-------
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BORON
TABLE OF CONTENTS
Page
FOREWORD 1-1
I. BORDN INDUSTRY IN THE UNITED STATES 1-2
A. Producers and Sites 1-2
B. Costs and Physical Properties of Important Boron
Conpounds 1-12
II. PRODUCTION 1-16
A. Natural Sources of Borates 1-16
B. Manufacturing Processes 1-16
1. Elenental Boron 1-16
2. Borax 1-19
a. The Mining Process 1-19
b. Trona Process 1-21
3. Anhydrous Borax 1-21
4. Boric Acid 1-21
5. Boric Oxide (BaOa, boron trioxide) 1-24
6. Boron Trifluoride (BFs) 1-24
7. Boron Trichloride 1-24
8. Diborane and Higher Boranes (Pentaborane, etc.) 1-24
9. Refractory boron compounds (metal borides, boron
carbide, and boron nitride) 1-27
III. USES OF BORON COMPOUNDS 1-28
A. Uses of Boron Conpounds 1-28
B. Future and Potential Uses 1-34
IV. CURRENT PRACTICES 1-35
V. ENVIRONMENTAL CONTAMINATION 1-37
A. From Uses 1-37
1. Emissions to the Atmosphere (including from
production) 1-39
2. Amount Entering Waters and Earth 1-40
B. Frcm Production 1-40
1. Mining „ 1-40
2. Processing 1-40
C. Inadvertent 1-41
D. Total Amounts Entering Environment per Year ... 1-41
i.
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BORON
TABLE OF CONTENTS
(Can't)
Page
VI. MONITORING AND ANALYSIS 1-43
A. Monitoring 1-43
B. Analysis. 1-43
1. Determination of Boron in Water ........ 1-43
2. Determination of Boron in Plants and Biological
Materials 1-43
3. Analysis of Available Boron in Soil ...... 1-44
4. Detection of Boron in Airborne Contaminants
Collected in Air Filters 1-44
5. Analysis of Boron in Air by Colorimetry . . . . 1-44
VII. CHEMICAL REACTIVITY 1-45
A. Environmental and Use Associated Reactions .... 1-45
B. Aspects with Biological Inplication 1-45
VIII. BIOLOGY
A. Absorption, Excretion, Growth, and Nutrition. . . . 1-48
1. Humans 1-48
2. Nonhuman Mammals 1-48
3. Plants 1-49
4. Microorganisms 1-51
B. Biochemistry 1-51
1. Humans 1-51
2. Nonhuman Mammals 1-53
3. Nonmammalian Vertebrates 1-56
4. Plants 1-56
5. Microorganisms 1-58
C. Therapeutic Uses 1-59
1. Humans 1-59
2. Nonhuman Mammals 1-60
3. Plants 1-60
IX. ENVIRONMENTAL EFFECTS 1-62
A. Environmental Content, Transport, Contamination . . 1-62
B. Bioaccumulation and Content 1-64
1. Human 1-64
2. Mammals 1-65
3. Plants . 1-65
11.
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BORON
TABLE OF CONTENTS
(Can't)
Page
X. TOXICITY 1-66
A. Humans 1-66
1. Acute Toxicity 1-66
2. Chronic Toxicity 1-67
B. Mammals 1-68
1. Acute Toxicity 1-68
2. Chronic Toxicity 1-69
3. Teratogenicity 1-72
4. Allergic Reactions and Sensitization 1-73
5. Behavioral Effects 1-73
6. Carcinogenicity 1-73
C. Nonmanmalian Vertebrates 1-73
D. Invertebrates 1-74
E. Plants 1-77
F. Microorganisitis 1-84
G. Results of Personal Contacts with Medical Personnel 1-84
XI. CURRENT REGULATIONS AND EFFECTS LEVELS . 1-86
A. Toxicity Levels 1-86
B. Transportation and Handling Regulations 1-86
C. Foreign Regulations 1-87
XII. STANDARDS 1-88
XIII. SUMMARY AND CONCLUSIONS 1-89
A. Summary 1-89
B. Conclusions 1-90
C. Reocmrnendations 1-90
111.
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KR/AR INC.
BORON
UST OF TABLES
Page
1. Products and Producers . 1-2
2. Prices of Boron Minerals and Chemicals 1-13
3. Physical Properties 1-14
4. Production of Borates in the United States as of 1972 . . . 1-18
5. Uses 1-30
6. Emission Factors 1-38
7. Boron Emissions by Source, 1972 1-38
8. Relative Stabilities of Boron Hydrides 1-46
9. Diagnostic Criteria for Boron Nutrition of Field and Vegetable
Crops Based upon Hot Water Extraction of Soil Boron . . . 1-50
.10. Toxic Boron Concentrations of Saturation Extracts for
Sensitiw, Semitolerant Crop Species 1-78
11. Plant Growth as Affected by Boron 1-79
12. Symptoms of Boron Toxicity 1-82
IV.
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BORON
LIST OF FIGURES
Page
1. Location of Borate (deposits in California, Nevada and Oregon . 1-17
2. Borax production from ore . 1-20
3. Borax manufacture from Searles Lake brine 1-22
4. Anhydrous Borax process 1-23
5. Boric acid manufacture 1-25
6. Boric acid manufacture 1-26
7. Distribution of Boron uses 1-29
8. Boron concentration in plant tissues related to concentration
in soil solution . . 1-52
9. Effect of Boron concentration on plant growth 1-76
v.
-------
Volume I
Preliminary Investigation of Effects
on Environment of Boron and Its Compounds
FOREWORD
This is Volume I of a series of six reports on the environmental
effects of boron, indium, nickel, selenium, tin, and vanadium and their
conpounds. The information is based on literature reviews, direct con-
tact with representatives of companies involved in the production or
use of the materials, and consultation with knowledgeable individuals
from industry, academic institutions and the Federal Government.
-------
\R INC.
1-2
I. BORON INDUSTRY IN THE UNITED STATES
A. Producers and sites
Table I lists commercially significant chemical products and the
companies involved. For this study significant is defined as production
exceeding 1/2 metric ton or $1,000 value. Other materials may also be included
in the discussion because of their unusual properties, such as toxicity, or
their anticipated future significance.
Table 1
Boron Products and Producers
(1)
Producer
Chemical
Aluminum diboridc
Ammonium borate
(Ammonium acid tetraborate)
Ammonium fluoborate
(Ammonium borofluoride)
Antimony fluotorate
Barium borotunqstate
Boric acid (Boracic
acid)
Boric acid esters
Boron
Company, subordination
Ventron Corp., Alfa Products Div.
U.S. Borax & Chem. Corp.
Allied Chem. Corp.
Specialty Chems. Div.
Kawecki Beryloc Indust., Inc.
Kewanee Oil Co., Harshaw Chem. Co.,
Indust. Chems. Dept.
Allied Chem. Corp.
Specialty Chems. Div.
Harstan Chem. Corp.
City Chem. Corp.
Allied Chem. Corp.
Specialty Chems. Div.
Kerr-McGee Corp.
Kerr-McGee Chem. Corp., subsid.
Stauffer Chem. Co.
Indust. Chem. Div.
U.S. Borax & Chem. Corp.
U.S. Borax & Chem. Corp.
Belmont Smelting & Refining
Works, Inc.
Fairmount Chem. Co., Inc.
Kawecki Berylco Indust., Inc.
Location
Beverly, Mass.
Wilmington, Del.
Marcus Hook, Pa.
Boyertown, Pa.
Cleveland, Ohio
Marcus Hook, Pa.
Brooklyn, N.Y.
Jersey City, N.J.
Marcus Hook, Pa.
Trona, Calif.
San Francisco, Calif.
Wilmington, Calif.
Boron, Calif.
Brooklyn, N.Y.
Newark, N.J.
Boyertown, Pa.
-------
INC.
1-3
Table 1 (Con't)
Itoron Products and Producers'
Producer
(1)
Chemical
Boron (Con't)
Boron carbide
Boron fluoride-
cthylamine complex
(Ethyl amine boron
trifluoride)
Boron fluoride
orthophosphoric acid
Boron nitride
Boron oxide
Boron phosphate
Boron phosphide
Company, subordination
Kerr-McGee Corp.
Kerr-McGee.Chem. Corp., subsid.
Mine Safety Appliances Co.
Gallery Chem. Co., div.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp.,
Ventron Corp.
Chems. Div.
Apache Chains., Inc.
Fainrount Chem. Co., Inc.
Kawecki Berylco Indust., Inc.
Norton Co.
Ventron Corp.
Alfa Products Div.
Kewanee Oil Co.
Harahaw Chem. Co., div.
Indust. Chems. Dept.
Ozark-Mahoning Co.
Kewanee Oil Co.
Harshaw Chem. Co., div.
Indust. Chems. Dept.
The Carborundum Co.
Refractories and Electronics Div.
Fairmount Chem. Co., Inc.
Kawecki Berylco'Indust., Inc.
Ventron Corp.
Alfa. Products Div.
Allied Chem. Corp.
Specialty Chems. Div.
Eagle-Picher Indust., Inc.
Electronics Div.
Stauffer Chem. Co.
Indust. Chem. Div.
Ventron Corp.
Alfa Products Div.
Ventron Corp.
Alfa Products Div.
Location
Henderson, Nev.
Gallery, Pa.
subsid. Anaheim, Calif.
Wood Ridge, N.J.
Rockford, 111.
Newark, N.J.
Boyertown, Pa.
Worcester, Mass.
Beverly, Mass.
Cleveland, Ohio
Tulsa, Okla.
Cleveland, Ohio
Latrobe, Pa.
Newark, N.J.
Boyertown, Pa.
Beverly, Mass.
Marcus Hook, Pa.
Miami, Okla.
Quapaw, Okla.
San Francisco, Calif.
Beverly, Mass.
Beverly, Mass.
-------
fAK INC.
Chemical
Boron tribromide
Boron trichloride
Boron trifluoride
Table 1 (Can't)
Boron Products and Producers
Producer
(1)
Boron trifluoride ethyl
ether conplex
Company, subordination
Eagle-Picher Indust., Inc.
Electronics Div.
Kerr-McGee Corp.
Kerr-McGee Chem. Corp., subsid.
Allied Chem. Corp.
Specialty Chems. Div.
Kerr-McGee Corp.
Kerr-McGee Chem. Corp., subsid.
Allied Chem. Corp.
Specialty Chems. Div.
Kewanee Oil Co.
Harshaw Chem. Co., div.
Indust. Chems. Dept.
Allied Chem. Corp.
Specialty Chems. Div.
1-4
Location
Miami, Okla.
Quapaw, Okla.
Henderson, Nev.
Marcus Hook, Pa.
Henderson, Nev.
Marcus Hook, Pa.
Cleveland, Ohio
Cleveland, Ohio
Marcus Hook, Pa.
Boron trifluoride-
phenol conplex
Allied Chem. Corp.
Specialty Chems. Div.
Marcus Hook, Pa.
Boron triiodide
Ventron Corp.
Alfa Products Div.
Beverly, Mass.
Boroxines (unspecified)
Calcium borate
Calcium boride
(calcium hexaboride)
Chromium boride (mono)
Chromium fluoborato
Cobalt borate
(Cobaltous borate)
Cobalt fluoborate
(Cobaltous fluoborate)
Mine Safety Appliances Co.
Gallery Chem. Co., div.
Ttenneco Inc.
Tenneco Oil Co., Div.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp., subbid.
Molybdenum Corp. of America
Chains, and Pare Earth Div.
Ventron Corp.
Alfa Products Div.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp.
Ventron Corp., Alfa
Products Div.
Allied Chem. Corp.
Specialty Chems. Div.
The Shepherd Chem. Co.
Harstan Chem. Corp.
Ventron Chem. Corp.
Alfa Products Div.
Gallery, Pa.
Death Valley
Junction, Calif.
Anaheim, Calif.
Washington, Pa.
Beverly, Mass.
*
Anaheim, Calif.
Beverly, Mass.
Marcus Hook, Pa.
Cincinnati, Ohio
Brooklyn, N.Y.
Beverly, Mass.
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'AH INC.
Table 1 (Can't)
1-5
,(1)
Boron Products and Producers
Producer
Chemical
Copper borate
(Cupric borate)
Copper fluoborate
(Cupric fluoborate)
Indium fluoborate
Iron borate
(Ferric borate)
Iron fluoborate
(Ferrous fluoborate)
Lead borate
Lead fluoborate
(Plumbous fluoborate)
Lithium borohydride
Lithium fluoroborate
Magnesium borate
Magnesium fluoborate
Company, subordination
City Chem. Corp.
The Shepherd Chem. Co.
Allied Chem. Corp.
Specialty Chems. Div.
liars tan Chem. Corp.
Kewanee Oil Co.
Harshaw Chem. Co.
Indust. Chems. Dept.
Allied Chem. Corp.
Specialty Chems. Div.
Harstan Chem. Corp.
The Indium Corp, of America
City Chem. Corp.
Allied Chem. Corp.
Specialty Chems. Div.
Harstan Chem. Corp.
Humphrey Chem. Corp.
The Shepherd Chem. Co.
Allied Chem. Corp.
Specialty Chems. Div.
Harstan Chem. Corp.
Kewanee Chem. Co.
Harshaw Chem. Co.
Indust. Chems. Dept.
Mine Safety Appliances Co.
Gallery Chem. Co.
Ventron Corp.
Alfa Products Div.
Chems. Div.
Foote Mineral Co.
Ozark-Mahoning Co.
Ventron Corp.
Alfa Products Div.
The Shepherd Chem. Co.
Allied Chem. Corp.
Specialty Chems. Div.
Kewanee Oil Co.
Harshaw Chem. Co.
Indust. Chems. Dept.
Location
Jersey City, N.J.
Cincinnati, Ohio
Marcus Hook, Pa.
Brooklyn, N.Y.
Cleveland, Ohio
Cleveland, Ohio
Marcus Hook, Pa.
Brooklyn, N.Y.
Utica, N.Y.
Jersey City, N.J.
Marcus Hook, Pa.
Brooklyn, N.Y.
Edgewcod Arsenal, Md.
Cincinnati, Ohio
Marcus Hook, Pa.
Brooklyn, N.Y.
Cleveland, Ohio
Gallery, Pa.
Beverly, Mass.
Exton, Pa.
Tulsa, Okla.
Beverly, Mass.
Cincinnati, Ohio
Marcus Hook, Pa.
Cleveland, Ohio
-------
:R/AR IMC,
Chemical
Manganese borate
(Manqanous borate)
Manganese boride
Manganese fluoborate
(Manganous fluoborate)
Molybdenum boride, mono
, di-
Nickel fluoborate
(Nickelous fluoborate)
Table 1 (Can't)
l'3oron Products and Producers
(1)
1-6
Niobium boride
(Niobium dibbride)
Phosphine boranes
Potassium borohydride
Potassium fluoborate
Producer
Conpany, subordination
Chemetron Corp., Chains.
Group, Inorganic Chems. Div.
Gen. Metallic Oxides Co.
The Shepherd Chem. Co.
Molybdenum Corp. of America
Chems. and Rare Earth Div.
City Chem. Corp.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp.
Allied Chem. Corp.
Specialty Chems. Div.
American Can Co.
M&T Chems. Inc.
Harstan Chem. Corp.
Kewanee Oil Co.
Harshaw Chem. Co.
Indust. Chems. Dept.
Ozark-Mahoning Go.
Ventron Corp., Alfa
Products Div.
Kawecki Beryloo Indust., Inc.
U.S. Borax & Chem. Corp.
U.S0 Borax Research Corp.
Ventron Corp.
Alfa Products Div.
Mine Safety Appliances Co.
Gallery Chem. Co.
Mine Safety Appliances Co.
Gallery Chem.' Co., div.
Ventron Corp.
Chems. Div.
Allied Chem. Corp.
Specialty Chems. Div.
Borden Inc.
Borden Chems. Div.
Smith-Douglass
Kawecki Berylco Indust.,
Kewanee Oil Co.
Harshaw Chem. Co. div.
Indust. Chems. Dept.
Inc.
Location
Cleveland, Ohio
Jersey City, N.J.
Cincinnati, Ohio
Washington, Pa.
Jersey City, N.J.
Anaheim, Calif.
Marcus Hook, Pa.
East Chicago, Ind.
Brooklyn, N.Y.
Cleveland, Ohio
Tulsa, Okla.
Beverly, Mass.
Boyertcwn, Pa.
i
Anaheim, Calif.
Beverly, Mass.
Gallery, Pa.
Gallery, Pa.
Beverly, Mass.
Marcus Hook, Pa.
Plant City, Fla.
Boyertown, Pa.
Cleveland, Ohio
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'MjAR INC.
Table 1 (can't)
Boron Products and Producers
(1)
1-7
Producer
Chemical
Potassium fluoborats
(con't)
Rubidium borohydride
Silicon hexaboride
(Hexaboron silicide)
Silicon tetraboride
Silver fluorborate
Sodium borodeuteridc
Sodium borohydride
Sodium fluoborate
(Sodium borofluorido)
Sodium Octaborate
Sodium Pentoboratc
Sodium perborate,
monohydrato
Company, subordination
Ozark-Mahoning Co.
Ventron Corp.
Alfa Products Div.
Ventrcn Corp.
Alfa Products Div.
Ventron Corp.
Alfa Products Div.
