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    UNITED NATIONS ENVIRONMENT PROGRAMME
    INTERNATIONAL LABOUR ORGANISATION
    WORLD HEALTH ORGANIZATION


    INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY



    ENVIRONMENTAL HEALTH CRITERIA 204





    BORON















    This report contains the collective views of an international group of
    experts and does not necessarily represent the decisions or the stated
    policy of the United Nations Environment Programme, the International
    Labour Organisation, or the World Health Organization.


    First draft prepared by Ms C. Smallwood, US Environmental Protection
    Agency, Cincinnati, Ohio, USA

    Published under the joint sponsorship of the United Nations
    Environment Programme, the International Labour Organisation, and the
    World Health Organization, and produced within the framework of the
    Inter-Organization Programme for the Sound Management of Chemicals.


    World Health Organization          Geneva, 1998


         The International Programme on Chemical Safety (IPCS),
    established in 1980, is a joint venture of the United Nations
    Environment Programme (UNEP), the International Labour Organisation
    (ILO), and the World Health Organization (WHO).  The overall
    objectives of the IPCS are to establish the scientific basis for
    assessment of the risk to human health and the environment from
    exposure to chemicals, through international peer review processes, as
    a prerequisite for the promotion of chemical safety, and to provide
    technical assistance in strengthening national capacities for the
    sound management of chemicals.

         The Inter-Organization Programme for the Sound Management of
    Chemicals (IOMC) was established in 1995 by UNEP, ILO, the Food and
    Agriculture Organization of the United Nations, WHO, the United
    Nations Industrial Development Organization, the United Nations
    Institute for Training and Research, and the Organisation for Economic
    Co-operation and Development (Participating Organizations), following
    recommendations made by the 1992 UN Conference on Environment and
    Development to strengthen cooperation and increase coordination in the
    field of chemical safety.  The purpose of the IOMC is to promote
    coordination of the policies and activities pursued by the
    Participating Organizations, jointly or separately, to achieve the
    sound management of chemicals in relation to human health and the
    environment.

    WHO Library Cataloguing in Publication Data

    Boron.

         (Environmental health criteria ; 204)

         1.Boron    2.Environmental exposure
         I.International Programme on Chemical Safety    II.Series

         ISBN 92 4 157204 3           (NLM Classification: QD 181.B1)
         ISSN 0250-863X

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    (c) World Health Organization 1998

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         The mention of specific companies or of certain manufacturers'
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    World Health Organization in preference to others of a similar nature
    that are not mentioned.  Errors and omissions excepted, the names of
    proprietary products are distinguished by initial capital letters.

    CONTENTS

    ENVIRONMENTAL HEALTH CRITERIA FOR BORON

    PREAMBLE

    ABBREVIATIONS

    1. SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS

         1.1. Summary
              1.1.1. Identity, natural occurrence, and analytical methods
              1.1.2. Production, uses, environmental fate, and sources of
                      exposure
              1.1.3. Kinetics and biological monitoring
              1.1.4. Effects on experimental animals and humans
              1.1.5. Effects on organisms in the environment
         1.2. Conclusions
         1.3. Recommendations

    2. IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES, AND ANALYTICAL
         METHODS

         2.1. Identity
         2.2. Physical and chemical properties
         2.3. Conversion factors
              2.3.1. Conversion factors of ppm and mg/m3 for boron
              2.3.2. Conversion factors for boron compounds to boron
         2.4. Analytical methods

    3. SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE
         3.1. Natural occurrence
         3.2. Mining and production
         3.3. Uses and release

    4. ENVIRONMENTAL TRANSPORT, DISTRIBUTION, AND TRANSFORMATION

         4.1. Transport and distribution between media
              4.1.1. Air
              4.1.2. Water and sediment
              4.1.3. Soil
              4.1.4. Vegetation and wildlife
         4.2. Transformation
              4.2.1. Biotransformation
              4.2.2. Abiotic transformation
                      4.2.2.1   Air
                      4.2.2.2   Water
                      4.2.2.3   Soil
              4.2.3. Bioaccumulation
                      4.2.3.1   Aquatic organisms
                      4.2.3.2   Terrestrial plants
                      4.2.3.3   Birds
         4.3. Ultimate fate following use

    5. ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE

         5.1. Environmental levels
              5.1.1. Air
              5.1.2. Water
                      5.1.2.1   Groundwater
                      5.1.2.2   Surface water
                      5.1.2.3   Rainfall
              5.1.3. Sewage
              5.1.4. Soil
              5.1.5. Aquatic biota
              5.1.6. Terrestrial biota
         5.2. General population exposure
              5.2.1. Ambient air
              5.2.2. Drinking-water
              5.2.3. Soil intake
              5.2.4. Dietary intake
              5.2.5. Consumer products
         5.3. Occupational exposure

    6. KINETICS AND METABOLISM IN LABORATORY ANIMALS AND HUMANS

         6.1. Absorption
              6.1.1. Oral
              6.1.2. Inhalation
              6.1.3. Dermal
         6.2. Distribution
              6.2.1. Tissue levels
              6.2.2. Blood levels
         6.3. Metabolism
         6.4. Elimination and excretion

    7. EFFECTS ON LABORATORY MAMMALS AND  IN VITRO TEST SYSTEMS

         7.1. Short-term exposure
              7.1.1. Oral route
              7.1.2. Inhalation route
         7.2. Longer-term exposure
              7.2.1. Oral route
              7.2.2. Inhalation route
         7.3. Dermal and ocular effects
         7.4. Reproductive toxicity
         7.5. Developmental toxicity
         7.6. Mutagenicity and related end-points
         7.7. Carcinogenicity
         7.8. Toxicity effects summary
         7.9. Physiological effects

    8. EFFECTS ON HUMANS

         8.1. General population exposure
              8.1.1. Short-term toxicity and poisoning incidents
              8.1.2. Reproductive effects
         8.2. Occupational exposure
              8.2.1. Short-term irritative effects
              8.2.2. Male reproductive and other long-term health effects
         8.3. Carcinogenicity
         8.4. Physiological effects

    9. EFFECTS ON OTHER ORGANISMS IN THE LABORATORY AND FIELD
         9.1. Laboratory experiments
              9.1.1. Microorganisms
                      9.1.1.1   Water
                      9.1.1.2   Soil
              9.1.2. Aquatic organisms
                      9.1.2.1   Plants
                      9.1.2.2   Invertebrates
                      9.1.2.3   Vertebrates
              9.1.3. Terrestrial organisms
                      9.1.3.1   Plants
                      9.1.3.2   Invertebrates
                      9.1.3.3   Vertebrates
         9.2. Field observations
              9.2.1. Aquatic
              9.2.2. Terrestrial

    10. EVALUATION OF HUMAN HEALTH RISKS AND EFFECTS ON THE ENVIRONMENT

         10.1. Evaluation of human health exposures
         10.2. Choice of critical effect and application of uncertainty
              factors
         10.3. Derivation of the tolerable intake
         10.4. Derivation of guidance values
         10.5. Evaluation of effects on the environment
              10.5.1. Exposure
              10.5.2. Effects
              10.5.3. Risk evaluation

    11. CONCLUSIONS AND RECOMMENDATIONS FOR PROTECTION OF HUMAN HEALTH
         AND THE ENVIRONMENT

         11.1. Conclusions
         11.2. Recommendations

    12. FURTHER RESEARCH

    13. EVALUATIONS BY INTERNATIONAL BODIES

    REFERENCES

    APPENDIX

    RÉSUMÉ, CONCLUSIONS ET RECOMMANDATIONS

    RESUMEN, CONCLUSIONES Y RECOMENDACIONES
    

    NOTE TO READERS OF THE CRITERIA MONOGRAPHS

         Every effort has been made to present information in the criteria
    monographs as accurately as possible without unduly delaying their
    publication.  In the interest of all users of the Environmental Health
    Criteria monographs, readers are requested to communicate any errors
    that may have occurred to the Director of the International Programme
    on Chemical Safety, World Health Organization, Geneva, Switzerland, in
    order that they may be included in corrigenda.


                                 *     *     *


         A detailed data profile and a legal file can be obtained from the
    International Register of Potentially Toxic Chemicals, Case postale
    356, 1219 Châtelaine, Geneva, Switzerland (telephone no. + 41 22 -
    9799111, fax no. + 41 22 - 7973460, E-mail irptc@unep.ch).


    Environmental Health Criteria

    PREAMBLE

    Objectives

         In 1973, the WHO Environmental Health Criteria Programme was
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    (iv)   to promote the harmonization of toxicological and
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         The first Environmental Health Criteria (EHC) monograph, on
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         Since its inauguration, the EHC Programme has widened its scope,
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         The original impetus for the Programme came from World Health
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    Scope

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    Content

         The layout of EHC monographs for chemicals is outlined below. 

    *    Summary -- a review of the salient facts and the risk evaluation
         of the chemical
    *    Identity -- physical and chemical properties, analytical methods
    *    Sources of exposure
    *    Environmental transport, distribution, and transformation
    *    Environmental levels and human exposure
    *    Kinetics and metabolism in laboratory animals and humans
    *    Effects on laboratory mammals and  in vitro test systems
    *    Effects on humans
    *    Effects on other organisms in the laboratory and field
    *    Evaluation of human health risks and effects on the environment
    *    Conclusions and recommendations for protection of human health
         and the environment

    *    Further research
    *    Previous evaluations by international bodies, e.g. IARC, JECFA,
         JMPR

    Selection of chemicals

         Since the inception of the EHC Programme, the IPCS has organized
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    1980; Oxford, United Kingdom, 1984; Berlin, Germany, 1987; and North
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    data on the hazards are available.

