An Introduction to Boron: History, Sources, Uses, and Chemistry

Author(s): William G. Woods

Source: Environmental Health Perspectives , Nov., 1994, Vol. 102, Supplement 7: Health
Effects of Boron (Nov., 1994), pp. 5-11
Published by: The National Institute of Environmental Health Sciences

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 An Introduction to Boron: History,
Sources, Uses, and Chemistry
William G. Woods
Office of Environmental Health and Safety, University of California, Riverside, California

Following a brief overview of the terrestrial distribution of boron in rocks, soil, and water, the history of the discovery, early utilization, and g
origin of borate minerals is summmarized. Modern uses of borate-mineral concentrates, borax, boric acid, and other refined products incl
fiberglass, washing products, alloys and metals, fertilizers, wood treatments, insecticides, and microbiocides. The chemistry of boron is r
from the point of view of its possible health effects. It is concluded that boron probably is complexed with hydroxylated species in biologic
and that inhibition and stimulation of enzyme and coenzymes are pivotal in its mode of action. ? Environ Health Perspect 102(
5-11 (1994)

Key words: boron, borax, colemanite, glass, boric acid, health effects, enzyme, review

Introduction
retardants, as micronutrients in fertilizers were an important source of boric acid in
Boron is an ubiquitous element in rocks, and for many other purposes, as well. Europe from about 1820 to the 1950s.
soil, and water. Most of the earth's soils The varied chemistry and importance Borax also was made from Italian boric
have <10 ppm boron, with high concen? of boron is dominated by the ability acid of in England, France, and Germany.
trations found in parts of the western borates to form trigonal as well as tetrahe- The borate industry in Turkey com-
United States and in other sites stretchingdral bonding patterns and to create com- menced in 1865 with mining of the calci?
from the Mediterranean to Kazakhstan. plexes with organic functional groups, um borate pandermite (priceite,
The average soil boron concentration is many of biologic importance. 4Ca05B203-7H20). At about the same
10 to 20 ppm, with large areas of the The present review will give antime, several borate deposits were found
world boron deficient. Boron concentra? overview of boron from its sources to its in California and Nevada, including ulex-
tions in rocks range from 5 ppm inuses and chemistry to provide a back? ite (Na202Ca05B20316H20) and
basalts to 100 ppm in shales, and averagesground for the following papers dealing colemanite (2CaO-3B203-5H20) in
10 ppm in the earth's crust overall. Soils with its health effects. Death Valley. These minerals could be
have boron concentrations of 2 to 100 converted to borax by reaction with trona
ppm. Seawater contains an average of History4.6 and Sources (Na2C03NaHC03-2H20).
ppm boron, but ranges from 0.5 to 9.6 The Babylonians have been credited with The Kramer deposit, at what is now
ppm. Freshwaters normally range from importing borax from the Far East over Boron, California, in the Mojave Desert,
<0.01 to 1.5 ppm, with higher concentra? 4000 years ago for use as a flux for work- was discovered in 1913, first as a cole?
tions in regions of high boron soil levels ing gold. Mummifying, medicinal and manite ore source. In 1925, tincal ore was
{1,2). metallurgic applications of boron are found and in 1926, the new mineral
Highly concentrated, economically sometimes attributed to the ancient rasorite (kernite, Na202B203-4H20)
sized deposits of boron minerals, always Egyptians. None of this very old borax was encountered (4). It is the largest
in the form of compounds with boron history has been verified, but solidborate evi- deposit outside of Turkey and has
bonded to oxygen, are rare and generally dence exists that tinkar (i.e., supplied a sizable portion of world borate
are found in arid areas with a history of Na2B4O710H2O, tincal, the mineral demand for over 50 years.
volcanism or hydrothermal activity. Such borax) was first used in the eighth century Turkey has supplied colemanite for
deposits are being exploited in Turkey, around Mecca and Medina, having manybeen
years to boric acid producers in
the United States, and several other coun- brought there (and to China) byEurope. Arab Sodium borates were discovered
tries (3). Borate-mineral concentrates traders (4). The use of borax flux byin 1960 and other deposits have
at Kirka
and refined products are produced and European goldsmiths dates to about since been found and developed in
the
sold worldwide. They are used in a myri- 12th century. Anatolia. As a result, today Turkey is the
ad of ways: in glass and related vitreous The earliest source of borax is believed largest producer of borate products in the
applications, in laundry bleaches, in fire to have been Tibetan lakes. The borax world (5), exporting mineral concentrates
was transported in bags tied to sheep, of tincal, colemanite, and ulexite, plus
which were driven over the Himalayasrefined to borax decahydrate, borax pen-
This paper was presented at the International India.
Symposium on Health Effects of Boron and Its
tahydrate (Na20-2B203-5H20), anhy-
Compounds held 16-17 September 1992 at the Volatility of boric acid with steam drous
is borax (Na20-2B203), and boric
University of California, Irvine, California. believed by geologists to be the primary acid(B[OH]3).
Address correspondence to Dr. William G. Woods, mechanism for the formation of borate Borates in the United States are pro?
Office of Environmental Health and Safety, University
of California, Riverside, Riverside, CA 92521. deposits (3). A prime example of this areduced entirely in the Mojave Desert of
Telephone (909) 687-1568. Fax (909)787-5122. the geysers (soffioni) in Tuscany, whichsouthern California. United States Borax

