouses.   In either case, the
collected material is recycled back to the sinter operation.
                              18

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                                         Gas  off  lake
                                                 Hood
                                                     and seal
                                                  ^Working floor
                                                  A_
                                Windbox
                        cleaning chute
                                                      Dust Hopper
                                                       Air inlet
Figure 3.  Cross section of a typical updraft sinter in-i rachinc.
                            19

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The sintered product fed to the blast furnace will  vary  in
composition  depending  on  the  primary source of lead con-
centrates.  The following tabulation  is  an  example  of  a
finished sinter composition.

                                    Weight
               Constituent         Percent

                   Pb               45-50
                   Fe               12-13
                   CaO              10-11
                   Si02             10-12
                   S                 1-2
                   Zn                4-8
                   Cu              0.3-3.0


Blast	Furnace.   The blast furnace is the primary reduction
unit in a lead  smelter.   By  a  combination  of  heat  and
reducing  gases,  it  separates  the  constituents  into two
phases: molten metal and slag.  The metals that  are  easily
reduced,  such  as  lead,  copper,  silver,  gold,  bismuth,
antimony, and arsenic,  become  part  of  the  metal  phase;
whereas,  metals  that are not easily reduced become part of
the slag phase along with the nonmetallic elements.

The lead  blast  furnace  is  water-cooled,  rectangular  in
shape,  6.7  to 8.5 meters  (22 to 28 feet)  in length and 4.6
to 6.1 meters  (15 to 20 feet)  in height, and  may  range  in
width from 1.5 to 3.0 meters  (5 to 10 feet), sometimes being
tapered  from  3.0  meters  (10  feet)   wide at the top to a
minimum width of 1.5 meters (5 feet)  at the bottom.   It  is
vertical,  generally  with  a  thimble-top design, where the
furnace is charged on both sides  at  the  top.   Associated
facilities   include  materials-handling  equipment  and  an
exhaust gas handling system, an air supply system of  bustle
pipes, a conveyor system for introducing the charge, tuyeres
for the introduction of air to the charge at several levels,
and  a  refractory  crucible  structure  at  the bottom with
provisions for continuous or intermittent  tapping  of  lead
bullion  and  slag.  A general arrangement is illustrated in
Figure 4.

The charge to the  blast  furnace  always  includes  sinter,
coke,   and  fluxing or slagging additions such as silica and
limestone,  and  usually   includes   recycled   slag   from
associated  operations,  cadmium  plant  residues,  refinery
dross, and fume from dust-collecting equipment.

The products of the blast furnace are as follows:
                             20

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                      Flue to
                   Cooling Chamber
                        X
Ventilation Fan
           y
                                               [\_Control for Movable
                                                     Charge Bins
                                                                      ^-Granulator
                                                                       \ Pump
                                                          /-Granulating
                                                             Launder
Blast Furnace
    Air
                                                                                    Bucket
                                                                                   glevator
        Figure 4.  General arrangement of a typical blast furnace and associated facilities.

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(a)   Lead bullion,  which normally contains quantities of
     copper,   arsenic,   antimony,  or  bismuth.     These
     impurities must be removed by further processing to
     produce   an acceptable lead.  The lead bullion also
     may contain precious metals in quantities that  are
     worth recovering.    The  composition  of  the lead
     bullion  will vary  from plant to plant, but will  in
     general    contain    95  to  99  percent  lead  with
     impurities ranging as follows:
            Copper - up to 2.5 percent,
            Zinc - negligible.
            Antimony -  up to 2 percent,
            Arsenic - up to 1 percent.
            Bismuth - up to 0.03 percent.
(b)   Slag which consists of iron,  calcium,  and magnesium
     silicates,  small    quantities   of   arsenic   and
     antimony,   and  variable  amounts  of   lead (1.5 to
     about 4 percent).   Where the  amount of zinc in  the
     concentrate  is  sufficient,  the common practice is
     to treat the slag   in  a  slag  fuming  furnace  to
     recover  the  zinc.    In the  slag fuming operation,
     the slag,  usually  while still molten,  is charged to
     a  zinc  fuming  furnace,   which  is   commonly   a
     reverberatory-type   furnace,   with   or   without
     additions of  other  zinc-bearing  materials  (cold
     slag,  other  recycled  drosses, dusts, etc.).   The
     charge is heated  to  a  high  temperature  through
     addition  of  fuel (coal)  and air is blown into the
     molten slag.   The  zinc is boiled off  and  oxidized
     to  zinc  oxide dust particles,  which  are collected
     in dust  collecting  equipment  such  as  cyclones,
     precipitators,  dust chambers, and baghouses.   Slag
     after zinc  fuming,   or  that  which  is  discarded
     without  fuming,  is usually granulated by impacting
     a stream of the molten slag with  a high  pressure
     water  jet.    The   granulated slag may be dewatered
     and either recycled as part of the charge materials
     to  the  sinter  process,   or,  depending  on  slag
     composition  and  plant  facilities, may be totally
     discarded.

(c)   Matte and speiss in some  blast  furnace  practice.
     The  matte  phase   consisting  of  copper  and iron
     sulfides and precious metals  may  be  formed  as  a
     discrete liquid layer between bullion  and slag.   If
     considerable  arsenic  is  present  in  the charge,
     speiss is present.    These materials   are  usually
                           22

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         sent  to  copper smelters or outside processors for
         further treatment.

Refining Operations.   In some operations where the  refinery
is  a considerable distance from the smelter, the first step
of   the   refining   operation,   the    dressing-byproduct
reverberatory  furnace decopperizing operation, is performed
at the smelter as shown in the  generalized  flow  sheet  in
Figure  2.  In other cases, where the smelter is adjacent to
the refinery, the dressing operation  is  carried  on  as  a
refinery  function.   In either case, it is always the first
step in the refining  of  the  lead  bullion.   The  various
industrial  approaches  used in domestic dressing operations
are described below.

Drossing.  Dressing is performed in vessels referred  to  as
kettles.   The kettles are generally hemispherical in shape,
up to 7.3 meters  (24 feet) in diameter, and are  constructed
of  welded  steel plate up to 3.8 centimeters  (1-1/2 inches)
thick, holding up to 227 kkg (250 tons).   The  kettles  are
gas   heated  with  external  refractory  brick  insulation.
Permanent  auxiliary  equipment  for   stirring,   skimming,
transfer  of  products,  etc.,  is  generally provided.  The
major  purpose  of  dressing  is  to  remove  copper.    The
separation of copper is effected by lowering the temperature
of the metal close to, but still above, the melting point of
lead.  At this temperature, the solubility of copper in lead
is  minimal  and  excess copper is rejected from the melt to
form a crust or head  on  the  melt,  and  is  separated  by
skimming from the liquid lead.  Sulfur is sometimes added to
the  dressing  kettle  to  enhance  the removal of copper as
copper sulfide.

By dressing, the copper content of the lead is reduced  from
as  high  as  several tenths of a percent to as low as 0.005
percent.  The liquid lead is then transferred  to  a  second
kettle, where a second decopperizing cycle may be performed.
The dross, which may typically contain about 90 percent lead
oxide,  2  percent  copper,  and  2  percent  antimony, with
entrained  gold  and  silver,  is  treated  in  a  byproduct
reverberatory  furnace   (i.e., dross reverb) to recover lead
as bullion and to produce  a  copper  matte  for  subsequent
treatment by copper smelter practice.

Softening.   After  dressing,  the bullion is subjected to  a
"softening" step.  This refining operation is  performed  to
remove antimony and produces a product of lower hardness and
strength.   In  contrast,  lead  alloyed  with  antimony  is
commonly referred to as "hard lead" or antimonial lead.

-------
The  softening may be done  in  either  of  two ways,  either   by
air  oxidation  of  the  molten   bullion  in  a reverberatory
furnace or by oxidative  slagging with a  flux  of   sodium
hydroxide and sodium nitrate.

The  air  oxidation process consists of treatment of drossed
lead in a reverberatory type  furnace   with   air  introduced
into the bath through pipes or lances.  In the air oxidation
method of softening, most  of  the  impurities are removed in a
primary  slag,  which  is  skimmed  off.   The  aeration   is
continued with the formation  of a final  slag.   This  two-
stage  slagging  permits   the  maximum  degree of removal  of
impurities.   The  slag  produced contains   the  oxides   of
copper,  arsenic,  antimony,  and  tin as complex oxides  (lead
stannate, lead  arsenate,  lead   antimonate)   and  entrained
metal, and is further treated to  recovery antimony, antimony
oxide,  antimonial (hard)  lead, a tin-rich skim (sold to tin
recovery  operations),  and   sodium   arsenate,   which    is
generally discarded.

After  softening by the air-oxidation,  reverberatory-furnace
treatment, the lead bullion is drained  from beneath the slag
and treated further by fire-refining methods.

An alternative method of softening is an oxidative  slagging
technique in which a sodium hydroxide-sodium  nitrate mixture
is   stirred  into  the  molten   lead   to  oxidize  arsenic,
antimony, tin, etc.   These  impurities  enter  the  slag   as
arsenates,  antimonates,   and stannates of sodium.  At least
two versions of the oxidative slagging  process are used, the
kettle process and the Harris process.  The major difference
between these two processes is that the kettle process  slag
is  discarded  to  waste,  while  the Harris  process slag  is
extensively  treated  by  a  hydrometallurgical  process   to
recover  sodium  hydroxide  and,   where  indicated, arsenic,
antimony, and tin products.


Desilverizing and Debismuthizinq bv. Fire  Refining  Methods.
Electrolytic   refining   of  softened  lead  is  no  longer
practiced in the United States.    All  U.S.   refineries  use
fire refining to effect a separation of gold and silver and,
if  necessary,   bismuth from the lead bullion at this point.
The processing steps  involved are as follows:

    (1)   Desilverizing by the so-called Parke's process,  in
         which  the   softened  lead  is  treated for several
         hours with  zinc metal at about 90(TF with stirring.
         The zinc  combines  preferentially  with  gold  and
         silver   to    form   zinc-gold   and  zinc-  silver
                             24

-------
         compounds.   These compounds  are virtually insoluble
         in lead.   Enough zinc is added to combine with  all
         the  gold  and silver and to saturate the lead with
         zinc.   The zinc-precious metal alloys accumulate on
         the surface and are skimmed  off.   By conducting the
         desilverizing in two  stages,   it  is  possible  to
         isolate high- gold and high-silver Dore silver-gold
         alloys  to  facilitate the recovery of these metals
         in subsequent  processing.    However,  most  plants
         produce only a high silver-gold skim and separation
         is made later from the combined Dore.
    (2)   After removal of  the  gold   and  silver,  zinc  is
         removed by a process called  vacuum dezincing, which
         is  conducted  in  a  separate  kettle.  A portable
         bell-shaped vessel with an open bottom  is  lowered
         onto  the  liquid  lead  to   form  a seal and allow
         evacuation of the space above the melt.  The  upper
         portion   of   the  dezincing  chamber  contains  a
         condenser, a stirrer extending down into the  melt,
         and connections to a vacuum  system.  As a vacuum is
         applied to the chamber, any  zinc in the lead leaves
         the  melt  by  vaporization   and  condenses  on the
         condenser.

Debismuthizincf.  Formerly, the  electrolytic  method,  which
utilized"  a  hydrofluosilicic  electrolyte,  was  the  only
feasible method for producing refined lead with an extremely
low bismuth content.  With the  Betterton  process,  bismuth
can be removed down to a content of below 0.01 percent.  The
simultaneous  addition  of  calcium  and  magnesium produces
CaMg2Bi2 crystals as  a  precipitate,  which  float  to  the
surface  of  the  kettle and can be skimmed off.  Subsequent
treatments with antimony or  organic   agents  are  sometimes
used  to reduce the bismuth content further by improving the
physical separability of the fine bismuthide crystals  still
remaining in the bath.


The  CaMg2Bi2  crystals  form  a rich bismuth crust which is
transferred "to  another  kettle  where  it  is  melted  and
subjected  to  a chloridizing gas treatment.  The gas reacts
with the calcium and magnesium to form chlorides; these,  in
turn, are treated with an oxidizing flux which forms a slag,
and  also  oxidizes  other  impurities  that may be present.
After  the  slag  containing  the  impurities  are  removed,
charcoal  is  added as a cover to maintain the bismuth metal
in a reduced condition while it is being cast.
                              25

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                of  the  Debismuthized  Lead.   Calcium   and
magnesium  remaining  in  the  lead ""after debismuthizing is
removed by stirring caustic  soda  (sodium hydroxide)  into  the
molten lead in  the final refining kettle.  A   dry   dross   is
produced,  which  is retreated at the smelter.  Any residual
zinc, antimony, or arsenic remaining in  the   lead   at  this
point  is  also removed.  Sodium nitrate is sometimes added
along with caustic soda  to  effect  the  removal   of  these
impurities.

Summary.   The  processes  employed  by the six primary lead
smelters  are   basically  the  same.   Various  degrees    of
refining  are   required  depending upon ore constituents,  as
discussed below.  The one primary  refinery,  which is   not
located  on-site  with  a  primary smelter, does not produce
process waste water pollutants, as defined in this  document.
Therefore, from the  standpoint  of  manufacturing   process,
this  one  refinery  should not be considered as part of  the
primary lead subcategory; whereas, the six remaining primary
lead facilities should,  for  the  purpose  of  establishing
effluent limitations, be considered as one subcategory.

Age of_Plant

A  factor  shared  by  all  U.S.  smelters  is similarity  in
processing procedures in the smelting operations.   All   are
conventional  sinter-blast  furnace  smelters.   As shown  in
Table 4, two of the  six  domestic  smelters  were  recently
constructed;   whereas,  the  original  starting dates of the
remaining four make them much  older.   These  older  plants
have all been modernized, producing a commonality of process
equipment  for  all  six  facilities.   This  commonality  is
basically the updraft sinter machine and the hood-type blast
furnace.  Age of  facilities  also  has  no  effect  on  the
refining steps used to purify lead bullion.

Thus,  age  of  the  plant  does  not  affect  the  industry
characterization.

Size

On the basis  of annual production of refined lead,   Plant  A
is  larger than the others by approximately a factor of two,
(Table H).   If the single-company complex of  Plants  E,  F,
and  G  is considered as a single smelter-refinery unit, the
production of the four smelter- refineries,  B,  C,  D, and the
Plant E,  F,  and G Complex,  can each be considered  as  unity
(vis-a-vis.   Plant A's factor of two).   Thus,  there are five
important units  sharing  U.S.   production,   none  of  which
require a separate categorization on the basis of size.   The
                            26

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production  figures  for  concentrates  and  refined lead is
evidence of the fact that the Missouri smelters  operate  on
lead  concentrates  containing  a larger percentage of lead.
The western smelters handle lower grade, larger  variety  of
concentrates to obtain a given amount of refined lead.
Raw Materials and Products
The  primary  ore  minerals  of  lead  are shown in Table 5.
Table 6 illustrates  the  ranges  of  compositions  of  lead
concentrates  produced by gravity and floatation procedures.
Table 7 lists the chemical requirements of various types  of
refined lead.
Smelters,	Treating	Concentrates,	From Southeastern Missouri
Ores.  There is a marked  difference  between  the  type  of
concentrate  handled  by  the  western  smelters  and  those
treated  by   southeastern   Missouri   smelters.    Typical
compositions  of  southeastern  Missouri  concentrates  from
mills, which have both copper and zinc removal circuits  are
shown in Table 8  (figures are in percent, except for silver,
which is in ounces per ton).
The  lead content of all Missouri lead concentrates is above
70 percent; zinc does not exceed 2.5-3 percent, nor copper 2
percent.  There are only trace amounts of antimony, arsenic,
and bismuth.  Zinc is not high  enough  to  warrant  a  slag
fuming  plant,  so  it  is discarded as a constituent of the
slag.   Cadmium,  which  builds  up  in  the   recirculating
baghouse  dust, is bled off for cadmium recovery.  Thus, the
major end products from the refineries associated with these
Missouri  smelters  are  limited  to  refined  lead  and   a
relatively  small  amount  of  copper  as  matte, and silver
bullion;  for  every  90,700  kkg  (100,000  tons)   of  lead
produced,  there  is  an  associated 1810 - 2270 kkg (2000 -
2500 tons)  of copper matte (containing about 45 percent  Cu,
10  to  20  percent  Pb)   produced, along with approximately
2,840 to 3,410 kg of silver.   Because of the lower  impurity
content,   especially  bismuth,  fewer  refining  steps  are
required for Missouri refined lead production.


Western Smelters Treating_Domestic and_ImBorted_Ores All the
U.S. smelters outside the Missouri group (Plants D,  E,  and
F)  are custom smelters,  handling both domestic and imported
ores.  There is, of course,  no  such  thing  as  a  typical
                            2'7

-------
                     TABLE 5.   ORE MINERALS OF LEAD
Mineral
Chemical Composition
                                                       Remarks
Galena
Cerussite
       PbS
       PbCO,
Anglesite
       PbSO,
Principal ore mineral,
commonly associated with
cerussite and anglesite

Results of weathering of
galena; frequently occur-
ring within a galena
deposit

          Ditto
                                 28

-------
TABLC 6.  RANGES OF COMPOSITION;. OF LEAD CONCENTRATES PRODUCLD
          BY GRAVITY 7\ND FLOATATION  rROCEDUREE

Constituent
Pb
Zn
Au(a)
Ag(a)
Cu
As
Sb
Fe
Insolubles
CaO
S
Bi
Cd
Percent
Lead Concentrates
45-80
0-5.0
0-17
0-3800
0-3
0.01-4.0
0.01-2.0
1.0-8.0
0.5-4.0
Trace -3.0
10-30
Trace -0.1
Trace -0.2

     (a)  Grams/metric ton.
                              29

-------
                       TABLE 7.  CHEMICAL REQUIREMENTS
Composition, percent

Silver, max
Silver, min
Copper, max
Copper, min
Silver and copper together,
Corroding
Lead
0.0015
—
0.0015
--

Chemical
Lead
0.020
0.002
0.080
0.040

Acid-
Copper
Lead
0.002
--
0.080
0.040

Common
Desilverized
Lead
0.002
—
0.0025
--

  max
Arsenic, antimony, and tin
  together, max
Zinc, max
Iron, max
Bismuth, max
Lead (by difference),  min
0.0025
0.002
0.001
0.002
0.050
99.94
0.002
0.001
0.002
0.005
99.90
0.002
0.001
0.002
0.025
99.90
0.005
0.002
0.002
0.150
99.85
                                30

-------
   TABLE 8.  TYPICAL SOUTHEASTERN MISSOURI LEAD CONCENTRATE ANALYSES
       Pb
Cu
Zn
Fe
Ni
Co
                                                 As
Insol  CaO  MqO
1.42  74.8  0.64  1.05  2.08  0.10  0.06  15.1  0.009  1.1   1.34  0.90




1.4   76.1  0.85  1.29  1.04  0.2   0.08  15.4  0.006  1.3   0.94  0.75

-------
analysis  of  the  concentrates  handled  by  these  plants.
However/  an  understanding of the complexity and variety of
the concentrates treated by these smelters  can  be  had  by
examining  the operation at one of them. Plant E.  Last year
this smelter treated 107,000  kkg   (118,000  tons)  of  lead
concentrate  with a reported average analysis of 0.50 oz/ton
Au, 168.8 oz/ton Ag, 38 percent  Pb,  and  5.4  percent  Cu.
From  these  concentrates   (with additions of siliceous lead
ore,  residues  from  the  zinc  fuming  plant,  etc.),  the
intermediate products shown in Table 9 were produced.