Mallinckrodt Chem. Vforks
Indust. Chems. Div.
Ventron Corp.
Alfa Products Div.
Allied Chem. Corp.
Specialty Chems. Div.
Harstan Chem. Corp.
Ozark-Mahoning Co.
Ventron Corp.
Alfa Chems. Div.
Ventron Corp.
Alfa Products Div.,
Chains. Div.
Mine Safety Appliances, Co.
Gallery Chem. Co., div.
Ventron Corp.
Alfa Products Div.
Chems. Div.
Allied Chem. Corp.
Specialty Chems. Div.
Kawecki Berylco Indust., Inc.
Kewanee Oil Co.
Harshaw Chem. Co., div.
Indust. Chems. Dept.
Ozark-Mahoning Co.
Ventron Corp.
Alfa Products Div.
U.S. Borax & Chem. Corp.
Kerr-McGee Corp.
Kerr-McGee Chem. Corp., subsid.
Corp.
Inorganic Chems. Div.
Location
Tulsa, Okla.
Beverly, Mass.
Beverly, Mass.
Beverly, Mass.
St. Louis, Mo.
Beverly, Mass.
Marcus Hook, Pa.
Brooklyn, N.Y.
Tulsa, Okla.
Beverly, Mass.
Beverly, Mass.
Beverly, Mass.
Gallery, Pa.
Beverly, Mass.
Beverly, Mass.
Marcus Hook, Pa.
Boyertown, Pa.
Cleveland, Ohio
Tulsa, Okla.
Beverly, Mass.
Wilmington, Calif.
Trona, Calif.
Buffalo, N.Y.
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'A R INC.
Table 1 (Can't)
F3oron Products and Producers
(1)
1-8
Producer
Chemical
Sodium perborate
tetrahydrate (Sodium
metaborate peroxyhydrate)
Sodium tetraborate (Borax)
(Produced as Anhydrous
Borax, Borax decahydrate,
and Borax pentahydrate)
Sodium tetraphenylboror
(Sodium tetraphenylborate)
Tantalum diboride
Tin fluoborate
(Stannous fluoborate)
Titanium diboride
(Titanium boride)
Tunqsten monoboride
Vanadium diboride
Zinc borate
Company, subordination
E. I. duPont de Nemours & Co., Inc.
Indust. Chems. Dept.
Filo Color & Chem. Corp.
EMC Corp.
Inorganic Chems. Div.
Kerr-McGee Corp.
Kerr-MoGee Chem. Corp., subsid.
Occidental Petroleum Corp.
Searles Lake Chem. Co., subsid.*
Stauffer Chem. Co.
Indust. Chem. Div.
U.S. Borax & Chem. Corp.
Allied Chem. Corp.
Specialty Chems. Div.
Richardson-Msrrell, Inc.
J.T. Baker Chem. Co., subsid.
Kawecki Berylco Indust., Inc.
Allied Chem. Corp.
Specialty Chems. Div.
Harstan Chem. Corp.
Kewanee Chem. Corp.
Harshaw Chem. Co.
Indust. Chems. Dept.
Kawecki Berylco Indust., Inc.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp.
Ventron Corp.
Alfa Products Div.
U.S. Borax & Chem. Corp.
.U.S. Borax Research Corp.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp.
Ventron Corp.,
Alfa Products Div.
Hunphrey Chem. Corp.
Maryland Zinc & Research Co.
U.S. Borax & Chem. Corp.
Ventron Corp.
Alfa Products Div.
Location
Memphis, Term.
Newark, N.J.
Buffalo, N.Y.
Trona, Calif.
Searles Lake, Calif.
West End, Calif.
Boron, Calif.
Marcus Hook, Pa.
Phillipsburg, N.J.
Boyertown, Pa.
Marcus Hook, Pa.
Brooklyn, N.Y.
Cleveland, Ohio
Boyertown, Pa.
Anaheim, Calif.
Beverly, Mass.
Anaheim, Calif.
Anaheim, Calif.
Beverly, Mass.
Edgewood Arsenal, Md.
Cockeysville, Md.
Wilmington, Calif.
Beverly, Mass.
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KK/AR INC,
1-9
Chemical
Zinc fluoborate
Zirconium diborido
(Zirconium boride)
Table 1 (Con't) «.
Boron Products and Producers
Producer
Company, subordination
Allied Chem. Corp.
Specialty Chems. Div.
Harstan Chem. Corp.
Kewanee Oil Co.
Harshaw Chem. Co.
Indust. Chems. Dept.
Mineral Research and Dev. Corp.
Ventron Corp.
Alfa Products Div.
Kawecki Berylco Indust. Inc.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp.
Location
Marcus Hook, Pa.
Brooklyn, N.Y.
Cleveland, Ohio
Concord, N.C.
Beverly, Mass.
Boyertown, Pa.
Anaheim, Calif.
Decaborane
Diborane
Octadecaborane
Pcntaboranc
BORANES (Inorganic)
Mine Safety Appliances Co.
Gallery Chem. Co., div.
Mine Safety Appliances Co.
Gallery Chem. Co., div.
G. D. Searle & Co.
Will Ross, Inc., subsid.
Matheson Gas Products, div.
Ventron Corp.
Alfa Products Div.
Mine Safety Appliances Co.
Gallery Chem. Co., div.
Gallery, Pa.
Gallery, Pa.
Cucamonga, Calif.
East Rutherford, N.J.
Gloucester, Mass.
Joliet, 111.
La Porte, Tex.
Morrow, Ga.
Newark, Calif.
Beverly, Mass.
Gallery, Pa.
ORGANIC BORON COMPOUNDS
Dimethylamine borone
Dioxaborii lanes
Mine Safety Appliances Co.
Gallery Chem. Co., div.
U.S. Borax & Chem. Corp.
Gallery, Pa.
Boron, Calif.
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I
W/AR INC.
1-10
Table 1 (Can't)
(1)
iBoron Products and Producers
Producer
Chemical
Hexylene borate
Morpholine borane
Company, subordination
Kipers Labs.
Ventron Corp.
Alfa Products Div.
Chems. Div.
Sodium tetraphenylkoron Allied Chem. Corp.
(Sodium tetraphenyllxirate) Specialty Chems. Div.
Richardson-Merrell, Inc.
J.T. Baker Chem. Co., subsid.
tert-Butylamine borane
Trialkyl boranes
Tributyl borate
(Butyl borate)
Tri-m, p-cresyl borate
Tricyclohexyl borate
Triethanolamine borate
TriethyIborane
(Triethylborine)
Triethyl borate
(Tricthoxy borane)
Triethyloxonium tetra-
fluoroborate
Tri (hexylcne glycol)
biborate
Tri isobutyIborane
Triisopropyl borate
Mine Safety Appliances Co.
Gallery Chem. Co., div.
Ventron Corp.
Alfa Products Div.
Stauffer Chem. Co.
Specialty Chem. Div.
Anderson Dev. Co.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp., subsid.
Anderson Dev. Co.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp., subsid.
Mine Safety Appliances Co.
Gallery Chem. Co., div.
Texas AlkyIs, Inc.
Ventron Corp.
Alfa Products Div.
Anderson Dev. Co.
U.S. Borax & Chem. Corp. y
U.S. Borax Research Corp., subsid.
Ventron Corp.
Alfa Products Div.
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp., subsid.
Texas AlkyIs, Inc.
Anderson Dev. Co.
Stauffer Chem..Co.
Specialty Chem. Div.
Ventron Corp.
Alfa Products Div.
Location
Santa Ana, Calif.
Beverly, Mass.
Beverly, Mass.
Marcus Hook, Pa.
Phillipsburg, N.J.
Gallery, Pa.
Beverly, Mass.
Vfeston, Mich.
Adrian, Mich.
Anaheim, Calif.
Adrian, Mich.
Anaheim, Calif.
Gallery, Pa.
Deer Park, Tex.
Beverly, Mass.
Adrian, Mich.
Anaheim, Calif.
Beverly, Mass.
Anaheim, Calif.
Deer Park, Tex.
Adrian, Mich.
Weston, Mich.
Beverly, Mass.
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/
KRfAR INC,
1-11
Table 1 (Cant) »»
Boron Products and Producers
Producer
Chemical
Trinethoxyboroxine
(Methyl metaborate)
Tri-2-methoxyethyl borate
Trimethyl borate
(Methyl borate)
(Trimethoxyborine)
Trimethyl borate-
methanol azeotrope
Company/ subordination
Mine Safety Appliances Co.
Gallery Chem. Co., div.
Stauffer Chem. Co.
Specialty Chem. Div.
Anderson Dev. Co.
Anderson Dev. Co.
Mine Safety Appliances Co.
Gallery Chem. Co., div.
Stauffer Chem. Co.
Specialty Chem. Div.
Ventron Corp.
Chems. Div.
Ventron Corp.
Alfa Products Div.
Location
Gallery, Pa.
Weston, Mich.
Adrian, Mich.
Adrian, Mich.
Gallery, Pa.
Wsston, Mich.
Danvers, Mass.
Beverly, Mass.
* Scheduled late 1974
-------
1-12
B. Costs and Physical Properties of Important Boron Compounds
The prices of selected boron minerals and chemicals are given
in Table 2. The materials listed are the most commercially significant
of the boron family. Another common factor is that their most important
applications are based on their boron oxide (B^O.,) content. In many
instances these materials are interchangeable. In 1970 anhydrous borax
was the least expensive in B-CL content, but under 1974 prices borax
pentahydrate is cheapest. Physical properties of the most important
boron compounds are presented in Table 3.
A
Many metals form borides of various compositions. Most are
specialty materials only, but a few are used in the aerospace industry. In
general, environmental effects are minimal.
Many of the netal borides oxidize in air considerably below the
listed melting points. This limits the significance of the high melting points
(e.g., vanadium and tungsten borides oxidize in air at less than 1200C versus
listed melting points of 2000 - 3000C. As a rule the melting point of a parti-
cular boride composition increases with the atomic weight in a Group but de-
creases with increasing atomic weight in each period. Hafnium and tantalum
borides therefore have the highest malting points - 3250 ± 100C and 3400 ± 50C.
-------
Table 2
(2)
Prices of Boron Minerals and Chemicals
Borax
decahydrate
Borax
pentahydrate
Anhydrous
borax
Boric
acid
Boric
oxide
bags
buLk
bags
.bulk
bags
bulk
bags
bulk
bags
bags
bulk
B_0,
Content , % .
36.3
36.3
47.56
47.56
68.5
68.5
56.24
56.24
99.9
95-96
95-96
Price in Carlots, f.o.b. Plant
1970 Prices (?)
per metric ton per unit B?C
53
45
68
60
93
84
113
104
360
159
149
1.46
1.24
1.43
1.26
1,
1,
2,
1.
3.
1,
36
26
01
83
60
67
1974 Prices (5)
per metric ton per unit
73
60
86
73
159
145
169
148
573
2.01
1.65
-1.81
1.53
2.33
2.12
3.01
2.63
57.2
1.56
I
CO
-------
Table 3
Physical Properties
Chemical
Bcron
Sodium tetraborate
Decahydrate (Borax)
Sodium tetraborate
Pentahydrate
Sodium tetraborate
Anhydrous
Colemanite*
Boric Acid
Boric oxide
Boron trifluoride
Boron trichJ.oride
Sodium fluoborate
Potassium fluoborate
Anmonium fluoborate
Specific
Gravity
2 . ? 4 crys
2.37 amor
1.73
1.815
2.67
2.42-
2.43
1.435
15°C
2.46 crys
1.812 glass
2.99 g/1
(gas)
1 i**
1.349/1
4
2.4720
2.49820
Siting
Point
°C
23CO
75
120
-H20
741
—
169
to HBO2
460
-126.7
-107.3
si d
384
d350
Boiling
Point
°C
2550 sub
320
-10H20
—
1575
d
— " —
300
-1 1/2 H20
1860
-99.9
12.5
d
d
Solubility
Water
g/lOOcc °C
Insol.
2.01 g 0
170 g 100
22.65 g 65
52.3 8 100
1.05 8 0
8.79 8 40
^""^
6.3530
27.6100
inn
15. 7100
106 cold
d hot
d hot
10826
i nn
2101UU
0.44-mn
(• 0-7-LUU
D .^ /
Coiments
0.001% earth's crust
combined form only
Natural mineral
%D C\ 1C. "5
B_U^ — jo . J
Natural mineral
S B203- 47.5
% B.O - 68.5
2 3
Natural mineral
HBO
Ortho form
boron
trioxide
fumes in moist air
pungent odor
fumes in moist air
emits hydrogen chloride
Natural
avogadrite
1.871
15
subl
25
97
100
**Sp.Gr. at 11°C referenced to water at 4°C
-------
Chemical
Diborane
Boron (betra) carbide
Boron nitride
Specific
Gravitv
J-.1Q.
0.447
2.52
2.25
-11
-165.5
2350
subl ca
3000
Table 3 (Con't)
Physical Properties
Boiling
Point
°C
-92.5
73500
Solubility
Water
g/lOQcc °C
si. s, d
cold water
Conrnents
Boron
hydride
i cold, si d hot
i
Ol
-------
M/AR INC, 1-16
II. PRODUCTION
A. Natural Sources of Borates
The nap in Figure 1 shows the location of the significant borate
deposits in the United States. They produce virtually all of the raw materials
for the boron industry, in the U.S. Approximately 20% of the present production
stems from the utilization of Searles Lake brines. Significant colemanite (Table 3)
rtiining is also performed by Tenneoo. Total borate production by company and
location is presented in Table 4.'
B. Manufacturing Processes
1. Elemental Boron
Although widespread in nature boron occurs naturally only in
combined form. Elemental boron is not one of the more inportant commercial
forms of boron.
Three general techniques are used to prepare boron from its
compounds: (1) Chemical reduction with active elements, (2) Non-aqueous electro-
lytic reduction, and (3) Thermal decomposition. Beduction of boron compounds to
elemental boron has been carried out with magnesium, hydrogen, and many other
elements. Among the boron compounds used are borates, boron oxides, boron
halidas, fluoborates, and borohydrides. The most common method for producing
large amounts of elemental boron is the exothermic reduction (thermit reaction)
of boric oxide with magnesium. The product of this reaction, a finely-divided
powder known as "Moissum's boron" is amorphous as is boron produced from any
of the chemical reduction methods except for high temperatuie reduction by
hydrogen. The latter method, especially when involving hot filament reaction
of hydrogen with boron tribromide, has become a conventional means for obtaining
boron with purities of 99% and higher.
Electrolytic preparation of boron usually involves the passage of
a current through fused melts of boric oxide in potassium halides or oxides.
Electrolysis of potassium fluorborate-potassium chloride or potassium chloride-
sodium chloride melts is performed with a boron carbide anode. The purity of
the product obtained by these methods has been 87-99.8%. Direct electrolysis
-------
1-17
OREGON
>CHELCO(PRICEITE)
BORATE DEPOSITS IN OREGON
DISCOVERED AND WORKED DURING
EARLY PERIOD
LAKE
NEVADA
TEELS MARSH
RHODES MARSH
COLUMBUS MARSH
FISH LAKE VALLEY
SAN FRANCISCO
C ALIFORNIA
(BORAX CRYSTALS
MUD)FIRST
DISCOVERY OF
BORAX 1856
PRODUCTION 1864-1874
SEARLES L
, (BRINE)
' CURRENT SOURCE
SAM
BERNARD/NO
1COUNTY
DEPOSITS NOW ABANDONED
BUT WERE IMPORTANT
SOURCES DURING EARLY
STAGES
BARTLETT
(BRINE)
SMALL
PRODUCTION
1929-1953
TRONA
FRAZIER MOUNTAIN
DISTRICT (COLEMANITE)
PRODUCTION 1899-1907,
1911 -1913
KRAMER DISTRICT*BORON)-"
(BORAX AND KERNITE ORE)
MAIN SOURCE SINCE 1927
CAVE SPRING (VEINLETS OF SEARLESITE)
ACE CREEK DISTRICT (LAKE
DEPOSITS AND COLEMANITE) MAIN
SOURCE OF PRODUCTION 1915-1926
ILA C. MINE (COLEMANITE)
LARGEST PRODUCER IN 1912
ESTLEY-SHOSHONE MINE(ULEXITE
AND COLEMANITE) PRODUCTION
1915-1926
LANG (COLEMANITE)
PRODUCTION 1908-1923
WHITE BASIN(COLEMANITE)
PRODUCTION 1924-1962
CALLVILLE WASH
(COLEMANITE)
PRODUCTION 1921-1927
IR CORNERS
(COLEMANITE)
CALICO MOUNTAIN
DISTRICT {COLEMANITE)
PRODUCTION 1887-1907
Figure I
Location of Borate deposits
in
-------
1-18
Table 4
74)
Production of Borates in the United States
as of 1972
Company
U.S. Borax &
Chemical Corp.
Quantity
> 500,000 metric tons
as B^O, combined
capacity
23
annual ~
Location
Boron, California
Products
crude borax
refined borax
anhydrous borax
boric acid
boric oxide
Kerr-McGee
Chemical Corp.
Stauffer
Chcm. Corp.
Tenneco Oil
Company
Searles Lake
Chem. Co.