         If an EHC monograph is proposed for a chemical not on the
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    Procedures

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         The draft document, when received by the RO, may require an
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    FIGURE 1

    WHO TASK GROUP ON ENVIRONMENTAL HEALTH CRITERIA FOR BORON

     Members

         Dr G.M. Buck, Department of Social and Preventive Medicine, State
         University of New York at Buffalo, Buffalo, New York, USA

         Dr R. Chapin, Department of Health and Human Services, National
         Institutes of Health, National Institute of Environmental Health
         Sciences, Research Triangle Park, North Carolina, USA

         Dr M.L. Dourson, Toxicology Excellence for Risk Assessment,
         Cincinnati, Ohio, USA

         Dr P. Foster, Chemical Industry Institute of Toxicology, Research
         Triangle Park, North Carolina, USA

         Dr R.A. Goyer, 6405 Huntingridge Road, Chapel Hill, North
         Carolina, USA  (Chairman)

         Mr P. Howe, Institute of Terrestrial Ecology, Monks Wood, Abbots
         Ripton, Cambs., United Kingdom  (Co-Rapporteur)

         Dr R. Luoto, National Public Health Institute, Department of
         Epidemiology and Health Promotion, Helsinki, Finland

         Dr F.H. Nielsen, US Department of Agriculture, Agricultural
         Research Service, Grand Forks Human Nutrition Research Center,
         Grand Forks, North Dakota, USA

         Dr C.J. Price, Center for Life Sciences and Toxicology, Research
         Triangle Institute, Research Triangle Park, North Carolina, USA

         Dr W.G. Woods, Office of Environmental Health and Safety,
         University of California, Riverside, California, USA

     Observers

         Dr B.D. Culver, University of California, Department of Medicine,
         Irvine, California, USA (representing International Commission on
         Occupational Health)

         Dr S. Dyer, Procter & Gamble, Ecosystems Research Station,
         Environmental Science Department, Cincinnati, Ohio, USA
         (representing European Centre for Ecotoxicology, Toxicology of
         Chemicals)

         Dr J.A. Moore, Institute for Evaluating Health Risks, Washington,
         DC, USA (representing the American Industrial Health Council)

         Dr F.J. Murray, 6611 Northridge Drive, San Jose, California, USA
         (representing International Life Sciences Institute)

         Mrs M. Richold, Unilever Research ESL, Sharnbrook, Bedford,
         United Kingdom (representing International Life Sciences
         Institute)

     Secretariat

         Dr B.H. Chen, International Programme on Chemical Safety, World
         Health Organization, Geneva, Switzerland  (Secretary)

         Dr L. Galvao, Pan American Health Organization, World Health
         Organization, Geneva, Switzerland

         Dr H. Otterstetter, Pan American Health Organization, World
         Health Organization, Geneva, Switzerland

         Ms C. Smallwood, US Environmental Protection Agency, National
         Center for Environmental Assessment, Cincinnati, Ohio, USA 
          (Co-Rapporteur)

    IPCS TASK GROUP ON ENVIRONMENTAL HEALTH CRITERIA FOR BORON

         A WHO Task Group on Environmental Health Criteria for Boron met
    in Washington, DC, USA, from 18 to 22 November 1996.  The meeting was
    organized by the WHO Regional Office for the Americas (AMRO) on behalf
    of the IPCS.  Dr H. Otterstetter, WHO AMRO, opened the meeting and
    welcomed the participants.  Dr B.H. Chen, IPCS, welcomed the
    participants on behalf of the Director of IPCS and the three IPCS
    cooperating organizations (UNEP/ILO/WHO).  The Task Group reviewed and
    revised the draft criteria monograph and made an evaluation of the
    risks for human health and the environment from exposure to boron.

         The first draft of this monograph was prepared by Ms C. Smallwood
    of the US EPA in Cincinnati.  The second draft was also prepared by Ms
    Smallwood, incorporating comments received following the circulation
    of the first draft to the IPCS Contact Points for Environmental Health
    Criteria monographs. Dr R. Goyer, Chairman of the Task Group,
    contributed significantly to the final text of the EHC for Boron.

         Dr B.H. Chen, member of the IPCS Central Unit, and Ms M. Sheffer,
    Scientific Editor, Ottawa, Canada, were responsible for the overall
    scientific content and linguistic editing, respectively.

         The efforts of all who helped in the preparation and finalization
    of the document are gratefully acknowledged.

         Financial support for this Task Group meeting was provided by the
    US EPA.


    ABBREVIATIONS


    BMD     Benchmark dose
    CAS     Chemical Abstracts Service
    CL      Confidence limit
    CNS     Central nervous system
    EPA     Environmental Protection Agency (USA)
    FDA     Food and Drug Administration (USA)
    FSH     Follicle stimulating hormone
    GLP     Good Laboratory Practices
    HSDB    Hazardous Substances Data Bank
    ICP     Inductively coupled plasma
    ICP-AES Inductively coupled plasma atomic emission spectroscopy
    ICP-MS  Inductively coupled plasma mass spectroscopy
    LH      Luteinizing hormone
    LOAEL   Lowest-observed-adverse-effect level
            (human and animal toxicity)
    LOEC    Lowest-observed-effect concentration
            (environmental effects)
    MATC    Maximum acceptable toxicant concentration
            (environmental effects)
    MMAD    Median mass aerodynamic diameter
    NADPH   Reduced nicotinamide adenine dinucleotide phosphate
    NIOSH   National Institute for Occupational Safety and Health
    NOAEL   No-observed-adverse-effect level 
            (human and animal toxicity)
    NOEC    No-observed-effect concentration
            (environmental effects)
    NOHS    National Occupational Hazard Survey
    RR      Rate ratio (or Relative risk)
    RTECS   Registry of Toxic Effects of Chemical Substances
    SBR     Standardized birth ratio
    SGOT    Serum glutamic-oxaloacetic transaminase
    SGPT    Serum glutamic-pyruvic transaminase
    TI      Tolerable intake
    TLV     Threshold limit value
    TRI     Toxic Release Inventory (US EPA)

    1.  SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS

    1.1  Summary

    1.1.1  Identity, natural occurrence, and analytical methods

         Boron is a naturally occurring element that is found in the form
    of borates in the oceans, sedimentary rocks, coal, shale, and some
    soils. It is widely distributed in nature, with concentrations of
    about 10 mg/kg in the Earth's crust (range: 5 mg/kg in basalts to 100
    mg/kg in shales) and about 4.5 mg/litre in the ocean.

         The most important commercial borate products and minerals are
    borax pentahydrate, borax, sodium perborate, boric acid, colemanite,
    and ulexite. At the low concentrations and near-neutral pH found in
    most biological fluids, monomeric B(OH)3 will be the predominant
    species present (with some B(OH)4œ), regardless of whether the
    boron source is boric acid or one of the borates. This is because
    boric acid is a very weak acid (p Ka 9.15). Sodium perborate
    hydrolyses to give hydrogen peroxide plus metaborate; consequently, it
    may exhibit chemical and toxicological properties that are somewhat
    different from those of the other borates.

         Inductively coupled plasma (ICP) methods are preferred for the
    analysis of the low levels of boron found in biological and
    environmental samples; colorimetric methods must be used with caution.

    1.1.2  Production, uses, environmental fate, and sources of exposure

         Economic borate deposits are rare, occurring in arid regions of
    Turkey, the USA, Argentina, Chile, Russia, China, and Peru. Total
    world production of boron minerals -- mainly colemanite, ulexite,
    tincal, and kernite -- was approximately 2 750 000 tonnes in 1994.
    About 800 000 tonnes of commercial borate products, expressed as
    B2O3, were manufactured from the boron minerals.

         Major end uses for borate include insulation- and textile-grade
    fibreglass, laundry bleach (sodium perborate), borosilicate glass,
    fire retardants, agricultural fertilizers and herbicides (as a trace
    element), and enamels, frits, and ceramic glazes, as well as a myriad
    of miscellaneous applications.

         Boron enters the environment mainly through the weathering of
    rocks, boric acid volatilization from seawater, and volcanic activity.
    Boron is also released from anthropogenic sources to a lesser extent.
    Anthropogenic sources include agricultural, refuse, and fuel wood
    burning, power generation using coal and oil, glass product
    manufacture, use of borates/perborates in the home and industry,
    borate mining/processing, leaching of treated wood/paper, and 
    sewage/sludge disposal. Many of these sources are difficult to
    quantify.

         Atmospheric emissions of borates and boric acid in particulate
    and vapour form occur as a result of volatilization from the sea,
    volcanic activity, and, to a lesser extent, mining operations, glass
    and ceramics manufacturing, the application of agricultural chemicals,
    and coal-fired power plants. Boron is not present in the atmosphere at
    significant levels; however, the total amount present in the
    atmosphere at any one time is significant owing to the huge volume of
    the atmosphere. Based on their water solubility, borates would not be
    expected to persist to a significant degree in the atmosphere.

         Boron can be released into water and soil water through
    weathering processes and, to a much smaller extent, through
    anthropogenic discharges such as sewage outfalls.
    Adsorption-desorption reactions are expected to be the only
    significant mechanism influencing the fate of boron in water. The
    extent of boron adsorption depends on the pH of the water and the
    concentration of boron in solution.

         Boron is adsorbed onto soil particles, with the degree of
    adsorption depending on the type of soil, pH, salinity, organic matter
    content, iron and aluminium oxide content, iron- and aluminium-hydroxy
    content, and clay content. Boron adsorption can vary from being fully
    reversible to irreversible, depending on the soil type and condition.

         Borate ions present in aqueous solution are essentially in their
    fully oxidized state. No aerobic processes are likely to affect their
    speciation, and no biotransformation processes are reported.
    Therefore, there are unlikely to be any differences in boron species
    due to biotransformation.

         The octanol/water partition coefficient of boric acid has been
    measured as 0.175, indicating a low bioaccumulation potential.
    Laboratory experiments with aquatic organisms have confirmed this
    potential. Plants accumulate boron; however, uptake is affected by the
    pH of the soil solution, temperature, light intensity, and the
    concentration of other elements (e.g. calcium and potassium). The
    results of studies of boron accumulation in plants, insects, and fish
    have shown that boron bioaccumulates in plants but does not biomagnify
    in aquatic food-chains.

         Boron occurs in soils at concentrations ranging from 10 to 300
    mg/kg (average 30 mg/kg), depending on the type of soil, amount of
    organic matter, and amount of rainfall. Concentrations of boron in
    surface water are dependent on such factors as the geochemical nature
    of the drainage area, proximity to marine coastal regions, and inputs
    from industrial and municipal effluent discharges. Concentrations of
    boron in surface water range widely, from 0.001 to as much as 360
    mg/litre. However, mean boron concentrations for waters of Europe,
    Pakistan, Russia, and Turkey are typically well below 0.6 mg/litre.
    Concentrations of boron in water in Japan, South Africa, and South
    America are generally below 0.3 mg/litre. Typical boron concentrations
    in North American waters are below 0.1 mg/litre, with about 90% at or
    below 0.4 mg/litre.

         Boron accumulates in aquatic and terrestrial plants but does not
    magnify through the food-chain. Concentrations of boron have been
    shown to range between 26 and 382 mg/kg in submerged aquatic
    freshwater plants, from 11.3 to 57 mg/kg in freshwater emergent
    vegetation, and from 2.3 to 94.7 mg/kg dry weight in terrestrial
    plants. Based on wet weights, boron concentrations in marine
    invertebrates and fish are similar to the levels found in the exposure
    media, between 0.5 and 4 mg/kg. The bioconcentration factor for two
    freshwater fish species was found to be 0.3.

         Boron concentrations in ambient air range from <0.5 to
    approximately 80 ng/m3, with an average over the continents of
    20 ng/m3.

         Close similarity of boron concentrations in groundwater, fresh
    surface water, and drinking-water indicates that boron is not removed
    in the treatment of groundwater and fresh surface water used for
    drinking-water.

         Intakes of boron for humans are expected to be 0.44 µg/day from
    ambient air, 0.2-0.6 mg/day from drinking-water, and 1.2 mg/day from
    the diet. Average boron intake from the soil is considered to be 0.5
    µg/day. A reasonable estimate of boron exposure from consumer products
    is 0.1 mg/day.