Lead  bullion  from  this plant is sent to a refinery, which
also treats bullion from Plant  F.   Last  year  a  combined
bullion  from  both  plants amounted to 119,720 kkg  (132,000
tons).  This with 3630 kkg  (4,000 tons)  of  secondary  lead
and  dross  was  treated to produce gold and silver Dore and
the following base metal products:

       Refined Lead             103,400 kkg (114,000 tons)
       Antimonial Lead Alloys    12,150 kkg (13,400 tons)
       Other Lead Alloys          6,666 kkg (7,350 tons)
       Refined Bismuth (99.99
         Percent)                    544 kkg (600 tons)
       Copper Matte                 254 kkg (280 tons)
       Telluride Slag               109 kkg (120 tons)

The concentrate handled at Plant D had a higher average lead
content than Plant E concentrates (a reported 62 percent  Pb
with  6.6  percent  S).   Last year, the refinery at Plant D
produced the following product mix:

       Refined Lead             120,630 kkg (133,000 tons)
       Gold                         239 kg  (8,400 oz)
       Silver                   305,584 kg  (10,760,000 oz)
       Antimony                     580 kkg (639 tons)

Generally, a large  number  of  products  are  made  at  the
western  smelters,  but  this additional production does not
produce additional  process  waste  water.   One  byproduct,
metallurgically produced sulfuric acid, does produce process
waste  water  at  lead  smelters.  This subject is discussed
below.
Location
Of the seven primary lead plants in the United  States,  one
 (Plant F) has no discharge by virtue of climatic conditions,
one other (Plant G) discharges noncontact cooling water, but
                              32

-------
            TABLE 9.    INTERMEDIATE PRODUCTS OF A WESTERN SMELTER
          Gold,  Silver,   Lead,   Copper,  Cadmium,  Zinc,
         oz/ton  oz/ton     %       %        %        %   (Tons)     kkg
Lead
 Bullion   1.7     3.48   97.5                           (64,000)    58,048

Soda Ash
 Matte     0.1    88       6.4     43.5                   (6,700)     6,077

Soda Ash
 Speiss    6.8   440       6.8     64                    (11,000)     9,980

Lead Baghouse
  Dust     0.5     6.7    17.5              17.6          (1,200)     1,090

Zinc Fume          2.7     7.7      0.17             70  (36,000)    32,650

-------
has  no  discharge  of  process  waste  waters  by virtue of
process variation (i.e., refining operations only), and  the
balance  of  the  plants  all have some discharge of process
waste water pollutants to navigable waters.  The data on net
annual accumulation of water and mean temperature  given  in
Table  10  indicate  that  not  all  existing  plants in the
industry have the available option of achieving no discharge
by means of total impoundment and solar evaporation.


Air Pollution Control

Particulate^Matter.   Large amounts  of  dust  and  fume  are
generated  during  sintering  and  reduction  in  the  blast
furnace.  The conventional dust collection  device  used  at
primary lead smelters is the baghouse.  One baghouse is used
on  the  sinter  machine  offgas, while a second baghouse is
employed on the blast furnace effluent.  There is  only  one
known  application  of  an  electrostatic  precipitator to a
sinter machine offgas at one domestic smelter.   These  dust
collection  techniques  operate  dry,  except  when water is
injected into the gas stream for gas cooling  prior  to  the
baghouse.   This  water  is  evaporated.   Other particulate
control points (i.e., transfer points, hygiene areas,  etc.)
are   usually  either  controlled  by  the  main  baghouses,
separate, smaller  baghouses,  or  smaller  closed-loop  wet
collection  devices.   The dusts collected are usually mixed
with water in a pugmill and then returned to the process  as
recycle material.

Sulfur  Oxide Control.  The majority of the sulfur contained
in the feed is converted to  sulfur  dioxide  in  the  front
portion   of   the  sinter  machine.   This  gas  stream  is
segregated  from  the  weaker  (lower   SO2   concentration)
offgases  from  the  rear  section  of the sinter machine at
three of the six domestic smelters.  The strong SO2 effluent
is sent to a metallurgical  sulfuric  acid  plant  at  these
three  smelters.   The other three plants collect all of the
sinter machine offgases in one flue and  pass  them  to  the
baghouse  with no sulfur oxide control.  Since the potential
of sulfur oxide control at these three smelters  exists  and
may  result  in  the  operation of an acid plant at a future
date, a separate category based upon air  pollution  control
is not warranted.
Industry Categorization Summary

Since  one  of  the  six  currently  operating  primary lead
smelters operates at no discharge  of  process  waste  water
                               34

-------
                     TABLE  10  CLIMATIC CHARACTERISTICS AT  U.S.  LEAD SMELTER LOCATIONS
OJ
Plant
A
B
C
D
E
F
G
Mean Max
Temp,
January,
C (F)
7
8
8
-1
-3
13
0.
(44)
(46)
(46)
(30)
(26)
(56)
6(33)
Mean Min
Temp,
January,
C (F)
-4
-3
-2
-8
-13
•» 1
-11
(24)
(27)
(28)
(18)
(8)
(30)
(12)
Mean Max
Temp,
July,
C (F)
33
32
32
29
30
34
32
(91)
(90)
(90)
(84)
(86)
(94)
(90)
Mean Min
Temp,
July,
C (F)
19
18
17
9
11
20
19
(66)
(64)
(62)
(48)
(52)
(68)
(66)
Mean Annual
Precipitation,
Cm (in)
97
107
107
79
25
20
66
(38)
(42)
(42)
(31)
(10)
(8)
(26)
Mean Annual
Lake
Evaporation,
Cm ( in)
91
97
97
76
66
183
102
(36)
(38)
(38)
(30)
(26)
(72)
(40)
Annual
Accumulation,
Cm ( in)
+6
+10
+10
+3
-41
-163
-36
(+2)
(+4)
(+4)
(+1)
(-16)
(-64)
(-14)

-------
pollutants   by   virtue   of  location,  the  primary  lead
subcategory  should  be  segmented  for  the   purposes   of
establishing  effluent  limitations  into  two  geographical
groups, smelters geographically  located  in  areas  of  net
evaporation  and smelters geographically located in areas of
net precipitation.   The  one  primary  lead  refinery,  not
physically  located  on-site  with  a  primary lead smelter,
should not  be  considered  as  part  of  the  primary  lead
subcategory,  since,  due  to processes employed at this one
site, process waste waters are not produced.
                                 36

-------
                         SECTION V

                   WASTE CHARACTERIZATION


                        Introduction
The sources of waste water within the primary lead  industry
are  set  forth  in  this section.  The kinds and amounts of
waste  water  characteristics  are  discussed  in  terms  of
volumes  of  flow  and are related to process operations and
current control and treatment practices.
                   Sources of Waste Water
The process operations found  in  primary  lead  plants  are
discussed  in  the  previous  section.  The sources of waste
water are indicated in  the  generalized  diagram  given  in
Figure 5, and are discussed in the following paragraphs.

Various  applications  of  noncontact  cooling  are found in
primary  lead  smelters.   These  applications  include  the
cooling  of various parts of sinter machines and the jackets
or outer shells of the blast furnace, cooling of door frames
or other portions of reverberatory  furnaces  (if  present),
bearing  cooling,  and,  if one is present at the plant, the
cooling  of  sulfuric  acid   plant   reactors   and   other
components.  Other noncontact cooling water applications may
be  related to power and steam plants if they are present at
the lead smelter.   In  the  primary  lead  industry,  metal
casting  cooling  water  is  characteristically a noncontact
cooling water source.  The waste  water  streams  from  such
noncontact  cooling  operations  are not within the scope of
this document and are only discussed here  to  differentiate
them from process waste waters.  Process waste water streams
identified within lead smelter operations include:

    •    Streams from the gas cleaning train associated with
         acid plant operations, including  water  from  such
         sources   as   gas   conditioning  (humidification)
         chambers,  electrostatic  precipitator  sumps,   or
         bleed streams from weak acid wet scrubbers;
    •    Streams from blast  furnace  slag,  speiss,  and/or
         dross  granulation  operations,  usually a bleed or
         intermittent overflow stream from  a  recirculating
         water system;
                                37

-------
CO
00
                              Cooling  Tower
                              or  Reservoir
             Sinter
             Plant
 Blast
Furnace
     Noncontact
       Cooling
        Water
                    I
                    I	SO,,  -:
     Gas Cleaning
         Train
         Acid
        Plant
      Blowdown
 Acid
Plant
                  Blast
                Furnace
                  Slag
              Granulation
                                                                       Recycle
                                                                        Pond
                                                                                                     Ventilation
                                                                                                     Scrubbers
                                                                       Settling

           Figure 5.  Generalized diagram of water uses and v/aste water sources in prirrary lead plants.

-------
    •    Similarly, water circuits for cooling of hot  gases
         from  either  the  blast  furnace  or the sintering
         operation, or for  air  pollution  control  in  wet
         scrubbers.   These  were  found  to be operating in
         closed loop fashion  (i.e.,  without  an  effluent)
         except in the case of one plant.

The  process waste water streams identified as components of
discharge waters  include  acid  plant  blowdown  (in  three
plants),  slag granulation waste water (in five plants), and
wet scrubber waste water (in four plants).   Data  developed
on  the  identifiable  constituents  of plant discharges and
calculated unit waste loads for one smelter (given in Tables
11 and 12)  represent discharges from the plant  as  reported
in 1971.  The discharge at that time totaled about 8,175,600
I/day  (1500  gpm)  and  contained  suspended  and dissolved
solids (mostly sulfates), as well as identifiable amounts of
cadmium, lead, and zinc.   The data in Table 13 represent the
discharge  anticipated  after  the  revision  of  the  water
circuits  at  the  plant.  In order to achieve the projected
waste loads, the total flow of effluent will be reduced from
8,175,600 I/day   (1500  gal/min)  to  1,635,120  I/day  (300
gal/min), with lime treatment of the acid plant blowdown, to
achieve  the  projected waste loads listed in Table 13.  The
calculated specific discharge rate  would  be  reduced  from
about  14,000  1/kkg  (3400  gal/ton)   to  2,900  1/kkg (690
gal/ton).  This latter figure would  include  408,780  I/day
(75  gpm)  of  treated  acid plant blowdown, equivalent to a
calculated minimum rate  of  blowdown  of  1500  I/day  (360
gal/ton)  of acid produced or 713 1/kkg (170 gal/ton)  of lead
produced.   Similarly,  waste characteristics for other lead
smelters are given in Tables 14 through 17,  which  indicate
the  waste  characteristics before and after revision of the
water systems.

For example, waste characteristics for one lead  smelter  in
1971  are  shown  in  Table 14.  According to present plans,
this discharge will be greatly  reduced  before  1975.   The
reduction  in effluent will be achieved by various measures,
some  presently  completed,  including  closed-loop  cooling
water  circuits  for  the  acid  plant, with a cooling tower
installed in the metal  casting  cooling  circuit  and  acid
plant blowdown being appropriately treated and then used for
dross   and   slag  granulation.   Ventilation  air  venturi
scrubbers will operate in closed circuits and  will  provide
additional evaporative capacity.

The  waste  characteristics  given  in  Table 15 are for the
discharge from settling ponds which receive waste water from
a slag granulating operation.  This is  the  only  discharge
                              39

-------
                               TABLL  11. WASTE EFFLUENTS FROM PLANT A  (OUTFALL No. 001)
                             Contributing Operations:   Slag granulation ,  blast-furnace
                                                        cooling water, miscellaneous blowdowns
Parameter
pH
Alkalinity
COD
Total Solids
Dissolved Solids
Suspended Solids
Oil and Grease
Sulfate (as S)
Chloride
Cyanide
A lumi rum
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Mercury
Molybdenum
Nickel
Po t a s s i uin
Selenium
Silver
Sodium
To llur ium
Zi nc
Flow,
I/day
(gal /day)
Production,
kkg/d^y
(l ons/day)
Total
Plant
Intake ,
mg/1
7.6
203
8
--
408
3
—
145
18
__
—
—
—
70
—
0.02
1.70
0.12
.31
--
—
0.03
—
—
—
—
--
0.12


(2,592,000)

571.4
(630)
Total
Plant
Discharge ,
mg/1
8.3
186
8
—
500
36
--
215
—
—
—
--
—
—
—
0.02
—
0.30
--
—
--
0.04
—
--
—
—
—
0.50

5,995,440
(1,584,000)

571.4
(630)
Net
Change,
mg/1

-17
0
—
92
33
-_
70
—
—
--
--
--
—
—
0
--
0.18
--
--
--
0.02
--
--
—
—
—
0.38






Net Loading_
kg /day kg/kkg

NLC(a)
0
--
551.54 0.97
197.84 0.35
_-
419.65 0.73
—
—
-_
--
__
-_
—
0 0
__
1.08 0.002
--
—
__
0.12 0.0002
--
-_
--
—
—
2.28 0.004






Ib/ton

--
0
-.
1.94
0.70
-_
1.46
--
--
_-
__
__
__
-_
0
__
0.004
—
--
--
0.0004
__
__
--
—
--
0.008






Source:   This contract and 1971 RAPP data.

(a)  NLC = no load calculable.
                                            40

-------
                               TABLE  12. WASTE EFFLUENTS FROM PLANT  A (OUTFALL No.:  002)
                             Contributing Operations: Casting, cooling, acid-plant blowdown,
                                                      dross granulation, noncontact cooling water
Parameter
PH
Alkalinity
COD
Total Solids
Dissolved Solids
Suspended Solids
Oil and Grease
Sulfate (as S)
Chloride
Cyanide
Altimirum
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Mercury
Molybdenum
Nickel
Potassium
Selenium
Silver
Sodium
Tellurium
Zinc
Flow,
I/day
(gal /day)
Production,
kkg/day
(tons/day)
Total
Plant
Intake,
mg/1
7.6
203
8
—
408
3
--
145
18
--
--
—
--
70
--
0.02
1.70
0.12
0.31
--
—
0.03
—
—
—
—
—
0.12


(2,592,000)

571.4
(630)
Total
Plant
Discharge ,
mg/1
6.8
260
200
—
980
500
--
500
—
—
--
—
1.9
40
—
0.10
1.0
0.50
—
—
—
--
—
—
—
200
--
10

2,180,160
(576,000)

571.4
(630)
Net
Change,
mg/1
__
'57
192
—
572
497
--
355
—
—
—
--
1.9
-30
—
0.08
-9.7
0.38
--
—
—
—
—
—
—
—
—
9.88






Net Loading
kg/day
__
124.26
418.56
—
1246.96
1083.46
--
773.90
—
--
—
—
4.13
NLC
—
0.17
NLC
0.83
—
—
—
—
—
—
_-
—
—
21.54






kg/kkg
..
0.22
0.73
--
2.18
1.90
_-
1.35
—
--
—
—
0.007
--
—
0.0003
—
0.001
—
--
--
--
--
—
__
—
--
0.038






Ib/ton
..
0.44
1.46
__
4.36
3.80
__
2.70
-_
--
—
--
0.014
--
—
0.0006
—
0.002
--
-_
__
_-
__
—
__
-_
__
0.076






Source:  1971 RAPP Data.
                                             41

-------
                               TABLE  13-   WASTE  EFFLUENTS  FROM PLANT A
                                           (EFFLUENT  FROM PROJECTED  TREATMENT  PLANT WITH
                                           REVISED WATER CIRCUITS)
Parametc •
pH
Alkalini i
COD
Total So '•
Dissolve h- il ids
Suspend '-'i>lids
Oil and i -,se
Sulfatt S)
Chloric-
Cyanide
A lumii i,
Arsenic
Cadmium
Calci uni
Chromiuii
Copper
Iron
Lead
Magnesium
Mercury
Molybdenum
Nickel
Potassium
S e 1 e n i um
S ilver
Sodium
Tellurium
Zinc
Flow,
I/day 9
(gal/day) (2
Production ,
kkg/day
(tons/day )
Total
Plant
Intake ,
mg/1
7.6
203
8
__
408
3
--
145
18
--
--
—
—
70
--
0.02
1.70
0.12
31
--
--
0.03
--
--
__
.-
--
0.16

,810,720
,592,000)

571.4
(630)
Total
Plant Net
Discharge, Change. Net Loading
niR/1 mg/1 kg/day kg/kkg Ib /ton
8.0
--
--
— «- — — 	
550 142 232.17 0.41 0.82
30 27 44.15 0.08 0.16
--
215 50 81.75 0.14 0.28
--
—
--
--
--
--
—
0.02 000 0
0.6 -1.1 NLC
0.30 0.18 0.29 0.0005 0.001
--
—
--
0.08 0.05 0.08 0.0001 0.0002
--
__
__ 	 	 	 	
-— — — — - __ __
-- — — __ __ __
°'50 0.34 0.56 0.001 0.002

1,635,120
(432,000)

571.4
(630)
Source:  This contract,  1973.
                                             42

-------
                               TABLE  14. WASTE EFFLUENTS FROM PLANT B  (OUTFALL No.: 001)
                             Contributing Operations:  Noncontact cooling, treated acid-
                                                       plant blowdown
Parameter
P«
Alkalinity
COD
Total Solids
Dissolved Solids
Suspended Solids
Oil and Grease
Sulfate (as S)
Chloride
Cyanide
Aluminum
Arsenic
Cadmium
Ca ] cium
Chromium
Copper
] von
], .-id
t-'!.i",nes ium
;•' T.ury
Mo I vbdcnum
Nickel
Potassium
Se len i IUTI
Silver
Sod iuin
Te llur j urn
Zinc
Flow,
1/da^
(gal/L,,^ )
Product 01, ,
kkg/n
(tons/, )
Total
Plant
Intake,
mg/1
7.1
110
8
._
4,481
2
6.0
338
45
--
—
--
--
112
--
0.20
—
—
56
--
--
0.12
--
—
--
34.5
--
0.44