Subsid. of
Occidental
Pet. Corp.
approx. 100,000
metric tons B-O,
capacity :
25-30,000
metric tons
capacity
B2°3
Searles Lake,
Trona, California
Searles Lake,
Trona, California
Design-150,000 metric
tons raw colemanite
Design- 70,000 metric
tons calcined colemanite
Production: metric tons
calcined colemanite
6,300 metric tons
24,000 metric tons*
Furnace Creek,
California
Searles Lake,
Calif.
boron compounds
boron compounds
colemanite ore
calcined colemanite
borax
'Scheduled late 1974. Miy be indefinitely postponed.
-------
VKR/A
\f
fAR IMC, 1-19
of alkali or alkaline earth berates yields a product of J.ower purity.
Electrolysis has not been an important commercial method for the production
of elemental boron.
Boron compounds that can be decomposed to high purity forms of
boron are limited to the halides and hydrides. Boron tribromide, boron
triiodide, and boron hydrides (from diborane to decaborane) have been de-
composed on a wide variety of substrates ranging from glass to tungsten
at temperatures from 800 to 1500C.
2. Borax
The entire U.S. production of borax is carried out in the desert
areas of California by two processes. The borax ore is either mined and
extracted or, as in Searles Lake, taken from the brines by the Trona process.
a. The Mining Process
The mining operation starts at the larger, deep open pit
mines. Explosives and electric shovels break up the ore. An automatic ore
conveyor belt, starting in the pit at the 225 foot level, then carries the
ore to the surface and nearby concentrating and refining plants. This natural
material is principally borax (sodium tetraborate decahydrate) and kernite
(sodium tetraborate tetrahydrate). Both of these minerals must be processed
to remove impurities and produce the primary commercial compounds:
(1) sodium tetraborate decahydrate;
(2) sodium tetraborate pentahydrate; and
(3) anhydrous sodium tetraborate.
The refining process begins by crushing and dissolving the ore to remove the
impurities. The ore is next thickened, recrystalized and dried. Some of the
material is crystallized and produced as decahydrate,, some as pentahydrate.
The remainder is fused in a furnace to the anhydrous state. (Figure 2) Waste-
water treatment consists of percolation-proof evaporation ponds„ Tl >ei~ i •* no
plant effluent and the intake water and wastewater sent to the evaporation
ponds are thoroughly monitored. '
-------
BORAX ORE
I-10
CRUSHER
WATER-
-m
, RECYCLE
< MOTHER
/ LIQUOR
WASH
WATER
DIS80LVER
THICKENER
CRYSTALLIZER
CENTRIFUGE
•WASTE WATER
'CONTACT COOLING
.WATER
DRYING
AND
SCREENING
;TS
»VENT
Borax production from ore
-------
KR/Alt INC. 1-21
b. Trona Process
Brine from Searles Lake is processed to produce borax and
other chemicals at two highly integrated facilities located at Trona, Cali-
fornia. The recovery processes and raw materials are unique to this location.
The area is desert land immediately adjacent to Searles Lake, a large residual
evaporate salt body filled with saline brines. The brines ore pumped into
the processing facilities. The procedures used to yield crude borax are
shown in Figure 3. The residual brines, salts, end liquors, and added process
waters are returned to the salt body to maintain the saline brine volume.
The recycle liquors are actually the medium for producing the raw material
for the processes so there is not a "discharge". The crude borax combined
with borax solids from the separate carbonation-refrigeration process, is
purified by recrystallization, dried, and packaged.
3. Anhydrous Borax
Anhydrous borax is either made from coarse granular decahydrate
or from wet decahydrate from the centrifuges. Figure 4 shows a diagram of
one process used for the manufacture of anhydrous borax. Two features of
this process deserve comment. First, the dust from the calciners is recovered
and reprocessed and second, the product can be obtained in either the crystalline
or annrphous form. Commercial anhydrous borax is mainly the latter type.
4. Boric Acid
lioric acid is made by reacting borax and sulfuric acid. Since the
U.S. sources of: borax production are in the California desert areas, that is
where the boric acid production is located. Approximately 70 percent of U.S.
production of boric ncid is based on borax from mined ore, the remainder cones
from borax extracted from lake brines.
To produce boric acid from the mined ore borax tetraborate and
sulfuric acid are reacted and the resulting slurry is vacuum filtered,, The
solid boric acid is dissolved in water, filtered, reprecipitated in air coolerss
separated by oentrifugation, washed, dried, and packaged. The original liquor
is recycled with excess liquor wasted because of water imbalance. Diagrams of
-------
1-22
RAW
BRINE
HEAT EXCHANGER
TRIPLE EFFECT EVAPORATORS
CRYSTALLIZER
(
!
SALT SEPARATOR |
SOLIDS
TO OTHER
PROCESSES
AMMONIA
COOLING
WATER•
STEAM •
VACUUM COOLER
CONE SETTLER
AND FILTER
BORAX
LIQUOR
DORR THICKENER
FILTER
DISSOLVER
FILTER
DRYER
KCI TO OTHER
PLANT USE
CRYSTAi
' ' |
> DEPLETED LIQUOR
KCI PRODUCT
x RETURN TO
/BRINE SOURCE
DEPLETED LIQUOR
VACUUM CRYSTALLIZER
CENTRIFUGE
DRYER
Figure 3
Borax manufacture from Seariss Lake
CRUDE
BORAX
-------
BORAX
CALCINERS
OUST
WATER—C=^
FUSION
FUKNACE
WATER-
COOLED
ROLLS
CRUSHING
AM)
SCREENS
AMORPHOUS
PRODUCT
MOLDS
J3WSTALUKE
4
K>
CO
-------
KR/AR INC. i-24
processes used at two installations are shown in Figures 5 and 6. '
5. Boric oxide (B203, boron trioxide)
Boric oxide may be prepared by the fusion of boric acid. If
this method is used, tlie boric oxide generally contains up to 0.5% water,
depending on the temperature and other fusion parameters. If the temperature
is at least 1300C, the product is nearly anhydrous. If ground boric acid
is heated slowly to 260-27OC in a 1 to 2 mm mercury vacuum and maintained
at this temperature for six hours, an active, practically anhydrous form-of
boric oxide is produced. This boric oxide dissolves very rapidly in water
with a hissing sound.
6. Boron tri fluoride (BFj
Two processes are in general commercial use for the production of
boron trifluoride. In one, borax is added slowly to hydrofluoric acid to
produce water and Na20(BF3)4. The latter, "fluoborax", is treated with cold
fuming sulfuric acid in a generator. The reaction mixture is slowly heated.
The generation of boron trifluoride is controlled by the temperature. This
method can also be used by mixing boric acid with ammonium bifluoride, in
which case the boron trifluoride complex from which boron trifluoride is gener-
ated is (NHJJXBF-) ... The other commercial process is to react fluorosulfonic
4 £ j (8)
acid with boric acid.
7. Boron trichloride
Boron trichloride is commercially produced by several different
methods. One method is by chlorinating a mixture of finely divided carbon and
boric oxide at 870 to 980 C. A second method is heating boric oxide with
sodium, potassium, or lithium chloride at 800 to 1000C. Between 500 and 1500C
sodium borofluoride and magnesium chloride can also be combined to produce
/g\
boron trichloride.
8. Diborane and higher boranes (pentaborane, etc.)
Diborane is prepared by the reaction of boron trichloride with
lithium aluminum hydride in anhydrous diethyl ether or with lithium hydride,
sodium borohydride, or sodium trimethoxyborohydride in diethyl ether solution.
(8)
'itie higher boranes ore produced by the controlled pyrolysis of diborane.
-------
1-25
SULFURIC ACID
BORAX
REACTOR
RECYCLE
LIQUOR
WASTE
LIOUOR
FILTER
fir CAKE
REPULPER
AND
REDISSOLVER
FILTER
AIR COOLER
CENTRIFUGE
TECHNICAL GRADE
BORIC ACID PRODUCT
Boric acid
-.WASTE
LIOUOR
.WASH DOWN
WASTE
-------
SULFURIC
ACH>
FINE
BORAX
REACTION
TANK
TANK
S'ENT
TO OTHER
\«»TER VAPOR
t
VACUUM
CRYS1ALLJZER
CENTRIFUGE
SFENT LIQUOR
WATER -
STEAM-
DRTER
CRU3E
AOD
PROiXICT
DSSSGLVER
RERNSD
Figure 6
Boric acid manufacture
-------
I
KR/AR INC. 1-27
9. Refractory boron compounds (metal borides, boron carbide,
and boron nitride)
The most extensively used methods for producing refractory
boron compounds are the following:
(a) The direct reduction of metallic boron with the metal.
(b) The use of reducing agents such as aluminum, silicon,
magnesium, carbon, or boron and boric oxide-metal oxide
mixtures.
(c) The electrolysis of fused-salt mixtures containing metal
oxides and boron oxides.
(d) Deposition from the vapor phase.
The first, and the most common method for making boron carbide,
is .reacting boron oxide and carbon at 1400-2300C. The use of finely divided
carbon such as carbon black speeds the reaction.
The cubic crystal form of boron nitride is made by the synthetic
diamond production techniques of high temperatures and high pressures. At
this point, its commercial significance is fairly limited; however, it is
available.
-------
1-28
\R INC.
IIT. USES OF BORON COMPOUNDS
A. The majority of boron used in the United States is in the form of
borax (Na?B 0•10H-0). Figure 7 presents an overall picture of the uses of
boron and its compounds. A detailed summary of current boron usage is presented
in Table 5.
-------
1-29
ENAMELS, FRITS
GLAZES!
26%
MINOR USES
15%
SOAPS
CLEANSERS
HERBICIDES
\
FERTILIZER
40-45%
GLASS MANUFACTURE
Figure 7
Distribution of Boron uses
-------
Borcn
Conpound
Elemental
boron
Use
Steel
Non ferrous
metallurgy
Table of Uses
Table 5.
(4,5,7,8,9)
Purpose
Deoxidizing and alloying element
in the form of ferroboron alloy
Increases hardness of steel
Alloying agent
Gormen ts
Dissolves rapidly in molten steel
Amount used under 0.003%
Boron concentration varies from
20% to less than 0.1%
Borax
Boric Acid and
Anhydrous Borax
Manufacture of
borosilicate and
similar glasses
Optical glass
Gives desired properties including
the index of refraction
BO- essential to impart the low
coefficient of expansion required
For glass, to maintain the proper
acid-alkali ratio borax is supple-
mented with substantial quantities
of boric acid
Borax
Glass containers
Novelty ware
Structural glass
Flat glasses
Cleaning room of
enamel plants
Aids in the melting, finishing, and
forming operation
Enhances color, durability, scratch
resistance and strength of finished
product
Used as an alkali
Borax only used in small amounts
Steel and steel
plating
Leather industry
Detergent, hand
cleaner, face
cream, cosmetics
Final dip serves as a rust preventative
and aid in bonding the first coat to
the iron body.
Mild alkali and preservative
Mild alkali and buffer
Used alone or in conjunction with
other materials.
Used blended with soap
Bacterial characteristics and easy
solubility in water
-------
Table of Uses
Boron
Ccrpound
Borax and
Anhydrous
Borax
Borax and
Boric Acid
Use
Manufacture of
vitreous enamel
frits
Pottery glazes
Colored glass for
decoration and
marking purposes
Other
Table 5
(Con't)
Purpose
Same benefits as in alass manufacture
Comments
Improves the resistance to fire of
textiles, lurrber and other conbus.tible
materials
Treatment for epilepsy, soothing oint-
ments, rectal and colonic irrigations
and vaginal douches
Wood is impregnated under pressure
with preservatives such as pentachloro-
phenol and borate solution for fire
proofing in a single pass through a
pressure chamber
Mildly antiseptic and antifungal,
but not sufficiently so for most
purposes
Boric Acid
Manufacture of metal
berates, hydrids,
master alloys, and as
a catalyst in many
organic reactions
Use as a catalyst in air oxidation
of hydrocarbons accounted for more
than 3% of overall boron consumption
Boron
Trifluoride
Petroleum Refining
Organic synthesis
Catalyst in isomerization, alkylation,
polymerization, esterification, con-
densation, cyclization, hydration, de-
hydration, sulfonation, desulfurization,
nitration, halogenation, oxidation and
acylation
Catalyst in the Friedel-Crafts type of
reaction, the synthesis of saturated
hydrocarbons, olefins, alcohols, thiols,
ketones and ethers, in cracking hydro-
carbons
i
OJ
-------
Table of Uses
Table 5.
(Can't)
Boron
Compound
Boron
Trlfuoride
Use
Preparation of
boranes
Magnesium alloy
castings
Puroose
Conments
Diborane is the only commercial
borane of importance being pro-
duced at oresent
Protects molten magnesium and alloys
from oxidation during casting and a
flux for soldering magnesium
Boron
Trichloride
Refining aluminum,
magnesium, zinc,
and copper alloys
Soldering flux for
alloys of aluminum,
iron, zinc, tung-
sten and monel.
Aluminum castings
Removes nitrides, carbides and oxides
from the molten metal
Removes occluded gases, such as
gen, nitrogen, carbon monoxide,
nitrides, carbides and oxides
hydro-
Manufacture of
electrical resistors
Extinguishing mag-
nesium fires in
heating furnaces
High energy fuels
and rocket pro-
pellants
Catalyst
A source of boron for raising the
BTU value
Suggested use in the polymerization
of styrene
Grain growth of aluminum also retarded
making it more uniform
Improves the tensile strength and will
permit the remelting of the aluminum
without substantially changing the
grain structure
Uniform and lasting adhesive carbon
film can be put over a ceramic base by
a process that has been developed in-
volving the addition of boron tri-
chloride to benzene at high temperatures
Forms a magnesium chloride film that
smothers the fire by preventing air
from reaching the metal
GJ
NJ
Reportedly yields polymers with 3X the
molecular weight of those produced
with other catalysts
-------
Table of uses
Table 5.
(Can't)
Boron
Compound
Diborane
Use
Plastics Pro-
duction
Rubber Vulcanization
Other
Purpose
Catalyst for ethylene, styrene,
acrylic and vinyl polymerization
Reducing agent
Flame-speed acceleration
Inte mediate for high boron hydrides
Doping gas
Comments
Boron
Carbide
Grinding highly
abrasive material
Refractory usage
Jet aircraft parts, rocket chambers
and gas turbines
Self-bonding ability allows it to
be molded in graphite and pressed at
temperatures up to 2400C into
high-density, nonporous shapes
Negative thermal coefficient of
electrical resistance
Considered a semiconductor
Boron
nitride
High-teniperature
abrasive
Properties similar to boron carbide
and can be used for the sane purposes
When present in the cubic crystal form
more stable than diamond in air at
high temperatures
CO
CO
-------
/
KR/AR INC, i_34
B. Futupe and Potential Uses
The annual U.S. producticn of boron minerals and chemicals from raw
material supplies has increased steadily at a rate of six. to seven per cent
per year since the early 1960's. Roughly half of the boron produced is retained
for domestic consumption. No new or expanded uses of boron are anticipated to
effect the industry in the near future.
Elemental boron has found only limited use as a thermistor material,
on intrinsic semiconductor, a photoconductor and a heat-resistant infrared
window material. Tte main obstacle to these uses has been the lack of suitable
production and analytical techniques. Progress has been made, however, in
elemental boron purification technique. This should enable greater use of this
material in electronic and optical devices.
The demand for glass fibers should increase through the 1970's. In
part this will be due to the demand for auto tires, but to a considerably
greater extent increased demand can be attributed to the popularity of rein-
forced plastics. Colemanite is highly desirable in this application as a non-
sodium source of B,0^. One estimate is that the demand for glass fibers in
reinforced plastics would increase from 115.4 million kg in 1969 to 412.8 million
C2\
kg in 1975 and 757.5 million kg by 1980.v '
A potentially significant demand for borates, possibly colemanite,
as a substitute for fluorspar in the basic oxygen-furnace steel manufacturing
process has been under consideration for over five years. At the present time
this does not appear promising. The substitution of oolemanite for fluorspar
(4)
did not go beyond the pilot plan stage in ,1972.
Many companies have shown a great deal of interest in boron industry.
Many organic and inorganic boron monomers and polymers have been synthesized
and studied. So far no new large-volume boron-containing chemical has emerged
(2)
and none appears likely.
-------
KR/AR INC. 1-35
IV. CURRENT PRACTICES
Borax, colemanite, sodium tetraborate, the various forms of borax,
oolemanite and anhydrous borax (sodium tetraborate) are sold in bags, barrels/
and bulk. Boron trifluoride is included in the "List of Explosives and
Other Dangerous Articles". The Interstate Ccnnreroe Commission therefore
regulates its shipment by land, water, and rail. Boron trifluoride is classi-
fied as a nonflammable compressed gas and stored and shipped in I.C.C.-
approved compressed gas cylinders. Personnel handling boron trifluoride
should wear chemical safety goggles and rubber gloves. Gas masks approved
for acid gases or masks with an independent oxygen or air supply should be
available in case of emergency. The cylinders used for boron trifluoride
should be pretested for leaks with dry air and aqueous ammonia. Leaking con-
tainers of boron trifluoride which cannot be corrected should be discharged
in a hood and techniques for disposing acid gases utilized.
Boron trichloride is classified by the I.C.C. as a corrosive liquid
and is also considered "a dangerous article" in transport. On contact with
water or moist air it releases hydrochloric acid so chemical goggles, rubber
gloves, and rubber aprons should be used in handling. Leaky containers which
cannot be corrected should be disposed of using hood procedures for the
disposal of acid gases.