    1.1.3  Kinetics and biological monitoring

         The pharmacokinetics of boron appear to be quite similar across
    species in the following respects:

    a)    Absorption of borates is essentially complete (approximately
         95% in humans and rats), and boron appears rapidly in the blood
         and body tissues of several mammalian species following
         ingestion.

    b)    Distribution of boron in mammals appears to occur by passive
         diffusion throughout the body fluids. In contrast to soft tissues
         and blood, bone shows selective uptake of boron (>4 times
         higher than serum) and significantly longer retention times.

    c)    Metabolism of boric acid is thermodynamically unfavourable in
         biological systems. Thus, the ionic species in systemic
         circulation are expected to be equivalent across mammals. This
         eliminates a major source of potential uncertainty for risk
         extrapolation, as interspecies differences in enzymatic pathways
         and/or metabolic rates do not need to be taken into
         consideration.

    d)    Elimination kinetics (especially route of elimination and
         terminal half-life) also appear to be similar for humans and
         rats.

         The similarities in pharmacokinetic parameters between humans and
    rats, the species defining the no-observed-adverse-effect level
    (NOAEL) for laboratory studies, reduce the uncertainty for risk
    extrapolation between these two species.

    1.1.4  Effects on experimental animals and humans

         The data regarding developmental and reproductive toxicity show
    that lower fetal body weight in rats is the critical effect. The NOAEL
    for lower fetal body weight is 9.6 mg boron/kg body weight per day.
    The lowest-observed-adverse-effect level (LOAEL), at which rats show
    slight (approx. 5%) fetal body weight differences and rib anomalies,
    is about 13 mg boron/kg body weight per day. As dose level increases,
    the effects that are seen (and the doses at which they are seen) are:

    a)   further rib effects and testicular pathology in the rat (approx.
         25 mg boron/kg body weight per day);

    b)   decreased fetal body weight and increased fetal cardiovascular
         malformations in the rabbit, and severe testicular pathology in
         the rat (approx. 40 mg boron/kg body weight per day);

    c)   testicular atrophy and sterility in the rat (approx. 55 mg
         boron/kg body weight per day); and

    d)   reduced fetal body weight in the mouse (approx. 80 mg boron/kg
         body weight per day).

         Animal studies on mice and rats showed no evidence of
    carcinogenicity of boric acid. Based on the lack of human data and the
    limited animal data, boron is not classifiable as to its human
    carcinogenicity.

         Only a few human studies have been conducted to assess health
    effects associated with exposure to boron compounds. The available
    data show that exposure is associated with short-term irritant effects
    on the upper respiratory tract, nasopharynx, and eye. These effects,
    however, appear to be short-term and reversible. The sole long-term
    (7-year) follow-up study failed to identify any long-term health
    effects, although a healthy worker effect cannot be entirely ruled out
    given the rate of attrition (47%). Two descriptive studies assessed
    fertility and secondary sex ratios in relation to exposure. Neither
    study reported a detrimental effect on demonstrated fertility for its
    select sample. Although an excess percentage of female births has been
    suggested, the absence of statistical significance and attention to
    other co-variates known to affect sex ratios warrants careful
    interpretation of this finding. No studies have been identified that
    assess the spectrum of reproductive outcomes, such as
    time-to-pregnancy, conception delays, spontaneous abortions, and sperm
    analyses in males. The role of other lifestyle or behavioural factors
    in relation to health and fertility requires further study to identify
    potentially sensitive populations and to evaluate reproductive effects
    more fully.

    1.1.5  Effects on organisms in the environment

         Bacteria are relatively tolerant towards boron. Acute and chronic
    effect concentrations range between 8 and 340 mg boron/litre, with
    most values greater than 18 mg boron/litre. More sensitive are
    protozoa. Tests with  Entosiphon and  Paramecium yielded 72-h
    no-observed-effect concentrations (NOECs) and EC3 values between 
    0.3 and 18 mg boron/litre.

         Boron is an essential micronutrient for cyanobacteria and
    diatoms. Standard chronic tests with freshwater green algae resulted
    in no-effect concentrations between 10 and 24 mg boron/litre.
    Blue-green algae appear to be similar in sensitivity, with an 8-day
    EC3 of 20 mg boron/litre.

         Based on acute toxicity values, invertebrates are less sensitive
    to boron than microorganisms. For several species, 24- to 48-h EC50
    values ranged from 95 to 1376 mg boron/litre, with most values in the
    100-200 mg boron/litre range. Chronic toxicity studies with 
     Daphnia magna gave NOECs ranging between 6 and 10 mg boron/litre.
    Slightly lower NOEC values were obtained from laboratory and field
    biocenosis studies. The 28-day laboratory study consisting of six
    trophic stages yielded a NOEC of 2.5 mg boron/litre. Long-term outdoor
    pond and field studies (not including fish) yielded NOECs up to 1.52
    mg boron/litre.

         Acute tests with several fish species yielded toxicity values
    ranging from about 10 to nearly 300 mg boron/litre. Rainbow trout
     (Oncorhynchus mykiss) and zebra fish  (Brachydanio rerio) were the
    most sensitive, providing values around 10 mg boron/litre.

         The toxicity of boron to early life stages of fish has been
    documented for several species in reconstituted water. Embryonic and
    early larval stages of rainbow trout, largemouth bass  (Micropterus 
     salmoides), channel catfish  (Ictalurus punctatus), and goldfish
     (Carassius auratus) were exposed to boron, as boric acid or borax,
    from fertilization up to 8 days post-hatch in soft or hard water.
    Neither water hardness nor the form of boron consistently affected
    embryo-larval survival of fish. Rainbow trout was the most sensitive
    species. The NOECs for rainbow trout ranged from 0.009 to 0.103 mg
    boron/litre.

         The effect of natural dilution water on boron toxicity was
    determined by using surface waters collected from three locations,
    with boron concentrations of 0.023, 0.091, and 0.75 mg/litre. No
    adverse effects were determined up to 0.75 mg boron/litre.
    Lowest-observed-effect concentrations (LOECs) ranged from 1.1 to 1.73
    mg boron/litre. One test using deep (600 m) well-water, typically used
    for aquatic toxicity tests, from a contract laboratory located in
    Wareham, Massachusetts, USA, yielded a NOEC of >18.0 mg boron/litre.
    Hence, reconstituted water exposures appeared to overestimate the
    toxicity determined in natural waters, possibly as a result of
    nutrient deficiency in the former.

         Boron has been known since the 1920s to be an essential
    micronutrient for higher plants, with interspecies differences in the
    levels required for optimum growth. Boron plays a role in cell
    division, metabolism, and membrane structure and function. Boron in
    the form of borates occurs naturally in fruits, nuts, and vegetables.
    There is a small range between deficiency and excess uptake (toxicity)
    in plants. Boron deficiencies in terrestrial plants have been reported
    in many countries. Boron deficiency is more likely to occur in
    light-textured, acid soils in humid regions because of boron's
    susceptibility to leaching. Boron excesses usually occur in soil
    solutions from geologically young deposits, arid soils, soils derived
    from marine sediments, and soils contaminated by pollutant sources,
    such as releases from coal-fired power plants and mining operations.
    Irrigation water is one of the main sources of high boron levels
    resulting in toxicity in the field.

         Mallard  (Anas platyrhynchos) duckling growth was adversely
    affected at dietary levels of 30 and 300 mg boron/kg, and survival was
    reduced at 1000 mg/kg.

    1.2  Conclusions

         Boron is a naturally occurring element that is found in nature in
    the form of borates in the oceans, sedimentary rocks, coal, shale, and
    some soils. Natural sources of borates released into the environment
    are the oceans, geothermal steam, and natural weathering of clay-rich
    sedimentary rocks. Boron is also released from anthropogenic sources
    to a lesser extent.

         Boron is an essential micronutrient for higher plants, with
    interspecies differences in the levels required for optimum growth.
    Boron deficiency in terrestrial plants has been observed in many
    countries throughout the world. There is a small range between
    deficiency and toxicity in some plants.

         Comparison of the environmental no-effect concentration
    (1 mg/litre) with the general ambient environmental levels of boron
    indicates that the risk of adverse effects of boron on the aquatic
    ecosystem is low. In a few boron-rich environments, natural levels
    will be higher. It is reasonable to assume that aquatic organisms in
    such habitats may be adapted to the local conditions.

         For humans, boron exposure occurs primarily through the diet and
    drinking-water. The mean global boron concentration in drinking-water
    was considered to be between 0.1 and 0.3 mg boron/litre.

         For the general population, the greatest boron exposure comes
    from the oral intake of food. The mean daily intake of boron in the
    diet is about 1.2 mg.

         In humans and animals, boric acid and borate are absorbed from
    the gastrointestinal and respiratory tracts. More than 90% of
    administered doses of these compounds are absorbed, as evidenced by
    excretion in the urine, which is rapid, occurring over a few to
    several days.

         Animal experiments have shown that boron in the form of boric
    acid and borate demonstrates reproductive and developmental toxicity
    at levels that are approximately 100- to 1000-fold greater than normal
    exposure levels. There is a lack of sufficient toxicity data on
    humans. The tolerable intake (TI) of boron was set as 0.4 mg/kg body
    weight per day. The allocation of the TI in various media should be
    based on the exposure data of individual countries.

    1.3  Recommendations

    a)   Water and food guideline values should be based on the TI
         provided by this document.

    b)   The TI should be applied with the understanding that boron may
         provide a physiological benefit for human health.

    c)   It should be recognized in applying standards that boron is
         essential for some constituents of the environment (e.g. boron is
         an essential micronutrient for higher plants).

    d)   Dietary supplements that exceed the TI should be avoided.

    2.  IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES, AND ANALYTICAL METHODS

         This chapter deals with the identity and physical and chemical
    properties of the inorganic borates of importance in commerce, as well
    as the analytical methods used to determine boron concentrations in
    various media.

    2.1  Identity

         Elemental boron (B) is a member of Group IIIB of the periodic
    table, along with aluminium, gallium, indium, and thallium. It has an
    atomic number of 5 and a relative atomic mass of 10.81. Boron is never
    found in the elemental form in nature. Its chemistry is complex and
    resembles that of silicon (Cotton & Wilkinson, 1988). The Chemical
    Abstracts Service (CAS), National Institute for Occupational Safety
    and Health (NIOSH) Registry of Toxic Effects of Chemical Substances
    (RTECS), and Hazardous Substances Data Bank (HSDB) numbers for boron
    are 7440-42-8, ED7350000, and 4482, respectively.

         The borates used most widely in commerce are listed in
    approximate decreasing order of usage in Table 1, along with their
    formulae and CAS numbers. Elemental boron is included, even though its
    production is quite small. Throughout this document, the term "borax"
    refers to disodium tetraborate decahydrate (see Table 1).