2,725,200
(720,000)

331
(365)
Total
Plant
Discharge ,
mg/1
6.5
8
21
__
1,565
15
0.4
975
49.7
—
—
0.01
1.2
290
—
0.020
0.4
0.52
63
0.0005
--
0.250
--
—
—
67
--
5.5

408,780
(108,000)

331
(365)
Net
Change,
mg/1
..
-102
13
_-
-2,916
13
-5.6
637
4.7
—
--
--
1.2
178
—
-0.18
NLC
0.52
7
'--
--
0.13
--
—
--
32.5
--
5.06






Net Loading
kg/day

NLC
5.31
__
NLC
5.31
NLC
260.39
1.92
—
__
-_
0.49
72.76
--
NLC
NLC
0.21
2.86
—
--
0.05
—
—
—
13.29
—
2.07






kg/kkg

--
0.016
__
—
0.016
—
0.79
0.006
—
__
__
0.001
0.22
--
--
--
0.0006
0.009
--
--
0.0002
—
—
—
0.04
—
0.006






Ib/ton

_-
0.032
__
—
0.032
__
1.58
0.012
--
__
__
0.002
0.44
__
__
--
0.0012
0.018
--
--
0.0004
—
—
—
0.08
—
0.012






Source:   RAPP Data.
                                              43

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                               TABLE  15'  WASTE EFFLUENTS FROM  PLANT c (OUTFALL FROM SETTLING
                                          POND)


                             Contributing Operations:   Slag granulation
Parameter
pH
Alkalinity
COD
Total Solids
Dissolved Solid ,
Suspended Solid--
Oil and Grease
Sulfate (as S)
Chloride
Cyanide
Alumirum
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Mercury
Molybdenum
Nickel
Potassium
Selenium
Silver
Sodium
Tellurium
Zinc
Flow,
I/day
(gal/day)
Production ,
kkg/day
(tons/day)
Total Total
Plant Plant
Intake, Discharge,
mg/1 ms/1
8.0
0
<4
198
18
_ —
2
14
Nil
_ —
__
44
0.055
__
Nil
21
--
<0.05
__
__
__
1.2
—
0.03

1,506,430 1,477
(398,900) (390

268.5
(296)
7.6
8
4.4
301
15

112
14
Nil

< 0.02
0.08
48
<0.01
0.009
__
0.85
23
0.0024

0.05
__
_ —
_..
12
_„
1.2

,058
,240)

268.5
(296)
Net
Change,
mg/1

8
0.4
103
-3

110
0
0


0.08
4
-0.046

0.85
2

_M



10.8
*. •.
1.17






Net Loading_
kg/day

11.82
0.59
152.14
NLC

162.48
o
o


00.12
5.91
NLC

1.26
2.95





15.95

1.73






kg/kkg

0.04
0.002
0.57

0.61
n



0.0004
0.02


0.005
0.01





0.06

0.006






Ib/ton

0.08
0.004
1.14

1.22


""
0.0008
0.04


0.01
0.02





0 12

0.012






Source:   Producer's  data.
                                             44

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                                TABLE 16.   PRESENT CONTROL AND TREATMENT METHODS  FOR
                                            PROCESS hASTE WATER IN PRIMARY LEAD  INDUSTRY
Acid Plant Blowdown Slag Granulation Scrubbing Current^ Process
Plant Recycle Lime Effluent Recycle
Designation Treatment cu m/day(gpm)
A Yes Yes 409 'a' Yes
(75)
B Yes Yes 251(a'b) Yes
(46)
C (c) (c) (c) Yes
D Yes Yes 272  Yes
(75)
No 0(a> (c)
(d)
No 3815 No
(700)

No 0 Yes
Treatment Effluent Discharge cu m/day (gpm)
No 0 1640
(300)
No 0 330
(50)
(c) (c) 0
Yes 1090(a Ole)
(200)
0
No 0
(a)   Reused as process water for some other integrated function.
(b)   Discharged,  either directly or commingled, to navigable water.
(c)   Not applicable.
(dj   Consumed in  slag pile.
(e)   Except for smalljhighly  intermittent flow produced during periodic clean-out  of  settling pond.

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  TABLL  17.  CONCENTRATIONS OF SELECTED CONSTITUENTS OF ACID PLANT
             BLCWDCMI AFTER LIMING FROM FRT1ARY NOKFERROOS SMELTERS

Pollutant
Parameter
pH
Cadmium
Lead
Mercury
Zinc
Concentrations, mg/1
Copper
Smelter
7.1
0.06
0.19
0.0001
18.9
Zinc (a)
Smelter
8.2
0.02
0.15
0.004
50
Smelter
9.5
0.7
2.7
0.0009
1.2

(a)   Data obtained under EPA Contract No.  68-01-1518.
(b)   Limed and-settled acid plant blowdown at Plant B.
                                46

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from  the  subject lead smelter.  All other uses of water in
the smelter (which does not include an acid plant)   are  for
indirect   cooling,   with  a  bleed  stream  being  totally
evaporated by use  for  cooling  of  gases  from  the  blast
furnace  and sintering plant.  Current plans at this smelter
include reuse of granulation water for sinter  plant  offgas
cooling.

In  the  case  of  another lead smelting operation for which
data were obtained, the only discharge was blowdown  from  a
cooling  tower serving indirect cooling water circuits.  The
process water streams at this smelter,  consisting  of  slag
granulation  and  gas  conditioning  circuits,  operate in a
closed loop fashion with no bleed streams.   No  acid  plant
was included in the operations at this smelter.
                          Summary


The   development   of   data   on   process   waste   water
characteristics in the primary lead  smelting  industry  has
established   that,  for  those  existing  primary  smelters
currently discharging process waste water, three  (soon to be
two) discharges contain waste water  from  slag  granulation
operations  and  two (of the three with acid plants) contain
components from lime treated acid plant blowdown.

In those effluents containing the above process waste  water
components,  the characteristic constituents identifiable in
the   effluent   include   dissolved   solids    (principally
sulfates),   cadmium,   lead,   mercury,  and  zinc.   Waste
characteristics  are  strongly  influenced  by  the  current
practices  of  lime  treatment  of  acid  plant blowdown and
settling of slag granulation water, and, in some cases,  the
total control through recycle and reuse of such streams.
                              47

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                         SECTION VI


             SELECTION OF POLLUTANT PARAMETERS


                        Introduction
The  previous section provided quantitative data on a number
of parameters that characterized  the  process  waste  water
discharges   from   domestic   primary   lead  smelters  and
refineries.  On the basis of rationales  presented  in  this
section for selecting and excluding individual constituents,
the  following pollutant parameters were identified to occur
in  sufficient  quantities  to  warrant  their  control  and
treatment:

          PH
          Total suspended solids
          Cadmium
          Mercury
          Lead
          Zinc

A  broad  range  of  possible  pollutants were considered as
potential constituent additions to the waste waters from  U.
S.  smelters and refineries.  The results of this survey are
summarized in the previous section where the compositions of
each of these constituents in both the source and  discharge
water  for  each  smelter are given.  Aside from the obvious
reason that the constituent in question was not  present  in
important  enough  amounts  to  be  considered a significant
parameter, the following reasoning  was  used  to  determine
whether or not to exclude a given item from consideration as
a pollutant requiring an effluent limitation.

     (1)  There are insufficient data on  which  to  base  an
         effluent limitation.
     (2)  The availability and cost of the  required  control
         or  treatment  technology  is  beyond  the scope of
         "best practicable" or "best available"  as  defined
         by   the   Federal   Water  Pollution  Control  Act
         Amendments of  1972.
     (3)  The  pollutant  in   question   will   be   removed
         simultaneously   with   another  pollutant  by  co-
         precipitation, clarification, etc.
                              49

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In  light  of  this  reasoning,  the   following   discussion
presents  rationales used to establish which are significant
parameters, and which are not.  The waste  water  parameters
of pollutional significance are considered first.

                Rationale for the Selection
                  of Pollutant Parameters


The  control and treatment technologies discussed in Section
VII describe the current practices, as well as  those  which
are  under  construction,  by the industry which are used to
treat and  control  the  selected  pollutants.   From  these
discussions,  it  was  concluded that  the discharge of total
suspended solids and heavy  (trace) metals can be  controlled
by pH adjustment and suspended solids  removal.

Setting  effluent limitations on cadmium and zinc, which are
the principal pollutant metals in the  process  waste  waters
from  the  primary  lead industry, and specifying a pH range
will in turn limit the other trace  metals  found  in  these
waste  waters.   Such  metals  include  aluminum,  antimony,
cobalt,  chromium,  iron,  magnesium,   manganese,   nickel,
selenium, silver and tin.

There  is  an  optimum  pH  for precipitation of each metal,
which results in its greatest reduction  by  solids  removal
(settling  or  filtration).   The pH selected for the mixture
of metals associated with the primary  lead  industry  is  a
compromise  between the maximum removal of cadmium and zinc,
as hydroxides, and that suited for the  maximum  removal  of
other  metals  associated  with  the  process  waste waters.
Coprecipitation of these heavy metal hydroxides with cadmium
and zinc hydroxide (and also aluminum,  iron  and  magnesium
hydroxide,  if they are present in the waste waters)  at a pH
at which optimum Coprecipitation  occurs  is  used  in  good
water  treatment  practice.    Therefore,  an  appropriate pH
adjustment followed by solids removal will  reduce  all  the
metals to levels consistent with the best control technology
currently available.

pH, Acidity and Alkalinity

Acidity  and  alkalinity  are  reciprocal terms.   Acidity is
produced  by  substances  that  yield  hydrogen  ions   upon
hydrolysis  and  alkalinity  is  produced by substances that
yield hydroxyl ions.   The terms "total acidity"  and  "total
alkalinity" are often used to express the buffering capacity
of  a  solution.    Acidity  in  natural  waters is caused by
carbon dioxide mineral acids,  weakly dissociated acids,  and
                             50

-------
the  salts  of  strong  acids and weak bases.  Alkalinity is
caused by strong bases and the salts of strong alkalies  and
weak acids.

The term pH is a logarithmic expression of the concentration
of  hydrogen  ions.  At a pH of 7, the hydrogen and hydroxyl
ion concentrations are essentially equal and  the  water  is
neutral.   Lower  pH  values  indicate  acidity while higher
values indicate alkalinity.  The relationship between pH and
acidity or alkalinity is not necessarily linear or direct.

Waters with a pH below 6.0  are  corrosive  to  water  works
structures,   distribution  lines,  and  household  plumbing
fixtures and can thus  add  such  constituents  to  drinking
water as iron, copper, zinc, cadmium and lead.  The hydrogen
ion concentration can affect the "taste" of the water.  At a
low  pH,  water  tastes  "sour".  The bactericidal effect of
chlorine  is  weakened  as  the  pH  increases,  and  it  is
advantageous  to  keep  the  pH  close  to  7.  This is very
significant for providing safe drinking water.

Extremes  cf  pH  or  rapid  pH  changes  can  exert  stress
conditions  or  kill  aquatic  life  outright.   Dead  fish,
associated algal blooms, and  foul  stenches  are  aesthetic
liabilities  of  any  waterway.   Even moderate changes from
"acceptable" criteria limits of pH are deleterious  to  some
species.   The  relative  toxicity  to  aquatic life of many
materials  is  increased  by  changes  in  the   water   pH.
Metalocyanide  complexes  can  increase  a  thousand"fold in
toxicity with a drop of 1.5 pH units.  The  availability  of
many  nutrient  substances  varies  with  the alkalinity and
acidity.  Ammonia is more lethal with a higher pH.

The  lacrimal  fluid  of  the  human  eye  has   a   pH   of
approximately  7.0  and  a deviation of 0.1 pH unit from the
norm  may  result  in  eye  irritation  for   the   swimmer.
Appreciable irritation will cause severe pain.

When  in  the range of pH 7 to 10, the acid wastes have been
neutralized, but  are  not  excessively  alkaline.   Overall
concentrations  of dissolved metals can be expected to be at
a minimum when pH of the discharge  is  maintained  in  this
range.

Total_Suspended_Sglids

Suspended   solids   include   both  organic  and  inorganic
materials.  The inorganic components include sand, silt, and
clay.  The  organic  fraction  includes  such  materials  as
grease, oil, tar, animal and vegetable fats, various fibers,
                             51

-------
sawdust,  hair,  and  various  materials from sewers.  These
solids may settle out rapidly and bottom deposits are  often
a  mixture  of  both  organic  and  inorganic  solids.  They
adversely affect fisheries by covering  the  bottom  of  the
stream  or lake with a blanket of material that destroys the
fish-food bottom fauna  or  the  spawning  ground  of  fish.
Deposits  containing  organic  materials  may deplete bottom
oxygen  supplies  and  produce  hydrogen   sulfide,   carbon
dioxide, methane, and other noxious gases.

In  raw  water  sources for domestic use, state and regional
agencies generally specify that suspended solids in  streams
shall  not  be  present  in  sufficient  concentration to be
objectionable  or  to  interfere   with   normal   treatment
processes.   Suspended  solids  in  water may interfere with
many industrial processes, and cause foaming in boilers,  or
encrustations  on  equipment exposed to water, especially as
the temperature rises.  Suspended solids are undesirable  in
water  for  textile  industries,  paper and pulp, beverages,
dairy  products,  laundries,  dyeing,  photography,  cooling
systems,  and  power plants.  Suspended particles also serve
as  a  transport  mechanism   for   pesticides   and   other
substances,  which  are  readily  sorbed  into  or onto clay
particles.

Solids may be suspended in water for a time, and then settle
to the bed of the stream or lake.  These  settleable  solids
discharged   with   man's   wastes   may  be  inert,  slowly
biodegradable materials, or rapidly decomposable substances.
While in suspension, they  increase  the  turbidity  of  the
water,    reduce    light   penetration   and   impair   the
photosynthetic activity of aquatic plants.

Solids in suspension are  aesthetically  displeasing.   When
they  settle  to  form sludge deposits on the stream or lake
bed, they are often much more damaging to the life in water,
and they  retain  the  capacity  to  displease  the  senses.
Solids,  when  transformed  to  sludge  deposits,  may  do a
variety of damaging things, including blanketing the  stream
or  lake  bed  and  thereby destroying the living spaces for
those benthic organisms  that  would  otherwise  occupy  the
habitat.   When  of  an  organic  and therefore decomposable
nature, solids use a portion or all of the dissolved  oxygen
available  in  the  area.  Organic materials also serve as a
seemingly inexhaustible  food  source  for  sludgeworms  and
associated organisms.

Turbidity  is  principally  a measure of the light absorbing
properties of suspended solids.  It is frequently used as  a
                         52

-------
substitute  method of quickly estimating the total suspended
solids when the concentration is relatively low.

Total suspended solids is a  gross  measure  of  the  solids
remaining  in suspension following treatment of precipitated
dissolved metals.  Compliance with a TSS limitation  insures
that   effective   phase   separation   has  been  achieved.
Relatively unsophisticated methods, the simplest of which is
provision for adequate settling time in a settling pond, are
available for the treatment of waste water to  decrease  the
suspended solids content.

Cadmium

Cadmium in drinking water supplies is extremely hazardous to
humans,  and  conventional  treatment,  as  practiced in the
United States, does not remove it.  Cadmium is cumulative in
the liver, kidney, pancreas, and thyroid of humans and other
animals.  A severe bone and kidney  syndrome  in  Japan  has
been  associated  with  the  ingestion  of  as little as 600
ug/day of cadmium.

Cadmium  is  an  extremely  dangerous  cumulative  toxicant,
causing  insidious progressive chronic poisoning in mammals,
fish, and probably other animals because the  metal  is  not
excreted.   Cadmium could form organic compounds which might
lead to mutagenic or teratogenic effects.  Cadmium is  known
to   have  marked  acute  and  chronic  effects  on  aquatic
organisms also.

Cadmium acts synergistically with other metals.  Copper  and
zinc   substantially  increase  its  toxicity.   Cadmium  is
concentrated by  marine  organisms,  particularly  molluscs,
which  accumulate  cadmium  in calcareous tissues and in the
viscera.  A concentration factor of 1000 for cadmium in fish
muscle has been reported, as have concentration  factors  of
3000  in  marine  plants, and up to 29,600 in certain marine
animals.  The eggs and larvae of fish  are  apparently  more
sensitive  than  adult  fish  to  poisoning  by cadmium, and
crustaceans appear to be more sensitive than fish  eggs  and
larvae.

Cadmium  is  associated  with lead concentrates and is often
recovered from recirculating  baghouse  catches  at  primary
lead smelters.
Although  elemental  mercury  occurs as a free metal in some
parts of the  world,  it  is  rather  inert  chemically  and
                         53

-------
insoluble  in  water;  hence, it is not likely to occur as a
water pollutant.  It is used in  scientific  and  electrical
instruments,  in dentistry, in power generation, in solders,
and in the manufacture of lamps.  Mercuric  salts  occur  in
nature  chiefly  as  the sulfide HgS, known as cinnabar, but
numerous synthetic organic and inorganic  salts  of  mercury
are   used  commercially  and  industrially.   Many  of  the
mercuric and mercurous salts are highly soluble in water.

Mercury and mercuric salts are considered to be highly toxic
to  humans.   They  are  readily  absorbed  by  way  of  the
gastrointestinal  tract, and fatal doses for man vary from 3
to 30 grams.  Adults may safely drink water containing about
4 to 12 mg of Hg per day and a  fatal  dose  of  such  water
would be about 75 to 300 mg per day.

Mercuric  ions  are considered to be highly toxic to aquatic
life.  For freshwater fish, concentrations of 0.004 to  0.02
mg/1  of Hg have been reported harmful.  Mercury salts, such
as the unstable compounds mercuric sulfate and nitrate, have
killed minnows at a concentration of 0.01 mg/1  as  mercury,
after 80-92 days.  At concentrations of 0.05 and 0.1 mg/1 as
mercury,   fish   were   killed   in  6  to  12  days.   For
phytoplankton, the minimum lethal concentration  of  mercury
salts  has been reported to range from 0.9 to 60 mg/1 of Hg.
The toxic effects of mercuric salts are accentuated  by  the
presence of trace amounts cf copper.

Mercury  was  included  as  a pollutant parameter because it
appeared  in  the  waste  water  of  a   complex   operation
consisting  of  both  a lead smelter and a zinc electrolytic
plant.  Mercury is associated with some  lead  concentrates,
such  as  those  of the Coeur d'Alene area and some imported
ones.