Diborane is classified by the Department of Transportation as a "Class A"
poisonous and flammable gas. Diborane and the higher boranes are classified
as "dangerous articles" in transport. They are shipped in cylinders pressurized
with a diluent gas such as hydrogen, argon, nitrogen or helium. Diborane is
highly unstable so no more than 0.1 kg can be shipped in a cylinder. To
dispose of diborane the gas is fed into the bottom of a small vessel containing
water. The water-diborane reaction produces hydrogen and boric acid.
Procedures for shipping organo-boron compounds vary with the particular
compound involved, amyl borates when contacted with water produce phenols
so they are treated as corrosive chemicals. Lower alkyl borates are flammable
methyl, ethyl, and butyl borates have flash points of 0, 32, and 94C respectively,
and must be stored in approved areas. Other compounds, such as hexylene glyool
diborate, offer no hazard and may be shipped or stored in any convenient manner.
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W/AR INC. 1-36
Organic boron-oxygen compounds readily hydrolyze so they should be stored
and transferred in an inert atmosphere. Usually glass containers are used
for shipping small quantities; and steel cans,, drums, or tank cars are used
for bulk iterns.(5)
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'KR/AR IMC,
1-37
V. ENVIRONMENTAL CONTAMINATION
Boron is a ubiquitous element, generally occurring at concentrations
of 10-30 ppm in soils, approximately 0.1 ppm in surface waters and about 4.5
ppm in sea water. Departures from these norms occur only in the very limited
areas where natural boron sources are concentrated, such as in certain arid
regions of California. Air monitoring data do not measure boron concentration
as there is no evidence that it is present in the atmosphere to a significant
(9)
degree.
In a relatively few areas there is concern about boron concentration.
In irrigation waters the boron limit is set at 1.0 ppm. Nuclear reactor
materials cnn tolerate boron only in bare trace amounts. There is also con-
cern about boron concentration in processes where boron dust may be excessive,
such as in the mining and handling of borax ore.
A. From Uses
Virtually all boron-containing materials and products requiring boron
compounds in their manufacture constitute potential sources of boron contamin-
ation. Little is done to check the boron content of surface .and river waters
in the U.S. Through the use of boron compounds in detergents and other products,
the boron concentration in surface waters can be expected to increase. Since
sodium perborate is widely used in Europe in place of the American-type of
chlorine-based bleach, the trend toward a build-up of boron concentration in
surface waters should be more pronounced there. By following the buildup of
boron in European waters it may be possible to establish the point where the
(2)
agricultural ecology of the U.S. will be upset.
This treno would not be affected by sewage treatment since con-
ventional sewage treatment removes little or no boron. Boron is ingested in
the normal human diet, primarily from fruits and vegetables, at the rate of
10 to 20 my/day and excreted at the sane rate with little or no accumulation
in the body. Boron in sewage is present as undissociated boric acid.
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f4/M
1. Emissions to the atmosphere (including from production).
Although the incidence of boron and boron compounds in the at-
mosphere is quite limited, such emissions are known to occur and may be of local
concern even if not sufficiently widespread to constitute an environmental pro-
blem. Recent analysis of this problem considered potential sources of boron
emissions. Emission factors have been determined for individual sources,
by using: (1) direct observations and plant processing and engineering data; (2)
literature; (3) observations of plant operators and others knowledgeable in the
field; (4) calculations based on process data; and (5) analytical results where
available. Based on the emission factors oa Table & and the 1972 use figures,
(6)
estimated emissions to air are given in Table 7.
Details of boron emissions from use pattern are given below.
Glass - The principal sources of particulate matter in the furnace
exhaust gases are raw materials entrained in combustion gases and materials
from the melt. Particulates expelled from the furnace are the result of many
physical and chemical reactions that occur during melting. One factor which
appears significant is the furnace production rate - as the latter is increased
the quantity of particulates increases disproportionately.
Ceramic Goatings - The principal emissions of boron from the
production and use of ceramic coatings occur during the manufacture of the frit.
'ine smelting operation causes the most significant dust and fume emissions.
There are also dust emissions from handling the raw materials as they are re-
ceived, stored, measured, and mixed prior to charging the smelter. The atmos-
pheric emissions of boron during frit smelting consist primarily of oxides in
vapor form and in particulates. The magnitude of emissions varies considerably
depending upon the amount of boron in the charge, the combination of ingredients,
and the type of smelter.
Agriculture Chemical - Emissions to the atmosphere occur principally
when the materials are applied as sprays or dusts. Too many factors are in-
volved (air movement,.drop size, nozzle type, etc.) to give an accurate estimate
of emissions.
Soap sand. Detergents - Boron compounds in the particulates emitted
to Uie atmosphere arc refjorted to be sodium perborate, sodium tetraborate, and
sodium borohydride; the particle size ranges from 1 to 10 microns.
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"iK INC.
1-39
Table 6. Air Emission Factors for Boron
Mining
Processing
End product uses of boron
Glass manufacture
Ceramic coatings
Other emission sources
Coal
Sewage and sludge
0.5 kg/netric ton boron mined
14 kg/tnetric ton boron processed
35 kg/metric -con boron processed
40 kg/netric ton boron processed
9 kg/1,000 metric tons coal burned
28 kg/1000 metric tons sewage
and sludge burned
Table 7. Air Emissions of Boron by Source, 1972
Source
Mining
Processing
End Product
Other Sources
Source Group
Glass
Ceramic Coating
Agricultural Chemicals
Soap and Detergents
Miscellaneous
Coal
Sewage and Sludge
Emission—Metric Tons
91
2,400
1,000
472
1,800
13
500
4,250
18
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KH/AR INC. 1-40
2. Amount entering waters and earth
The major source of boron entering U.S. surface and ground waters
arises from the use of boron-oontaining laundry products. 'iMs source, all
of which may be assumed to enter the environment shortly after production,
amounts to 15 per cent of the domestic consumption (which is roughly half of
the total production). Thus, based on about 600,000 mt total production in
4
1972 as B-0^, approximately 1.4 x 10 mt of boron may be considered to enter
the water per year through the use of boron-containing laundry products.
Direct application to the land or crops as fertilizer or herbicides
accounts for about seven per cent of domestic usage. This may also be con-
sidered as entering the environment immediately upon production. Again, based
on 1972 production, approximately 7 x 10 mt of boron appears to enter the
environment per year from this source. Soros of this was included on Table 7
in air emissions.
B. From Production
1. Mining
Mining of borax using explosives and its subsequent shipping and
handling created a serious dust problem. A three-year, $10 million program to cut
down dust emissions at Boron, California was concluded in 1972. Nevertheless,
(4)
the operation is still not satisfactory and efforts to improve it are continuing. '
There are no detectable emissions in connection with the operation at Searles Lake.
2. Processing
The primary emission from the processing of boron is sodium
borate in various degrees of hydration, primarily from 1 to 3 moles of water.
Boric oxide, boric acid, and sodium pentaborate are also enitted as these
compounds are being produced. Particulate sizes range from less than 1 to 45
microns. Boron emissions vary considerably from plant to plant, ranging
from 100 to 2000 mgAg of product.
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KR/AR /NC.
The major industrial waste in the boron-related industries
appears to arise in the sodium borate effluent from B^O, manufacture. This
amounts to about 400 kkg per year as boron.
Phosphate rock contains 20-100 ppm boron, but even at a total
phosphate rock production of 120 x 10 mt per year and an average boron
content of 50 ppm, the boron effluent (water-borne or landfilled) from this
industry amounts to only a few metric tons per year.
C. Inadvertent
These items are considered contaminators only in view of the special
applications involved. Boron content of the materials used for construction
and the chemicals used in nuclear reactors, for example, must be extremely low.
This is because of the high atomic cross section of boron for thermal neutrons.
In sone cases boron must foe removed from water used in the production of nuclear
reactor materials. Sea water being used for magnesium oxide production as a
refractory material and magnesium chloride brines being processed for magnesium
metal when used in connection with nuclear reactors are prepared in this manner.
Kunin of Rohm and Haas has developed a boron-selective ion-exchange resin which
is available commercially as Amberlite I RA-943.
In the case of irrigation water, a standard of 1 ppm boron has been
established. Normally this limit is attained through dilution with other
waters. The manufacturers of the Amberlite IRA-943 resin hc.ve made recent
improvements and now claim that deboration of the average irrigation water
can be effected at costs "well below 3 cents per 3.8 cu. m. '
D. Total Amounts Entering Environment per Year
Total boron released to the environment based on 1972 production
and use figures may be summarized by:
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M/AR INC. i-42
Source Amount (metric ton)
Laundry Products . 14,000
Agricultural Chemicals,
Fertilizers
Mining and Processing
Glass and Ceramics
Combustion of Coal
Miscellaneous
Total
Of the estimated total of 32,000 mt per year, most ends up in
the waters because of the relatively high solubility of all the compounds.
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mjAR INC. MS
VI. MONITORING AND ANALYSIS
A. Monitoring
Monitoring data on the boron content of U.S. waters is limited.
For this reason, results of a survey conducted in Europe is cf interest. A
study was made for the National Swedish Environmental Protection Board, Uppsala,
of boron in Swedish and Norwegian fresh waters. The study began in 1970 and
took a year to complete. Regional variations due to differences in geology,
land use, and population density were found, but there were only small seasonal
variations. The enrichment of boron in aquatic plants was very sinall conpared
to that of phosphorus and nitrogen. Sewage water showed a lower boron content
than that of England. 'Ihe mean concentration of boron in Swedish and Norwegian
fresh waters was low and close to that of other rivers of the world. The median
boron content in 355 sarrplcs was approximately 12 micrograms/liter. '
D. Analysis
1. Determination of boron in water.
Colorimetric and spectrographic methods have been used to analyze
boron in fresh water in concentrations of less than 1 ppm. One of the most use-
ful methods is "the identical pH" method with which a sensitivity of +_ 0.05 ppm
boron can be obtained if a 500 ml sample is used. With this method separation
or special sample treatment is not required. Detection of the boron by electro-
metric instead of coiorimetric technique is recommended. For use with more than
1 PJOT boron, the standard mannitol borate procedure may be used after removing
(14)
intcrfcrring bicarbonate and netal ions.
'lhc analysis of boron in sea water represents a special case. A high
cbcjrce of precision and accuracy are required because the ratio of boron to toal
salt content is almost constant throughout the world. Only bicarbonate ion
removal is required for the mannitol borate procedure. Polynydroxy organic
(14)
natter causes low results by complexing the boron.
2. Determination of boron in plants and biological materials.
The boron analysis in plants is important for avoiding toxicity
on the one hand and deficiency on the other. The ppm range is normally involved
and the best techniques are coiorimetric and spectrographic. The treatment of
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1-44
the sample must be care fully carried out to avoid both loss of boron and
contamination from borosilicate glassware. Almost all methods for boron analysis
in biological materials involve ignition of the sample which may cause some
loss of boron. Contamination with boron from the ovens may be experienced.
Spectroqraphic and flame photometric procedures are more convenient than those
(14)
requiring extensive treatment after ashing.
3. Analysis of available boron in soil.
Boron is analyzed in soil by boiling a 1:2 soil to water suspension
for five minutes in a reflux condenser. The solution phase is separated to
determine boron.
4. Detection of boron in airborne contaminants collected in
air filters.
To detect boron in airborne contaminants collected in air filters
a small portion of the filter is rolled up into a cylinder and placed in a
hollow graphite electrode. This portion of the air filter is directly excited
by the condensed spark discharge in an oxygen atmosphere. The sample bums,
exciting the spectra. A photographic recording is used to interpret the
spectra and, when improved precision is required, line intensities are measured
with a microphotometcr. The limits of detection are 0.1 to 1.0 micrograms.
The results obtained from the rapid emission spectrographic method are compatible
with results obtained with the more conventional technique of ashing the filter,
mixing it with a spectrographic buffer, and exciting it in a D.C. arc.
5. Analysis of boron in air by coloriiretry.
in the coloriirEtry method of analysis, about 1,000 liters of airh
passes at a rate of two to three liters per minute through four collecting
tubes chilled in a methanol-dry ice bath. The collected boron is dissolved in
10 ml. water and added to 1.5 ml. of curcumin reagent solution. The solution is
evaporated until the odor of phenol disappears. The residue is dissolved in
10 ml. cthanol and absorbance is measured at 548 millimicrons.
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1-45
VII. CHEMICAL REACTIVITY
A. Environmental and Use Associated^ Reactions
Borax solutions, usually a buffer mixture of sodium borate and
boric acid, are widely used for pH control in: cutting fluids, detergents and
soaps, electroplating, dyeing of natural and synthetic fibers, photographic
processing, Pharmaceuticals, cosmetic preparations, plastics manufacture
and vitreous enamelling. The pH value of a O.lM solution of borax is 9.2.
Na~B 0 . 10H_0 -*• 2Na + 2B(OH) ~ + 2H^BO_ + 3H_O
Boron trichloride and boron trifluoride hydrolyze rapidly on con-
tact with water to form boric acid and the corresponding hydrochloric or
hydrofluoric acid.
The manufacture of boron-containing combined fertilizer by the direct
action of sulfuric or nitric acid on phosphate rock with fluoride impurities
results in a product containing a boron-fluoride complex similar to potassium
fluoborate. In Switzerland's Rhone Valley, apricot orchards and vineyards using
a certain fertilizer showed high fluoride content in the plants and typical
(18)
fluoride-induced necroses of the foliage.
The effect of the environment on diborane and higher boranes is given
in Table 8. In the case of pentaborane, conflicting data are reported.
B. Aspects with Biological Implication
The complexing ability of the boron atom is considered to be the key
explanation of its essentiality to higher plants. The exact mechanism of its
action is still unknown, and is the subject of much research. One theory is
that the complexing action of boron facilitates the transport of organic com-
pounds such as sugars in plants. Other biological inplications under consider-
ation as an explanation of the effect of boron on plants are: its effect on
plant enzymes, the interrelationship between boron and plant hormones synthesis
(plant growth regulator response), nucleic acid biosynthesis relationship to
cellular growth and differentiation, cell wall formation and pectic synthesis,
phenolic acid biosynthesis and liquification, increased carbohydrate metabolism
and respiration, cell wall and membrane metabolism, and pollen germination. All
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Table 8. Relative Stabilities of Boron Hydrides
(5)
Compound
diborane
tetraborane
pentaborane
hexaborane
decaborane
Room temperature,
no oxygen
fairly stable, 10% deoom-
ppsition in presence of
hydrogen
fairly rapid decomposition
(a)stable for years; decomposes
slowly at 150 C
(b) begins to decompose within
1 hr
deocnposes slowly
very stable; can be heated
for some time at 150 C;
noticeable decomposition
at 170 C
Room temperature,
presence of air
spontaneously flammable
above 40 C and at
room temperature in
presence of impurities
not spontaneously flam-
mable if pure
spontaneously flammable
quite stable; not spon-
taneously flammable
very stable; not spon-
taneously flammable;
explodes in oxygen at
100 C
Presence of water
hydrolyzes instantaneo"usly
and almost quantitatively
at room temperature
hydrolyzes completely within
24 hr at room temperature
hydrolyzes only at elevated
temperatures
hydrolyzes rapidly
hydrolyzes completely only
at elevated temperatures
hydrolyzes very slowly at
room temperature
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/
KR/AR INC, M7
of these effects ot boron on plant growth probably play some role in its
(19)
benefits. The primary effects, however, have not yet been determined.
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ER/AR INC, i-48
VEIL BIOLOGY
A. Absorption, Excretion, Growth, and Nutrition
1. Humans
The average concentration of boron in the blood and urine of
154 American males of various occupations and ages is 9.85 ygrams per 100 grams
ns t]
(21)
and 7.15 mg per liter, respectively. The skeletal tissue contains the
highest boron concentration (0.90 ppm) of all body tissues analyzed.
Sinoe boron is widely distributed in fruits and other foods,
(22)
humans constantly ingest and excrete this element. Conflicting information
as to the transcutaneous absorption of boric acid from talc exists. No increase
in boron was observed in the blood of infants maintained on a regimen of boric
(22)
acid dusting powder "ad. lib" for a year. , In another study, children using
baby powder containing three per cent boric acid had significantly more boron
(23)
in their blood than the control group.
A fatal case of transcutaneous absorption of boric acid occurred
in a seven-month-old male infant being treated for dermatitis with three per cent
boric acid powder. The boron concentrations in the bile, intestinal contents
(24)
and spleen were 20.2, 18.3, and 18.2 mg %, respectively.
After vaginal administration of 40g of boric acid, the serum boron
level rose from 0 to 750 ygrams % within 48 hours in a patient with healthy
epithelial tissue in the vagina and on the portio, but up to 2150 ygrams % in
a patient with vaginitis and erosion of the portio. In patients with vaginitis
receiving daily 20g doses of boric acid, the serum boron was a maximum of 850
(25)
iicjrams % after five days of treatment, and 1900 ygrams % after seven days.
Phenylmercuric borate was not absorbed by the epidermis or cutis
(26)
in man or rats when applied without a protective dressing.
2. Nonhuman Mammals
Boron compounds are preferentially accumulated by the brain and
(27 28 29)
tumor tissue of animals. ' ' Localization in the brain can be ration-
alized in terms of one parameter obtained from the waterroctanol partition co-
efficients. Localization in the tumor depends also upon the electronic para-
(29)
meter.