    2.2  Physical and chemical properties

         Elemental boron exists as a solid at room temperature, either as
    black monoclinic crystals or as a yellow or brown amorphous powder
    when impure. The amorphous and crystalline forms of boron have
    specific gravities of 2.37 and 2.34, respectively. Boron exists as a
    mixture of the 10B (19.78%) and 11B (80.22%) isotopes (Budavari et
    al., 1989). Boron is a relatively inert metalloid except when in
    contact with strong oxidizing agents. Boron dust exposed to air is
    flammable and an explosion hazard. It also reacts violently when
    ground with lead fluoride and silver fluoride (Lewis, 1992). Physical
    and chemical properties of elemental boron and the most important
    borates in commerce are provided in Table 2.

         Sodium perborates are persalts that are hydrolytically unstable
    because they contain characteristic boron-oxygen-oxygen bonds that
    react with water to form hydrogen peroxide and stable sodium
    metaborate (NaBO2.nH2O). This hydrolysis reaction is the basis of
    the use of perborates as bleaches in detergents at high (70-100°C)
    temperature. At lower washing temperatures (25-70°C), activators are
    needed; these react with peroxide to give peracids, which are stronger
    oxidants and give bleaching effects at lower temperatures.

    Table 1.  Boron compounds of commerce in approximate decreasing order 
    of usagea

                                                                           

    Substance                         Formula                   CAS No.
                                                                           

    Borax pentahydrate (disodium      Na2[B4O5(OH)4].3H2O       3754418
    tetraborate pentahydrate)         (Na2B4O7.5H2O)

    Borax (disodium tetraborate       Na2[B4O5(OH)4].8H2O       1303-96-4
    decahydrate)                      (Na2B4O7.10H2O)

    Ulexite                           NaCa[B5O6(OH)6].5H2O      1319-33-1
                                      (Na2O.2CaO.5B2O3.16H2O)

    Colemanite                        Ca[B3O4(OH)3].H2O         1318-33-8
                                      (2CaO.3B2O3.5H2O)

    Sodium perborate tetrahydrate     Na2[B2O4(OH)4].6H2O       10486-00-7
                                      (NaBO3.4H2O)

    Sodium perborate monohydrate      Na2[B2O4(OH)4]            10332-33-9
                                      (NaBO3.H2O)

    Boric acid                        B(OH)3                    10043-35-3
                                      (H3BO3)

    Anhydrous borax                   Na2B4O7 (amorphous)       1330-43-4
    (disodium tetraborate)

    Boron oxide                       B2O3 (amorphous)          1303-86-2

    Boronb                            B                         7440-42-8
                                                                           

    a    US EPA (1991); ATSDR (1992); Culver et al. (1994b).
    b    Produced in small quantities.

        Table 2.  Physical and chemical properties of elemental boron and the most important borates in commercea

                                                                                                                                            

    Substance             Relative     Colour             % boron   Relative        Water solubility         Melting point    Boiling point
                          molecular                                 density                                  (°C)             (°C)
                          mass
                                                                                                                                            

    Borax pentahydrate    291.35       White              14.85     1.81            3.6 g/100 g @ 20 °C      742              -
    Borax                 381.37       Colourless         11.34     1.73            5.92 g/100 g @ 25 °C     75, decomposes   -
    Ulexite               810.6        White              13.33     1.62            Slightly soluble         Decomposes       -
    Colemanite            411.1        White              15.78     2.42            Slightly soluble         Decomposes       -
    Sodium perborate
      tetrahydrate        153.9        White              7.03      1.73            23 g/litre @ 20 °C       Decomposes       -
    Sodium perborate
      monohydrate         99.8         White              10.83     -               15 g/litre @ 20 °C       Decomposes       -
    Boric acid            61.84        Colourless         17.48     1.435 @ 15 °C   63.5 g/litre @ 30 °C     169              -
    Anhydrous borax       201.22       White              21.49     2.367           2.5556 g/100 g @ 25 °C   741              1575
    Boron oxide           69.62        Colourless         31.06     2.46            Slightly soluble         450              1860
    Boron                 10.81        Black crystal or 
                                       yellow-brown 
                                       amorphous          100       2.3             Insoluble                2300             approx. 3500
                                                                                                                                            

    a    Muetterties (1967); Windholz et al. (1983); Weast et al. (1985); ACGIH (1991); ATSDR (1992); Lewis (1993); US NLM (1993); 
         Culver et al. (1994b).
    
         Boric acid is a very weak acid, with a p Ka of 9.15, and
    therefore boric acid and the sodium borates exist predominantly as
    undissociated boric acid [B(OH)3] in dilute aqueous solution below pH
    7; above pH 10, the metaborate anion B(OH)4œ becomes the main
    species in solution. Between pH 6 and pH 11 and at high concentration
    (>0.025 mol/litre), highly water soluble polyborate ions such as
    B3O3(OH)4œ, B4O5(OH)4, and B5O6(OH)4œ are formed.

         The chemical and toxicological properties of borax pentahydrate,
    borax, boric acid, and other borates are expected to be similar on a
    mol boron/litre equivalent basis when dissolved in water or biological
    fluids at the same pH and low concentration. Boric oxide will exhibit
    properties identical to those of boric acid, as it is an anhydride
    that will hydrolyse to give boric acid. Sodium perborate monohydrate
    and tetrahydrate hydrolyse to give hydrogen peroxide and borate. Thus,
    they are oxidants and may have chemical and toxicological properties
    that are different from those of the other borates.

         The chemical properties of sodium metaborate differ from those of
    the other sodium borates, in that the metaborate has a much higher
    solubility and alkalinity in aqueous solution. Thus, the solubility in
    water at 20°C is 41.9 parts sodium metaborate octahydrate (compared
    with 4.7 for borax) per hundred parts saturated solution by weight.
    The pH of an aqueous solution of the metaborate at 20°C ranges from
    10.5 at 0.1% w/w to 12.0 at 18% w/w (compared with pH 9.24 for borax
    over a wide range of concentrations).

    2.3  Conversion factors

    2.3.1  Conversion factors of ppm and mg/m3 for boron

         1 ppm = 0.4421 mg/m3
         1 mg/m3 = 2.262 ppm

    2.3.2  Conversion factors for boron compounds to boron

         dose of boric acid × 0.175 = equivalent dose of boron
         dose of borax × 0.113 = equivalent dose of boron
         dose of anhydrous borax × 0.215 = equivalent dose of boron 
         dose of sodium perborate tetrahydrate × 0.070 = equivalent dose
              of boron
         dose of sodium perborate monohydrate × 0.108 = equivalent dose of
              boron 
         dose of metaboric acid × 0.247 = equivalent dose of boron

    2.4  Analytical methods

         Analyses of environmental and biological samples for boron
    content utilize a variety of preparative methods (see Table 3).

    Table 3.  Preparative methods for analysing boron content in
    environmental and biological samples

                                                                              

    Media         Extraction method                  Reference
                                                                              

    Biological    Acid digestion with:
                    Microwave                        Pennington et al. (1991)
                    Dry ashing                       Wilkner (1986)
                    Wet ashing                       Kowalenko (1979)
                                                     Banuelos et al. (1992)
                    Low temperature, wet ashing      Hunt & Shuler (1989)

                  Freeze drying                      Iyengar et al. (1990)
                                                     Smith et al. (1991)

    Soil          Hot water solubility               Odom (1980)
                                                     Cumakov (1991)

    Water         Liquid-liquid extraction from 
                  acidified solutions into 
                  chloroform                         Aznarez et al. (1985)

                  Ion exchange column                Sekerka & Lechner (1990)
                                                                              


         The preferred method for analysis of boron in bone, plasma, and
    food is inductively coupled plasma atomic emission spectroscopy
    (ICP-AES) (Hunt, 1989). It is also used for tumour, blood, liver,
    skin, and cell suspensions (Barth et al., 1991). It also has been used
    for wastewater (Huber, 1982) and fish tissues (Hamilton & Wiedmeyer,
    1990). Detection limits range from 0.005 to 0.05 mg boron/litre in the
    solution analysed.

         Inductively coupled plasma mass spectroscopy (ICP-MS) is used to
    measure boron concentrations in plant, rat, and human samples. Isotope
    ratios (10B/11B) can be measured accurately (Vanderpool et al.,
    1994). Using direct nebulization, ICP-MS can give a detection limit of
    1 ng/g in human blood, human serum, orchard leaves, and total diet
    (Smith et al., 1991).

         ICP-MS is the most widely used non-spectrophotometric method for
    analysis of boron, as it uses small volumes of sample, is fast, and
    applies to a wide range of materials (fresh and saline water, sewage
    wastewater, soils, and plant samples, as well as the biological
    materials mentioned above). Interferences are minimal or can be
    removed (Gregoire, 1990). ICP-MS can detect boron down to 0.15
    µg/litre.

         The ability to measure the boron isotope ratio accurately allows
    studies starting with pure 10B compounds and following the isotopic
    dilution in biological systems. This is particularly useful, as no
    stable radioactive boron isotopes usable as tracers exist. A number of
    boron compounds made with nearly isotopically pure 10B are available
    for such studies.

         When expensive ICP equipment is not available,
    colorimetric/spectrophotometric methods can be utilized. However, many
    of these methods are subject to interference and should be used with
    caution; they should also preferably be calibrated against an ICP
    method.

         Azomethine-H has been used to analyse boron in environmental
    water samples and is very sensitive, with a detection limit of 0.02
    mg/litre (Lopez et al., 1993). The well-known curcumin method is
    subject to interference by nitrate, chloride, and fluoride but is
    claimed to be applicable to samples with 0.1-1 mg boron/litre (Black
    et al., 1993).

         A simple, sensitive spectrophotometric method for determination
    of boron in soils, plant materials, and water uses Alizarin Red S but
    is also subject to interference (Garcia-Campana et al., 1992). Flow
    injection analysis utilizing the sorbitol/borate complex and Methyl
    Orange indicator for eye lotion samples has a detection limit of
    0.02 mg/litre (Nose & Zenki, 1991).

         Another method of analysis of boron uses neutron activation and
    mass spectrometric analysis. Mass spectrometric assay of 3He from
    decay of tritium produced by thermal neutron irradiation of boron to
    give 4He has been described by Clarke et al. (1987a). The method,
    useful for trace levels of boron in blood and other biological
    samples, can detect 10œ8 g boron/g of sample (Clarke et al., 1987b).
    Iyengar et al. (1990) used this method to determine boron in citrus
    leaves, human erythrocytes, and food items, all with freeze-dried
    samples.

    3.  SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE

    3.1  Natural occurrence

         Boron, in the form of various inorganic borates, is widely
    distributed in low concentrations throughout nature. It constitutes
    about 10 mg/kg of the Earth's crust, ranging from 5 mg/kg in basalts
    to 100 mg/kg in shales (Woods, 1994). The majority of the boron
    resides in the ocean, at an average concentration of about 4.5
    mg/litre (Weast et al., 1985). Economic deposits of borate minerals
    are rare and are usually found in arid desert regions with a
    geological history of volcanic and/or hydrothermal activity (Mellor,
    1980). Major world deposits are found in Turkey, the USA, Argentina,
    Russia, Chile, China, and Peru (Culver et al., 1994b).