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W. G. WOODS

low sodium, so boric acid or colemanite are

used. Glass batch melting is aided by B203
which acts as a flux to improve the melting
rate of more refractory components (e.g.,
Si02). As an added benefit, water given off
by the borates also accelerates the melting.
The alkali/alkaline earth oxide content
Figure 1. Aerial view of the US Borax mine and refinery at Boron, CA. (US Borax, Inc. photo)
is quite important to the effect of B203 on
the structure and properties of glass.
Adding Na20, for example, progressively
Table 1. Important refined borate products and mineral concentrates. changes trigonal B03 groupings to tetrahe-
Name Formula PercentB203 dral B04" groups, which initially causes an
increase in the glass transition temperature
Borax pentahydrate Na2[B405(0H)J-3H20 47.8
(Tg). Further addition of Na20 converts
Borax (tincal) Na2[B405(0H)4]-8H20 36.5 B04" bonding groups to nonbonding
Colemanite Ca[B304(0H)3]-H20 50.8 B03" n units, which decreases T^ as well as
Ulexite NaCa[B506(OH)6]-5H20 43.0 the melt viscosity. The latter helps in elimi-
Boricacid B(0H)3 56.3 nating bubbles from the finished glass and
Anhydrous borax Na2B407(glass) 69.2 gives good homogeneity and flattens the
viscosity-temperature curve. The latter
allows more latitude during manufacture
& Chemical Corporation, a subsidiary
and the former USSR also produce someof (forming) of the finished glass product, and
Rio Tinto Zinc (RTZ), borates. is the largest the lower viscosity allows higher pro?
source, producing borax pentahydrate
Table 1 gives a list of the commercially duction rates.
and decahydrate, and anhydrous
important borax
refined borate products and Borosilicate glass has increased thermal
from tincal ore, and mineral
boric concentrates.
acid from The formulas
ker-are shock resistance because B203 lowers the
nite ore (Equation 1). written in a form reflecting their structures.expansion coefficient. In fiberglass, boric
Na2B407-4H20 + H2S04 + H20 -> oxide gives desirable drawing qualities and
Uses
increases mechanical strength and chemical
4B(OH)3 + Na2S04 [1] Table 2 lists the uses of boron minerals and
durability.
An aerial photo of the US Borax chemicals
mine in the United States glass and Another 12% of United States B203 is
related uses consume about half of the
and refmery is shown in Figure 1. Another consumed in detergents and bleaches; the
US Borax plant at Los Angeles harborborates
pro- as boric anhydride (B203) in the percentage is even higher in Europe. Borax
duces ammonium and potassium borates, United States (6). Fiberglass accounts forhas been used as a laundry additive since
boric oxide, zinc borate, and spray the driedlargest share, comprising about 77%about
of 1900. It can contribute to the soft-
polyborates, in addition to serving the as an
total (54% for insulation fiberglass,ening of hard water by tying up calcium
export terminal. ions, as well as acting as a buffer agent. A
23% for textile grade). Heat-resistant pyrex
North American Chemical recovers and other low-thermal expansion glasses traditional use as a sweetening agent for
borax and boric acid as byproducts from consume about 18%, while enamels, frits, diaper pails is thought to involve the borate
potash, soda ash, and salt-cake extrac?and ceramic glazes consume 5%. Small inhibition of the urease enzyme, (prevent-
tion operations on Searles Lake brine. amounts are used in sealing and optical ing ammonia formation). The same effect
Ore concentrates are produced by has been patented for deodorizing animal
glasses, Vycor, and vitrifying nuclear waste.
Newport Mineral Ventures on the edge Boric oxide can be added to the glass litter (8). Products based on borax and for-
of Death Valley. formulation as borax pentahydrate, boric mulated with additives can give bleachlike
Peru and Chile produce ulexite concen? acid, or colemanite, with price and cation activity when added to the wash.
trates and boric acid, and Boroquimica in compatibility determining which is used Sodium perborates [NaB03lH20 or
4H20; PBS1 or PBS4]' are true persalts
Argentina operates a tincal deposit. China (7). For example, textile fiberglass requires