Lead

Some natural waters contain lead in  solution,  as  much  as
0.4-0.8 mg/1, where mountain limestone and galena are found.
In  the  U.S.A.,  lead  concentrations in surface and ground
waters used for domestic supplies range from traces to  0.04
mg/1 averaging about 0.01 mg/1.  Lead may also be introduced
into water as a constituent of various industrial and mining
effluents, or as a result of the action of the water on lead
in pipes.

Foreign  to the human body, lead is a cumulative poison.  It
tends to be deposited in bone as a cumulative  poison.   The
intake  that  can be regarded as safe for everyone cannot be
stated definitely, because the sensitivity of individuals to
                         54

-------
lead differs considerably.   Typical  symptoms  of  advanced
lead  poisoning  are constipation, loss of appetite, anemia,
abdominal pain, and tenderness, pain, and gradual  paralysis
in  the muscles, especially of the arms.  A milder and often
undiagnosed form of lead poisoning also occurs in which  the
only  symptoms  may  be  lethargy, moroseness, constipation,
flatulence, and occasional abdominal pains.  Lead  poisoning
usually  results  from  the cumulative toxic effects of lead
after continuous consumption over a  long  period  of  time,
rather  than  from occasional small doses.  Immunity to lead
cannot  be  acquired,  but  sensitivity  to  lead  seems  to
increase.  Lead is not among the metals considered essential
to the nutrition of aninr.als or human beings.  Lead may enter
the  body  through  food,  air, and tobacco smoke as well as
from water and other beverages.  The exact  level  at  which
the  intake of lead by the human body will exceed the amount
excreted has not been  established,  but  it  probably  lies
between  0.3  and  1.0 mg per day.  The mean daily intake of
lead by adults in North America is about 0.33 mg.   Of  this
quantity,  0.01  to  0.03  mg per day are derived from water
used for cooking and  drinking.   A  total  intake  of  lead
appreciably  in  excess  of 0.6 mg per day may result in the
accumulation of  a  dangerous  quantity  of  lead  during  a
lifetime.  Lead in an amount of 0.1 mg ingested daily over a
period  of  years has been reported to cause lead poisoning.
The daily ingesticn of 0.2 mg lead is  considered  excessive
by  one  authority.   Lead  poisoning  among human beings is
reported to have  been  caused  by  the  drinking  of  water
containing lead in ccncentrations varying from 0.042 mg/1 to
1.0  mg/1  or  more.   There  is a feeling that 0.1 mg/1 may
cause chronic poisoning if the water is  used  continuously,
expecially  among  hypersensitive  persons.  For many years,
the mandatory limit for lead in  the  USPHS  Drinking  Water
Standards was 0.1 mg/1; but in the 1962 Standards, the limit
for lead was lowered to 0.05 mg/1.  In the WHO International
Standard  and WHO European Standards, the limit for lead has
been set a 0.1 mg/1.  Uruguay has used a standard as low  as
0.02 mg/1.  Several countries use 0.1 mg/1 as a standard.

Traces  of  lead  in  metal-plating  baths  will  affect the
smoothness and brightness of deposits.  Inorganic lead salts
in irrigation water may be toxic to plants.  In the  culture
of  oats and potatoes, lead nitrate in concentrations of 1.5
to 25 mg/1 had a stimulating effect, but  at  concentrations
over  50  irg/1  all plants died in a week's time.  Lead at a
concentration of 51.8 rrg/1 of nutrient solution was slightly
injurious to sugar beets grown in sand culture.  Germination
of  cress  and  mustard  seeds  in  solution   culture   was
completely inhibited by a 2760 mg/1 lead solution, during an
                         55

-------
exposure  period  of  18  days.  Germination was delayed and
growth was retarded by 345-1380 mg/1 of lead.

Farm animals are poisoned  by  lead  from  various  sources,
including  paint,  more  frequently  than  by other metallic
poisons.  It is not unusual for cattle  to  be  poisoned  by
lead  in  the  water;  the  lead  need not necessarily be in
solution, but may be in suspension.  Chronic lead  poisoning
among  animals  has been caused by 0.18 mg/1 of lead in soft
water.  Chronic changes in the  central  nervous  system  of
white  rats  were observed after an ingestion of 0.005 mg of
lead per kg of body weight.  Most authorities agree that 0.5
mg/1 of lead is the maximum safe limit for lead in a potable
supply for animals.

The toxic concentration of  lead  for  aerobic  bacteria  is
reported  to be 1.0 mg/1; for flagellates and infusoria, 0.5
mg/1.  The bacterial  decomposition  of  organic  matter  is
inhibited  by  0.1 to 0.5 mg/1 of lead.  In water containing
lead salts, a film of coagulated mucus forms, first over the
gills, and then over the whole bcdy of the fish, probably as
a  result  of  a  reaction  between  lead  and  an   organic
constituent  of  mucus.   The death of the fish is caused by
suffocation due to this obstructive layer.  In  soft  water,
lead   may   be   very   toxic;  in  hard  water  equivalent
concentrations of lead are less toxic.

Zinc

Occurring abundantly in rocks  and  ores,  zinc  is  readily
refined into a stable pure metal and is used extensively for
galvanizing, in alloys, for electrical purposes, in printing
plates,  for  dye-manufacture  and for dyeing processes, and
for many other industrial purposes.  Zinc salts are used  in
paint    pigments,    cosmetics,    Pharmaceuticals,   dyes,
insecticides,  and  other  products  too  numerous  to  list
herein.   Many  of these salts (e.g., zinc chloride and zinc
sulfate)  are highly scluble in water;  hence  it  is  to  be
expected  that  zinc  might occur in many industrial wastes.
On the other hand, some zinc  salts  (zinc  carbonate,  zinc
oxide, zinc sulfide)  are insoluble in water and consequently
it  is to be expected that some zinc will precipitate and be
removed readily in most natural waters.

In zinc mining areas, zinc  has  been  found  in  waters  in
concentrations  as  high  as  50  mg/1.  In most surface and
ground waters, it is present only in trace  amounts.   There
is  some  evidence  that zinc ions are adsorbed strongly and
permanently on silt, resulting in inactivation of the zinc.
                         56

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 Concentrations of zinc in excess of 5 mg/1 in raw water used
 tor drinking water supplies cause an undesirable taste which
 persists through conventional treatment.  Zinc can  have  an
 adverse effect on man and animals at high concentrations.

 In  soft  water,  concentrations of zinc ranging from 0.1 to
 1.0 mg/1 have been reported to be lethal to fish.   zinc  is
 thought  to  exert  its  toxic  action  by forming insoluble
 compounds with the mucous that covers the gills,  by  damage
 to the gill epithelium, or possibly by acting as an internal
 poison.   The  sensitivity  of  fish  to  zinc  varies  with
 species, age and condition,  as well as with the physical and
 chemical characteristics of the water.  Some acclimatization
 to the presence of zinc  is   possible.   it  has  also  been
 observed  that  the effects  of zinc poisoning may not become
 apparent  immediately,  so  that  fish  removed  from  zinc-
 contaminated to zinc-free water (after 4-6 hours of exposure
 to  zinc)  may die 48  hours later.   The presence of copper in
 water  may  increase   the  toxicity  of  zinc   to   aquatic
 organisms,   but  the   presence  of   calcium  or hardness may
 decrease the relative toxicity.

 Observed values for the distribution of zinc  in ocean waters
 vary widely.  The  major  concern   with  zinc  compounds  in
 marine  waters  is  not one  of acute toxicity,  but rather  of
 the long-term sub-lethal effects of the  metallic  compounds
 and  complexes.   From  an  acute   toxicity   point   of view
 invertebrate marine animals  seem to be  the   most  sensitive
 organisms   tested.    The  growth  of  the sea   urchin,   for
 example, has been retarded by  as little  as 30 ug/1  of  zinc.

 Zinc  sulfate has  also   been  found   to   be  lethal   to  many
 plants,  and  it  could  impair  agricultural  uses.


        BStionale_for__Rejection_of_gther__ Was te_ Water
             £2£Stituents_as_Pollutant_Parameters


Arsenic

Arsenic  is  found  to  a  small  extent  in  nature  in the
elemental form.  It occurs mostly in the form  of  arsenites
of metals or as pyrites.
 *o    oiS  ?ormally Present in sea water at concentrations
ot 2 to 3 ug/1 and tends to be accumulated  by  oysters  and
other  shellfish.   Concentrations  of  100  mg/kg have been
reported in certain  shellfish.   Arsenic  is  a  cumulative
poison  with  long-term  chronic  effects  on  both  aquatic
                           57

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organisms and on mammalian species and a succession of small
doses may add up to a final lethal dose.  It  is  moderately
toxic  to  plants  and highly toxic to animals especially as
AsH3.

Arsenic trioxide,  which  also  is  exceedingly  toxic,  was
studied in concentrations of 1.96 to 40 mg/1 and found to be
harmful  in that range to fish and other aquatic life.  Work
by the Washington Department of Fisheries on pink salmon has
shown that at a level of 5.3 mg/1 of As2O3 for  8  days  was
extremely harmful to this species; on mussels, a level of 16
mg/1 was lethal in 3 to 16 days.

Severe    human   poisoning   can   result   from   100   mg
concentrations, and  130 mg has proved   fatal.   Arsenic  can
accumulate  in  the  body faster than it is excreted  and can
build to toxic levels, from small amounts taken periodically
through lung and intestinal walls from  the  air,  water  and
food.

Arsenic   is  a  normal  constituent  of  most  soils,  with
concentrations ranging up to 500 mg/kg.  Although  very  low
concentrations   of   arsenates  may  actually stimulate plant
growth,  the  presence  of  excessive   soluble  arsenic   in
irrigation  waters   will reduce the yield of crops, the main
effect  appearing to  be the destruction  of chlorophyll in the
foliaqe.  Plants grown  in  water  containing   one  mg/1  of
arsenic  trioxides   showed  a   blackening   of   the  vascular
bundles  in  the  leaves.   Beans  and   cucumbers  are very
sensitive,   while    turnips,   cereals,    and  grasses  are
relatively resistant.  Old orchard soils in Washington that
contained   4 to  12  mg/kg  of arsenic  trioxide  in the  top soil
were found to have become  unproductive.

Data on arsenic  content   of   process   waste  water  is very
 sparse   and  a  firm conclusion regarding its significance  can
not be  reached  at  this  time.   It  is  assumed that  most of  the
 arsenic remains  with any  formed speiss and  that  all  speiss
 granulation  operations  have  closed water loops.

 Chemical_Oxi£en_Demand

 The  chemical   oxygen demand is a measure  of the  quantity of
 the oxidizable materials  present in water   and  varies  with
 water   composition,   temperature,    and  other  functions.
 Dissolved oxygen (DO) is  a water quality  constituent  that,
 in appropriate concentrations, is essential not only to keep
 organisms  living  but also to sustain species reproduction,
 vigor,   and  the  development  of  populations.    Organisms
 undergo  stress  at reduced DO concentrations that make them
                            58

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 less competitive and able to sustain  their  species  within
 the   aquatic   environment.    For   example,   reduced  DO
 concentrations  have  been  shown  to  interfere  with  fiSh
 population  through  delayed  hatching of eggs, reduced size
 and vigor of embryos, production of  deformities  in  young
 interference  with  food  digestion,  acceleration  ofY£lSod
 clotting  decreased tolerance to certain toxicants,  reduced
 snSt.i ^flciency  and  growth  rate,  and  reduced  maximum
 sustained swimming speed.  Fish food organisms are  likewise
 affected  adversely in conditions with suppressed DO   Since
 ovv^n   iLaqUatlC  Or9anisms  need  a  certain  amount  of
 oxygen,   the  consequences of total lack of dissolved oxygen
 due to a high COD can kill all inhabitants of  the  affected
 3.3T€cfc •

 If  a  high  COD  is  present,   the  quality of the water is
 usually  visually degraded by  the  presence7 of  decomposing
 materials  and  algae  blooms   due to the uptake of degraded
 materials that form the foodstuffs of the algal populations?

 The low  concentrations   of  oil   and  grease  found  in   the
 process   waste  waters   of  this  industry will minimise the
 organic  sources  of  COD.    Limitations  OnY pH  wiS  control
 ferrous-iron content  of effluents.                    conrroi


 Cyanide

 Cyanides   in  water   derive  their  toxicity  primarily  from
 undissolved  hydrogen  cyanide   (HCN)  rather   than   fro£  the
 cyanide ion  (CN-).  HCN  dissociates in water  into H* and CN-
 in  a  pH-dependent  reaction.   At a pH of 7 or below,  less
 8^.} *e"^.°i,^^™i? }; *™* - <:»-; ""a 'PHleSS~
87  nr  ^ JH a PH °5 9' ^ ^c^' and at a pH of   ,
87  percent  of the cyanide is dissociated.  The toxicity of
         "
Cyanide  has  been  shown to be poisonous to humans- amounts
over 18 ppm can have adverse  effects.   A  sinqlS  dSsS  of
about 50-60 mg is reported to be fatal.      Sln9le  dose  of

                aquatic organisms are extremely sensitive to

          „                               --.
                          59

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When  fish  are  poisoned  by  cyanide,  the  gills   become
considerably  brighter  in  color than those of normal fish,
owing  to  the  inhibition  by  cyanide   of   the   oxidase
responsible  for  oxygen  transfer  from  the  blood  to the
tissues.

Only nil amounts of total cyanide were reported in the  data
collected from documented sources.  Check analyses indicated
that  the  amount  of  cyanide  in the waste water from lead
smelter slag granulation and acid  plants,  which  use  mine
water  as  a  source,  is  of the order of 0.002 rng/1.  This
level is considered negligible.  Thus, cyanide was  excluded
as a significant parameter.

Oil and_Grease

Oil  and grease exhibit  an oxygen demand.  Oil emulsions  may
adhere  to the gills of fish  or  coat   and  destroy  algae   or
other   plankton.   Deposition of oil  in the  bottom sediments
can  serve  to  inhibit   normal   benthic    growths,   thus
interrupting the  aquatic food chain.   Soluble and  emulsified
material   ingested by fish  may taint the flavor of  the  fish
 flesh.  Water  soluble components  may  exert  toxic   action   on
 fish.   Floating  oil  may reduce the re-aeration  of the water
 surface and in  conjunction with emulsified  oil may interfere
with photosynthesis.   Water  insoluble components  damage   the
 plumage  and   coats   of   water   animals   and fowls.   Oil  and
 grease  in  a   water   can  result  in   the   formation    of
 objectionable   surface  slicks  preventing the full aesthetic
 enjoyment of  the water.

 Oil spills can damage the surface of boats and  can  destroy
 the aesthetic characteristics of beaches and shorelines.

 Only  nil  amounts of oil and grease were reported except in
 the case of mine input water at Smelter B.   The practice  of
 installing  oil  and  grease skimmers in settling tanks is a
 control practice which  provides  oil  and  grease  pollution
 reduction.   Where   such control devices are absent, oil and
 grease might be considered as a parameter subject to control
 and treatment.

 Temperature

 Temperature is one of the   most  important   and   influential
 water quality characteristics.  Temperature  determines those
 species  that  may   be  present; it activates the  hatching  of
 young,  regulates  their    activity,   and   stimulates    or
 suppresses  their growth   and development;  it attracts,  and
 may kill when  the water becomes too  hot  or   becomes   chilled
                              60

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  too     suddenly.     colder   water    generally    suppresses
  development.  Warmer water   generally   accelerates  activity
  and  may  be a primary cause of aquatic plant nuisances when
  other environmental factors  are suitable.

  Temperature is a prime regulator of natural processes within
  the water environment.  It governs  physiological  functions
  in   organisms   and,   acting  directly  or  indirectly  in
  combination  with  other  water  quality  constituents,   it
  affects  aquatic  life  with  each  change.   These  effects
  include  chemical  reaction  rates,   enzymatic    functions,
  molecular   movements,   and   molecular  exchanges  between
  membranes within and between the physiological  systems  and
  the organs of an animal.

 Chemical  reaction rates  vary with temperature and generally
  increase as the temperature is increased.   The solubility of
  gases in water varies with temperature.  Dissolved oxygen is
 decreased by the decay or decomposition of dissolved organic
  substances and the decay  rate increases as  the  temperature
     vi    W^er  lncreases  reaching  a maximum at about 30°C
           The  temperature  of  stream  water,   even  during
           ^  bel°W  th!   °Ptimum  for  Pollution-associated
 h       i   Incfeas^nF.   Predominant algal specie^  change?
 oraanfL/   T1?1 ,±S  decreased'  *nd bottom  associa?ed
 organisms may be  depleted or  altered drastically in  numbers
 SuatfcSt^ f ^   Increased  wat« temperatures  may Sause
 favSrabl?     nuis^nces when  other environmental factors are


Synergistic actions of pollutants are more severe at  higher
water  temperatures.   Given  amounts  of  domestic   sewage,
refinery wastes,  oils, tars, insecticides,   detergents?  2nd
fertilizers  more  rapidly deplete oxygen in water at higher
                             61

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temperatures, and the  respective  toxicities  are  likewise
increased.

When  water  temperatures  increase,  the  predominant algal
species may change from diatoms to green algae, and  finally
at high temperatures to blue-green algae, because of species
temperature   preferentials.   Blue-green  algae  can  cause
serious odor  problems.   The  number  and  distribution  of
benthic  organisms  decreases as water temperatures increase
above 90°F, which is close to the tolerance  limit  for  the
population.   This  could seriously affect certain fish that
depend on benthic organisms as a food source.

The  cost  of  fish being attracted to heated water  in  winter
months may be considerable, due to  fish  mortalities that may
result when  the fish return to the  cooler water.

Rising  temperatures   stimulate the decomposition of  sludge,
formation of   sludge  gas,   multiplication  of  saprophytic
bacteria   and fungi  (particularly in  the presence of  organic
wastes),  and the   consumption  of  oxygen   by  putrefactive
processes,   thus   affecting   the  esthetic   value of  a  water
course.

In general,  marine  water  temperatures  do  not change  as
rapidly  or  range  as widely as  those  of  freshwaters.   Marine
and  estuarine   fishes,   therefore,  are  less  tolerant  of
temperature   variation.    Although  this  limited tolerance is
 greater in estuarine than  in  open  water  marine   species,
 temperature   changes  are  more important to those  fishes in
 estuaries and bays than  to  those   in  open  marine  areas,
 because  of   the  nursery and replenishment functions of the
 estuary  that  can  be   adversely   affected   by   extreme
 temperature changes.

 Although  the  maximum  discharge temperature of waste water
 issuing from domestic smelters was reported to be 130  F  in
 earlier   (1971)  Corps  of Engineers reports,  temperature is
 not considered a  significant  pollution  parameter  because
 such  water  is  now impounded in cooling ponds before it is
 released.