         The most abundant boron mineral is tourmaline, an aluminium
    borosilicate that contains about 3.1% boron (Muetterties, 1967). It is
    not a practicable source of usable boron, as it is widely distributed
    as a minor component of rocks. Economic borate minerals include
    tincal, kernite, colemanite, and ulexite.

         Natural sources of borate released to air are the oceans
    (largest), volcanoes, and geothermal steam (Graedel, 1978). Natural
    weathering of clay-rich sedimentary rocks on land surfaces accounts
    for a large proportion of the boron mobilized into soils and the
    aquatic environment, amounting to some 360 000 tonnes of boron
    annually (Bertine & Goldberg, 1971). Although few data are available
    for quantifying boron released from industrial sources, natural
    weathering and seawater evaporation are considered greater sources
    than industrial emissions (see chapter 4).

    3.2  Mining and production

         The total world production of boron minerals in 1994 was
    approximately 2 750 000 tonnes (Lyday, 1996). The main commercial
    borate minerals are colemanite, kernite, ulexite, and tincal.
    Approximately 800 000 tonnes of commercial borate products, expressed
    as B2O3, were manufactured from boron minerals in 1994. The two
    largest producers are the USA and Turkey. Further mining and
    production facilities exist in Argentina, Bolivia, China, Chile, Peru,
    and Russia (Lyday, 1996). Most US production of borates occurs in
    California, where colemanite, ulexite, tincal, kernite, and brines are
    processed. These minerals are also processed elsewhere in the world,
    as are ascharite, hydroboracite, datolite, etc.

         Disodium tetraborate (borax) containing 5 or 10 molecules of
    water is produced mainly from sodium-containing borate ores. The mined
    ore is crushed and ground before dissolution in a hot recycled aqueous
    solution containing some borax. Insoluble gangue (clay particles)
    present in the hot slurry is separated off to produce a clear
    concentrated borax solution. Evaporative cooling of this solution to
    selected temperatures results in crystallization of the desired

    products, which are then separated from the residual liquor and dried
    (personal communication from Borax US to the IPCS, 1995).

         Boric acid is produced mainly from sodium- or calcium-containing
    borate ores. The mined ore is crushed and ground before being reacted
    with sulfuric acid in the presence of a hot aqueous recycled liquor
    containing some boric acid. The resultant slurry contains insoluble
    gangue and either calcium or sodium sulfate by-product. After
    separation of unwanted insoluble gangue, recovery of the boric acid
    product is similar to that for borax (personal communication from
    Borax US to the IPCS, 1995).

    3.3  Uses and release

         The end uses of boron minerals and of borate products are
    diverse. Estimated amounts of borate consumed in the USA for the major
    end uses in 1992 are listed in Table 4 (Lyday, 1993). Partial data for
    Europe are also included (ECETOC, 1997). It should be noted that
    vitreous products such as fibreglass, borosilicate glass, and enamels,
    frits, and glazes are not significant sources of potential human
    exposure, because the boron is tied up tightly in the glassy
    structure. All of the boron from the sodium perborate contained in
    detergents ultimately enters the wastewater stream.

    Table 4.  Estimated amount consumed (as B2O3) for boric acid, borates,
    and boron minerals in the USA in 1992a and in Europe in 1993b

                                                                     

    Use                                     Consumption (tonnes)
                                                USA        Europe
                                                                     

    Insulation-grade fibreglass             129 000        44 600c
    Textile-grade fibreglass                 78 500        27 100c
    Soaps and detergents                     38 600       142 500 
    Borosilicate glass                       34 400        12 200 
    Fire retardants                          13 400             -d
    Agriculture                              11 100             -d
    Enamels, frits, and ceramic glazes        9 300         3 500 
    Metallurgy                                3 700             -d
    Nuclear applications                        900             -d
                                                                     

    a   Lyday (1993).
    b   ECETOC (1997).
    c   Does not include minerals.
    d   No data.

         The average market shares for the USA, Europe, and Japan in 1992
    were about 23% (fibreglass), 17% (detergents), 11% (enamels/glazes),
    and 11% (glass) for major end uses (personal communication from Borax
    US to the IPCS, 1995).

         Other minor uses include cosmetics and pharmaceuticals (as a pH
    buffer), boron neutron capture therapy (for cancer treatment), and
    pesticides (personal communication from Borax US to the IPCS, 1995).
    The cancer treatment application utilizes a boron compound made with
    all 10B isotope, which preferentially accumulates in tumour versus
    normal tissue (Barth & Soloway, 1994). Subsequent irradiation of the
    patient with thermal neutrons produces 7Li plus alpha particles. The
    latter have a destructive path length of about the diameter of a cell,
    thereby selectively destroying the cancer. Research in this field is
    being pursued in Japan and, to a lesser extent, in the USA.

         Boron enters the environment mainly through the weathering of
    rocks, volatilization from seawater, agricultural, refuse, and fuel
    wood burning, power generators (coal and oil combustion), the
    manufacture of glass products and other boron-containing compounds,
    the industrial and household use of boron-containing products
    (including soaps and detergents), borax mining and processing,
    leaching from treated wood and paper, geothermal releases, chemical
    plants, and sewage and sludge disposal (Versar, Inc., 1975; Larsen,
    1988; ATSDR, 1992; Anderson et al., 1994a). Boron is not present in
    the atmosphere at significant levels because of its low volatility,
    but the total amount in the air is very significant owing to the huge
    volume of the atmosphere (see chapter 4).

         Boron releases to water occur from municipal sewage containing
    perborates from detergents and also in runoff from areas using
    boron-containing herbicides or fertilizers (Waggott, 1969; Nolte,
    1988; Butterwick et al., 1989). Boron levels in sewage sludge from 23
    cities in the USA ranged from 7.1 to 53.3 mg/kg (Mumma et al., 1984).
    It has been estimated that 11 800 tonnes of boron are released yearly
    in coal fly ash from coal combustion (Bertine & Goldberg, 1971).
    Versar, Inc. (1975) estimated US boron air emissions as 10 500 tonnes
    annually from mining, processing, and coal burning. Few quantitative
    data on boron releases are available, because boron is not included in
    the US Environmental Protection Agency (EPA) Toxic Release Inventory
    (TRI) (ATSDR, 1992).

    4.  ENVIRONMENTAL TRANSPORT, DISTRIBUTION, AND TRANSFORMATION

    4.1  Transport and distribution between media

    4.1.1  Air

         Boron is not present in the atmosphere at significant levels
    (Sprague, 1972), but the total amount in the air is very significant
    owing to the huge volume of the atmosphere. Borates exhibit low
    volatility; consequently, boron would not be expected to be present to
    a significant degree as a vapour in the atmosphere. Atmospheric
    emissions of borates and boric acid in particulate (<1-45 µm in size)
    or vapour form occur as a result of volatilization of boric acid from
    the sea, volcanic activity, mining operations, glass and ceramics
    manufacturing, the application of agricultural chemicals, and
    coal-fired power plants. As a particulate, boron would be removed from
    the atmosphere either by dry deposition or by wet deposition because
    of its relatively high water solubility (Versar, Inc., 1975; Gladney
    et al., 1978). Based on analogy with data on general particulate
    residence times (Nriagu, 1979), the half-life of airborne boron
    particles is expected to be on the order of days, depending on the
    size of the particles and atmospheric conditions.

         Seawater evaporation is the biggest contribution to boron in air.
    The global removal of boron from marine sources has been estimated at
    between 800 000 and 4 000 000 tonnes/year and compares with an
    estimate of 2 000 000-7 200 000 tonnes/year for the total global
    release (Anderson et al., 1994a). Anderson et al. (1994a) estimate
    that the total anthropogenic release of boron to the atmosphere is
    between 180 000 and 650 000 tonnes/year (9-27% of the total global
    release). In spite of all these releases, the atmospheric
    concentration of boron is low (mean boron concentrations range from
    <0.5 to approximately 80 ng/m3).

    4.1.2  Water and sediment

         Waterborne boron may be adsorbed by soils and sediments.
    Adsorption-desorption reactions are expected to be the only
    significant mechanism influencing the fate of boron in water (Rai et
    al., 1986). The extent of boron adsorption depends on the pH of the
    water and the concentration of boron in solution. The greatest
    adsorption is generally observed at pH 7.5-9.0 (Waggott, 1969; Keren &
    Mezuman, 1981; Keren et al., 1981).

         Simsiman et al. (1987) conducted a field investigation to
    determine the leachability and groundwater transport of major and
    minor elements, including boron, from ash disposal ponds at the
    coal-fired Columbia Power Plant in Portage, Wisconsin, USA. The site
    is underlain by sands interspersed with lenses of silt and clay
    overlying sandstone (10-20 m below the surface). The soil pH ranged
    from 7.1 to 8.8, and the organic matter content was 0.2-0.8%. Boron
    plumes were identified in the groundwater at least 120 m down-gradient
    of the ponds. The boron plume from the secondary fly ash pond extended

    into the sandstone (26-30 m), which suggested rapid downward
    infiltration of the leachate. However, attenuation of the boron
    occurred at some point between the pond and the aquifer, based on
    observed decreases of approximately 40% in the boron concentration.

         Barber et al. (1988) monitored the extent of groundwater
    contamination emanating from sewage disposal beds near Falmouth,
    Massachusetts, USA, by mapping the distribution of boron. Under the pH
    conditions of the aquifer (pH 5-7), dissolved boron occurred as the
    neutral undissociated orthoboric acid species, which should be
    transported with little sorption. The boron plume was 3500 m long,
    1100 m wide, and 30 m deep during sampling in 1985.

         Deverel & Millard (1988) demonstrated that boron is present in
    the oxidized, alkaline, shallow groundwater of the western San Joaquin
    Valley, California, USA. Boron was found to be geochemically mobile,
    with concentrations significantly correlated (alpha = 0.05) with
    groundwater salinity in the alluvial-fan and basin-trough geological
    zones.

         Corwin (1986) speculated that the adsorption of boron on
    sediments provides a means by which boron may persist for long periods
    of time in aquatic systems. The desorption (or leaching) of boron from
    the sediments would provide a long-term source until a system
    equilibrium could be reached, based on differences in the
    concentrations of boron in the water column and in the sediment both
    at the sediment-water interface and with increasing depth below the
    interface. The primary desorption mechanism would be diffusion.

         Boron levels (as admixed borate salt) as high as 1900 mg/kg have
    been reported in coal fly ash. Cox et al. (1978) reported that
    approximately 50% of the boron in 0.5-g samples of fly ash was leached
    from the ash into water within 2 h; the leaching rate increased with
    increased acidity. In a boron dissolution study, Hollis et al. (1988)
    observed that 60% of the boron was removed from 6 g of ash after three
    extractions at pH 9, whereas 100% was removed at pH 6 after two
    extractions. In a long-term (2-year) leachability study, Dudas (1981)
    observed that boron was readily leached, probably as a result of the
    moderate solubility of borate salts. Consequently, the disposal of
    coal fly ash in lagoons could provide a source of boron contamination
    in aquatic systems.