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 INTRODUCTION TO BORON: HISTORY, SOURCES, USES, AND CHEMISTRY

that traditionally have been blended into

powdered detergents in Europe as bleach-
HO Ov OH HO O OH
ing agents. Dilution in alkaline wash water B B B B,
results in hydrolysis of PBS to give
hydroperoxide ion (Eq. 2).
I I I TOH
Na2[(HO)2B(00)2B(OH)J
?6H20 + 20H--> HO OH HO OH
2NaB(OH), + 2QOH" + 4H20
[2]
B,03(OHV B303(OH)5"
Sodium perborate (PBS) is effective as a
broad-range bleach only at washing tem? O
peratures above about 60?C, unless an acti-
ftOH H(X />H
>\ >0. /0-BN
vator is present. Activators are organic acyl
derivatives, which react with the hydroper?
oxide ion formed by hydrolysis of the
perborate leading to peracid formation (Eq. XI ox o >N p
3). These peracids are effective bleaching
agents at low temperature. HO^ O'/ ^O OH HO X)H
HO
CH3(CH2)7COO -<^)-S03Na
SNOBS

or
B4Os(OH)4" BsO?(OH)4
(CH3CO) 2NCH 2CH 2N(COCH3 )2
TAED Figure 2. Polymeric borate anions (14).

+ 1 or2-OOH--> crops (2). Some crops susceptible to

Adequate boron is required for in
boron deficiency are apples, tion of phosphorus
alfalfa, sugar into RNA a
beets, and oil palms. Boron Lack
is one
ofof the also is suspected of
boron
CH3(CH2)7COOOH or 2CH3COOOH indoleacetic
more important essential elements for acid (IAA) in pla
[3] inhibiting
plant growth, and can be applied either IAA
to oxidase (2).
the soil or to the foliage. Although
Boratessmall
are used extensively in
At present, sodium 4-nonanoyloyben- amounts of boron are needed wood to by all
protect against decay b
zenesulfonate (SNOBS) is used in several plants, high concentrationsandcan be toxic
white rot, and staining by fun
detergents with bleach products in the to certain species. Borates andInsecticidal
combina- use of borates is attractive
United States, and tetraacetylethylenedi- tions of borates with organic herbicides
because of their low mammalian toxicity
amine (TAED) is used widely in Europe as are used to control weeds.
and lack of insect resistance compared with
well as in many other countries. The exact role of boron in plant metab?
the organic insecticides. The literature con-
tains over 150
PBS-based powdered bleach also is sold in olism is not known. Boron deficiency references in this field.
alters
the United States. Borax or boric acid can the plasmalemma of rootSpecies cells, which
showing promise for control by
be used to stabilize protease enzymes in results in reduced absorptionborate-based
of potassium, insecticides are the powder
liquid laundry detergents (9,10). chloride, and rubidium, as well
post as cessation
beetle (Lyctus brunneus) in hardwoods
Alloy and metal production consume (12) and
of root growth. Enzymes such aslarvae of several other beetles
glucan
another 5.5% of the total B203. Welding synthetase involved in pollenwhich
tube attack
cellsoft
wallwood. Some species of
rods and other fluxes use borates because growth apparently require subterranean
boron. Boron termites like Coptotermes
of their excellent metal oxide solubilizing also may control the amountand ofReticulitermes
phenols in which contain gut pro-
ability. Boron usage in amorphous metal cells. Apical meristem abnormalities maybecause boron is toxic
tozoa are susceptible,
alloys for electrical equipment and mag- be a secondary effect of vascular tissue
to these cellulose-digesting organisms and
nets is slowly increasing. Borates are used damage caused by lack of boron. An ade-
leads to starvation of the host as well as sys-
temic effects.
extensively as fire retardants, particularlyquate supply of boron is essential Less research has been done
for prop-
borax and boric acid in shredded cellu- er seed set and normal fruitondevelopment.
drywood termites, but some success has
losic insulation and zinc borate in plas- Breakdown of parenchyma inobtained
been cell walls
with Cryptotermes. Sodium
tics. Concerns about the toxicity of other which results in reduced lignification
octaborate, a highly issoluble polyborate, is
treatments have increased the interest in another symptom of boron starvation.
of interest both for pre and posttreatment
borates for wood preservation. of wood.
Sugar buildup in leaves of boron-deficient
Agriculturally, borates are used in fer- plants is attributed to reducedControl
sugar of cockroaches
con? with boric acid
tilizer (4% of United States B203) to cor- sumption and plasmalemma has abnormalities
had great success, particularly against
rect trace boron-deficiency in certain inhibiting sugar transport outthe
ofGerman roach Blattella germanica in
the leaves.