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>M/AK INC. M9
An aqueous jelly and two oleaginous ointments containing less
than three per cent boric acid were applied to the skin of anesthetized rats,
and boron absorption was monitored by measuring boron in the urine. Little
or no increase was observed after eight hours if the application was made to
intact skin, but when the ointments were applied to damaged skin, four to eight
times the control level of boron appeared in the urine. Only 25% of the original
boron remained in the ointment after treatment of an enclosed area of damaged
skin, but 98% remained in the jelly. In the urine, 25% and 1%, respectively,
of the total boron from the jelly and ointment applications were recovered, in-
dicating that a high rate of absorption with inadequate excretion occurred
with the aqueous jelly, but the slight absorption from the ointments was
followed by rapid excretion. '
Sodium me thy Iterate (0.2g B per kg in 2% physiological serum) was
injected into pregnant rats on the 18th and 19th days of gestation. Boron pene-
trated into the amniotic fluid more rapidly on the 19th day than on the 18th,
and the diffusion of boron into the amniotic fluid increased as gestation
progressed. '
The amount of boron in cow's milk varies with the amount of boron
in the feed. About one quarter of the total boron is in the cream, the re-
(32)
mainder in the skim nalk.
3. Plants
As shown in Table 9, nutritional requirements for boron vary
greatly. Boron deficiency in plants induces severe symptoms. These include
cessation of root and leaf growth, necrosis of leaf primorcfia and primary root
tips, spongy mesophyll layers of leaves, necrosis of stem and leaf phloem, bark
splitting, reduced pollen germination and pollen tube growth, reduced fluor-
escence, abnormal cell differentiation, reduced growth, and death if the de-
ficiency is not corrected. Normal growth and development usually resumes when
boron is added to the growth medium.
Boron is absorbed by the roots of the plant and translocated to
the leaves, where it occurs in highest concentration. In a study on sunflowers,
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KK/AK INC. i-so
Table 9. Diagnostic Criteria for Boron Nutrition
of Field and Vegetable Crops Based upon
Hot Water Extraction of Soil Boron
(169)
Boron Content of Soils for Optimum Growth
0.1 iigram of B/gram 0.1-0.5 ygram of B/gram 0.5 ygram of B/gram
Small grain Tobacco Apple
Corn Tomato Alfalfa
Soybean Lettuce Clovers
Pea and bean Peach Beets
Strawberry Pear Turnips
Potato Cherry Cruciferae
Grass Olive Asparagus
Flax . Pecan Radish
Cotton Celery
Sveet Potato Rutabaga
Peanut
Carrot
Onion
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I
wjAR IMC. 1-51
boron accumulation required nitrogen in the nutrient solution. Once in the
leaves, boron was not transported to other parts of the plant.' ' As boron
in the nutrient solution increased, boron in the leaves increased in the
carnation, Dianthus caryophyllus, but not in the reproductive organs.
Figure 8 relates boron concentration in plant tissues to the concentration in
soil solution. Similar results were observed in studies on tobacco,
(36) (37)
onions, and birch.
Borate absorption by excised sugarcane leaves occurred in a two
stage transport system. The first stage is a rapid, reversible influx into the
mesophyll cells of the leaves, followed by a slower, irreversible accumulating
phase. Stage two consists of three absorptive reactions. The first two re-
actions involve active transport of borate across the cell membrane; the third
carries the borate across tie vacuolar membrane. Calcium is essential for
maximum boron uptake, and all three reactions are inhibited by hydroxide ions.
factions one and two are apparently coupled to the electron transport system.
/TO\
The third mayibai linked to ioxidative phosphorylation.
Phenylboric acid, which is split into phenol and boric acid by
horse radish peroxidase and oxygen, promotes the lengthening of roots in Phaseolus
vulgaris primarily by stimulating the rate of cell elongation. Phenylboric acid
also stimulated the initiation of xylem development and the full elongation of
(39)
epidermal cells at a greater distance from the apex than in controls.
4. Microorganisms
The thermostability of Paramecium caudatum at 40 C was increased
by the addition of 0.01 and 0.05 per cent boric acid to Losina-losihsky saline
solution at a pH of 7.0-7.2. At pH 6.4 or lower, however, the addition of boric
(40)
acid caused a decrease in the thermal stability of the ciliates.
B. Biochemistry
1. Humans
No requirement for boron in humans is known. Since boron is ex-
(41)
creted from the body very slowly, accumulation in the tissues is likely to occur.
The long term effects of drinking water high in boron (4,6 mg per liter) on the
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1-52
2000 r
1500-
(0 1000-
500
r
5 10 15 20
PPM BORON IN SOIL SOLUTION
25
Figure 8
Boron concentration in plant tissues
related to concentration in soil solution
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'KR/AR INC. 1-53
gastrointestinal tract were studied in 288 persons. In people drinking high-boron
waters, the incidence of hypoacidity doubled in adults, and enterokinase activity
in feces of children was 25% of that in persons drinking low boron water. ^ • '
Borates cause nonoompetitive inhibition of nonspecific ester hydrolysis
by chymotrypsin, perhaps by interacting with the free electron pair on an
imidazole moiety at the active site. Changes in ionic strength (0.06 - 0.4)
do not significantly affect the inhibition, but changes in pH do. Aryl and
alkyl boronic acids act as competitive inhibitors of 6-chymotrypsin. The ionic
borate group apparently interacts with histidine and/or imidazole residues at
the active site, and the organic residues interact with hydrophobic sites.
n-Hexylborortic acid had the strongest inhibitory effect of the n-alkylboronic
(45)
acids studied.
2. Nonhunan Mamnals
Boric acid and its salts affect diverse metabolic pathways in animals.
In rats fed a low-borate diet (0.001 ppm boron), liver RNA synthesis as measured
14 14
by C-orotic acid and C-uridine incorporation is stimulated by the intra-
peritoneal injection of borate. Feeding of 1 ppm boron diminished this effect.
The activity of rat liver DNA-dependent RNA polymerase was stimulated in vitro
by 10 to 10 M borate, but higher concentrations were inhibitory. '
Inhibition of oxygen utilization in the brain by boric acid and sodium
metaborate can be significantly alleviated by the presence of glucose and pyruvate
(28)
in the median. In the rat, boric acid was found to inhibit glucose-6-
phosphatasc, phosphoglucomutase and phosphohexose isomerase in the liver, brain
and kidney, except that kidney phosphoglucomutase was stimulated by borate.
iterate competitively inhibited glyceraldehyde phosphate dehydrogenase in rat
and guinea pig liver homogenates, causing fructose-6-phosphate and fructose-1,
6-diphosphate to accumulate. Lactate dehydrogenase was not affected by borate.
Anaerobic glycolysis in guinea pig erythrocytes was inhibited by addition of
(49)
borate to the blood, and rnethemoglobin increased substantially. The in-
hibition of methemoglobin reduction by borate, which is greater in man and pigs
than in rats, guinea pigs and rabbits, may be alleviated by the addition of
(49)
NADU,,. The loss of activity may occur via glyceraldehyde phosphate dehydro-
ijunnse inhibition. The ratio of NAD:NADH2 increases in the presence of borate,
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'Mi/Alt INC.
[-54
indicating restricted generation of NADH». The NADPH system was not as
(49)
greatly affected by borates as the NADH system.v '
Changes in the EPR spectra of heire and non-heme iron complexes
(50)
were observed in livers of mice with bone acid intoxication. A sharp
decrease in the electron spin resonance signal of pigment 450 in the respiratory
chain of microsomas was also noted.
The addition of 2-3 mg per liter or more of boron to the drinking
water of dogs resulted in decreased gastric secretions, free and total gastric
hypoacidity and inhibition of fecal enterokinase activity. In rabbits re-
ceiving daily gastric administrations of 100 mg per kg calcium borate, a slight
decrease in total serum lipids and free sulfhydryl groups in the serum was
observed. Inhalation treatments (120-150 mg/m /2 hr/day for 10 weeks) resulted
in an increase in urinary excretion of nitrogen compounds. The urate
oxidase activity of ammonia extracts of ox kidney acetone powder was increased
290% in 3-100 nM borate buffer. The borate effect was chiefly due to stabiliz-
ation of the enzyme.
Borate inhibited the adrenalin activation of dog liver dephospho-
phosphorylase. A mixture of borate and L-serine inhibited Y-glutamyl
transpeptidase in various guinea pig tissues (kidney, liver, spleen, uterus,
14
lung, intestine, heart, brain and muscle). Intravenous injection of j-lr- C-
cj.l utamyl-a-naphthylamide as substrate accompanied by borate-lr-serine treatment
resulted in n decrease in (i-naphthylamine and transpeptidation products and
(54)
increased amounts of substrate in the urine.
Tetraphenylboron (TPB) strongly inhibits protein synthesis.
14
In isolated rat liver cells, TPB administration reduced oxidation of u- C-glucose,
14
glycogen concentration and the effect of insulin. The incorporation of C-
leucine into protein was lowered, as were the activities of glucose-6-phosphate
phosphohydrolase and lactate dehydrogenase. In rat liver mitochondria,
TPB exerted a powerful uncoupling of oxidative phosphorylation. Reversed
32
electron transfer, calcium transport, and ATP- P exchange were inhibited. TPB
stimulated ATP hydrolysis. Sodium TPB inhibited rat liver aminopeptidase
D as evidenced by the decreased rate of hydrolysis of N-L-arginyl-2-naphthylamine.
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'KR/AK INC. 1-55
The antitubocurarine action of TPB irost closely resembles that
of tetraaranionium triethylcholine and phenol. In the biventer cervicis muscle
of the chick, TPB increases acetylcholine release and also exerts a weakly
i exe
(60)
(59)
anticholinesterase effect. TPB exerts a blocking action on acetylcholine-
sterase in guinea pig smooth muscle.
Organic derivatives of boric acid exert a wide variety of effects
on diverse tissues. o-Methoxybenzene-boronic acid exerts a peripheral hypotensive
action, which is not accompanied by a hypnotic effect. This compound stimulates
an increase in cardiac contraction and increased cerebral blood flow. '
Pentaerythritol di-(p-methylbenzene boronate), p-methylhenzeneboronic acid, and
methyl-p-itethylbenzeboronate are not hypnotic, but enhance the hypnotic effects
of chloral hydrate and hexobarbital. The first drug causes an increase
.i.n arterial blood pressure, but it acts as a peripheral dilator and depresses
cardiac contractile activity, and inhibits the hypertensive action of exogenous
and indirect amines. o-,m- and p-tolylboronic acids become localized in
the cerebrum; for example, one hour after intraperitoneal infection of sodium-
o-tolylboronate, the boron content in the cerebrum was six times that of the
blood. 'J-4y^ Spasmolytic activity of seven arylboronic acid compounds was studied
in isolated guinea pig duodenum. The substitution of one hydroxyl group in
boric acid by a methyl-benzene group conferred spasmolytic activity. o-Methoxy-
benzeneboronic acid differed from other derivatives in that it e>aarted a specific
musculotropic spasmolytic activity and no neurotropic activity. ' Some of the
derivatives exerted an antiserotonergic effect on the uterine tissue of virgin
t (61)
rats.
Itorancs produce extensive changes in tissue amino acid levels in
(62)
the rat by inhibition of pyridoxal-dependent enzymes such as aminotransferasesv '
' and histidine decarboxylase.^ ' Tissue histamine levels were greatly
reduced by injection of decaborane (15 ing per kg). Histamine was reduced in
liver, kidney, stomach, brain and urine, but not in heart. Brain levels fell
50% and were still depleted one week after injection, whereas rat stomach de-
pletion lasted only 48 hours. Changes induced by pyridoxine deficiency
in rat are accentuated by intraperitoneal borane injection (20 mg per kg): '
-------
i-56
However, aspartate aminotransf erase (AAT) ac±ivity is greater in the tissues
of pyridoxine-deficient rats, and decaborane does not significantly affect it.
Decaborane does inhibit MT in the liver, heart, brain, and kidneys of normal
rats. Lactate dehydrogenase is moderately inhibited by decaborane in the heart
and kidney of normal and pyridoxal-deficient rats and in the brain of normal
rats.(63'66)
Borohydrides readily reduce the double bond of the Schiff base
formed from cytochromc oxidase. '
3. Nonmammalian Vertebrates
Boric acid produced malformation of the posterior extremities of
the chicken embryo, possibly by interfering with the process of extension of the
/gq\
collagen fibers in the cartilage.
Vitamin C was useful in protecting the tadpoles of Rana temporaria
from the toxic effects of phenylmercuriborate.
p-Nitrobenzene[N]diazonium fluoroborate and its trimethyl deriva-
tive are potent inhibitors of the carbamyl-choline-induced depolarization of
the electroplax and also of acetylcholinesterase. These organoboron compounds
are believed to form covalent bonds with the acetylcholine receptor and esteratic
sites on the electroplax.
4. Plants
The essentiality of boron to higher plant reproduction, growth and
metabolism is firmly established. Boron deficiency symptoms are browning and
spotting of leaves, chlorosis, necrosis and finally death. No single specific.
role has been found for boron; in fact boron apparently exerts many effects on
a variety of metabolic sites. The following summary of boron biochemistry in
plants is primarily based on a review article by Dagger.
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'RR/AR JNC.
1-57
Boron apparently controls plant metabolism by inhibiting
certain key enzymatic reactions in plants. Several sites of inhibition occur
in carbohydrate metabolism. Effects of boron deficiency which may be ex-
plained via effects on carbohydrate metabolism are increased starch accumulation,
increased pentose-shunt activity, leading to an accumulation of polyphenol
compounds and an increase in phenolic acids and indoleacetic acid (IM). An
increase in cell wall products of altered composition were also observed.
Reproduction and growth are adversely effected.
Starch accumulates as a result of alleviation of borate in-
hibition of starch phosphorylase, reducing the amounts of free reducing sugars.
Uninhibited activity of UDPG transglycolase, phosphoglucomutase permit increased
hexose metabolism via the pentose shunt. The products from this cycle are con-
verted into polyphenolic compounds, which are normally complexed by borate and
not further oxidized. Under conditions of borate deficiency, oxidative enzymes
(including catechol oxidase, xanthine oxidase, horse radish peroxidase, tyrosinase
and alcohol dehydrogenase) convert these compounds to toxic polyphenolic acids.
IAA accumulates due to its reduced oxidation due to the presence of other poly-
phenolic substrates. Reduced polymerization of phenolic compounds into lignins
also occurred.
Nucleic acid metabolism and protein synthesis are also disrupted
by boron deficiency. Boron controls ENAase activity by inhibition or seques-
tration. In boron deficient plants, RNAase activity is greatly increased and
RNA content greatly reduced. DNA synthesis, RNA synthesis, and aminoacyl tRNA
levels are maintained, but rate of protein synthesis is decreased, and an
increase in free amino acids and total nitrogen content in plants occurs.
Growth and reproduction are almost certainly aberrant in boron-deficient plants
due to inadequate protein synthesis resulting from disturbed nucleic acid
metabolism.
In boron-deficient plants, ATPase activity doubles and ATP levels
arc quite low. The reduction of available ATP also prevents the normal pro-
gress of energy-requiring synthetic reactions, including chlorophyll synthesis
and protein synthesis.
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WR/AR
1-58
Boron promotes the uptake and translocation of carbohydrates
and reduces nitrogen absorption in nitrogen sufficient plants.
Xylem proliferation is stimulated by boron. Borate ions in the itBdium clearly
inhibited chloride absorption, but not iodine uptake, in Lemna minor.
Boron fertilization reduced water loss in sugar beets throughout the entire
vegetative period, and the addition of lime prevented the toxic effect of
(74)
too much boron and actually increased the boron requirements. The
accumulation and disposition of thiamine to the ootyledonous shoots of lupine
(75)
was facilitated by boron.
5. Microorganisms
No nutritional requirement for boron has been established in
microorganisms, but borates added to the medium produce definite metabolic
effects, primarily inhibitory and toxic.
In yeast in sucrose solution, boric acid favored anaerobic res-
piration at the expense of aerobic. The number of cells rich in glycogen
decreased with one to two per cent boric acid, but little effect was observed
with four per cent probably due to a larger proportion of the more active
Cjc\
orthoboric acid in more dilute solution.v Fructose-1, 6-diphosphate and
ADP accumulated in boron-toxic cultures of Saccharomyces cerevisiae, whereas
phosphoglyceric acid and ATP levels decreased. This effect was explained by
(38)
the uncompetitive. inhibition of aldolase by boric acid. Yeast alcohol
(77)
dehydrogenase was also inhibited by borate. Borate buffer also influenced
the production of 5'-nucleotides via the autodegradation of intracellular PNA
in yeast. (78)
In fungi, o-diphenol oxidase was competitively inhibited by borate.
(46)
Borax inhibited the formation of HCN by a normally cyanogenic isolate
:id c
(38)
(79)
of the snow mold of alfalfa. Boric acid eserted a toxic effect on fungi
by preventing O~ uptake and 00- evolution.
Erythromycin, produced by Streptomyces, is known to lose its
biologic activity in borate buffer solution by the formation of complexes in-
(80)
volving dihydroerythrcmyciji. Boric acid prevents the incorporation of
separately-formed sugars into erythromycin by complexation, and also causes the
synthesis of structurally-changed sugars which result in biologically inactive
. (81)
erythromycin.