    4.1.3  Soil

         Boron is adsorbed onto the surfaces of soil particles, with the
    degree of adsorption depending on the type of soil, pH, salinity,
    organic matter content, iron and aluminium oxide content, iron- and
    aluminium-hydroxy content, and clay content (Sprague, 1972). Boron
    adsorption can vary from being fully reversible to irreversible (Rai
    et al., 1986; Shani et al., 1992). The lack of reversibility may be
    the result of solid-phase formation on mineral surfaces (Rai et al.,
    1986) and/or the slow release of boron by diffusion from the interior
    of clay minerals (Griffin & Burau, 1974).

         At acidic pH, boron exists in solutions in the form of
    undissociated boric acid; at alkaline pH, it is present as a borate
    ion, which reaches maximum adsorption at pH 8.5-9 (Sprague, 1972).
    Sims & Bingham (1967) reported that hydroxy iron and aluminium
    compounds, present as interlayer-contained materials, coatings on
    individual particles, or impurities, resulted in increased boron
    retention in layer silicates. Rhoades et al. (1970) observed that in
    the silt and sand fractions of arid-zone soils, the sites of boron
    adsorption are the magnesium-hydroxy clusters and coatings found on
    the weathering surfaces of ferromagnesian minerals and micaceous layer
    silicate minerals. Marzadoori et al. (1991) reported that the amount
    of boron adsorbed by soil was considerably greater after the organic
    matter had been removed from the soil. An increase in
    oxalate-extractable iron and aluminium in the soil was observed after
    destruction of the organic matter. It was suggested that a portion of
    the iron and aluminium oxides as well as other possible adsorption
    sites are generally coated or occluded by organic matter and become
    active only after its removal.

         Couch & Grim (1968) studied the uptake of boron in illite clays
    and determined that uptake was enhanced at higher boron soil solution
    concentrations in direct relationship to the salinity and temperature
    of the solution. Following 30 days of treatment in soils containing
    1 mol boric acid/litre at salinities of 0.1, 1.0, or 3.0 mol
    CaCl2/litre, boron levels increased by 56, 70, and 98 mg/kg,
    respectively. Treatment of illites at 1 mol boric acid/litre for 30
    days at 60°C yielded 55 mg boron/kg, whereas the same concentration at
    215°C for 12 h yielded 180 mg boron/kg. The investigators also
    observed a direct relationship between the specific surface area of
    the clay types and boron uptake. Boron uptake in the illite clays was
    characterized as initially rapid adsorption, followed by diffusion of
    boron into the clay structure, requiring several months to reach
    equilibrium.

         Several investigators have used either the Langmuir or the
    Freundlich adsorption equation to describe the relationship between
    adsorption and desorption of boron in soils. The Langmuir equation is
    based on the total adsorptive capacity of the soil, the concentrations
    of adsorbed boron and boron in solution, and an adsorption equilibrium
    constant  (K), which represents the bonding energy of the soil. Using
    this equation, Hatcher & Bower (1958) determined that an equilibrium
    exists between boron in solid and liquid phases. At soil pH values of
    6.6-7.7, the predominant boron species in the aqueous phase is
    undissociated boric acid, and the principal mechanism of retention is
    by reversible, molecular adsorption, which is non-uniform based on the
    energy characteristics of the bonding sites. These investigators also
    showed that boron desorption was reversible; in other words, boron
    that leached into the soil solution could again be adsorbed. However,
    based on the Freundlich adsorption isotherms, Elrashidi & O'Connor
    (1982) observed incomplete adsorption reversibility in some soils from
    New Mexico, USA, at higher boron concentrations.

         Biggar & Fireman (1960) determined that the fixation of boron in
    soils occurs by one of three mechanisms: physical (molecular)
    adsorption, in which the boron is held to the surface of the soil by
    van der Waals bonds; anion exchange; or chemical precipitation.
    Chemical adsorption involves ionic and covalent bonding. The
    investigators speculated that the initial adsorption is probably
    molecular in nature, followed by the formation of surface compounds
    that result in an increase in adsorption sites, particularly at higher
    boron concentrations in the soil solution. At higher concentrations,
    chemical bonding of borate ions with hydroxyl ions on the soil surface
    results in boron fixation to soluble aluminium, silicon, and iron.
    This same mechanism (chemisorption) was observed by Couch & Grim
    (1968) for the uptake of borate ions to clay mineral surfaces. The
    presence of calcium ions, drying, and high pH values will tend to
    increase the amount of fixed boron. Wetting and drying of the soil
    will increase the maximum adsorption capacity and bonding energy of
    the soil for boron.

         Many of the surface boron compounds initially formed by
    adsorption mechanisms may be unstable and leached by water. However,
    as a result of the equilibrium that exists between adsorbed and
    dissolved boron in soils, the adsorbed boron may act as a buffer,
    impeding the leaching of excess boron from soils. Wierenga et al.
    (1975) conducted a study to determine the downward movement of boron
    through a sandstone formation in New Mexico, USA. The experimental
    dispersion coefficient was calculated as 1.06 cm2/day, primarily
    resulting from diffusion. Assuming an average annual rainfall of 20
    cm/year and an average annual recharge of 10% of the annual
    precipitation, the investigators determined that it would take 500
    years for the boron front to reach a depth of 35 m into the sandstone.
    As the groundwater table at this site is at 86 m, Wierenga et al.
    (1975) calculated that it would take 1628 years for boron, at a
    concentration one-half that of the surface concentration, to reach the
    groundwater. A 10-fold increase in annual recharge from precipitation
    would reduce the transit time by one-tenth.

         Bingham et al. (1971) concluded that the single most important
    property of soil that will influence the mobility of boron is the
    abundance of amorphous aluminium oxide. Gerritse et al. (1982) showed
    that the mobility of boron in sludge-amended sandy and sandy loam
    soils was increased as a result of complexation with dissolved organic
    compounds, high ionic strengths of the soil solutions, and other
    factors.

    4.1.4  Vegetation and wildlife

         Hingston (1986) investigated the components of the biogeochemical
    cycle for boron in two eucalypt forests. The importance of the
    biological component of the cycle was indicated by the amount of boron
    stored within trees (2.1 and 2.5 kg/ha for the two forests) compared
    with the amount of extractable boron in the soils to a depth of 1 m (2
    and 7 kg/ha), and by the highly significant correlations between
    hot-water-soluble boron and organic carbon for these soils.

    4.2  Transformation

    4.2.1  Biotransformation

         Borate ions present in aqueous solution are essentially in their
    fully oxidized state. No aerobic processes are likely to affect their
    speciation, and no biotransformation processes are reported in the
    literature (personal communication from Borax US to the IPCS, 1995).
    Therefore, there are unlikely to be any differences in boron species
    due to biotransformation.

    4.2.2  Abiotic transformation

         Inorganic borates such as boric acid, boric oxide, and sodium
    borates are stable, except for dehydration at high temperatures.
    Organoboron compounds are sufficiently uncommon in nature to be
    irrelevant to this document. In aqueous media, the chemical speciation
    of boron-oxygen compounds is pH and concentration dependent.

    4.2.2.1  Air

         No information was available in the current literature concerning
    the photolysis, oxidation, or hydrolysis of boron-oxygen compounds in
    the atmosphere. The small amount of boron in air is assumed to be in
    the form of boric acid.

    4.2.2.2  Water

         In natural waters, boron exists primarily as undissociated boric
    acid with some borate ions. As a group, the boron-oxygen compounds are
    sufficiently soluble in water to achieve the levels that have been
    observed (Sprague, 1972; see chapter 5).

         In seawater, inorganic boron content generally bears a linear
    relationship to the amount of chloride ion present; a ratio of
    0.000 24 g boron/g of total halogen expressed as chloride ion has been
    calculated (Mellor, 1980). Byrne & Kester (1974) demonstrated that
    weakly dissociated boric acid is the predominant species but also that
    there are weakly associated ion pair neutral and positively charged
    borate complexes of sodium, magnesium, and calcium. The metaborate ion
    will undergo rapid hydrolysis in seawater to form the borate ion and
    the weakly dissociated boric acid. Noakes & Hood (1961) concluded that
    organically bound boron contributes very little, if any, to the total
    boron content of seawater. Boron associated with organic matter was
    found to vary with oxygen content, with the lowest concentrations
    occurring in the minimum oxygen zone. Mance et al. (1988) described
    boron as a significant constituent of seawater, with an average
    concentration of 4.5 mg/litre.

         Boric acid is a very weak acid, with a p Ka of 9.15; in fresh
    water, therefore, boric acid and sodium borates exist predominantly as
    undissociated boric acid below pH 7, but the metaborate anion becomes
    the main species in solution above pH 10. Between these two pH bands,
    there is also a characteristic presence of complex polyborate anions
    in solution when the concentration is increased, leading to enhanced
    solubility.

    4.2.2.3  Soil

         Borates as such cannot degrade, but borate complexes with organic
    matter or sod mineral surfaces can be altered by water leaching or pH
    change.

    4.2.3  Bioaccumulation

    4.2.3.1  Aquatic organisms

         Highly water soluble materials are unlikely to bioaccumulate to
    any significant degree, and borate species are all present essentially
    as undissociated boric acid at neutral pH. The octanol/water partition
    coefficient for boric acid has been measured as 0.175 (Barres, 1967),
    indicating low bioaccumulation potential.

         Thompson et al. (1976) studied boron uptake in two saltwater
    species, juvenile Pacific oysters  (Crassostrea gigas) and
    underyearling sockeye salmon  (Oncorhynchus nerka), in
    continuous-flow systems with 95% solution replacement every 6 h.
    Oysters (30/tank) were exposed to two boron levels (1 mg/litre above
    background and 10 mg/litre above background) for 47 days, and salmon
    (3/tank) were exposed only to the higher concentration for 21 days.
    Control tanks received only seawater inflow. The background
    concentration of boron in seawater in this study was approximately
    3.98 mg/litre. The oysters were sampled on days 0, 8, 16, 36, and 47
    of exposure. After this time, the remaining oysters were maintained in
    seawater alone for another 24 days and then analysed for boron uptake.
    Following the 21-day exposure period, the sockeye salmon were killed
    and the boron concentration was determined in gill, liver, kidney,
    muscle, and bone tissue. For both species, the tissue levels
    approximated the boron concentrations in the test water, indicating
    that these species take up boron in relation to its availability.

         In the oyster, tissue concentrations returned to background
    levels (3.67-4.13 µg/g) by the 71st day of the study, indicating a
    fairly rapid clearance of boron with no evidence of long-term
    retention. Boron concentrations in sockeye salmon tissues in normal
    seawater ranged from 0.5 to 1.5 µg/g wet weight, with concentrations
    increasing from muscle to gill and kidney, to liver, and to bone.
    Boron levels were elevated in the bone and kidney tissue (5.9-17 µg/g
    wet weight and 4.5-11.9 µg/g wet weight, respectively) of the exposed
    salmon; however, they were not significantly different from test water
    levels. Consequently, there was no evidence for active bioaccumulation
    of boron in these species (Thompson et al., 1976).