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W. G. WOODS

t 00
tions have been shown by NMR and
Raman spectra, as well as by titrimetric evi-
dence, to contain polyborate ions of the
types shown in Figure 2 (14). The distrib-
080 ution of these species as a function of pH is
given in Figure 3 (15).
At the pH of human blood (7.4), the
expected low concentrations of borate will
be present as 98.4% B(OH)3 and only
060 B(OH)4 1.6% as the B(OH)4" ion because of the
weak acidity (pKa 9.2) of boric acid.
Simple alcohols react with boric acid to
give esters (Eq. 4). In aqueous solution,
this equilibrium usually lies far to the left.
0 40

B(OH)3 + 3ROH -? B(OR)3 + 3H20

[4]

B303(OH)5 The partially esterified species

0 20
(RO)2BOH and ROB(OH)2 probably also
are involved (16). Polyhydric alcohols
form cyclic esters with boric acid. For
example, hexylene glycol boric anhydride
(Structure 1)

? 6 8 10 12 14
PH
Figure 3. Distribution of polyborate species as a function of pH, 0.40M boric acid (15).

Structure 1

and 1,3-butylene glycol biborate (Structure

2)

H C B O Ca++ Structure 2

? ? o o O
are mixed
Figure 4. Diastereomeric borate-saccharate complexes showing calcium coordination to
(18). give the jet fuel microbiocide
Biobor JF. This additive prevents the
the US Boric acid does not act ductor growth
dopants, and a multitude
as a repel- of of Cladosporium resinae and
other
small
lant, (a problem with many organic uses comprise 21% of the Pseudomonas
blatti- utilization aeruginosa in fuel tanks by
cides), and it is inexpensive, safe,of B203
and in the United States.
effec? distributing itself between the water and
tive (13). When powdered boric acid is fuel phases. This hydrocarbon-metaboliz-
Chemistry
combined with an anticaking agent, the ing fungus and bacterium grow at the
roach contacts the chemical andThe aqueous chemistry of the borates is
eventually fuel-water interface and can cause corro-
dependentand
dies through cuticular absorption on concentration and pH. sion as well as foul the fuel filter (17).
ingestion by grooming. Dilute aqueous boric acid solutions are Sugars with the proper disposition of
comprised
Promising work also has been done solely of B(OH)3 and B(OH)4~
with hydroxyl groups also form ester complexes
species.
boron insecticides on ants, carpet Rapid exchange on the nuclear
beetles, with boric acid. A striking example is the
and fleas. magnetic resonance (NMR) time scale sugar diacid disodium saccharate (glu-
Miscellaneous applications in starch
results in a single peak in the boron-11 carate) which forms a 2:1 sugar acid:borate
NMRborohy-
adhesives, raw material for sodium spectrum which moves steadily up as complex in aqueous solution that has the
dride, borides, boron trifluoride,
the semicon-
pH is increased. Concentrated solu- ability to complex calcium ions. The two

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 INTRODUCTION TO BORON: HISTORY, SOURCES, USES, AND CHEMISTRY

His-57

Asp-102
J X)~H?N / N--H+ CH
,-CH-f
Ser-195

H?Ov - O HN
O O?H
X /
H H

Figure 5. Boromycin [20).