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'i:\\JAR IMC. 1-59
Sodium borate inhibits the decomposition, presumably by micro-
(82)
organisms, of two protein hydrolysates attractive to the Mexican fruit fly.
Borate sensitivity in staphylococci correlated well with lysozyme and a-toxin
(83)
production in the coagulase-positive strain.
Borotungstate had an inhibitory effect on RNA-dependent DMA
polymerase of mouse oncogenic viruses and, on RNA-dependent RNA polymarases
of various RNA viruses.
C. Therapeutic Uses
1. Humans
Doric acid and borates, as well as complex organic boron compounds,
have a variety of medical uses. Saturated, three per cent and two per cent solu-
tions of boric acid inhibited the growth of Salmonella typhosa, Escherichia coli,
Staphyloooccus aurtsus, and Proteus vulgaris for over a week, although no bacter-
TEST
icidal activity was observed. Boric acid is a useful preservative of urine
specimens. A three per cent boric acid solution preserves the urine specimen
t fifi}
for up to 24 hours. Of 235 strains of coagulase-positive £>. aureus, 221
(94%) were inhibited by 1.5 x 10 M sodium borate. Only 6 out of 57 (10.5%) of
the coagulase-negative strains were inhibited at this concentration, Pour of
(83)
the six strains were food poisoning strains, and one was a hospital pathogen.
The antifungal action of boric acid is increased in the presence
of sorrc polyhydroxy compounds, including nontoxic agents which .conplex with
boric acid such as lactic acid and mannitol, and toxic agents, such as salicylic
acid, oxalic acid and pentachlorophenol, which complex with boric acid and
exhibit strong synergism. Penicillium careicolun, P. expansum, P. glaucum
(88)
Aspergillus niger, and Mucor racemosus were studied.
Phenylmercuric borate (0.05-0.06%) has been shown to be quite use-
ful in treatment of various mycotic infections (dermatophytes, tinea cruris,
(c)
crythrasma, pityriasis versicolor), especially of mold and yeast. Zyma
(0.06% phenylmercuric borate) and Exomycol gel (0.05% phenylmercuric borate)
(89 90)
arc two marketed preparations. ' Phenylmercuric borate (0.04%) combined
(91)
with 3% hexachlorophene in a bland emulsion serves as a good surgical disinfectant.
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VR/AR INC. i-60
The antimicrobial action of Remanex, a canmsrcial mixture of the two com-
pounds, was much more effective upon Streptomyces sp. than either of its
(92)
components alone.
Orthoanisyl boric acid, exhibiting a low toxicity and readily
eliminated, serves as a nonhypnotic sedative which reinforces the action of
(93)
hypnotics and anticonvulsants. ' Pentaerythritol di-(p-methylbenzeneboron-
ate) acts as an anticonvulsant for Metrazol and electroshxk seizures but
has no effect on strychnine convulsions.
Tumor-specific boron-containing compounds have been evaluted for
use in tumor therapy by neutron capture techniques. 3-amino-4-carboxybenzene
boronic acid, m-boronosuccinanilic acid and sodium perhydrodecaborate, * '
/QC\
as well as boron-labelled antibodies and elemental boron, ' have been tested
as neutron targets.
An 0.5% solution of levepinephrine borate enhanced the hypotensive
response to pilocarpine. Maximum response occurred with a 4% solution.
2. Nonhuman Mammals
A three percent solution of boric acid was the most effective
(97)
therapeutic agent in treating Thelazia infestations in 250 calves. '
Phenylmercuric borate at three concentrations (0.125%, 0.25%,
and 0.50%) was effective in inhibiting dental caries in fissures and smooth
(98)
surfaces of teeth in Osbome-Mendal rats fed a high-sucrose diet.
Borotungstate was inhibitory to mouse sarcoma-leukemia virus
(99)
infection of cultured cells. Absolute control of an experimental sarcoma
in mice was attained by boron thermal neutron interaction.
3. Plants
Treatment with boric acid protects plants against insect and fungus
infection. The two-toothed longhom beetle, Ambeodontus tristis, in sapwood
kahikatea, Podocarpus dacrydioides, did not survive a treatment of 0.142% or
more boric acid. Boric acid solutions greater than 1.09% were effective
against several termite species: Nasutitermes exitiosus, Coptotermes lacteus,
and C. acinaciformis. Boric acid was useful as a stomach poison in
killing the wood-destroying larvae of Hylotrupes bajulus in wood not exposed
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1-61
to wax. ' When boll-weevils are fed B-boric acid and irradiated
with neutrons, a ten-fold increase in mortality and tvo-fold increase in sterility
occurred in the adults. The presence of McPhail traps baited with a cotton-
seed hydrolysate and borax reduced infestation of navel oranges and mangoes
by the Mexican fruit fly (Anastrepha ludem) by 68% and 98% respectively. '
Boric acid and borax are both cleared by the FDA for post-harvest
use on citrus fruits as fungicides. An 0.2% solution of boric acid pre-
vents attack of wood rotting fungi such as lyctus brunneus Steph, Merulius
lacrymang, Coniophora oerebella, Lezites trabea, and Lentinus lepideus.
Mold growth was completely inhibited by 2.5% boric acid or borax.
Application of boron-calcium or boron-calcium naphthalene acetamide
foliar sprays significantly reduced the number of cork spots per fruit in York
Imperial apple trees. The number of spots on fruit flesh and peel decreased as
the boron and calcium content of the leaves increased. Borax applications
were effective in preventing Fames annosus (root rot) infection in several species
of conifer. Dry powder applications prevented root rot in Jeffrey pine stumps
and white fir stumps. The growth of mycelium was prohibited by 75 ppm
borax; germination of conidia, by 65 ppm; and basidiospore formation at 90 ppm.
Application of 660 ppm total anhydrous borax to oven dry wood of the loblolly pine
(Pinus taeda) raised the pH of the wood from 4.8 to 7.6-8.1 and prevented the
growth of Fomes annosus.
Tetraborate application was only partially effective in controlling
coppicing in teak (Tectona grandis L). A one per cent solution of borax
was effective in inhibiting the growth of Penicillium oxalicum and Helminthosporum
cyclops, the most active microorganisms infecting Egyptian canesugar.
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1-62
IX. ENVIRONMENTAL EFFECTS
A. Environmental Content, Transport, Contamination
Boron exists in several forms in the soil. Boron is present in
organic matter, in various soil minerals such as tourmaline, and in the soil
solution in equilibrium with boron adsorbed on the surfaces of soil particles.
The bulk of the total boron comes from soil minerals, hence the soil boron
content is primarily related to the parent material of the soil. Soils from
marine shales are particularly rich in boron, with sedimentary soils next,
followed by igneous. Small and variable amounts of boron are found in soil
organic matter. This boron becomes available to plants as it becomes mineralized
and redistributed in the soil-water system. In soils above the detrital cone
of the Danube in Hungary, boron was shown to accumulate in the upper soil
levels, which contained 1.67 bo 3.06 times the amount of boron found in the
(182)
parent material of the soil.
The boron in soil solution and the boron adsorbed to soil minerals is
in an equilibrium dependent upon the boron concentration of the solution
(particularly the horate ion), pH, organic matter content, and the number of
active adsorption sites per unit weight of soil. Although plants absorb boron
directly from the soil solution, it is the adsorbed boron which provides a
source of boron to maintain the soil solution level.
The adsorption sites for boron are associated with broken silicon-
oxygen and aluminum-oxygen bonds exposed at the edges of aluminosilicate metals,
with surfaces of amorphous hydroxides such as allophane and hydroxyaluminum and
iron aonpounds, with magnesium hydroxide coatings and clusters that form on
the exposed surfaces of ferromagnesium minerals and micaceous, layer silicates
in arid soils, and with sesquioxide coatings on the surfaces of clays. Volcanic
ash soils adsorb the highest amounts of boron. '
Boron adsorption occurs independently of pH in the acid range, with
increased adsorption in the alkaline range, and maximum adsorption at pH 9.0.
These pH effects suggest that it is molecular boric acid that is adsorbed under
acid conditions, while it is the borate ion which is adsorbed as the pH approaches
9.0.
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wjAK INC. 1-63
Boron adsorption takes place independently of concomitant adsorption
of other anions. Adsorbed boron tends to leach relatively easily from soils.
In a study of the heath podzol and gray-brown soils in Schleswig-Holstein,
the low leaching of the heath podzol indicates the relatively high capacity of
raw humus to bind boron. Water-soluble boron is usually determined by a hot
water extraction technique or a saturation-equilibration method followed by
vacuum extraction. Significant correlations were found between hot-water
extractable boron and salinity,(185'186)organic matter content,(182/183/186/187)
pH and fineness of soil texture.
Liming of two acid soils with calcium carbonate decreased boron mobility(188)
(34 189)
depresses soluble soil boron reserves. '
Seasonal variations in the boron content of the waters of Sweden and
were
(191)
Norway were small. Increased levels of boron were observed in rainfall
in the southeastern U.S. during the winter months.
In sandy soil, twenty pounds of borax per feddan is toxic to berseem.
In loamy soil, fifty pounds per feddan is required to produce toxicity symptoms.
Heavily calcareous soils offset the boron toxicity. In saline and alkaline soils,
boron toxicity could be corrected by leaching and replacing sodium with calcium.
The soil content of boron may not only be altered by application
of boron-containing fertilizers, which leach to varying degrees, but also
by airborne boron, presumably from human activities. In urban garden soils
of Scotland, the water-soluble boron levels were two to three times the
' ash"
(194)
levels in arable rural soils. In "fly ash", boron (not manganese or
aluminum) is the toxic substance to plants.
In certain industries, such as boron carbide and boron fertilizer
industries, workers are exposed to air pollution and aerosols which may
produce a chronic health problem. ' ' The maximum permissible levels
of calcium borate in the air in the industry should be four to six mg per m
c • (52)
of air.
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1-64
Due to CXT>P sensitivity to boron, the levels of boron in waters used
for irrigation should not exceed the critical boron concentration for the
(169 196)
particular crop species as follows: ' '
Crop Species Critical Boron Concentration (ygram B/itil)
Sensitive 0.3-1.0
Semitolerant 1.0-2.0
Tolerant 2.0-4.0
A serious criticism of this type of limitation is the lack of provision for
soil type, irrigation.management and climate.
Sources of boron introduction to waters are soil minerals, rainfall,
industry, and sewage effluents. The majority of surface waters in the United
States have boron concentrations ranging from 0.1 to 0.3 ygram B/ml.^1&9' in a
study of boron content in rainfall in two sites in Mississippi and one in
South Carolina, the boron concentration was 10 ppb, and the input of boron by
rainfall amounted to 62.7-74.2 grams per hectare for a one year period.
The Santa Ana River basin in southern California is a good example
of the effects of urbanization on the water supply. The volume of return flow
from irrigation is steadily decreasing while the input from municipalities is
increasing. The waste discharge accounts for 0.75-1.50 ygram of B/ml depending
upon the city and the season. As much as 50% of the boron in effluents originates
from household use such as in laundry detergents. In limiting the inputs
from sewage effluents, the downstream rainfall must be considered, as well as
the type of soil. The hazard of boron is essentially eliminated if the effluent
percolates through the soil.
B. Bioaccumulation and Content
1. Human
The average urine and serum levels of boron in workers from
various occupations and geographical locations were: 9.85 yg per 100 ml of blood
and 7.15 ug per liter of urine. The beta-hydroxyethy?. derivative of boron
and its phosphate ester appeared to be strongly bound to tumor tissue and gave
(198)
vnry favorable tumor:blood boron ratios.
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1-65
2. Mamnals
Boric acid accumulated in the brain after repeated inject-
(27)
ions.
Boron, which appears to be a normal constituent of cow's
milk, increased from 270 to 630 micrograitE per liter on the average in the
milk of cows fed 300 mg sodium tetraborate per day for two weeks. The oon-
(32)
cent ration of boron did not vary with the amount of milk produced. About
25% of the total amount of boron in cow's milk was found in the cream; 75% in
(32)
the skim milk.
3. Plants
The boron contents of plants depend not only on their taxon-
(199)
omic position, but also on the content of soil boron and degree of availability.
On the ninth day after boron treatment in sand culture, groundnut accumu-
lated excessive boron in the basal, mature middle and apical developing leaves
(2.51, 2.86 and 2.62 mg per gram dry weight). Boron levels in 22 species
of aquatic macrophytes from a reservoir ranged from 1.2 to 11.3 ppm dry weight.
Boron uptake studies on the swamp plant, Typha latifolia, however, showed no
significant correlation between boron in the soil and plant tissue levels.
Boron concentrations in plants may vary with the season.
0.91)
Typha latifolia exhibited maximum boron uptake during early spring growth.
The leaves of the trees in an oak - hornbeam forest (Quercus petrae, Q. cerris,
Carpinus betulus, Acer campestre, Comus mas, Crataegus oxyacantha and Ligustrum
vulgare) accumulated boron and calcium up to three times the levels found in the .
leaves in the spring.
Disease state may affect boron accumulation. The boron content
of a clubroot-sensitive cabbage cultivar was higher than in a clubroot-resistant
one. As clubroot infection in the sensitive strain worsened, the boron content
increased even more. In the resistant strain, however, the boron content in-
itially increased slightly and then decreased during clubroot infection.
Boron can affect the accumulation of other substances„ In
dry matter from vineyards and apricot orchards in the Rhone Valley in Switzerland^
a fluoride content up to 600 ppm was due to a boron-containing combined fertilizer.
A particular boron-fluoride chemical combination of unknown composition, but
si.irii.lar to KBF. is formed in the fertilizer during the manufacturing.
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x. Toxicm
A. Humans
1. Acute Toxicity
The minimum lethal dose of boric acid or borates for man is not
established. Intakes of up to four grams per day have been reported in an adult
without incident, but single doses of 18 to 20 grams in adults have been
claimed to be fatal. Intravenous doses in excess of 20 grams have been used
in neutron capture therapy of brain tumors without permanent effect.
The most common intoxications from boric acid result from oral
intake by infants or from absorption through the skin or bladder after treat-
ment for infections. The symptoms of boric acid poisoning, regardless of the
route of administration, include nausea, vomiting, headache, diarrhea, erythema,
hypothermy, restlessness, weariness, desquamation, renal injury, and death
from circulatory collapse and shock within five days. The clinical picture
of boric acid poisoning was indistinquishable from toxic epidermal necrolysis
in the newborn infant. An autopsy of an infant fatally poisoned by treat-
ment of oral cavity sores with boric acid solution and treatment of consequent
erythema with boric acid powder revealed congestion and edema of the brain,
myocardium, lungs and other organs, with fatty infiltration of the liver.
Several cases of fatal poisoning due to boric acid irrigation of the bladder
(118 119)
after prostatectomy have been reported. ' The National Clearinghouse
for Poison Control Centers reported 166 cases of boric acid poisoning, in 1972,
117 for children less than 5 years old.
Infants have been accidentally poisoned in hospitals from .formulas
(41)
prepared with boric acid. Since no antidote exists, but equally effective
treatments do, many workers feel boric acid should not be used for medical pur-
poses. Some evidence exists, however, that boric acid poisoning by absorption
through the skin is a serious possibility only in patients with kidney damage.
Experiments conducted with rabbits showed that the biological half life of
boric acid was significantly prolonged in rabbits with kidney damage.
Borax is also absorbed through the skin and produces similar
symptoms. Boric acid toxicity may be detected by the analysis of borates in
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KR/AR INC. i-67
(122)
ths urine by the polyvxnyl aloohol-borate-iodine reaction since borates
are rapidly excreted by the kidney in largely unchanged form.
Hypoacidity in adults and decreased fecal enterokinase activity
in children were observed in 288 persons drinking high boron water for pro-
longed periods.
Decaborane in low doses is known to have severe disruptive
effects upon behavior. The symptoms include depression, catatonia,
muscular fasciculations, and occasional convulsions. Little or no central
nervous system damage has been reported as a result of toxicological research
. . . (126)
on borano fuels.
Boron trifluoride is corrosive to the eyes, skin, and mucous
nnEmbranes, and will cause burns on the skin similar to, but not as penetrating
as, hydrogen fluoride. Boron trichloride and boron tribromide are also very
corrosive. These effects are apparently due to hydrolysis of the boron trihalides
to the halogen acids and not to boron.
Organic derivatives of boric acid potentiate the sedative action
of hypnotics.
2. Chronic Toxicity
Workers engaged in the packaging of boron fertilizers complained
(52)
of poor appetite, nausea, and loss of weight. Aerosols and inadequate
shieldinc) in the boron carbide industry may create a risk of pneumoconiosis and
. (128)
pneumosclorosis.
Concentrations of boron compounds in the.fumss and aerosol of
boric acid production were two to five times permissible levels, sulfuric acid
fumes were above normal in 64% of the samples, and high temperature and humidity
prevailed. Medical examinations of 291 workers revealed alterations of upper
respiratory tract muoosa, arthralgia and arthropathies. The percentage of
(52)
gynecological diseases was rather high. Man engaged in boric acid pro-
duction showed weakened sexual activity, decreased seminal volume, low sperm
(129)
count and motility, and increased seminal fructose.