         Suloway et al. (1983) studied the bioaccumulation potential of
    the components of coal fly ash extract in fathead minnows 
     (Pimephales promelas) and green sunfish  (Lepomis cyanellus). Five
    fish of each species were exposed for 30 days to fly ash extracts
    containing boron at concentrations ranging from 1.23 to 91.7 mg/litre.
    Whole-body concentrations of boron ranged from 1.16 to 4.15 µg/g in
    the exposed fathead minnows and from 1.08 to 4.62 µg/g in the exposed
    green sunfish. The reported bioconcentration factor was 0.3 for both
    species. These results are consistent with those described above and
    indicate that boron does not bioaccumulate significantly in fish.

    4.2.3.2  Terrestrial plants

         Eaton (1944) investigated growth reaction and boron accumulation
    characteristics of plants grown in outdoor sand culture beds where
    cultures were supplied with nutrient solutions containing differing
    concentrations of boron. The concentrations of boron ranged from 58 to
    1804 µg/g dry weight in the leaves of plants grown in 5 mg boron/litre
    and from 209 to 3875 µg/g dry weight in the leaves of plants grown in
    25 mg boron/litre. The boron concentrations were generally lower in
    roots, stems, and fruits than in the leaves. This is consistent with
    the fact that boron is absorbed from the soil solution by the roots
    and passively carried in the transpiration stream to the leaves, where
    the water evaporates and the boron accumulates. The absorption into
    the roots usually occurs as active transport against a concentration
    gradient (the concentration in the soil solution is generally lower
    than in the root tissues); therefore, an expenditure of energy is
    required. However, at higher boron soil solution concentrations, which
    are toxic to some plant species, the mechanism of uptake is passive
    diffusion (Bingham et al., 1970). Boron is relatively immobile in the
    phloem; consequently, the accumulated boron does not move out of the
    leaf tissues and into the fruit and other tissues (Kohl & Oertli,
    1961).

         Several factors affect the uptake of boron, including the pH of
    the soil solution, temperature, light intensity, and the concentration
    of other elements (e.g. calcium and potassium). Uptake is reduced by a
    factor of four as soil pH increases from 4 to 9 (Bingham et al., 1970)
    and increased by an increase in light intensity (Tanaka, 1966); the
    rate of boron absorption rapidly increases at temperatures ranging
    from 10 to 30°C and is sharply reduced above 35°C (Reisenauer & Cox,
    1971).

    4.2.3.3  Birds

         Pendleton et al. (1995) exposed adult male mallard ducks to a
    dietary concentration of 1600 mg boron/kg for up to 48 days.
    Equilibrium levels were reached between days 2 and 15. Boron
    concentrations were highest in the blood, followed by the brain and
    liver. Boron was rapidly eliminated, with few detectable residues
    after 1 day on a "clean diet." The presence of arsenic (300 mg/kg) in
    the diet slowed the accumulation of boron.

    4.3  Ultimate fate following use

         No information was available in the current literature concerning
    the disposal of boron or boron compounds. Information was located,
    however, regarding the reclamation and revegetation of coal combustion
    products (i.e. ash) that contain high concentrations of metals,
    including boron. Although the chemical and physical properties of coal
    ash tend to be detrimental to plant growth and establishment,
    additions of fertilizer and manure provide a more suitable medium
    (Schwab et al., 1991). Plant establishment on the site is only the
    first phase of the reclamation process. It is also necessary to ensure
    that leachate from the ash does not contaminate the surface water and
    groundwater in the immediate region and that uptake of metals in the
    plant materials does not result in metal concentrations that are toxic
    to livestock or wildlife. In a study of the revegetation of several
    ash disposal sites in Kansas, USA, Schwab et al. (1991) noted
    variations in plant uptake of boron from coal ash owing to differences
    in ash type, plant species, and ash treatment. Boron contained in
    detergents after use releases to the municipal sewage system. It
    should be noted that boron is not removed by the usual water treatment
    processes. Landfill will tend to be the ultimate fate of many boron
    products.

    5.  ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE

    5.1  Environmental levels

    5.1.1  Air

         Boron, as boric acid, is released into the atmosphere during
    volcanic eruptions; however, most is captured by the oceans
    (Muetterties, 1967). Coal-fired power plants and agricultural burning
    are major sources of atmospheric boron contamination; at least 30% of
    boron in coal is lost in this manner (Eisler, 1990). Nevertheless,
    boron does not appear to be present in ambient air at significant
    levels (Sprague, 1972), presumably because of rapid transport to other
    media (see section 4.1.1). Although the concentration is low, the
    atmosphere carries a significant amount of boron as boric acid vapour.

         Mean boron concentrations in emissions from active volcanic sites
    range from <2.5 to 31.4 µg/m3 for gaseous boron and are below 
    4 µg/m3 for particulate boron. Volcanic lake fumes (El Chichon,
    Mexico) contained mean boron concentrations of up to 8.5 µg/m3 for
    particulate boron and up to 16.1 µg/m3 for gaseous boron (Anderson et
    al., 1994a).

         Anderson et al. (1994a) monitored atmospheric concentrations of
    boron at continental, coastal, and remote marine sites. Mean
    particulate boron concentrations ranged from 1.8 to 12.2 ng/m3, from
    2.4 to 3.7 ng/m3, and from <0.5 to 2.8 ng/m3 for the three types of
    site, respectively. Mean gaseous boron concentrations ranged from
    <0.5 to 20.7 ng/m3, from 3.5 to 82.8 ng/m3, and from 0.6 to
    25 ng/m3, respectively. Anderson et al. (1994a) assumed 90% of boron
    in the air is gaseous and 10% is in particulate form.

    5.1.2  Water

    5.1.2.1  Groundwater

         Naturally occurring boron is present in groundwater primarily as
    a result of leaching from rocks and soils containing borates and
    borosilicates (i.e. local geology). Concentrations of boron in
    groundwater throughout the world range widely, from <0.3 to 
    >100 mg/litre. Boron levels in European groundwaters are presented in
    Table 5. In general, concentrations of boron were greatest in southern
    Europe (Italy, Spain, but not Greece) and least in northern Europe
    (Denmark, France, Germany, Netherlands, and the United Kingdom). For
    Italy and Spain, mean boron concentrations ranged from 0.5 to
    1.5 mg/litre. Concentrations ranged up to approximately 0.6 mg
    boron/litre in the Netherlands and United Kingdom, and levels in
    approximately 90% of samples in Denmark, France, and Germany were
    found to be below 0.3, 0.3, and 0.1 mg boron/litre, respectively.

        Table 5.  Concentrations of boron in European groundwatera

                                                                                    
    Country              Area                    No. of         Boron concentration 
                                                 samples        (mg/litre)
                                                                                    
    Denmark                                        525          92.2% < 0.3
                                                                7.4% > 0.3
                                                                0.4% > 1.0

    France                                         716          99.5 < 0.3
                                                                0.5 > 0.3

    Germany              Baden-Wurttemberg        2574          89% < 0.1
                                                                10.7% > 0.1
                                                                0.3% > 1.0
                         Lower Saxony              188          96% < 1.0
                                                                4% > 1.0

    Greece               Patras                     10          100% < 0.1
                         Halkidiki                   3          2.3-5.4

    Italy                North of Rome             423          Mean = 1.0
                         Sicily                     18          Mean = 1.5
                         Paglia                    102          Mean = 0.75

    Netherlands          Inland                                 0.08-0.6

    Spain                Valencia                   21          Mean = 0.64
                         Almeria                    17          Mean = 0.98
                         Murcia                     15          Mean = 0.51

    United Kingdom       London                     21          0.02-0.54
                         Northumbria               164          Mean = 0.31
                         Dumfries and Galloway                  Mean = 0.04
                         Permo-Triassic 
                         (Scotland)
                                                                                    

    a  ECETOC (1997).
    
         Groundwater contaminated with excessive concentrations of boron
    from surface water recharge has been noted beneath the Kesterson
    Reservoir, California, USA. This reservoir serves as an evaporative
    sink for several metalloids, including boron, and receives
    agricultural drainage from farmlands within the San Joaquin River
    Valley. Benson et al. (1991) reported an average boron concentration
    of 15 mg/litre. Concentrations of boron elsewhere within the San
    Joaquin River Valley have been shown to range from 0.14 to 120
    mg/litre, with a median of 4 mg/litre (Deverel & Millard, 1988;
    Butterwick et al., 1989).

    5.1.2.2  Surface water

         The majority of the Earth's boron occurs in the oceans, with an
    average concentration of 4.5 mg/litre (Weast et al., 1985). The amount
    of boron in fresh water depends on such factors as the geochemical
    nature of the drainage area, proximity to marine coastal regions, and
    inputs from industrial and municipal effluents (Butterwick et al.,
    1989). Concentrations of boron in fresh surface water are summarized
    in Table 6.

         Concentrations ranged from 0.001 to 2 mg boron/litre in Europe,
    with mean values typically below 0.6 mg/litre. Similar concentrations
    have been reported for water bodies within Pakistan, Russia, and
    Turkey; concentrations range from <0.01 to 7 mg boron/litre, with
    most values below 0.5 mg/litre. Concentrations ranged up to 0.01 mg
    boron/litre in Japan and up to 0.3 mg boron/litre in South African
    surface waters. Samples taken in surface waters from two South
    American rivers (Rio Arenales, Argentina, and Loa River, Chile)
    contained boron at concentrations ranging between 4 and 26 mg/litre in
    areas rich in boron-containing soils. In other areas, the Rio Arenales
    contained less than 0.3 mg boron/litre. Concentrations of boron in
    surface waters of North America (Canada, USA) ranged from
    0.02 mg/litre to as much as 360 mg/litre, indicative of boron-rich
    deposits. However, typical boron concentrations were less than
    0.1 mg/litre, with a 90th-percentile boron concentration of
    approximately 0.4 mg/litre.

    5.1.2.3  Rainfall

         The median and mean concentrations of borate in rain and snow at
    six sites in western Switzerland were found to be 0.0031 and 0.0056 mg
    boron/litre, respectively (Atteia et al., 1993).

    5.1.3  Sewage

         Concentrations of boron in sewage waters are summarized in Table
    7.

         The majority of the boron present in sewage occurs primarily as
    undissociated boric acid; reported levels of boron in sewage in the
    USA range from 0.4 to 1.5 mg/litre and up to 4.05 mg/litre because of
    industrial waste discharges (Banerji, 1969). In Europe, sewage from
    domestic and industrial sources typically has an average boron
    concentration of 2 mg/litre, with levels up to 5 mg/litre (Butterwick
    et al., 1989). Calculations by the German Government Environment
    Agency attribute 50% of the boron in wastewater to the use of
    detergent products (Butterwick et al., 1989). In boron mine drainage
    waters in Turkey, the boron concentrations were reported to be 16-390
    mg/litre (Okay et al., 1985). Boron levels in sewage sludge in 23 US
    cities ranged from 7.1 to 53.3 mg/kg dry weight (Mumma et al., 1984).