 Bismuth

 Bismuth  is  a constituent of  some lead ores,   but  there  are
 insufficient  data  on  which to base pollutant limitations.
 It  is not ordinarily  reported on lead   smelter  waste  water
 effluents   analyses.    Salts   of  bismuth   are  virtually
 insoluble in water,  and  because of this, bismuth is  excluded
 as  a  significant  parameter.
                               62

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 Calcium^ MaqnegJ.UJT

 The   lead  veins  in  southeastern Missouri  are  located  in  a
 dolomite (CaC03.MgC03)  deposit.   Except  in  the   case of
 Smelter  B,  only  relatively  low  amounts  of   calcium and
 magnesium are  found in the waste waters  of  U.S.   smelters
 smelter  B  uses  mine  water  which  is  moderately high in
 calcium  and   magnesium  and,  thus,  requires   a   softSninq
 pretreatment.   However,  dolomite reacts with lead in basic
 solutions to yield insoluble lead carbonate, and it is  so
 used  to  recover lead.  Its presence, in the relatively  low
 amounts noted  in Section V, augments the effect  of  lime used
 as a control,  and in this sense, it might be considered as  a
 secondary parameter.

 Biochejnical_Oxy.q.en_Demand

 BOD is not   an  important  parameter  in  the  primary  lead
 n«£?£jn    ^S   the •  sanitar*   effluents,  containing
 practically all the organic compounds in the total  discharge
 from the smelters,  are now handled separately  from  process
 ?«« %*Ta  ?'    Jt W°Uld be considered as a parameter if the
 two effluents were combined.

 Dissglved_Chlor ides ^.Fluorides ^.Phosphates. _and_Carhnna*£s

 The amount  of chlorides  in  the source  water   entering   U.S.
 noSSefn +**  x    t,   and   there  are n° aPPreciable additions
  °JS\l       discharge.   The  amount  of   fluorides  entering
 ~™  * 5 STr°e ?ater  is  extremely low,  and the  measurements
 reported show   low  amounts in the discharge. The phosphate
 contents of both source  and discharge  water are   negligible.
 Data  was also requested  on the carbonates; the only  reported
 S~L J    ?H considerable  instability   in   that the amount
 present  in the  source  water was reduced  to  almost  half   as
 nho^h,i«   the^  dis^arge.    Thus,  chlorides, fluoride,
 parameter's:       carbonates   are   excluded   as   significant


 Qther__Metals

 Other  metals   for which there  were either no available data
 on effluent content or the reported effluent  concentrations
 were   insignificant  include  alurrinum,  copper,  magnesium
 manganese,  antimony,  chromium,   cobalt,    iron,    nick™'
 selenium,  silver  and tin.   Setting effluent limitations  on
 the  prescribed  heavy  metals,  which  are   the   principal
 pollutant  metals  in  the  process  waste  waters   from the
 primary lead industry, and specifying a  PH   range   wi™   in
turn Umit these other trace metals.
                            63

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                         SECTION VII

               CONTROL AND TREATMENT TECHNOLOGY


                         Introduction


 Specific water usage in primary lead smelters and refineries
 was  quantitatively  discussed  in  Section   V,   and   the
 compositions  of  waste  waters  from each smelter were also
 characterized.   The  selection  of  significant   pollution
 parameters  was  discussed  in  Section  VI.   This  section
 presents the control and  treatment  technology  of  primary
 lead smelter and refinery waste waters.


                      Wa st e_ Wat er_ Ef f luent s_a nd
 In  the context of this report the term "control technology"
 refers to any practice applied in order to reduce the volume
 of waste water discharged.   "Treatment technology" refers to
 any practice applied to a waste water stream to  reduce  the
 concentration of pollutants in the stream before discharge.

 The  control  technology  currently used by the primary lead
 industry comprise the following items:

           (1)   Segregation  of water streams (in lead
                smelters and refineries  these normally
                fall  into three categories (I)  non-
                contact cooling water,  (2)  process water,
                and (3)  smaller auxiliary,  sometimes
                intermittent,  streams  such as cooling
                tower or furnace jacket  blowdowns,  leaks,
                etc.);
           (2)   water conservation  techniques (e.q
                recycling) ;
           (3)   Housekeeping provisions  (for  spills,
                leaks,  storm water  runoff,  pond  failures,
                blowdowns  of cooling towers,  furnace
                jackets, and auxiliary equipment) ;
           (4)   Special  inplant  abatement measures.

Process water effluents from primary lead operations include
        °       6   ^ ?°urces:  <1> a wea* acid  bleed  from
an  acidnl                                        ee   from
an  acid plant wet scrubber (i.e., acid plant blowdown) ,  (2)
slag  granulation  water,  and  (3)   discharges   from   wet
                            65

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scrubbers  at  sinter  plants.  Current practices vary among
the plants with respect to the segregation of process  water
and  noncontact  cooling  water, and the extent to which the
process water is treated,  recycled,  and  discharged.   The
quantity  of process water usage compared with cooling water
usage is generally small.   For  this  reason,  any  further
treatment  of  process  water  will,  in all probability, be
economically benefited by the segregation of  process  water
and cooling water.

Current methods of treatment  and discharges of process water
at  four  plants   (Plant A through D) are shown in Table 16.
In Plant E, all of the process water effluent  is  recycled,
which results in no discharge of process water.

In  each of three plants which have a metallurgical  sulfuric
acid plant, the acid plant scrubber is  operated  with  weak
acid   recycle   and  a  bleed.   The  weak  acid  bleed  is
neutralized  with  lime  prior  to  discharge  to  the  slag
granulation  circuit.  Plant  B limes its acid plant  blowdown
and  then  commingles  it  with  other  plant  process   and
nonprocess  waste  waters.  The two ponds holding this water
provide recycle and reuse capability within the  smelter, and
an average discharge of  330 cu m/day  (50 gpm)  results  from
pond  overflow.    In  Plant   D, the bleed is discharged to  a
treatment plant, where it is  mixed with  other   waste water
streams  and then reused  and recycled.  The quantities of the
weak  acid  bleed  per   unit  of  lead production are fairly
uniform  among  the  three  plants.  They are:   715  1/kkg   (171
gal/ton)  at Plant  A;  756 1/kkg  (181  gal/ton)  at  Plant B; and
822 1/kkg  (197  gal/ton)  at Plant D.

Slag  granulation  water is  currently discharged to surface
waters  at three plants.   All  three  plants operate   partially
closed    circuits  with   recycle   and  bleed-off.    Plant   D
operates  a   once-through granulation   system,    but   this
effluent  is   lost  or   consumed   in  the  slag   pile and  no
discernible water  is   discharged.    Plant   C  is   currently
attempting  to  reuse   the   bleed   from  its  slag granulation
water system as a sinter machine   offgas  coolant  prior  to
 entrance  in the sinter baghouse.   Plant A  is making recycle
 changes to its slag  granulation   system,   so  that  a  flow
 reduction of from 8,200 cu m/day  (1500  gpm)  down to 1,640  cu
 m/day (300 gpm)  will be achieved.

 Recycle and reuse of scrubber water is practiced by all four
 smelters  using  such  devices.   As  with  its  acid  plant
 blowdown. Plant D treats its scrubber water,  commingles  it
 with  other  effluents,  and  both  recycles  it  within the
                              66

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    ath                -      °nSite  PhosPhate   fertilizer
  plant with no  resultant  discharge.




  JlLh t?6   primarv   lead  industry,   waste  water   treatment

  technology normally  involves  only chemical treatment.    Lime

  treatment,  with  mechanical  separation  of   the   resultina

  precipitates from the process stream, is the common chemical

  treatment practice used  by this industry.



  Chemical treatment technology is  discussed  first  in   this

  section,  because,   regardless of inplant control procedures


  "e                                             P
                   °ne  Sinc?le  mode  of  chemical  treatment

                    r^oval of the heavy metal pollutants  by

                   Subse^ent hydroxides and their mechanical
            from the process water) .
 includedUt?2LParameterS S*lected in  tne  Previous  section
 included  lead,  zinc,  cadmium, and mercury, as well as TSS
 anu pn.





 appearedWaSinnClthed " t P°llutant  parameter,  because  it
 appeared   in   the  waste  water  of  a  complex  ODerat i on


 p?antStinL°f b°th-a I6ad Smelter and an  -no  elec?rolytS
 plant.    Mercury  is  associated in significant amounts with

 some western and imported lead concentrates.
           P°ilutan^s are in solution as sulfates and  oxides

 contro  f63   Smelter  waste  water.   The standard means of
 control for removing these pollutants  is to precipitate them

 with lime additions   from  basic  solution  GsingP PH  as  a


 settTin'a    >£**  *° Separate the  Precipitated hydroxides by
 settling.    The remaining parameter that completes the list


 soli^9    CanVP°11Utant  parameters  ^  total  suspended
 solids,   consisting  mainly of granulated slag  particles with
 some unsettled  precipitates.                   parr.icj.es with




                              PreciP^ated  hydroxides   vary;

                               hydroxide  settles  very  slowly
          solubility data.  Becau   data    ained          c

equilibria  measurements,  and  even in practical laboratory
                            67

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  0.01
 0-001
o.oooi
    Figure 6.   Theoretical solubilities of metal ions as a
                function of pH.(7)
                                   68

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experimental work, have not accurately  mirrored  conditions
in  actual  practice, they are shown here only to illustrate
the basis for the differences between the  effectiveness  of
removal  of  individual pollutants using a relatively narrow
pH range as a means of control.  As shown by Figure  6,  the
optimum  pH  for the minimum solubility of cadmium is around
11; whereas, a pH range of 9 to 10 is optimum for minimizing
the solubility of  copper,  zinc,  lead,  and  nickel.   The
minimum  solubilities for mercury, arsenic, and antimony are
quite high.

Figures 7 and 8, adopted from  West  German  work  on  waste
water  purification  of  electroplating solutions, show zinc
and cadmium to have higher  minimum  solubilities  than  are
shown  in  the  curves  for  equilibrium  data  in Figure 6.
Furthermore, Figure 9, taken from the same West German work,
indicates that cadmium, and  to  some  extent  nickel,  have
progressively higher minimum solubility values as a function
of standing time  (in these experiments, up to 7 hours).

Precipitation  with lime is more effective than is indicated
in publications.  Concentrations can be  obtained  that  are
much lower than those obtained in theoretical and laboratory
experimental  work  on single solutions.  In the West German
work cited above, coprecipitation of copper and nickel  with
chromium  resulted  in  a  drastic  reduction in the minimum
solubilities of  copper  and  nickel.   In  a  like  manner,
coprecipitation  and adsorption on flocculating agents, such
as ferrous and ferric sulfates, have a significant effect in
reducing the concentration  of  the  metal  ions.   In  lead
smelter  waste  waters,  isomorphism is another factor which
relates to this effect.  As an example, strontium  carbonate
is  added  to  zinc  sulfate  solutions  to remove lead from
solution; the  resulting  strontium  sulfate  has  the  same
crystal structure and dimensions as lead sulfate.

On  the other hand, there are factors which operate to raise
the minimum solubilities of these  heavy  metal  pollutants.
Dissolved  solids,  made  up of noncommon ions, can increase
the solubility of the metal  hydroxides,  according  to  the
Debye-Huckel  theory.   Sodium  sulfate  in the lead smelter
waste waters exerts such an effect.  Sodium is present in U.
S. lead-smelter waste waters,  but  not  in  large  amounts.
Also,  the  presence  of complexing agents, such as cyanide,
generally increases  the  minimum  solubilities  of  metals.
Cyanides  were scarcely detectable in the lead smelter waste
waters studied.

Table 17 presents the results of liming and settling of acid
plant blowdown from a primary copper smelter, a primary zinc
                             69

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                                         mg/1 Soluble Zinc
               o
               •
               o
fD





I



E

8

I
H-

m
o
HI

N
 00
                                                                              o
                                                                              o
             00
        (D
             U)
o
o
o
                                     Mols/1 Soluble  Zinc

-------
    1000
     100
                           \  /—Experimental
           7    8     9    10    11    12    13
       O.Oll
                                                           o
                                                           2
Figure 8.  Experimental solubilities of cadmium.
                       71

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80 r-
70 :
60 -
>

pH = 7.5
— 1,11111
1 1 1 i i i i p
lOOr
80 =
60 -
r-* ,
pH = 8.5

pH = 9.0
1 1 1 1 1 1 i ,/

t *Y
o 20 -
c
N 10 -

0)
pH = 8.0
_ pH = 8.5

— i i 1 1 1 I 1
*f
•§ 20 -
u 10 -
0)
>— 1 /w
-1 * . . . - u 4 0
-Q 1
rH 1.6
O
w 1.2
rH
6 0.4
0
/ f
, 	 _ 	 pH . = 9.0


_ pH = 9 . 5
— pH = 10.1
1 1 I J 	 i 1 l

o 3.0
^ 2.0
g i.ol
)
n ?
012345678
C
Standing time, hours
t
pH = 9.5

l I 1 1 1 1 1 ,

— y

-^ 	 " pH = 10.0

i_ 1 1 1 i
-^ 	 pTT=-TO.!>
^- — '
1 I 1
) 123 4 5 67 8
Standing time, hours
ZINC

16
1 A
14
12
% 10

-------
 smelter,  and a primary lead smelter.  Input dissolved metal
 concentrations are not  identical   for  each  of  the  three
 cases.   output concentrations are  generally within the same
 range.
 n.™                  treatment  facility  at  one  domestic
 primary  lead-zinc  complex  is  currently  being lined-out.
 This new facility will treat the total  plant  waste  water
 which  includes  a  periodic discharge from the lead smelter
 during settling pond clean-out, process waste water from the
 primary zinc plant (4060 cu m/day  (745 gpm) ) . and the  waste
 nr^-«m  ^  plant's  integrated  mining  and  milling
 operations.   The  anticipated  concentrations  of  selected
 process  waste  water  pollutants  from this facility are as
 toilows:

              Process  Waste Water        Concentration
                     TSS                     60
                     C<3                       0.5
                     H9                       0.006
                     ^                       1.0
                     Zn                       1.7

 Plant  personnel  report that this  new treatment  facility  is
 currently operating  above  its  anticipated  expectations.

              Mditional_Treatment_TechnoloqY


 Additional  treatment   methods,   which  could  be  employed for
 further   reduction   of  pollutants   from   proceis   water
 discharges  include    (1)   hydrogen   sulfide   treatment,  12)
 reverse osmosis,  (3) evaporation, and  (4)  chemical  fixation.
Hydrogen sulfide treatment would be an effective method  for
                       metals SS sulfi^ precipitates, which
                  e?tr?m?1y low solubility.  Solubilities of
                typical heavy  metals  found  in  the  waste
Tabe 18   5?g^ ll°m t2?e P^mary lead industry are shown in
*?  in   „  iSCe the.solub^ities of the sulfides are higher
at  low PH, the precipitation reaction should be carried out
at a neutral or alkaline pH.
                             73

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TJ03LE  18.  SOLUBILITY OF METAL SULFIDES
                     Solubilityf
   Metal       Neutral Solution       Low pH





    Ni               < 1              100,000




    Cd               < 1                5,000




    Pb               < 1                   70




    Cu               < 1                < 1




    Hg               < 1                < 1
                        74

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  Reverse Osmosis

  s?r^me °Sm°sis (*0)  is a  Process  whereby  a  waste  water
  2nnn   •  f  PaSSSd  at  Pressures from 34 to 136 atm (500  to
  2000 psia)  over a membrane.  The membrane  is  cast  from  a
  solution  of  cellulose  acetate  and  has  the  property  or
  allowing passage of water through the  film,   but ?ejec?iSa
  ions.    The permeate  is almost completely of ionic ma^eriS

                  r'h                        ™ S.  ?

                                            ssr ',»
         chemically or by evaporation.        treated   further,
 Evaporation


ultlple.  effe«   evaporation/

         ^^     °   H
                    T
distillaion  proess
suspended soli§s°?o mini       eooofha




evaporation using  a separate evaDorifo?      £  by  comPlete
means such as  chlmica/ftxatiSn? ?      '  Or  by  S°me   other
                         75

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Disposal  of  process  waste  water  by   means   of   solar
evaporation  is an excellent treatment method, especially in
climatic areas of net evaporation.


Chemical ^Fixation
rhPmical fixation is a  process  for  detoxifying  hazardous
liquid  wastes  £y  means  of reaction of chemical additions
with  the  waste  material  to   form   a   chemically   and
mechanically  stable solid.  The process can be used for the
chemical fixation of polyvalent metal  ions  in  stable  and
SSSSble  inorganic compounds   Monovalent catxons and »any
anions  are physically   entrapped   in  the  matrix  structure
Resulting  from  the reaction process.  Chemical fixation  is
cos'tly  Shen compared with the  treatment  methods  Discussed
thus  far  and   probably  would  rarely be used  for Directly
treating the  large  volume of process waste  water  effluents
from  She  primary   lead  operation.   The process, however,
might prove useful  and economic  for the ultimate disposal  of
concentrated  liquor wastes  generated   from  reverse   osmosis
 and evaporative treatment of waste water.
                               76

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                          SECTION VIII


          COSTS,  ENERGY,  AND NONWATER QUALITY ASPECTS


                          Introduction


 This   section   deals  with  the  costs   associated   with  the
 various  treatment  strategies available  to the   primary  lead
 industry  to    reduce   the   pollutant   load   in  the
                          °ther
 Data  on  capital  costs  and on operating costs for present
 control and treatment practices were obtained from  selec?2d
 lead  smelters.   These  data were modified in the followina
 way to put all costs on a common basis.            following
           (1)   J^S??1**1 COStS rePorted were changed
                to 1971 dollars by the use of the
                Marshall and Swift Index (quarterly values
                ot this index appear in the publication
                                      McGraw Hill) .
           (2)   The annual costs were recalculated to
                reflect common capitalized charges.   To
                do this,  the annual  costs were calculated
                by using a factor method as follows:

                Operating and maintenance - as reported
                  by the  lead smelters,
                Depreciation - 5  percent of the 1971
                  capital,
                Administrative overhead  -  U  percent of
                  operating  and maintenance,
                 S?e^Y ^and insurance - 0.8 percent
                 of the 1971 capital,
               Interest - 8 percent of the 1971 capital,
               Other - as reported by the smelters.



Treatment cost study was performed  on  five  of  th-  seven
existing  primary lead plants.   The two plants excluded rrom
                               77

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the  cost  study include one primary smelter, located in the
Southwest, where the arid climate permits  no  discharge  of
process   waste   water   pollutants   by   means  of  solar
evaporation, and one lead refinery, where the use  of  water
is confined to indirect  (noncontact) cooling only.