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Inhalation of the dust from datolite ore (a mixture of 2CaO •
B 0 • 2SiO • H20 and Ca^FeMn] . Al3B(OH)Si.O _ containing 9.5% boron), ore
concentrate (15-17% boron), or silicon dioxide irritated the lungs and in-
(52)
hibited phagocytic activity m industrial workers.
The daily ingestion of 25g of boric tartrate over a period of
20 years in one case resulted in chronic boric acid poisoning. The symptoms
included cachexia, dermatitis, alopecia, hypoplastic anemia and gastric ulcer.
All symptoms disappeared when the drug was withdrawn, but reappeared when
therapy was resumed because of epilepsy. No medical evidence of chronic
effects of boron trifluoride has been found among workmen exposed to small
amounts for periods up to seven years. However, in persons subjected to
boron trifluoride, disturbances of vascular permeability, enhanced tendon
roflexos, joint diseases and atrophic changes in the nasal mucosa were
observed.{131)
B. Mammals
1. Acute Tbxicity
LDrQ doses of borax and boric acid were determined in rats as
shown below:
LDcn of Borax & Boric Acid
Sex & Strain
Sprague Dawley males
.Long Evans males
Sprague Dawley
females 5.98 0.57 4.C8 0.71
IA-n levels could rot be determined for dogs as they vomited high closes no matter
how they were disguised. The animals showed no toxic effects.
Acute effects of sodium pentaborate decahydrate and tetraborate
decahydrate were studied by intravenous and intraperitoneal injections of rats.
Acute toxicity was less with intraperitoneal injections, and injection of glucose
Borax
4.50
6.08
Boron Equiv.
0.51
0.69
Boric Acid
3.45
3.16
Boron Equiv.
0.60
0.55
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1-69
reduced toxic effects of pentaborate more when intraperitoneally injected
than intravenously injected.
Methylene blue added to a five per cent dextrose infusion 20
minutes after administration of 30 rogAg decaborane to rabbits followed by in-
fusion of dilute methylene blue for 47 hours prolonged the life of the animals
to over 24 or 48 hours. All untreated rabbits died within 24 hours. ^3)
In monkeys, intraperitoneal injections of decaborane (6 mg per kg)
resulted in death within three days. Daily injections of 1 mg per kg gave rise
to an altered electroencephalogram characterized by a high frequency pattern
of discharge and high voltage bursts in the hypothalamus .
The LCV_ doses for inhalation exposures to pentaborane for mice
and dogs were determined to be as follows:
of exposure
(min)
U:5Q (irg/m3)
Mice
1,034
342
136
50
Dogs
.
734
324
92
0.5
2
5
15
o 3
The 2-minute IA-0 for monkeys was 640 rag/m . Dogs and monkeys, showed severe
signs of intoxication after exposure to one half the I£r0 values, but not after
one fourth or one eighth the LCL0 valiKS. No notable changes in blood cell com-
ponents, BSP retention time and no gross or microscopic lesions were observed.
The conditioned avoidance response was altered after 1/2 LC exposures.
2. Chronic Toxicity
Effect levels in rats and dogs produced testicular degeneration in
males, ,-ind cjrowth suppression and decreased food intake in both sexes. The
"no effect" levels are shown below:
"No l'.:f feet" Levels of Borax and Boric Acid (ppm)
(35)
Borax Boric Acid
4600 3000
1540 3000
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fAK INC. 1-70
Reproduction studies showed sterility of both species with 1170
ppm boron equivalent for both chemicals, but normal fertility, litter size,
weight, and appearance occurred at 350 ppm boron equivalent. In mice
boric acid produced testicular atrophy with degeneration of the seminal cells.
Dogs given drinking water containing two to three mg boron per
liter had decreased gastric juice secretion and decreased free and total acidity.
Enterokinose activity was inhibited in intestinal juice and feces. Bats are
relatively resistant to boric acid poisoning; they can survive daily doses up
to 3gAg for 16 to 24 months. The males are more sensitive than the females. A
25% weight loss precedes death. Male mice given boric acid in their drinking
water died within two to six months, but only 10% of the females died. Male
rabbits given boric acid by gastric tube died within 36 days with up to 30%
weight loss. Male rats subjected to long term dosage with boric acid had
testicular atrophy and became sterile.
In rats experimentally poisoned with boric acid, potassium boro-
tartrate or tolboxane (2-methyl-2-propyl-l,3-propanediol p-tolylborate),
urinary elimination was relatively rapid after single or repeated small doses,
but was much slower with tolboxane in repeated doses than with other boron
compounds. Placental passage led to a considerable diminution of vitality in
young pregnant animals fed boric acid. Even though mobilization from tissues
was fairly rapid, longer retention of boron occurred in some organs of chronic-
ally poisoned rats..
Administration of boron to young rats during enamel formation
altered the shape of teeth.
Daily intragastric administration of 100 mg of calcium borate
per kg to rabbits for four months gave rise to a slight increase in total serum
lipids and free sulfhydryl groups in serum. Inhalation of calcium borate
3
(120-150 mg per m ) by rabbits, two hours a day for ten weeks, retarded normal
weight gain, increased nitrogen compounds in the urine and increased the size
of the liver. Considerable changes in the respiratory tract consisted of
chronic tracheitis and bronchitis, with signs of tissue destruction over the
(52)
entire length of the tract.
-------
/
KR/AR INC. 1-71
Marked inhibition of glycolytic enzymes and an increase in methemo-
qlobin was observed in erythrocytes of guinea pigs with borate toxicity. * •*••*"'
Groups of rats given boric acid and thiourea via a stomach catheter exhibited
more pronounced thyroid enlargement and slowing of the heart than the control
group or rats receiving thiourea alone. The largest decrease in rates of
radioactive iodine uptake and clearance was also observed in the former group. '
Rats were exposed to aerosols of boron oxide for as long as 24
weeks. The highest concentration used was 470 mg per m for 23 weeks. The mass
median diameter of the particles was 1.9 to 2.5 microns. No deaths or other
signs of intoxication were observed in rats exposed to aerosols of boron oxide
at a concentration of 470 mg per m for 10 weeks. Dogs exposed to 57 mg per m
exhibited increased urine volume, urine acidity and creatirine clearance.
Chronic intoxication with boric acid (0.20-0.80 g per kg) affected spermatogenesis
in rats, depending upon the physiological state of the testis. During the pre-
puberal period, boric acid has little effect on the testis, but during puberal
crisis, boric acid exerts its strongest effects. Mitotic activity in the testis
is greatly lowered, sometimes resulting in complete destruction of the spermato-
genie line. There is only partial sensitivity to boric acid during the adult
period. Rats poisoned with sodium borohydride apparently die due to
gaseous embolism subsequent to the discharge of hydrogen. ' Bradycardia,
elongation of the P-Q interval by 20%, and elongation of the electric systole
by 30% were some ot the cardiovascular changes observed in rabbits given 30 and
35 mg/kg doses of sodium borohydride by stomach tube. '
Decaborane (HEF-3) applications to the skin of rats gave rise to
hyperercietation, aggressive behavior and central depression. Slight changes
(144)
in the nerve cells were demonstrated. The intraperitoneal injection of
dccaborane (20 mg per kg) to rats produced a strong increase in the levels of
blood in the urine within a few hours after injection. This is apparently an
effect on nitrogen metabolism and not a result of kidney injury. ' Exten-
sive changes in tissue amino acid levels followed borane administration in rats.' 2'
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AR INC.
1-72
In conscious dogs, the administration of pentaborane and de-
caborane produced limitations of sympathetic activity evidenced by miosis,
relaxation of the nictitating membrane, bradycardia, dilation of superficial
vessels, and sedation with easy arousal. Anesthetized dogs showed an initial
rise in blood pressure, followed by hypotension, bradycardia and decreased
response to tyramine. Pentaborane is comparatively more active in producing
excitement and convulsions. Lethal injections of decaboranes in dogs
produced a progressive decrease in heart force to terminal levels, but numsrous
intervening sustained intervals of hypertension were observed. Progressive
changes included decrease in P wave height, slow A-V nodal rhythms,
occasional ectopic beats , and long periods of asystole .
Intravenous perfusion of rabbits with various organoboron compounds
revealed that the toxic effects of the di (parachlorobenzeneboronate) of penta-
erythritol were clearly distinguishable from the others. The symptoms produced
by this drug included augmentation of blood pressure with tachycardia and apnea,
(61)
interrupted by a sudden drop in blood pressure and bradycardia. In rats
and mice the toxicity of this compound was found to be relatively lew. The
sublethal dose (largest dose that can be given without causing mortality, however
long the period of observation) was more than 1 g/kg intraperitoneally and
2 to 3.5 gAg orally. Rats seemed to be more sensitive than mice. Sublethal
doses did not produce any signs of toxicity, but larger doses produced prolonged
coma up to 48 hours. The latent period for definite onset of action is two to
four days. The recovery of survivors is rapid, with no apparent sequelae. ^ '
3- Teratogenicity
Oral administration of 3.0 mg/g boric acid to mice on the first
clay of preqnancy prevented 93.8% of the embryos cultured in vitro from reaching
the blastocyst stage. Only 8.7% of the control embryos failed to reach the
blastocyst stage. Oral doses of 0.5 or 1.0 mg/g had similar but less significant
effects. Addition of .1 and .01 mg/ml boric acid to embryo cultures from un-
treated mothers inhibited embryonic development to the blastocyst stage by 100%
(147)
and 51* respectively. v
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M/i/< INC.
1-73
4. Allergic Reactions and Sensitization
No sensitizaticn to boric acid or borax was found. In 99
patients treated for mycoses of the feet with Exanycolcgel containing 0.05%
phenylrnercuric borate, five cases of eczematous irritation developed in patients
(89) c
who earlier had exhibited local eczema. Applications of Zyma , containing
0.06% phenylmercuric borate, under an occlusive bandage produced irritation,
but on open skin, little or no response was observed. (90) Reaction to these
gels is apparently due to mercury sensitivity.
Skin lesions and erythema in man and mouse have been
produced by thermal neutron boron-10 reactions with the skin following irradi-
ation.
5. Behavioral Effects
Decaborane in low doses is known to have severe disruptive
effects upon behavior ' Intraperitoneal injections of one mg per kg per
day of decaborane to monkeys with implanted brain electrodes produced changes
in the electroencephalogram consisting of high frequency patterns of activity,
and high voltage bursts in the hypothalamus. Accompanying behavior included
depression, somnolence, generalized twitching and short motor seizures.
Boron-deficiency in plants apparently renders them unattractive
to bees. Borax application restores the attraction. Boron apparently promotes
nectar secretion.
6. Carcincgenicity
No evidence has been presented for the role of boron as a possible
carcLnajon. Many studies on the long term selective uptake of boron by tumors
have been done for possible use in neutron-capture cancer therapy.
C. Nonmammalian Vertebrates
Boric acid treatment produces malformations in chicken and amphibian
embryos. After injection of a twenty-four-hour-old chicken yolk sac with 0.05
ml of sterile 5% boric acid solution, initial effects appeared in the three-day-
old embryo. The neural tube, notochord, tail-gut and tail blastema were deformed.
Pyknosis of the indifferent cell mass of the tail blastema appeared in 30-35%
of the boric-acid-treated embryos. Blood vasculature was not affected in these
-------
fAK INC. 1-74
rumpless chick embryos. Boric acid also produced malformations in liitfo
development in chicken embryos. The results were most clearly seen in the
tarsometatarsus, which was bent backwards and severly shortened. Abnormal
bends in the tibiotarsus were also seen. By day 13, the effect of boric acid
may be the on deswelling capacity, which affects the cartilage cells and the
cartilage matrix, thus weakening the supporting body effect. Boric acid may
further interfere with the process of extension of the collagen fibers,
/CQ\
especially those of the sinews.
Boric acid apparently exerts its teratogenic effects by conplexation
of fX)lyhydroxy compounds, interfering with metabolism on the cellular level.
Riboflavin content of livers of morphologically abnormal chicken embryos was
sharply reduced. Addition of riboflavin or polyhydroxy compounds such as D-
ribose, sorbitol, etc., to the boric acid treatment decreased teratogenic effects.
Plumage color of the mother had a definite effect on progeny response to boric
acid. A lower incidence of boric acid-induced abnormalities was observed in
the spring.
When embryos of Bufo vulgaris were treated with 0.5% boric acid for
24 hours from the two cell stage to the tail bud stage, the malformations ob-
served included edema, microcephalia with rudimentary stomodaeum or sucker,
approaching of the olfactory pits, short tail and a reduction or lack of external
gills. The epiphysis became befurcated into a pair of vesicles of less vacuolized
cells lying side by side. The forebrain showed a tendency to form a single
tube with a narrow ventricle. Manorhiny, synrhiny, anophthalmia, cyclopia, and
synophthalmia accompanied the suppression of forebrain development.. The bi-
furcation of the epiphysis and the inhibition of sense organ development, to-
getlier with the poorly developed forebrain, seem to be a result of the direct
action of boric acid on the ectoderm.
Vitamin C has been shown to decrease the phenylmgrcuriborate intoxic-
(70)
ation of Rana temperaria tadpoles.
D- Invertebrates
Boric acid has been demonstrated to be an effective stomach poison
for several species of insects. The effect of mixtures of boric acid and sugar
on the mortality of the German cockroach can be summarized as follows:
-------
1-75
Doric Acid:Sugar Mortality (%) after 72 hours
1:9 44.3
2:8 79.4
4:6 96.7
5:5 88.3
10:0 91.1
Other studies have produced similar results. ' ' Apparently the
cockroaches cannot detect the presence of boric acid. Mosquito larvae
differ in susceptibility to boric acid poisoning. Only 2% of the freshly
hatched larvae of Anopheles quadrimaculatus reached the adult stage after
treatment with 50 ppm netaboric acid. Treatment of the freshly hatched larvae
of Acdes aegypti and Culex quinquefasciatus with 250 ppm boric acid allowed
only 1% and 3% respectively to reach the adult stage. Elimination of various
larval stages of the three species within 48 hours could be acoonplished by
treatments with boric acid as follows:
Larval stage Boric acid required (ppm)
Freshly hatched 4,000
2nd instar 3,000
3rd instar 10,000
pupae 16,000
Insect infestation of wood and other substrates can be prevented by
pretreatment with boric acid or borax. Termite attack on tie matai and radiata
pine could be reduced by treatment with enough boric acid. Coptoternes spp.
was more susceptible than was Nasutitermes exitiosus. Larvae of the two-
toothed longhorn beetle, Ambeodontus tristis, did not survive in blocks of sap-
wood kahikatea (Podocarpus dacrydioides containing 0.142% or more boric acid.
3 3
Boric acid (0.4 kg/m of wood) and borax (0.55 kg/m of wood) were lethal to
egq-larvae of lly.lotrupes bajulus after 12 weeks. The lethal doses required for
_j ^ 3
elimination of Uic infestation within six months were 0.3 kg/m and 0.35 kg/m
respectively. Older larvae of H. bajulus and Anobium punctcvtum were only slowly
affected. Powder post beetle attack was prevented by treatment of the
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1-76
ZOO
ISO
'•-... SUGAR BEET
UJ
O
oc.
LU
Q.
5 10 15 20 25
PPM BORON IN SOIL SOLUTION
Effect of Boron concentration
-------
1-77
rubberwood (Hevea brasiliensis) with boron salts. ' Treatrtent of wool with
boric acid effectively controlled black carpet beetle larvae. '
Traps baited with cottonseed hydrolysate containing borax reduced
infestation of navel oranges by fruit flies (Anastrepha ludens) by 68%, and
in mangoes, by 98%.
The toxicity of organoboron compounds makes them useful as insecticides.
Isobomyl thiocyanoacetate (IBTA) had an LD5Q of 27.3 micrograms per insect
against domestic houseflies. Aerosol borttos containing IBTA had a KT-. (knock-
down time) of six minutes. The effectiveness of IBTA was greatly decreased in
concentrations below two per cent. Boronyl acetate from the volatile oils
of conifers was the most toxic of the components of the oil to the larvae of
Tribolium destructor.(165^
Boric acid and other boron compounds have been demonstrated to be
effective chemosterilants of the housefly, Musca domestica,(166' 16') and
the oottcn boll weevil.
E. Plants
Although boron is a nutritional requirement for most plants, too much
boron is toxic. The dual effects of boron are illustrated in Figure 9, ^•L&B' 3::>'
The amount of boron in saturation-extract concentrations of the soil is plotted
against the plant weight expressed as a percentage of the average weight of the
plant grown in soil containing trace boron.
Plants are classified as sensitive, semitolerant or tolerant to boron
in soil extracts in two ways. Table 10 lists crop species in groupings based
on the levels of boron in micrograms per ml of soil extract which produce toxic
effects. ' The most sensitive plants are listed at the top of each column.
Plants arc also classified into three categories based on a relative tolerance
index. The i.ndex is 100 tiircs the ratio of the averaged weight of plants
grown in 5, 10 and 15 ppm boron to the largest weight of plants grown in either
trace or 1 ppm boron Table 11 summarizes this data.
The toxic symptoms of boron include stunted growth, malformations of
loaves, browning and yellowing, chlorosis and necrosis. Pollen germination and
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\R INC.