Figure 6. Borate intermediate in serine hydrolase inhibit

diastereomeric forms of this complex are
shown in Figure 4. Proton and carbon-13
NMR spectra showed that the 3,4-diol
.CONH CONH,
portion of the tetrol fragment was involved

0
in coordinating with the boron atom {18).
These complexes are of interest as
biodegradable builders to replace phos?
phate in detergents (19). Adenoslne<PKP)- O - CH2 N
A small group of boron-containing
antibiotics contain a single tetrahedral boron
atom in the center of the structure, com-
plexed with two vicinal diol groups. The
first to be isolated and identified was
boromycin (20) (Figure 5) from Strepto-
myces antibioticus. The related aplas-
momycin was obtained from S. griseus
(21); both show antibiotic activity against
gram-positive bacteria and represent the
only isolated natural products containing
boron.
Figure 7. Borate inhibition of hydrogenase coenzyme by fibityl group complexing (37).
Bis(salicylato)borate salts (Structure 3)
are readily formed in aqueous solution
from salicylic acid solution and boricA recent mechanistic study of boric ited by boric acid (24), and simple borates
acid (22). acid complexation with 4-isopropyl- have been patented as protease stabilizers in
tropolone and with chromotropic acid, a liquid detergent formulations (9,10).
1,8-dihydroxynaphthalene derivative, has Reactions such as acylation and deacy-
shown that the rate-determining step is the lation are catalyzed by enzymes through
change in boron coordination from trigo- lowering of the energy of activation.
nal to tetrahedral (23). Binding and stabilization of the near tetra-
hedral oxyanion transition state by the
O active site of the enzyme is how this is
\ accomplished. Thus, a transition state ana-
log inhibitor is a species which binds the
2-Aminoalkanols form borate esters readily
because of the added stabilization of the
i active site in a way similar to that of the
substrate. Serine hydrolase enzymes react
N-B dative bond. A striking example is the with various borates, boronates, and bori-
formation of triethanolamine borate nates by forming a tetrahedral complex
Structure 4
(Structure 4) from a 1:1 aqueous solution between the serine hydroxyl group and the
of boric acid and triethanolamine (16). boron atom. Hydrogen bonding to the
Boron in plant roots is believed to be Tetrahedral borate or boronate com? imidazole ring of an adjacent histidine adds
reversibly bound as polysaccharide-borate
plexes have been shown to be involved in further stabilization.
complexes (2). enzyme inhibition. Serine proteases were X-ray structures have been worked out
proposed in early Russian work to be inhib-for the benzeneboronic and 2-phenyl-

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W. G. WOODS

ethaneboronic acid (PEBA) complexes of (31). It was concluded that goodenvironment and it is likely that life
matin
subtilisin BPN'(Novo) (25) and for the boronate inhibitors of CHT, like PEBA,evolved in the presence of the element.
PEBA complex of OC-chymotrypsin Boron is essential to plant life, but can
inhibit cell replication and that this effect is
(oc-CHT) dimer (26). Further stabilization
expected to be higher in rapidly proliferat-be herbicidal at high levels. Borates have
of the hydroxyls on boron is gained ingbycancer cells than in normal tissue (30). effects on a variety of bacteria, fungi,
hydrogen bonding to other amido groups Complexing of the ribose group ofand insects. Boron in biological systems
lining the oxyanion hole (Figure 6). nicotinamide adenine dinucleotide (NAD) can be expected to be associated with
Subtilisin Carlsberg (27) and choles-is preferred electrostatically over that of one or more OH groups.
terol esterase (28,29) also are inhibitedreduced
by a nicotinamide adenine dinucleotide Borates are used widely in industrial
range of aliphatic and aromatic boronic (NADH), leading to inhibition of thisand domestic applications. Boron has
acids. Work on inhibiting OC-CHT andcoenzyme
cell system (Figure 7) (32). Thebeen shown to influence a variety of
replication with a variety of boronic effects
acids of boron compounds on enzymeenzymes, involving both stimulation and
concluded that the OC-CHT activitycatalyzed
was reactions have been thoroughlyinhibition. Enzyme interactions proba?
associated with chromatin in normal and reviewed through 1979 by Kliegel (33). bly represent the most important feature
tumorous tissue of mice (30). It has been of boron chemistry from the point of
demonstrated that certain boronic acids Conclusions view of the health effects considered in
Boron is present in every part ofthe
inhibit protease activity in rat liver chro- thefollowing papers.

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10 Environmental Health Perspectives

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