The  treatment  costs  associated with the present practices
were obtained directly from four of the five smelters.   For
the  fifth smelter, the  costs were estimated on the basis of
the   treatment   process    description    and    equipment
specifications  supplied by the plant.  The costs associated
with additional waste water  treatment  beyond  the  current
practices were estimated by using published cost data rather
than  using  the  cost   data supplied by the smelters.  This
approach was considered  necessary in view of the  fact  that
either  the  pertinent cost data were not available from the
smelters or the reported plant cost  data  show  substantial
variation  owing  to the differences among the smelters with
respect to water  usage   and  treatment  and  cost  reporting
procedures.
 The  cost  data for the present waste water practices in the
 primary lead industry  are  summarized  in  Table  19.    The
 variation in the cost data reflects the difference among the
 smelters  with  respect  to  smelter  operation  (e.g.,  the
 presence or absence of  an  acid  plant  as  part  of  plant
 operation) ,  extent  cf  plant  water  circuit modification,
 water usage, and waste water treatment practices,  and  cost
 reporting  procedures  employed.   Ihe higher costs shown in
 Table  19  are  for  those  three   smelters   operating   a
 metallurgical sulfuric acid plant.
 Plant_A


 Operations  at  this  plant  include  the  smelting  of lead
 concentrates, refining, and a  metallurgical  sulfuric  acid
 plant.   waste water treatment costs were developed from the
 costs data supplied by the plant.


 Water  Usage,  Treatment^  and  Discharge.    A   simplified
 flowsheet  of the  plant water circuit is shown in Figure  10.
 Plant water is supplied from a  well.   The   discharge  from
 this plant is an overflow from a  cooling pond located within
                              78

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                                TABLE 19 .   CAPITAL AMD OPERATING COSTS OF PRESENT PROCESS WASTE
                                           WATER TREATMENT PRACTICES  IN PRIMARY LEAD INDUSTRY
1 	 	 — ' 	 _ ,
Annual Lead
Plant Production,
Designation kkg
(tons)
A 208,610
(230,000)
B 120,963
(133,366)
C 97,956
(108,000)
D 120,948
(133,349)
E 58, 048 
( 65,000)
Capital Costs
Total, $ $/Annual kkg
	 	 ($/ Annual Ton)
208,500 1.00
(0.91)
335,600 2.77
(2.50)
112,700 1.15
(1.04)
472,000 3.90
(3.54)
53,400 0.92
(0.83)
Operating Costs
Total, $/year $/kkg
($/ton)
79,000 o.38
(0.34)
191,500 1.58
(1.43)
52,900 0.54
(0.49)
114,600 0.94
(0.86)
40,000 0.70
(0.63)
Comments
Acid plant
Slag gran.
Acid plant,
ilag gran.
Slag gran.
Acid plant,
Slag gran.
Speiss gran.
• 	 — 	 _ 	 _ 	 — 	 	
(a)   Lead Bullion

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                            Scrubber
                           Bleed-off
                                                                                              Overflow
                       Discharge
                       to River
00
o
                                            Indirect Cooling Water
                                                                   Sinter
                                                                    Plant
                                                                 (Gas  Cooling
                                                               Blast  Furnace
                                                                and Refinery
                                                                  (Indirect
                                                                   cooling)
L:
  Cooling
   Tower
                                                                         Recycle
 Hot

Pond
                                            Sinter Plant
                                             Ventilation
                                             Scrubber
                             Figure 10.  Flow sheet for water circuit at Plant A.

-------
the  slag  granulation  circuit.   Water usage at this plant
includes that in the acid plant,  blast  furnace,  refinery,
blast  furnace slag granulation, and wet scrubbing of sinter
plant ventilation gases.

Water to the acid plant is supplied from the well.  Water is
used in the acid plant for gas cleaning by  a  wet  scrubber
and  for  indirect  cooling.  The scrubber water is recycled
between the scrubber and a cooling tower with  a  bleed-off,
which  is  passed  through a limestone-lined pit to the slag
granulation system.  Most of the indirect cooling  water  is
discharged to the slag granulation system, and the remainder
is  discharged  to  the  blast  furnace and refinery cooling
system.

Slag granulation water is recycled  in  a  partially  closed
circuit  between the granulation process and a cooling pond.
The overflow from this cooling pond is  currently  estimated
at  8,230  cu m/day  (1500 gpm) and is discharged to a river.
The present practices for this smelter include internal flow
revisions to reduce the discharge to  1,640  cu  m/day   (300
gpm) .

Treatment  Costs  of  the  Present  Practice.   Capital   and
operating cost data were furnished  by  the  plant  for   the
current treatment practice  (i.e., 1,640 cu m/day  (300 gpm)).
The cost data are summarized below:


             Basis:  Production = 208,610 kkg/yr
                      (230,000 tons/yr) refined lead

       Caeital_Costsi                     1971_Dollars

       Slag granulation system               48,UOO

       Sinter plant  ventilation scrubber
         recycle                             53,200

       Plant water circuit  revisions,
         including ancillary  equipment     _i££.t22P_

                     Total Capital Costs    $208,500

                     $/ Annual  kkg  (ton)             1.00  (0.91)
        Raw Materials                        Nominal
                              81

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        Operating and maintenance            $48,400

        Administrative overhead                1,900

        Depreciation                           10,400

        Interest                              16,600

        Tax  and insurance                       1^700

                     Total Operating  Costs    $79,000

                     $/kkg  (ton)                    0.38  (0.34)

 Plant  B

 This   plant  supplied fairly complete data on the  plant water
 circuit and  waste water treatment costs.  An acid  plant   is
 included as  part of  the smelter  operation at this plant.

 Water    Usac^  Treatment^  and pis charge.   A   simplified
 flowsheet of the plant water circuit is shown in  Figure   11.
 Plant   water  is supplied  from a  well  and a reservoir.
 Discharges from the  plant include overflows  from  two cooling
 ponds  (designated as No. 1 and No. 2).

 Indirect cooling water used in  the  blast   furnace,  sinter
 plant,   and  casting operation  is  cooled in a main cooling
 tower  and recycled.   The cooling tower blowdown   goes  to  a
 settling pit   located  in  the  slag  granulation  circuit.
 Cooling  water   makeup is  provided  from  the fresh  water
 supply,  the  No.  1 cooling  pond,  and  the acid plant  as
 indicated in the flowsheet.

 Slag granulation water is recycled between   the   granulation
 process  and  a  settling pit  and between the  latter and the
 No. 1 cooling  pond.   An overflow from  the   latter  pond   is
 discharged to  a  river.

 In  the  acid   plant  operation,  the effluent from a packed
 tower scrubber  goes   to  a  lime  sump  for   neutralization.
 Indirect cooling water is partially recycled through a cool-
 ing  tower.    The remainder of the indirect  cooling water  is
 discharged to the No. 2 cooling  pond.  The acid plant  blow-
 down is  treated  in the lime sump.  An overflow from the lime
 sump  provides makeup water for the slag granulation circuit
via the  settling pit  located in that circuit.  The remainder
of the lime  sump effluent is discharged in succession  to
                                                           a
                              82

-------
       Blast Furnace
         and Sinter
           Plant
       (Indirect Cool
           (Indirect
           Cooling)
             Slag

         Granulation
                 Indirect  Cooling
                  Indirect
                  Cooling
Discharge
   to
  River
Figure 11.  Flow sheet for water circuit at Plant B.
                             83

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lime  bed  and  to the No. 2 cooling pond.  An overflow from
the latter pond is discharged to a creek.

An average discharge from both ponds is about 273  cu  m/day
(50 gpm)  and is much lower during dry seasons.

Water employed in a wet scrubber is treated in a closed-loop
circuit   using   a  settling  basin  as  indicated  in  the
flowsheet.

Treatment Costs for Present __ Practices.   The  capital  cost
data "supplied  by  the  plant and updated to 1971 costs are
summarized below by treatment circuits keyed  to  the  plant
operations:

          Basis:  Production = 120,963 kkg/yr
                   (133,366 tons/yr) refined lead
     Casting operation cooling unit       7,200

     Slag granulation circuit           232,000

     Acid plant lime neutralization
       system                            2U,800

     Wet scrubber settling basin         20,000

     Cooling Pond No. 1                  36,000

     Cooling Pond No. 2                __ 15,600

            Total Capital Costs        $335,600

            S/Annual kkg  (ton)                $2.77  (2.50)


Operating   cost  data  supplied   by  the plant were  available
only for the consumption  of  lime  for the acid plant effluent
neutralization circuit, which  is  estimated   at  113.5   kg/hr
 (250  Ib/hr) ,  and for  the  operating  labor   requirement
specified at 2 men/shift.  The remainder of  the  annual  cost
items  were  estimated.  Operating  costs are summarized  below:

     pperating^Costsi

     Raw materials  (lime)                 27,400

     Utilities                            Nominal
                                84

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     Operating labor                     87,600

     Maintenance                         24,700

     Administrative overhead              4,500

     Depreciation                        17,800

     Interest                            26,800

     Tax and insurance                 	2.cZ.P_9.

              Total Operating Costs    $191,500

              $/kkg (ton)                     1.58  (1.43)

Plant C

This  plant  is engaged in smelting and refining operations.
No acid plant exists at this smelter.

Water  ysagex  Treatment^  and  Discharge.    A   simplified
flowsheet  of the plant water circuit is shown in Figure  12.
The plant water is supplied from a well  and  a  lake.   The
discharge  from  the  plant is an overflow from two settling
ponds located in the slag granulation circuit.

Indirect cooling  water  is  used  for  the  blast  furnace,
refining, casting, and various other process equipment, such
as  baghouse fans and air compressors.  The cooling water to
the blast furnace is totally evaporated.

The  cooling  water  used  in  the  refinery   and   casting
operations  are  recycled  using a sump.  The same sump also
receives the cooling water from the process  equipment.   An
overflow from the sump is used for cooling the blast furnace
and  the  sinter  plant gases and is totally evaporated into
the gas streams.

Slag granulation  is  currently  practiced  in  a  partially
closed  circuit.   A bleed-off from the circuit is discharged
to two settling ponds,  both of which overflow into a  creek.
Two  cooling  towers  are  included  in the slag granulation
system to provide cooling.  Immediate plans for this  system
include  the  usage of this small discharge as a gas cooling
media prior to passage through the sinter offgas baghouse.
                              85

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                                      Evaporation
oo
                             Blast  Furnace
                               (Indirect
                                Cooling)
                             Refining and
                                Casting
                              (Indirect
                               Cooling)
                               Process
                              Equipment
                               Cooling
                              (Indirect)
                                  Slag
                               Granulation
                                 System
                                                                                       Evaporation
Recycle
                                                           Sump
           Settling
           Ponds  (2)
                              Blast Furnace
                              and Sinter
                                 Plant
                             (Gas Cooling)
                                                                               .
                                                                               '
                                / Planned
                                  reuse  as  sinter
                                          cooling  media
Discharge
   to
  Creek
                       Figure 12.  Flow sheet of water circuit at Plant C.

-------
 Treatment Costs of Present Practice.   Treatment  costs  for
 this  plant were estimated on the basis of treatment process
 description and equipment  specifications  supplied  by  the
 plant.  The cost data are summarized below:

           Basis:  Production = 97,956 kkg/year
                   (108,000 tons/year)  refined lead
                                        1971_Dollars

        Slag granulation water recycle   112^7,00
               Total Capital Costs

               $/Annual  kkg (ton)

        Operating Cgsts^

        Raw materials

        Utilities

        Operating labor,  $5/hr,
          2 men/day

        Maintenance

        Administrative overhead

        Depreciation

        Interest

        Tax and insurance

               Total Operating Costs

               $/kkg (ton)
$112,700

       1.15  (1.04)

	$/Year	

 Nominal

 Nominal


  29,200

   6,800

   1,400

   5,600

   9,000

 	900

 $52,900

       0.54  (0.49)
Plant_D
This  plant  includes,  besides a lead smelting and refining
operation, a primary electrolytic zinc  plant,  a  phosphate
fertilizer  plant,  and  an  ore  concentrating  and  mining
operation.   The  plant  is  currently  in  the  process  of
extensive  modification  of  water  usage  and  waste  water
treatment with the installation of a new central waste water
treatment plant to serve  the  entire  plant  complex.   The
modification is scheduled to be completed in 1974.  The cost
                            87

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analysis  for  this  plant  was,  therefore,  based  on  the
modified plan for water usage and treatment.
   er Usaaex Treatment ^ and  Discharge.   The  water  usage,
treatment, and discharge are shown in Figure 13 for the lead
smelting   and   refining  operation   (referred  to  as  the
smelter) .  Feed water to the smelter consists of fresh water
supplied from the main plant reservoir, cooling  water  from
the  zinc  plant,  and recycle water from the lead smelter's
internal treatment plant.

Slag granulation water proceeds with the slag  to  the  slag
pile where it is totally consumed, and no known discharge to
navigable  water  occurs.   Acid  plant  blowdown,  baghouse
cleaning water, and scrubber water are combined and  treated
in  the  lead smelter's internal treatment plant, consisting
of lime precipitation, thickening, and filtration.  Most  of
the  resulting overflow is recycled back to the lead smelter
reservoir.  About 2,180 cu m/day  (400 gpm)  of this  overflow
is reused within the plant's phosphate fertilizer operation;
this  fertilizer  plant  operates  in a closed-water circuit
mode with a segregated portion of  the  central  impoundment
area.   The  remaining  discharge  from  the  lead smelter's
internal treatment plant is periodic in  nature  and  occurs
during  cleanout  of  the  internal  treatment plant's pond.
During cleanout, the pond's  volume  is  discharged  to  the
central impoundment area, where it commingles with effluents
from  the  primary  electrolytic zinc plant and from the ore
mining and concentrating operations.

The waste water collected in the central impoundment area is
treated in the central treatment plant by lime precipitation
and thickening.  The underflow sludge from the thickener  is
returned  to  the  central impoundment area and the overflow
(clarified  water)   is  partially  reused   in   the   plant
concentrator, with the remainder discharged to a creek.


§25§i£e£   Treatment   Facilities  C2§t§.   The  waste  water
treatment  facilities  at  the"" smelter  include  the   lime
precipitation  plant, the settling pond, the main reservoir,
and associated piping, pumps, and other auxiliary equipment.
The capital and operating costs were  estimated  as  follows
using the cost data supplied by the plant:

          Basis:  Production = 120,950 kkg/year
                  (133,349 tons/year)  refined lead
                             88

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   Zinc Plant
   Reservoir
   Overflow
   + Make-up
oo
VD
          Internal
          Lead
        rreatment
          PI a«<-
Periodic Pond
  Clean-out
    Discharge
                                                                                                     Final
                                                                                                 ^"Discharge
                                                                                                    to  Creek
                                                                        Closed-
                                                                       Circuit
              Figure  13.  Flowsheet of water circuit at Plant D.

-------
       C ap it a 1 _Co s t s^

          Total Capital Costs     $286rOOO

          I/Annual kkg  (ton)             2.36  (2.14)

       Qperating_Costs^
          Total Operating Costs   $ 99,000

          $/kkg  (ton)                    0.82  (C.74)

Central   Treatment   Plant  Costs...  The  central  treatment
facilities include the  central  impoundment   area  and  the
central  treatment plant for lime precipitation.  As pointed
out previously, the treatment complex is designed  to  serve
the integrated plant operation, of which the lead smelter is
a   part.   The  capital  costs  of  the  central  treatment
facilities associated with the  smelter  operation  include:
(1)  the retrofit costs for the smelter, (2) the cost of the
central impoundment area apportioned to the smelter, and  (3)
the cost of the central treatment plant apportioned  to  the
smelter.   Since  only  the  total costs are known or can be
calculated for the latter two items,  the  costs  associated
with  the  smelter  were estimated by apportioning the total
costs by the ratic of the waste  water  discharge  from  the
smelter  to the central impoundment area and the total waste
water input to  the  central  impoundment  area.   The  only
discharge  from  the lead smelter to the central impoundment
area occurs when the smelter's internal  treatment  pond  is
periodically  emptied  for  clean-out.   Plant  D  personnel
estimate this flow to average around 576 cu m/day (105 gpm)  .
The total flow to  the  central  treatment  plant  from  the
central  impoundment  area  is  27,800 cu m/day  (5,100 gpm),
which consists of 576 cu m/day (105 gpm)   average  from  the
lead  smelter; 4,060 cu m/day (745 gpm)  from the zinc plant;
6,660 cu m/day (1,210 gpm)  mill waters;  and 16,600 cu  m/day
(3,040 gpm)  mine drainage water.

Under  the above assumption, the capital and operating costs
for the smelter portion of the central treatment plant  were
estimated as follows:

          Basis:   (a) Production = 120,948 kkg/year
                  (133,349 tons/year)  refined lead
                  (b) Lead smelter/total plant input =
                  105/5,100 = 0.02.
                          90

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        Capital Costsj^

        Central Treatment Plant

                   Total

                   Smelter portion

        Central Impoundment Area

                   Total

                   Smelter portion

        Smelter retrofit costs

                   Total smelter

                   $/Annual kkg (ton)

        Operating Costs:

        Central Treatment Plant

                   Total

                   Smelter portion

        Central Impoundment Area (Smelter  Portion)

        Maintenance                     $     700
 1971 Dollars



 $518,000

 $  11,000



 $644,000

 $  13,000

 $162,000

 $186,000

       1.54  (1.40)

 	$/Year	



$656,000/year

$ 13,000/year
       Depreciation  (straight
       line over 17-year life)

       Tax and insurance

       Interest
$

$
800

100
                                       $	1^.000
                                       $   2,600
                Total Operating Costs  $  15,600/year

                $/kkg  (ton)                 0.13  (0.12)

Total  Costs  for  the Present Treatment Practice. The total
capital  and  operating  ccsts  for" the "present" treatment
practice  were estimated by adding the costs associated with
the smelter treatment facilities and the  central  treatment
facilities:
                          91

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       Capital costs           $472,000
       S/Annual kkg (ton)             3.90 (3.54)

       Operating Costs         $114,600/year
       $/kkg (ton)                    0.94 (0.86)
Plant E
This plant is  engaged  in  smelting  operations  only.   No
refining or acid plant operations are involved.
Watgr   Usa^e^   Treatment^  and  Discharge.   A  simplified
flowsheet of the plant water circuit is shown in Figure  14.
The  plant  water  is  supplied from a reservoir, wnich also
serves as a cooling pond.  Water usage at this plant can  be
categorized by indirect cooling and process water.  Indirect
cooling  water  is used on a once-through basis in the blast
furnace, the  sinter  plant,  and  the  dross  reverberatory
furnace  and  is then combined and cooled in a cooling tower
and discharged to a creek.  Cooling water used in  the  slag
fuming furnace is returned to the reservoir.