1-78
!U. 'l\)X.lt' lentil OuhifiMtralichB uf Etal uratidtt
Kxtracts for Sensitive, Semitolerant Crop
Species* (35)
Saturation-Extract Boron, ygrams of B/inl
0.5-1.0
Sensitive
Citrus
Avocado
Aprioot
Peach
Cherry
Persimmon
Fig
Grape
Apple
Pear
Plum
Navy bean
Jerusalem artichoke
WaJ-nut
1.0-5.0
Semitolerant
Lima bean
Sweet potato
Bell pepper
Oat
Milo
Com
Wheat
Barley
Olive
Field pea
Radish
Tomato
Cotton
Potato
5.0-10.0
Tolerant
Carrot
Lettuce
Cabbage
Turnip
Onion
Broad bean
Alfalfa
Garden beet
Mangel
Sugar beet
Palm
Asparagus
""Listed in each category according to susceptibility to boron injury (viz., citrus
is more sensitive than walnut, lima bean more than potato, etc.).
-------
INC,
1-79
PLANT
Table 11.
Plant Growth as Affected by Boron
(35)
Boron Cone. Lowest Cone.
For Best Growth For Injury
(ppm) (ppm)
Relative
Tolerance
Index
SENSITIVE PLANTS
Blackberry (Rubus sp.) Trace
Lemon (Citrus limonia osbeck) Trace
Elm (Cimus americana. L.) 1
Cherry (Prunus arium L.) 1
Peach (Prunus. pergica (L) Batsch) 1
Persimmon (Diospyrps kaki L.f.) 1
Fig (Ficus carica L.) 1
Strawberry (Fraqaria sp.) 1
Lupine (Lupinus hurtweqi Lindl.) 1
Grape (Vitis roxiifera L.) l
Violet (Viola odorata L.) Trace
I'ansy (Viola tricolor L.) Trace
Kidney bean (Phaseolus vulgaris L.) 1
Cowpea (Vigna sinensis (Torner)
Savl) Trace
Jerusalem artichoke
(Helianthus tuberosus L) 1
Larkspur (Delphinium sp.) 1
Zinnia (Zinnia elegans Jacq.) Trace
1
1
1
5
5
1
5
5
5
5
5
5
1
1
5
1
9
20
24
30
34
43
45
Boron
Deficiency Symptom;
With Trace Boron*
S
None
S
S
2
S
S
None
M
S
None
None
None
D
None
S
None
SEMI-TOLERANT PLANTS
Barley (llordeurn yulcjare L.)
Pea (Pisum satlvum L.I
.Lima tean~(jPhaseoTus tunatus L.)
Sweet Potato
(Ipoinoca batatas (L) Lam.)
Onion (A.1 .lium cepa L.)
Carrot (Daucus carota L.)
Red pepper
(Capsicum frutescens L.)
Kentucky bluegrass
(Poa pratensis L.)
Com (2ea mays L.)
Potato (Solanum tuberosum L.)
Cabbage (Brassica oleracea
var. capitata L.)
Milo (Sorghum vulgare Pers.)
Calendula
(Calendula officinalis L.)
Trace
1
Trace
Trace
Trace
Trace
Trace
5
1
1
1
Trace
Trace
5
5
1
5
1
10
1
5
1
10
5
51
55
57
63
68
70
71
86
53
78
78
(8)
80
D
None
S
S
None
None
None
None
None
S
None
M
None
-------
1-80
Table 11 (Can't)
Plant Growth as Affected by Boron
Boron Cone. Lowest Cone. Relative
For Best Growth For Injury Tolerance
PLANT (ppm) (ppm) Index
SEME-TOLERANT PLANTS (Con't)
Radish (Raphanus sativus L. ) 1 10 60
Oats (Avena sativa L. )
Celery (Apium graveolens L. )
Mustard (Brassica sp.)
Parsley (Petroselinum
crispum (Mill . ) Nym. )
Alfalfa (Medicago sativa L.)
Lettuce (Lactucca sativa L.)
Tobacco (Nicotiana tonientosa
Ruiz and Pav. )
Vetch (Vicia atropurpurea Desf.)
'lomato
(Lyoopcrsicon esculentum Mill.)
California Poppy
(Eschscholtzia califoimca Cham.)
Turnip (Brassica rapa L.)
Coimon beet (Beta vulgaris L.)
Leaf beet
(Beta vulgaris var. cicla L.)
Muskmelon (Cucumis melo L.)
Sweet clover
(melilotus indica(L.)All.)
Sweet pea (Lathyrus odoratus L. )
Sugar beet
(Beta vulgaris var. crassa Alef .)
Oxalis (Oxalis bowiei Herb.)
Cotton (Cossypium hirsutum L.)
Artichoke (Cynara scolymus L.)
5
15
1
5
10
5
15
5
10
5
TOLERANT
5
5
5
5
5
10
5
10
10
5
5
25
10
15
15
1
10
5
5
5
PLANTS
25
15
25
5
10
5
15
None
10
5
86
89
94
95
106
96
96
98
99
99
115
112
110
107
. 110
113
121
121
130
123
(Asparagus officinalis L.)
51
25
*S .= presence of leaf or other morphological abnormalities.
M = tinn of flowering or ripening substantially affected.
D = trace-boron plants more severly attacked by mildew.
W = severe wilting.
217
Boron
Deficiency Symptoms
With Trace Boron*
S
None
S
None
None
None
None
None
None
None
None
None
W
D
None
S
None
S
S
S
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1-81
and pollen tube growth may be inhabited. Symptoms of boron toxicity in various
plant species are summarized in Table 12.
Necrotic leaves in sugarcane averaged 657.7 ppm boron, while green
leaves averaged 55.7 ppm. In China asters, if analysis of old leaf
tissue reveals a boron content of 750 ppm (dry weight basis), boron is the
probable cause of injury. If the tissue of a newly matured leaf of
Mathipln incana contains 200 ppm boron or more (dry weight basis), the boron
injury will probably be severe enough at the time of harvest to make the
i n (170>
crop unsalable.
In turf grass species, the species with rapid boron accumulation
showed leaf tip injury first. The practice of mowing removed the high boron
concentration in the leaf tips. The boron concentration of small areas
of leaves of rough lemon may be 100 tines higher than that in the petioles, and
the boron toxicity symptoms are reflected in this distribution. '
The addition of lime to soils containing high concentrations of boron
reduces the degree of injury by boron. ' ' 2-Choroethanol apparently
increases the boron resistance of wheat seedlings subject to boron toxicity. '
Phenylboric acid (PhB) produces toxic effects at lower levels than boric
acid. Addition of 300 mg/1 PhB to tomato, Oospora lactis, produced conspicuous
abnormalities of cell and leaf form not observed with 300-500 mg/1 boric acid.' '
Severe flower malformations (open pistils, tripistilly, and pistilloidy)
in L'isuni plants resulted from a single PhB treatment. Lanceolate leaf
shape was induced in Solanum lycopersicuns by PhB. The foliage of
Stellaria media seedlings was altered by a 2x10 M solution of PhB. '
PhB stimulates the lanceolate gene in the tomato. In addition to a change in
leaf form, increases in the activities of tyrosinase, laccase, peroxidase, and
catalasc occur. It is suggested that the mutant alleles of the lanceolate gene,
as well as PhB, produce increased oxidative enzyme activity, which results in an
alteration in leaf form.'-'-'"'
Diarylboronic acids were toxic to wheat roots at 10 M; 4x10 ' M
benzeneboronic acid hampered pollen germination and pollen tube growth. '
-------
Table 12. Synptoms of Borcn loxicity
species
cucimber
squash
nuskrrelon
corn
carnation (Planthus
caryophyllus)
Mathiola incana
peach
citrus
Chrysanthemum morifolium
groundnut
horsebean
peach
sugar beet
sunflower
Pinus radiata hydro-
ponic culture
Boron Levels
6 ppm
12 ppn
' 12 per,
16
180g_or 270g
to soil
2 . 5 ppm
10 ppm
Synptoms Reference
50% decrease in top (87)
50% decrease in top (87)
50% decrease in top (87)
50% decrease in top (87)
Ibnecrosis of leaf tips (34)
"considerable injury" (213)
Sloughing off of necrotic ground (214)
parenchyma cells along abaxial
leaf midrib
Chlorotic leaves at top and base (215)
of affected shoots. Necrosis at
tip and margins more pronounced
in older leaves
Marginal and interveinal yellowing; (216)
necrosis
Severe yellowing of leaves, chlorosis (221)
Browning; necrosis chloroplasts dis- (217)
integrate, thykaloids of matrix first,
then grana and outer menbrane
Delayed and scant blossoming; mal- (218)
formed fruits
Ladle-shaped leaves, decreased yield; (180;74)
increased transpiration
Morphological changes (180)
Decreased amount and concentration (219)
of NgK, P, Ca, Mg, Cu, Zn
CO
-------
Species
Setaria sphacelata
tall wheat Cflgropyron
elcngatum)
maize
citrus fruits
Citrus sinesis
Citrus reticulata
berseem
oats
cabbage
Kalai
red bean
vable 12. Synptoms of Boron Tbxicity (Con't)
Boron Levels Synptcms
50 mg/1
3>38 pprr.
B, no Ca
0.47-5 ppr< in soil
around roots
> Ippm-sand
> 2ppn—loarn
Inhibition of pollen germination
and pollen tube growth
50% decrement in growth
Iteduced germination and pollen
tube growth
Less chlorophyll; higher water con-
tent; thicker, smaller leaves
tree collapse
water absorption affected
4.8 ppra
> 11 ppm
100 Ib/2xl06 Ibs soil
> 500g/10 acres reduced yield
Reference
(174)
(205)
(206)
(207)
(208)
(192)
(209)
(209)
(210)
(211)
CO
CO
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KR/AR INC. . i-84
Morphological changes in the sunflower characteristic of maternal
plants briefly deprived of boron persisted throughout one gsneration, and even
in the third generation, the changes were retained in isolated instances. ^180'
F. Microorganisms
The use of boric acid as a fungicide and an antiseptic is discussed
under "Therapeutic Uses."
A genetic transformation of Strain 1029 of Actinomyces indigocolor
which was previously grown and adapted to a low boron medium was effected with
the aid of DNA from A. indigocolor, Strain 1100, which was adapted to a medium
• • ~ *T~ 0.81)
containing an excess of boron.
After a 10 minute germicidal ultraviolet irradiation, the surviving
spores of an actinomycete (Streptornyces spp.) were highly resistant to phenyl-
msrcuric borate, a disinfectant. Spores irradiated for two minutes were not
so resistant.
G. Rasults of Personal Contacts with Medical Personnel
A total of 74 toxicologists and medical examiners in various parts
of the United States vere contacted by letter or telephone under this program.
It was inquired of these contacts whether they, in their professional experi-
ence, had encountered a case of human poisoning by boron compounds. Of the 31
responses, there were nine reports of poisonings by boron compounds. Of these,
five cases proved fatal.
Most of the cases reported for boron involved the misuse of boron
compounds (borax or boric acid solutions, boric acid powder) in hospitals. Of
the five fatal poisonings, four were of this type: (
3 arose fixan accidental substitution of boric acid solution for
water in infant formula
1 arose from accidental use of boric acid as a diapering powder
The other fatality apparently arose from the spraying of borax onto
forest fires. Although details are not known it is surmised that the victim
was inundated when a large amount of borax solution was dumped from a tank.
-------
f TT i-85
[\R INC,
One reply mentioned that boron (or its oonpounds) has soros repute
as an aphrodisiac, and that the respondent had noted a urine and gastric .
sample of unusually high boron content. The condition of the patient was
not known.
-------
\R INC.
XI. CURRENT REGULATIONS AND EFFECTS LEVELS
A. Toxicity Levels
LD50 (dosage at which 1/2 test animals die) - from tests on rats
(222)
by oral administration:
Material mg/kg of body weight
Borax 6050
Boric acid . 5140
Irrigation waters - limit of 1 ppm boron (no official limitation)
Proposed criteria according to type of crop to be irrigated:
Crop Species Critical boron concentration, ppm
Sensitive 0.3 - 1.0
Semi-tolerant 1.0 - 2.0
Tolerant 2.0-4.0
Sensitive plants: blackberry, lemon, elm, cherry, peach, persimmon,
fig, strawberry, lupine, grape, violet, pansy, kidney bean, cowpea, Jerusalem
artichoke, larkspur, zinnia.
The presence of boron in great enough concentration to cause crop
damage in some potential irrigation water in parts of Western United States has
prompted proposals for criteria for the boron content of irrigation water. No
(9)
official standard has been set yet.
(223)
B. Transportation and Handling Regulations
The only boron compounds covered in this survey are those which are
included in "Commodity List of Explosives and Other Dangerous Articles".
They are boron trichloride, boron trifluoride, decaborane and pentaborane.
Boron trichloride is classified by the Interstate Commerce Conmission
as a corrosive liquid, requiring a white label. The maximum quantity allowed
in containers by rail express is 1 liter. International Air Transport Associ-
ation (IATA) regulations limit its transport to 1 liter carried in cargo planes
only.
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1-87
rAR [N(l
Boron trifluoride is a nonflammable gas, requiring a green label.
It is restricted to 140 kg in one outside container by rail express. IATA
regulations permit the transport of up to 140 kg in cargo planes only.
Decaborane is classified as a flammable solid requiring a yellow
label. Rail transport is limited to 12 kg in one outside container. IATA
regulations permit cargo planes only to carry up to 12 kg of decaborane.
Pentaborane is a flamnable liquid, requiring a red label. It is
not accepted for rail express. IATA regulations prohibit its transport in
both passenger and cargo planes.
C. Foreign Regulations
In the U.S.S.R the recommended maximum permissible concentration
3 (224)
of calcium borate dust in the air of working locations is 4-6 mg/m of air.
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fAK INC.
XII. STANDARDS
3 (225)
Boron oxide - TLV - 10 mg/m .
This value was reoaranended in view of the very low toxicity of test
animals to boron oxide aerosols.
3 (225)
Boron trifluoride - TLV - 1 ppm*(approximately 3 mg/n ). '
Boron tribromide - TLV - 1 ppm*(approximately 10 mg/m ).^ '
*parts per million by volume
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1-89
XIII. SUMMARY AND CONCLUSIONS
A. Summary
Boron is a ubiquitous element, found in 10 to 30 ppms in soils,
about 0.1 ppm in surface waters, and 4.5 ppm in sea water. In spite of this,
the domestic sources of boron raw materials are concentrated in the desert
areas of California, and consequently the processing plants for these raw
materials and those for production of bulk boron chemicals are located within
a small region. The major raw material in this case is borax, which is the
keystone of the boron industry. A consequence of this situation is that con-
tamination of the environment from natural sources of boron materials is found
within a relatively limited area.
Boron enters the environment at a rate of approximately 32,000
metric tons per year for the United States. Most of this ends up in the waters.
About one-half of the total amount enters the water directly from laundry pro-
ducts and sewage.
Boron compounds are absorbed by the intestine, mucous membranes and
skin. Excretion is mainly via the urine, but complete excretion is slow and
boron may accumulate. Inorganic borates are quite toxic, apparently complexing
hydroxy compounds and interfering with protein synthesis. Organoborate compounds
exert physiological effects on the peripheral and central nervous system,
acting as spasmolytics, sedatives and convulsants, depending upon the structure.
Boranes produce toxic effects by creating embolisms of hydrogen gas as they
react with tissue.
No boron carcinogenic!ty has been reported. Erythema and swelling
may develop in individuals sensitive to boron. Boric acid is a potent teratogen
when applied directly to the embryo. Boron compounds are selectively accumu-
lated by some types of tumors and boron-10 compounds are used as neutron capture
targets for tumor localization and treatment.
Boron is a growth requirement for plants and not for animals, but
fax) much boron is phytotoxic. Plant species vary greatly in their sensitivity
to boron toxicity. Boron compounds have been widely used as fertilizers, in-
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1-90
secticides, fungicides, and bacteriocides.
The long range effects of boron oorrpounds on fish and birds
and other marine organisms have not been investigated.
Medical and household use of boric acid solutions as antiseptics
has led to numerous accidental poisonings through ingestion or absorption
through the skin, particularly in infants. Boric acid and borax are used
as insect control compounds in wood preservation. Boric acid is also used
to eradicate cockroaches.
D. Conclusions
The following conclusions are based on the material presented in
this report on environmental effects of boron and its compounds:
1. Environmental contamination of the air with boron compounds
does not appear to pose an environmental problem. Hazardous atmospheric con-
ditions stemming from high concentrations of boron or its compounds is entirely
localized.
2. Future build-up of boron in ground waters could cause detrimental
effects to aquatic and other species of plants and animals. This is presently
the case for areas where natural boron deposits are found. Plant toxicity effects
could become generalized if boron-containing cleansing agents become more
widely used in this country.
3. 'Che acute toxicity of humans to boric acid has led to an in-
ordinate number of poisonings which could probably have been prevented by
minimal use of warning labels or substitution.
C. Recommendations
The following recommendations are based on the conclusions pre-
sented in Section XIII C above:
(1) Boron increases in U.S. waters should be closely studied with
regard to effects on aquatic species should the use in this country of boron-
containing cleansing agents increase significantly. Any detrimental effects
should be noted first in Europe, where such usage of boron compounds is already
intensive.
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'Mi/Alt I ML '
(2) Use of boric acid (and, perhaps, other boron-containing
conpounds) as externally applied antiseptics (or similar uses) should be
discouraged because of its toxicity. Further study should be made to
ascertain proper regulation in this case.
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