Process water is used in the granulation of speiss, produced
from the dross reverberatory furnace, and spray conditioning
of  sinter plant flue gas for an electrostatic precipitator.
The effluents from these  two  operations  are  recycled  in
closed  circuits using a settling pond and settling sumps as
indicated in the flowsheet.
Treatment costs of	Present	Practice.   Capital  costs   for
the treatment processes as described above were estimated by
using  the  cost  and  equipment data supplied by the plant.
Cost data and calculations are summarized below:

          Basis:  Production = 58,048 kkg/year
                   (64,000 tons/year) lead bullion

       Cap_ital_Costs_:.                   1971  Dollars

       Speiss granulation water recycle $27,400

       Electrostatic precipitator  gas conditioning
         spray recycle                   $26^000

                  Total Capital Costs    $53,400
                             92

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              Reservoir

           (Cooling Pond)
co
                  Recycle
             Zinc  Fuming
               Furnace
             (Indirect
              Cooling)
                                         Blast Furnace

                                           (Indirect
                                            Cooling)
                                          Sinter Plant
                                         (Gas Cooling
                                          and Indirect
                                            Cooling)
                                          Reverberatory
                                             Furnace
                                           (Indirect
                                            Cooling)
  Speiss

Granulation
                                             Cottrell
                                               Gas
                                           Conditioning
                                               Sprays
                  Indirect
                  Cooling
                  Indirect
                  Cooling
                  Indirect
                  Cooling
^Discharge  to
     Creek
                                                             Recycle^
                  Recycle
                             Fiqure 14.   Flow sheet of water circuit at Plant E.

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                  $/Annual kkg  (ton)            0.92  (0.83)

      QEeration_Costs.:.               	$/Year	

      Raw materials

      Utilities

      Operating  labor

      Maintenance

      Administrative overhead

      Depreciation

      Interest

      Tax  and insurance

                Total Operating Costs

                    $/kkg (ton)


            jEcononjics_of_Additional^COQtrol and
            "~       Treatment Practicgs


Of  the seven primary lead facilities currently operating in
the United States, five plants,  by  virtue  of  either  the
current  control  and  treatment  practices  or  the lack of
process waste water  at  these  plants,  meet  the  proposed
effluent  limitations guidelines derived in this development
document.    These   five   plants,   therefore,   are   not
economically impacted by the proposed limitations.

The  economics  of   the  necessary   additional control  and
treatment practices  for  the  two   remaining  primary   lead
operations are discussed in the ensuing paragraphs.
Plant_A

Current   control   and   treatment   technology  used by  Plant  A
allows the  final  discharge  of  1,6UO  cu m/day   (300 gpm)  of
process   waste water after  usage  for slag  granulation.   This
effluent   contains acid plant   blcwdown.     The  proposed
effluent    limitations    for   Plant   A   (this    plant is
geographically located  in an  area of net precipitation)   are
                           94

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 based  upon a  selected discharge  flew rate of  835  1/kkg  (200
 gal/ton)   and   treated   process    waste    water    pollutant
 concentrations  after   liming  and settling.  One alternative
 for  achievement of  the proposed limitations for  this  plant
 is to reduce the plant discharge  by further recycle or reuse
 until the  selected  discharge flow rate is  achieved,  and  then
 use  a lime and settle  treatment facility.

 Based  upon an  annual  production  rate   of  208,610 kkg/yr
 (230,000 tons/yr) and  the selected discharge  flow  rate of
 835  1/kkg  (200 gal/ton),  Plant A's discharge should be about
 545   cu m/day  (TOO   gpm).   Cost estimates for pumping and
 piping the additional  recycle   water  are  not   currently
 available,   nor  are   economic estimates for reuse of such a
 volume.  In order to obtain an approximation of these costs,
 cost  estimates for  artificial evaporation  will be  used on
 the   1,090   cu  m/day  (200 gpm) flow  reduction.  These costs
 should represent the iraximum costs  seen through recycle  and
 reuse control  alternatives.

      £a£ital_Costs                    ,1971, Dollars

      Control alternatives              $1,084,000

      Qger.ating  Costs                  _$/year

      Operating  and  maintenance         $  132,000

      Fuel                                165,000

      Depreciation                          54,000

      Taxes  and  insurance                   22,000

      Interest                           _109A000_

               Total Operating Costs  $  482,000

The  costs for treating the resultant 545 cu m/day  (100 gpm)
of process waste waters prior to release to navigable waters
by lime and settle are estimated as follows:

     Ca£ital_Costs                    liII_Pollars

     Lime and settle treatment plant    $150,000

     Operating Costs                    . $/year

     Operating and maintenance            53,200
                          95

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     Depreciation                           7r50C

     Taxes and insurance                    3,000

     Interest                           	JL5XOGO

               Total Operating Costs    $ 78,700


The  total estimated costs for Plant A to achieve compliance
to the recommended limitations are:

     Total Capital Costs              $1,234,000

          $/Annual kkg                      5.90

          ($/Annual ton)                  (5.37)

     Total Operating Costs            $  560,700

          $/kkg  ($/ton)                     2.68  (2.44)


These costs are considered to represent the upper  limit  of
control  costs,  since  the  costs of artificial evaporation
were used to approximate the unknown costs of recycle and/or
reuse.


Plant B

The current discharge  of  process  waste  water  from  this
primary  lead  smelter  is  reported  to be 273 cu m/day  (50
gpm).  This plant is geographically located in  an  area  of
net  precipitation,  so  the selected discharge flow rate of
835 1/kkg (200  gal/ton)  can  be  used  to  calculate  this
plant's   discharge.   For  a  production  rate  of  120,963
kkg/year (133,366 tons/year), this plant's discharge  should
be  about  300  cu  m/day  (55  gpm).  Therefore, liming and
settling the resultant 273 cu m/day (50  gpm)   will  provide
compliance    to   the   proposed   limitations.    Effluent
concentration data from Plant B are contained  in  Table  14
and  indicate high discharge values of cadmium.  The primary
reason for these high values was due to an untreated  sinter
plant  spray  chamber  discharge entering one of the holding
lakes, from which the  final  discharge  occurs.   Recently,
plant  personnel  feel  that this problem has been solved by
the  installation  of  a  dry  electrostatic   precipitator.
Company  personnel  also feel that their currently used lime
                             96

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 pit  should be either modified or replaced with a new liming
 system.   Estimates of this replacement or modification are:

      Ca£ital_Costs                          1 97 1_ Dollars

      Modified or replaced liming system      $ 41,000

           S/Annual kkg                         $0.34

           ($/Annual ton)                       ($0.31)

      Operating Costs                         _$/£e.ar_

      (Assume 25% of capital)                  $ 10, 000

           $/kkg                                $0.08

           ($/ton)                              ($0.07)


 Total_Costs_
    ,       estimated  costs  to Plants A and B,  on the basis of
 1971  dollars,  are  $1,275,000 capital and $570,700  operating,
 most  of  which  is attributable to   additional   treatment  and
 control  technology   at Plant A.   These  values are lifted in
 Table 20.
Specific data on energy requirements were not available  from
most of  the  plants  surveyed.   The  current  waste  water
treatment practices are confined to cooling towers, settling
ponds,  and  lime  treatment, which require an insignificant
amount of electrical and thermal energy  relative  to  total
plant  operations.   Data  supplied  by  Plant  D  on a  lime
treatment process located in the sirelter  plant  indicate  a
power   consumption  estimated  at  about  5  kwhr/kkg   (4 5
kwhr/ton)  of lead produced.  Power  requirements  for  Plant
?««  total cornPle* liir.e and settle treatment plant are about
100 horsepower, or  the  equivalent  of  much  less  than  1
percent of total plant energy consumption.
                          97

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                   TABLE 20.  ADDITIONAL CONTROL AND TREATMENT COSTS  (1971  DOLLARS)
     Plant
  Designation
      Additional         Additional
Control and Treatment     Capital     $/Annual kkg
       Practice             Cost     ($/Annual Ton)
                              Additional
                               Operating
                                 Cost
                                                                                         $/kkg
                                                                                        ($/ton)
CO
                  Further  Reuse  and
                  Recycle  and  lime and
                  settle
                         $1,234,000
                $5.90
                (5.37)
              $560,700
 2.68
(2.44
       B
Modify or Replace
Liming System
$   41,000
 0.34
(0.31)
                                                                            10,000
 0.08
(0.07)
                         None
        D
      None
        E
      None
                         None
     TOTAL
                         $1,275,000
                                                                          $570,700

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Solid_Waste_Gener ation


Lime  treatment  processes  will  produce solid waste in the
form of dewatered  sludge  containing  calcium  sulfate  and
metal  hydroxides.   The  quantity  of  sludge produced on a
CaSO4 basis was estimated at 20 kg/kkg (40 Ib/ton)  of  lead
production  based  upon  data  supplied  by  Plant B on lime
consumption in neutralization of acid plant scrubber  bleed.
Sludge  production  is  small  and  can  be  disposed  of by
numerous means such as by reuse as a sinter-feed constituent
or as an input to the zinc fuming plant.   Disposal to either
the slag  pile  or  to  tailings  pond  (Plant  D)  is  also
possible.  In comparison to the mass generation of slag, the
production of solid waste through water pollution control is
nearly negligible.
                          99

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                         SECTION IX
       BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
         AVAILABLE—EFFLUENT LIMITATIONS GUIDELINES
                        Introduction
The effluent limitations that must be achieved  by  July  I,
1977  are  to  specify  the  degree  of  effluent  reduction
attainable through the application of the  best  practicable
control   technology   currently  available.   Such  control
technology is based on the average of the  best  performance
by  plants  of  various  sizes and ages, as well as the unit
processes within the industrial category.  This  average  is
not  based  upon  a broad range of plants within the primary
lead industry, but upon the performance levels  achieved  by
the  exemplary  plants.   Additional  consideration was also
given to:

           (1)  The total cost of application of
               technology in relation to the effluent
               reduction benefits to be achieved
               from such application.
           (2)  The size and age of the equipment and
               plant facilities involved.
           (3)  The process employed.
           (4)  The engineering aspects of the
               application of various types of
               control techniques.
           (5)  Process changes.
           (6)  Nonwater quality environmental
               impact  (including energy requirements).

The best practical control  technology  currently  available
emphasizes  effluent treatment at the end of a manufacturing
process.   It includes  the  control  technology  within   the
process  itself  when  the latter is considered to be normal
practice within the industry.

A  further  consideration  is  the  degree  of  economic   and
engineering  reliability,  which must be established for  the
technology to  be  currently  available.   As  a  result  of
demonstration projects, pilot plants, and general use, there
must  exist  a  high degree of confidence in the engineering
and economic practicability of the technology at the time of
commencement of construction or installation of the  control
or treatment facilities.
                             101

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         Indugtr^_Catec[orY_and Process Waste Waters


The primary lead industry as defined  herein  includes  that
segment  of  the  nonferrous  metals industry which extracts
and/or refines metallic  lead  from  ores  and  concentrates
containing  lead  as  the principal valuable metal.  For the
purposes of recommending  effluent  limitations  guidelines,
the   primary  lead  industry  is  considered  as  a  single
subcategory of point sources of process waste  waters.   The
rationale  for this categorization has been developed in the
previous sections of  this  document  as  being  principally
based on a nearly uniform pattern of water use and discharge
of  process  waste  waters,  including  similarities  in the
factors  of  processes,  production  process   waste   water
characteristics,   and  current  practices  in  control  and
treatment of process waste water pollutants.


Plant location is considered to have a bearing  on  specific
limitations  for  this  subcategory.   Two  of the currently
operating seven primary lead facilities  are  geographically
located in arid regions, providing a means  for process waste
water  disposal through solar evaporation.  One of the seven
operations, a primary lead  refinery,  not  located   on-site
with  a  primary  lead smelter, is net considered  as  part of
the primary lead  subcategory  since,  due  to  process,  no
process   waste   water  pollutants   (as  defined  for  this
subcategory) are  produced at this  facility.

The sources of  process waste water  from  the  primary  lead
industry  include acid plant blowdown, slag granulation, and
wet   scrubber   bleed  streams.    Storm  water  runoff which
commingles  with  process waste water  is also considered as  a
process waste water.
 Eiifflary. Lead Facilities Geographically, Located in  Areas  of
 N§t Evaporation

 The recommended effluent limitation based on the application
 of   the   best  practicable  control  technology  currently
 available is no discharge of process waste water  pollutants
 to navigable waters.
                             102

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The  achievement  of  this  limitation by use of control and
treatment technologies identified in this document leads  to
the  complete  recycle,  reuse,  or consumption of all water
within the  combined  processes  of  the  industry  with  an
associated result of no discharge of water.

Since   some  primary  lead  facilities  are  geographically
located in areas of  heavy  rainfall  event,  the  following
discharge  provisions  are  proposed  as  part of the BPCTCA
effluent limitations:

    A process waste water  impoundment  which  is  designed,
    constructed   and   operated   so   as  to  contain  the
    precipitation from the 10 year, 24 hour  rainfall  event
    as established by the National Climatic Center, National
    Oceanic  and Atmospheric Administration, for the area in
    which such impoundment is  located  may  discharge  that
    volume of process waste water which is equivalent to the
    volume   of   precipitation   that   falls   within  the
    impoundment in excess of that  attributable  to  the  10
    year, 24 hour rainfall event, when such event occurs.

    During any calendar month there may be discharged from a
    process  waste  water  impoundment  either  a  volume of
    process waste water equal to the difference between  the
    precipitation  for  that  month  that  falls  within the
    impoundment and the evaporation within  the  impoundment
    for  that  month,  or,  if  greater, a volume of process
    waste water equal to the  difference  between  the  mean
    precipitation  for  that  month  that  falls  within the
    impoundment and the mean evaporation for that  month  as
    established  by  the  National Climatic Center, National
    Oceanic and Atmospheric Administration, for the area  in
    which  such  impoundment  is  located   (or  as otherwise
    determined if no monthly data have been  established  by
    the National Climatic Center).

    Any process waste water discharged pursuant to the above
    paragraph  shall  comply  with  each  of  the  following
    requirements:
                                Effluent limitations
       Effluent                              Average of daily
    characteristic          Maximum for       values for 30
                             any  1 day       consecutive days
                                             shall not exceed
                            103

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                               	Metric units	tma/11
    TSS
    Cd
    Pb
    Zn
    pH
   50
    1
    1,
   10
       25
        0.
        0,
Within the range 7.0 to 10.5
                                    English units (ppm)
    TSS
    Cd
    Pb
    Zn
   50
    1.0
    1.0
   10
       25
        0.5
        0.5
        5
       	Within^the range 7.0 to 10.5	

    When commingled waters are contained in the  impoundment
    area,  the  volume  of  water  allowably  discharged  to
    navigable waters due to  the  conditions  of  the  above
    paragraphs will equal the volume calculated on the basis
    of  the  ratio  of  process waste water volume and total
    impoundment volume.
Net Rainfall
        L§£d Facilities Geoc[rap_hicallY Located in  Areas  of
The   recommended   effluent   limitations   based   on  the
application  of  the  best  practicable  control  technology
currently    available    for    primary   lead   facilities
geographically located in areas cf net rainfall are:
       Effluent
    characteristic
                                Effluent limitations
Maximum for
 any 1 day
Average of daily
 values for 30
consecutive days
shall not exceed
    TSS
    Cd
    Pb
    Hg
    Zn
    pH
                            Metric units (kilograms per 1,000 kg
                                            of
    0.042
    0.0008
    0.0008
    8.0x10-*
    0.008
        0.021
        0.0004
        0.0004
        4.0x10-6
        0.004
Within the range 7.0 to 10.0
                            104

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                            English units (pounds per 1,000 Ib
                           	gf^product)	
    TSS                         0.042                0.021
    Cd                          0.0008               0.0004
    Pb                          0.0008               0.0004
    Hg                          8.0x10-6             4.0x10-6
    Zn                          0.008                0.004
    pH	Within the range 7.0, to 10.0	
Idgntificatign and_Rationale of Best Practicable Control
Technology^Currently_Ayailablg

The  prior  sections  of  this   document   have   presented
information  on  current  discharges  cf process waste water
from primary lead facilities, consisting of waste water from
slag granulation,  scrubber  applications,  and  acid  plant
operations.   Further,  it has been observed that two of the
seven currently operating  plants  discharge  process  waste
water   from  their  slag  granulation-acid  plant  blowdown
circuit.

At  two  shelters  operating  metallurgical  sulfuric   acid
plants,  the blowdown from the acid plant is used as part of
the slag granulation water input.  At differing  degrees  of
recycle,  a  discharge  from  the  slag  granulation circuit
occurs.  The third smelter which operates an acid plant  for
sulfur-value  recovery  on  sinter machine offgases recycles
and reuses all of its process waste waters in integrated on-
site  operations.   The  one  Missouri  smelter,   currently
operating  without an acid plant, plans to recycle and reuse
all  of  its  slag  granulation  water  with  no   resultant
discharge  of  process  waste  water.  Some slag granulation
water will be used as a cooling media for  the  hot  smelter
gas  streams  prior  to  entrance  into  the  baghouse.  Two
smelters are located in areas of net  evaporation,  and  any
generated process waste water can be disposed of by means of
solar  evaporation,  after  maximumizaticn  of  recycle  and
reuse.

The recommended effluent limitations are based  on  reported
flow  and  concentration  data.   The  discussion  of  water
circuits and flows in Sections VII and VIII of this document
developed the calculated rates of acid  plant  blowdown  for
the  three  existing acid plants as 715 1/kkg  (171 gal/ton),
756 1/kkg  (181 gal/ton), and 822 1/kkg  (197  gal/ton).   The
latter   value  was  applied  for  the  development  of  the
recommended effluent limitations.  One of  the  elements  of
the  rationale  for the recommended guidelines is the intent
                            105

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to make the guidelines compatible with air pollution control
requirements.  Of the six primary  lead  smelters  currently
operating,  three have permanent SO2 control by means of the
conventional  metallurgical   sulfuric   acid   plant.    In
anticipation of those three smelters, which do not currently
have   permanent  control,  but  may  shortly,  due  to  air
pollution regulations, the effluent limitations prescribe  a
volumetric   discharge  for  an  acid  plant  blowdown.   In
accordance with this regulation, two of these three smelters
(with no permanent S02 control)  would be required to  comply
to   a  no  discharge  of  process  waste  water  pollutants
guideline, based  upon  geographical  location.   The  third
smelter,  located  in Missouri,  would be allowed a discharge
of acid plant blowdown in accordance  with  the  recommended
limitations, as identically applied to the other two primary
smelters  in  Missouri,  both  of  which  currently  operate
metallurgical acid plants.

The concentrations of selected pollutant parameters  applied
to  develop the guidelines were selected from available data
on effluents as contained  in  documents  of  record,  field
analyses,   and   projected   effluent  characteristics  (as
described in information supplied  by  the  industry).   The
relevant values are listed below:

         Pollutant             Concentration
         Parameter             ^	1203/1J	

           1SS                      25
           Cd                        0.5
           Pb                        o.S.
           Hg                        0.005
           Zn                        5

These  concentration  values  were  basically  taken  from a
composite analysis of the data contained  in  Table  17  and
Figures  6  through 9.  Data on arsenic for the primary lead
industry is inconclusive.

The  combination  of  neutralization  and  clarification  is
required   to   achieve   the  best  practicable  technology
currently available.  Clarification alone will  reduce  only
total suspended solids; neutralization without clarification
will  reduce  dissolved  metals, but not suspended ones, and
will  not  provide  an  effluent  of  satisfactory  quality.
Neutralization  with  lime to a pH in the 8 to 10 range will
reduce the concentrations of those  metals  precipitable  as
hydroxides,  and with properly designed retention facilities
will also reduce total suspended solids  to  below  effluent
limitations  guidelines.  Use of lime has the further advan-
                           106

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tage   that   it,  unlike  sodium-based  alkalies,  forms  a
relatively insoluble sulfate, CaSOU, which will tend to also
reduce  the  concentrations  of  dissolved  sulfate  in  the
effluent.   Neutralization  will  not  significantly  reduce
concentrations of those parameters which are soluble  at  an
alkaline pH.

Other considerations bearing on this recommendation include:

    (1)   The selected lime and settle  technology  has  been
         shown  to  be  capable of achieving significant re-
         ductions in the discharge of pollutants.
    (2)   The  technology   is   compatible   with   industry
         variations,  including:   age  and  size  of plant,
         processes employed, raw  material  variations,  and
         nonwater quality environmental impact.
    (3)   The technology, as an end-of-pipe treatment, can be
         an add-on to existing plants, and need  not  affect
         existing    internal    process    and    equipment
         arrangements.
    (>4)   The effluent reduction benefits balance  the  costs
         of the technology.  On the basis of the information
         contained  in  Section  VIII,  it is concluded that
         those  two  plants  not  presently  achieving   the
         recommended   best  practicable  limitations  would
         require  an   estimated   total   maximum   capital
         investment  of  about  $1,275,000  and an increased
         operating cost of about  $570,700/year  to  achieve
         these limitations.
                            107

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                         SECTION X
    BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE—
              EFFLUENT LIMITATIONS GUIDELINES
The  best  available  technology  economically achievable is
identical  to  the  best  practicable   control   technology
currently available.  The corresponding effluent limitations
are identical to those effluent limitations established from
usage  of  the best practicable control technology currently
available.
                              109

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                         SECTION XI


              NEW SOURCE PERFORMANCE STANDARDS


The  best   available   demonstrated   control   technology,
processes,  operating  methods,  or  other  alternatives are
identical  to  the  best  practicable   control   technology
currently   available.    The   corresponding   standard  of
performance  is  identical  to  the   effluent   limitations
guidelines   established   from   the   usage  of  the  best
practicable control technology currently available.
                            Ill

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                        SECTION XII
                      ACKNOWLEDGMENTS
This document was developed by the Environmental  Protection
Agency.   The  original  contractor's  draft  report,  dated
December 1973 was prepared by Battelle  Memorial  Institute,
Columbus,  Ohio, under contract no. 68-01-1518.  Mr. John B.
Hallowell  prepared  this  original    (contractor's)   draft
report.

This  study was conducted under the supervision and guidance
of  Mr.  George   S.   Thompson,   Jr.,   Project   Officer.
Preparation,  organizing,  editing,  and  final rewriting of
this report were accomplished by Mr. Thompson.

The following members  of  the  EPA  working  group/steering
committee provided detailed review, advice and assistance:

    W.J. Hunt, Chairman      Effluent Guidelines Division
    G.S. Thompson, Jr.,      Effluent Guidelines Division
                               Project Officer
    S. Davis                 Office of Planning and Evaluation
    D. Fink                  Office of Planning and Evaluation
    J. Ciancia               National Environmental Research
                               Center, Edison
    T. Powers                National Field Investigation Center,
                               Cincinnati

Excellent  guidance  and  assistance  was  provided  to  the
Project Officer by his associates  in the Effluent Guidelines
Division,  particularly  Messrs.   Allen   Cywin,   Director,
Effluent   Guidelines   Division,   Ernst  P.  Hall,  Deputy
Director, and Walter J. Hunt, Branch Chief.

The cooperation of individual primary  lead  companies,  who
offered  their  plants  for survey and contributed pertinent
data,  is greatly appreciated.  These include:
    American Smelting and Refining Company
    Missouri Lead operating Company
    Bunker Hill Company
    St. Joe Minerals Corporation

The cooperation of the Water Pollution Control  Subcommittee
of the American Mining Congress is also appreciated.

The   following  state  and  national   EPA officials  provided
considerable assistance: Mr. Thomas Jones, Missouri; Dr. Lee
                           113

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W. Stokes, Idaho; Mr. Mark Hopper, Region  X,  Seattle;  Mr.
Donald  G.  Willems,  Montana;  Mr.  Dick Montgomery, Region
VIII, Denver; Mr.  Donald  Benson,  Nebraska;  Mr.  John  B.
Latchford, Jr., Texas; Ms. Linda Nyatt, Texas; and Mr. Frank
Rozich, Colorado.

Acknowledgment  and  appreciation  is  also given to Ms. Kay
Starr, Ms. Nancy Zrubek,  and  Ms.  Alice  Thompson  of  the
Effluent Guidelines Division secretarial staff.
                             114

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               SECTION XIII
                REFERENCES
Brobst, D.A.,  and  Pratt,  W.P.,  editors,  United
States   Mineral   Resources,   Geological   Survey
Professional  Paper,   United   States   Government
Printing Office, Washington, D.C., 1973.

Bureau of Mines, Minerals Yearbook,  1971,  "Volume
I,  Metals,  Minerals,  and  Fuels",  United States
Department of the Interior, Bureau of  Mines,  U.S.
Government   Printing   Office,   Washington,  D.C.
(1973).

Bureau of Mines, "Mineral Facts and Problems,  1970
Edition",   Bureau  of  Mines  Bulletin  650,  U.S.
Department of the Interior, Bureau of  Mines,  U.S.
Government   Printing   Office,   Washington,  D.C.
(1970) .

Cotterill, C.H., and Cigan,  J.M.   (editors),  AIME
World  Symposium  of  Mining and Metallurgy of Lead
and Zinc, "Volume II, Extractive Metallurgy of Lead
and  Zinc",  The  American  Institute  of   Mining,
Metallurgical,  and  Petroleum Engineers Inc., Port
City Press, Baltimore, Maryland  (1970).

1970 E/MJ International  Directory  of  Mining  and
Mineral  Processing Operations, Published by Mining
Informational  Services,  Engineering  and   Mining
Journal, McGraw-Hill, New York (1970).

1973  Annual  Book  of  ASTM  Standards,  Part   7,
Nonferrous    Metals    and    Alloys,    "Standard
Specification for Lead", B29-55  (Reapproved 1971).

Pourbaix, M., "Atlas of Electrochemical  Equilibria
in Aqueous Solutions",  (1966), English Translation,
Pergamon Press, 644 pp.

Hartinger, L.; "Waste  Water  Purification  in  the
Metalworking  Industries,  Precipitation  of  Heavy
Metals", Part  1,  Problems,  Bander  Bleche  Rohre
Dusseldorf, October, 1963, pp 535-540.
                      115

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                         SECTION XIV


                           GLOSSARY


 Act

 The Federal Water Pollution Control Act Amendments of 1972.

 Acid Plant (Metallurgical)^

 In  primary  lead  smelting  operations, a plant adjoining a
 smelter  which  utilizes  SO2  gases  from   the   sintering
 operation to produce sulfuric acid.

 Baghouse

 An air  cleaning system consisting of multiple bag filters.

                                        Achievable
 Level  of  technology  applicable to effluent limitations to be
 achieved   by   July   1,   1983f   for  industrial discharges to
 surface waters as defined  by  Section  301(b)(2) (A)   of  the
 Act.

 Best Practicable Control TechnologY_Currentlv._Rva,i 1 able

 Level  of  technology  applicable to effluent  limitations to be
 achieved   by   July   1,   1977,   for  industrial discharges to
 surface water  as defined by  Section  301(B) (1) (A) of  the Act.

 Blast  Furnace

 In the primary lead  industry,  a shaft  reducing   furnace,
 usually   of rectangular cross  section,  in which concentrates
 are mixed  with fuel  and fluxes  and charged  from the   top  so
 that,  as  they descend  to   a   level  where an air  blast is
 admitted  (through nozzles  called tuyeres),   melting  takes
 place  under reducing conditions  to  form reduced metal  and a
 supernatant  slag,  which  may  be  tapped  continuously  or
 intermittantly.

Calcination

Heating  of a  solid to a temperature below its  melting  point
to bring about  a state of  thermal   decomposition  or   phase
transition other than melting.
                              117

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Capital^ Costs

Financial  charges  which  are  computed  as cost of capital
times the capital expenditures for pollution control.   Cost
of  capital  is based upon the average of the separate costs
of debt and equity.

Category^and Subcategory

Divisions of a particular industry which  possess  different
traits  that  affect  waste  water  treatability and require
different effluent limitations.

Cooling_Tgwer

A device in which hot water is pumped to the top of a  tower
and  cooled  by allowing it to flow downward in thin streams
from one container to another.

Concentrates

The product of milling operations in which the  ore  values,
usually  after  grinding  and  milling,  are  separated  and
concentrated.

Desilverizing

Removal of silver from  lead  bullion  during  the  refining
operation.

Dewatering Classifier^Isometimes referred
to as a dewatering bin or tank)

A  settling  tank for clarifying process water; the tank may
have a continuously operating  rake  at  the  bottom,  which
moves the settled solids or sludge towards an outlet pipe in
the bottom.

Prossing

Usually  the first step in refining, the purpose of which is
to remove copper.  Separation is effected  by  lowering  the
temperature  of  the  bullion in the kettle to a point where
copper comes out of metallic  solution.   Excess  copper  is
rejected  from  the  melt and forms a crust or "head" on its
surface.

Effluent

The waste water discharged from a point source.
                                118

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Electrostatic Precipitator

An  air  cleaning  system  in  which  dust   particles   are
electrically  charged  and  then  collected on plates of the
opposite electrical charge.

Final Refining

Final refinery operation in which the last traces  of  zinc,
antimony,  and  arsenic remaining in the bullion are removed
by treatment with caustic  soda,  sometimes  augmented  with
additions of sodium nitrate.

Flux

A substance added to a smelting furnace charge that promotes
fusing  of  minerals or metals, or prevents the formation of
oxides.

Gangue

A waste rock or slag material remaining after  most  of  the
metal values have been removed.

Gravity Concentration

Separation  of  ground  ore  into gangue and metal values by
virtue of difference in the density of the minerals in their
make-up, it can also be used to  separate  one  ore  mineral
from another if the differences in their specific gravity is
sufficiently large.

Flotation

A  method  of mineral separation in which a froth created in
water by air bubbles and a variety of  reagents  selectively
float some minerals (in a finely divided condition) by means
of  adherence  to oil-firm bubbles, while other minerals are
not so wetted and sink.

Harris Process

An  alternative  method  for   softening   lead.    Arsenic,
antimony,  and tin are oxidized by adding sodium nitrate and
lead oxide, and the oxides formed are caused to  react  with
sodium   hydroxide   and   chloride   to   form   arsenates,
antimonates, and stannates.
                          119

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Indirect Cooling

Water cooling in which water is  not  in  contact  with  any
material  in  process;  jacket cooling of the blast furnace,
slag fuming furnace, kettles, and the underside  of  casting
molds are examples.

Jig

A  device which separates crushed ore into values and gangue
by means of their differences in specific gravity in a water
medium.  In some cases, it  is  used  to  separate  one  ore
mineral of value from another.

Lead Bullion  (sometimes referred to as bullion)

The  metallic  product  of  the lead hearth or blast furnace;
normally it contains  quantities of copper, arsenic antimony,
or bismuth, which must be removed in  the_refining operations
to produce lead of  acceptable  specifications.

Lime Sump

A pit  or tank  to which lime  is  added   to   precipitate  out
dissolved  metallic  impurities  from the lead  smelter waste
water.

Matte

A metallic sulfide   mixture  produced  in   the   smelting  of
 sulfide ores.

 New Source Performance

 Level   of   technology  applicable  to effluent limitations  as
 outlined in Section 306  of the Act,  which provides  for   the
 control  of  the  discharge  of  pollutants and reflects the
 greatest degree of  effluent reduction achievable through the
 application  of  the  best  available  demonstrated  control
 technology,   processes,   operating   methods,   or   other
 alternatives,  including,  where  practicable,  a   standard
 permitting no discharge of pollutants.

 Ore

 A natural mineral  from which materials such as metals can be
 economically extracted.

 Parkes Process

 A  process  for  removing  silver and gold from lead bullion;
  zinc  is added to the bullion  in a refining  kettle, where   it
                           120

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combines  with  silver  and  gold to form compounds that are
virtually  insoluble  in  lead  and,  being  much   lighter,
accumulate on the surface where they can be skimmed off.

EH

The  logarithm,  to  the  base  10, of the reciprocal of the
concentration of hydrogen ions in an  aqueous  solution;  it
denotes the degree of acidity or basicity of a solution.  At
25  C,  seven  is the neutral value.  Acidity increases with
decreasing values  below  seven.   Basicity  increases  with
increasing values above seven.

Point Source

A  single  source  of  water  discharged  from an individual
plant.

Refining

In the primary lead industry, refining implies  the  removal
of  impurities  from  blast  furnace  or hearth smelted lead
bullion, usually by a series of treatments in  a  succession
of large hemispherically shaped kettles.

Reyerberatgry Furnace

A  furnace in which the charge is melted on a shallow hearth
by a  flame applied from one end and passes upward  over  the
charge,  which heats a low roof, shaped to reflect the  flame
and radiate heat onto the charge.

Settling Pond

A pond, natural or artificial, used for settling out  solids
by gravity from waste water effluents.

Sinter

The product of the sintering  machine; agglomerated masses of
relatively  sulfur-free  concentrates  of  suitable  size for
blast furnace  feed in which some of the impurities   such  as
arsenic  and   cadmium have been removed, at least partially,
by volatilization.

Sintering

In primary lead  smelting,  a process for removing sulfur from
the concentrates   by  oxidation,   and  impurities,   such  as
arsenic  and  cadmium by volatilization, and at the same time
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fritting the concentrates  together  into  manageably  sized
masses suitable for charging into the blast furnace.

Sintering Machine

A   horizontal   sintering   furnace  containing  traveling,
articulated grates  which  move  the  feed  continuously  in
conveyer   belt   fashion  under  controlled  conditions  of
combustion to produce a nearly sulfur-free sinter of a  size
suitable for furnace charging.

Skimmings

Wastes  from  melting  operations  that are removed from the
surface molten metal; the wastes consist of  metal  that  is
contained in oxidized metal.
The  fused agglomerate of oxides or salts, which  separates  in
metal   smelting  and  floats  on  the   surface of the molten
metal.   It is  formed by the combination of   gangue  of  the
ore, ash of  the  fuel, fluxes  and, in some cases, the furnace
lining.   The  slag  is  often  the medium by means of which
impurities may be  separated from metal.

Slaa_Fumin2_Furnace

A furnace used to  recover  zinc  from  lead  smelter  blast
furnace  slag;    zinc   is    separated from  the  slag  by
volatilization.

Slag Granulation

In the primary lead  industry, the   granulation   of  slag  is
produced  by  contact,  as  it  flows  from a  furnace,  with  jets
of high pressure water.

Smelting

 In the primary lead industry, smelting implies   a  reduction
 of  the  lead  oxide  in  the  ore to produce elemental  lead
  (bullion).   Fluxes in the  form of  limestone and silica unite
 with the gangue of the concentrate and ash of  the  fuel  to
 form a liquid slag which collects  some of the impurities.

 Softening

 A  refining  step  is  performed  usually  after dressing to
 remove antimony, arsenic,  and any tin  that is present in the
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lead bullion.  These impurities harden the lead,  and  their
removal renders it softer; hence, the term softening.  There
are two principal methods of softening, air-oxidation of the
molten  bullion  in  a  reverberatory  furnace or the Harris
process.

Speiss

A mixture of  arsenides  and  antimonides  produced  in  the
smelting of arsenical and antimonial ores.

Standard_of_Perfgrmance

A  maximum weight discharged per unit of production for each
constituent that is subject to limitations.  The  weight  is
applicable  to  new  sources as opposed to existing sources,
which are subject to effluent limitations.

Thickener

In  primary  lead  smelters,  a  vessel  or  apparatus   for
separating waste solids from waste water.

Tuyere

A nozzle through which an air blast is delivered to a cupola
or a blast furnace.

Venturi Air Scrubbers

An  air  cleaning  system  consisting of intense water-spray
cleaning of the air at a point where the air goes through  a
restriction  (venturi)  in the duct.

Waste Water Constituents

Materials  which  are  carried  by  or  dissolved in a water
stream for disposal.
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                                    TABLE  21




                                 CONVERSION TABLE

MULTIPLY  (ENGLISH UNITS)                   by                TO OBTAIN  (METRIC UNITS)

    ENGLISH UNIT      ABBREVIATION    CONVERSION   ABBREVIATION   METRIC UNIT
acre
acre - feet
British Thermal
  Unit
British Thermal
  Unit/pound
cubic feet/minute
cubic feet/second
cubic feet
cubic feet
cubic inches
degree Fahrenheit
feet
gallon
gallon/minute
horsepower
inches
inches of mercury
pounds
million gallons/day
mile
pound/square
  inch  (gauge)
square feet
square inches
ton  (short)
yard
* Actual conversion, not a multiplier
ac
ac ft
BTU
BTU/lb
cfm
cfs
cu ft
cu ft
cu in
%e
ft
gal
gpm
hp
in
in Hg
Ib
mgd
mi
psig
sq ft
sq in
ton
yd
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555PsF-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
*C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
hectares
cubic meters

kilogram - calories

kilogram calories/kilogram
cubic meters/Mnute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer

atmospheres  (absolute)
square meters
square centimeters
metric ton  (1000 kilograms)
meter
                                         124

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Environmental Protecuoa Agency
Region V8 Library
220 South Daarbo-rn
Chicago, Illinois

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U.S. ENVIRONMENTAL PROTECTION AGENCY (A-107)
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