        Table 6.  Concentrations of boron in fresh surface water

                                                                                         

    Area                        Boron concentration          Reference
                                (mg/litre)
                                                                                         

    USA                         Median = 0.076               ECETOC (1997)
                                90th percentile = 0.387

    Drainage basins, USA        0.019-0.289a                 Kopp & Kroner (1970)

    Coastal drainage waters,    15 (boron-rich deposits)     Deverel & Millard (1988)
    California, USA

    Lakes, California, USA      157-360 (boron-rich          Deverel & Millard (1988)
                                deposits)

    Ontario, Canada             0.029-0.086                  Sekerka & Lechner (1990)

    Cold River drainage         0.0627                       Tsui & McCart (1981)
    area, western Canada

    United Kingdom              0.046-0.822                  Mance et al. (1988)

    Italy                       0.4-1.0 (range of            Manfredi et al. (1975)
                                means)

                                <0.1-0.5                     Tartari & Camusso (1988)

    Sweden                      0.013 (0.001-1.046)          Ahl & Jönsson (1972)

    Germany                     0.02-2.0                     Graffmann et al. (1974)

    The Netherlands             Range of medians =           Unilever (1994)
                                0.09-0.145

    Rivers, Austria             <0.02-0.6 (background        Schöller & Bolzer (1989)
                                level)

    River Neva, Russia          0.01-0.02                    Huber (1994)

    Degh Nala, Pakistan         <0.01-0.46 (near             Tehseen et al. (1994)
                                effluent discharges)

    Simav River, Turkey         <0.5 (uncontaminated)        Okay et al. (1985)
                                4 (maximum 7) 
                                (contaminated with 
                                boron mine waste)
                                                                                         

    Table 6.  (continued)

                                                                                         
    Area                        Boron concentration          Reference
                                (mg/litre)
                                                                                         
    Rio Arenales, Argentina     <0.3                         Bundschuh (1992)
                                6.9 (near borate plant)

    Loa River Basin, Chile      3.99-26 (soil rich in        Cáceres et al. (1992)
                                minerals and natural 
                                salts; low rainfall)

    Japan (River Asahi)         0.009-0.0117                 Korenaga et al. (1980)

    South Africa                0.02-0.33                    Reid & Davies (1989)
                                                                                         


    a    Lowest concentration in the western Great Lakes Basin to highest concentration 
         in the western Gulf Basin.


    Table 7.  Concentrations of boron in sewage waters

                                                                                    
    Area/source                   Boron concentration      Reference 
                                  (mg/litre)
                                                                                    
    USA
     Industrial waste             0.4-1.5                  Banerji (1969)
     discharge                    (maximum 4.05)

    Europe
     Domestic and industrial      2 (maximum 5)            Butterwick et al. (1989)

    Egypt
     Sewage water                 0.32-0.38                El-Hassanin et al. (1993)

    Sweden
     Effluent                     0.34-0.436               Ahl & Jönsson (1972)

    Spain, Alicante
     Industrial waste             1.45                     Navarro et al. (1992)

    Spain, Elche
     Industrial waste             3                        Navarro et al. (1992)

    United Kingdom
     Municipal                    1.21-3.96                Waggott (1969)
                                  (range of means)
                                                                                    
    
    5.1.4  Soil

         According to Whetstone et al. (1942), boron occurs in soils at
    concentrations ranging from 10 to 300 mg/kg (average 30 mg/kg),
    depending on the type of soil, amount of soil organic matter, and
    amount of rainfall. Background boron levels in US soils were reported
    at a geometric mean concentration of 26 mg/kg, with a maximum
    concentration of 300 mg/kg (Eckel & Langley, 1988).

    5.1.5  Aquatic biota

         Concentrations of boron in aquatic biota are summarized in
    Table 8.

         Little specific information was found concerning the
    bioaccumulation of boron in aquatic plants. At Kesterson National
    Wildlife Refuge in the San Joaquin River Valley, California, USA (an
    evaporative sink that has high concentrations of boron, selenium, and
    arsenic and is supplied with subsurface drainage water from
    agricultural fields), studies of the aquatic food-chain contamination
    have suggested that aquatic plants bioaccumulate high levels of boron,
    but boron does not biomagnify in aquatic food-chains. The following
    studies report observed concentrations in marine algae and freshwater
    aquatic vascular species. Igelsrud et al. (1938) reported boron levels
    ranging from 4.2 to 14.9 mg/kg of dried material in marine algae.
    Yamamoto et al. (1973) compared the boron content in freshwater and
    marine phytoplankton and observed that minor differences occurred
    between forms, even though the boron content of seawater averages 460
    times that of fresh water.

         Adams et al. (1973) conducted a survey to determine the
    concentration of 11 potentially polluting ions, including boron, in a
    wide variety of aquatic plants from three major watersheds in
    Pennsylvania, USA: the Delaware, Susquehanna, and Allegheny rivers.
    Sources of pollution in this area are quite diverse, including
    lumbering activities, coal strip-mining, recreation, agricultural use,
    and urban-industrial centres. Boron constituent levels in 21 species
    of submerged and floating aquatic vascular plants ranged from 26.3 to
    170 µg/g, and levels in 8 species of emergent aquatic vascular plants
    ranged from 11.3 to 57 µg/g.

         Tsui & McCart (1981) studied the bioaccumulation of several
    elements, including boron, in five freshwater fish species from the
    Cold River drainage area in western Canada. Test species were selected
    to represent different feeding habits and modes of life. Northern pike
     (Esox lucius) and lake trout  (Salvelinus namaycush) are primarily
    predators; lake herring  (Coregonus artedii) is a plankton feeder;
    and lake whitefish  (Coregonus clupeaformis) and white sucker
     (Catostomus commersoni) are primarily bottom-feeders. The fish were
    collected during spring and summer of 1978 from seven lakes within
    this area, and the muscle tissue was analysed for the presence of
    boron. The maximum average concentration of boron in the lakes was


        Table 8.  Concentrations of boron in aquatic biota

                                                                                                                                             
    Species                         Area                                  Tissue          Boron concentration       Reference 
                                                                                          (mg/kg)a
                                                                                                                                             
    Marine algae                                                                          4.2-14.9 dw               Igelsrud et al. (1938)

    Filamentous algae               Lower San Joaquin River and its                       3.5-280 dw                Saiki et al. (1993)
                                    tributaries, California, USA

    Plankton                        Lower San Joaquin River and its                       1.1-46 dw                 Saiki et al. (1993)
                                    tributaries, California, USA

    Aquatic plants                  Lower San Joaquin River,                              382 (270-510) dw          Ohlendorf et al. (1986)
                                    California, USA

    Submerged and floating          Pennsylvania, USA                                     26.3-170                  Adams et al. (1973)
    aquatic vascular plants

    Emergent aquatic                Pennsylvania, USA                                     11.3-57                   Adams et al. (1973)
    vascular plants

    Various marine shellfish        British Columbia, Canada                              0.9-5.5 ww                Thompson et al. (1976)

    Benthic bivalve                 San Joaquin River and its 
    (Corbicula fluminea)            tributaries, California, USA          Soft tissue     <2-2 dw                   Leland & Scudder (1990)

    Clam (Elliptio dilitata)        Precambrian Shield lake,              Soft tissue     2.6 ww                    Wren et al. (1983)
                                    Ontario, Canada

    Chironomid larvae               Lower San Joaquin River and its 
                                    tributaries, California, USA                          <1.8-27 dw                Saiki et al. (1993)

    Amphipods                       Lower San Joaquin River and its                       <2.2-23 dw                Saiki et al. (1993)
                                    tributaries, California, USA

    Crayfish                        Lower San Joaquin River and its                       1.2-23 dw                 Saiki et al. (1993)
                                    tributaries, California, USA
                                                                                                                                             

    Table 8.  (continued)

                                                                                                                                             
    Species                         Area                                  Tissue          Boron concentration       Reference 
                                                                                          (mg/kg)a
                                                                                                                                             

    Freshwater fish                 Cold River drainage area,             Muscle          3.23-12.44                Tsui & McCart (1981)
                                    western Canada                                        (range of means)

    Freshwater fish                 Precambrian Shield lake,              Muscle          1.8-2.9 ww                Wren et al. (1983)
                                    Ontario, Canada

    Bluegill (Lepomis               San Joaquin River, California,        Whole body      14 dw (3.5 ww)            Saiki & May (1988)
    macrochirus)                    USA

                                    Lower San Joaquin River and its                       <1.8-7.9 dw               Saiki et al. (1993)
                                    tributaries, California, USA

    Largemouth bass                 Lower San Joaquin River and its                       <1.8-2.0 dw               Saiki et al. (1993)
    (Micropterus salmoides)         tributaries, California, USA

    Common carp                     San Joaquin River, California,        Whole body      20 dw (5 ww)              Saiki & May (1988)
    (Cyprinus carpio)               USA

                                    San Joaquin River, California,        Whole body      0.5-6.2 dwb               Klasing & Pilch (1988)
                                    USA

    Mosquitofish                    Lower San Joaquin River and its                       <1.9-8.4 dw               Saiki et al. (1993)
    (Gambusia affinis)              tributaries, California, USA

                                    Volta, California, USA                Whole body      mean = 2.8 dw             Ohlendorf et al. (1986)

                                    Kesterson, California, USA            Whole body      mean = 11.1 dw            Ohlendorf et al. (1986)

    Tilapia spp.                    Mexicali Valley, Baja California,     Muscle          2.9 ww                    Mora & Anderson (1995)
                                    Mexico

    Mugil spp.                      Mexicali Valley, Baja California,     Muscle          1.9 ww                    Mora & Anderson (1995)
                                    Mexico
                                                                                                                                             

    Table 8.  (continued)

                                                                                                                                             
    Species                         Area                                  Tissue          Boron concentration       Reference 
                                                                                          (mg/kg)a
                                                                                                                                             
    Sockeye salmon                  British Columbia, Canada              Gill            mean = 0.6 ww             Thompson et al. (1976)
    (Oncorhynchus nerka)                                                  Liver           mean = 0.7 ww
                                                                          Bone            mean = 1.5 ww

    Atlantic cod (Gadus             Northwest Atlantic Ocean              Muscle          28 (1-93) ww              Hellou et al. (1992)
    morhua)                                                               Liver           9.7 (5.2-35.4) ww
                                                                          Ovaries         <0.8

    Anchoveta                                                             Whole body      3.3-3.8 aw                Jenkins (1980)
    (Cetengraulis 
    mysticetus)

    Aquatic birds                   Precambrian Shield lake,              Muscle          2.5-3.7 ww                Wren et al. (1983)
                                    Ontario, Canada

                                    Grassland water district,             Liver           1.7-40 dw                 Paveglio et al. (1992)
                                    California, USA

    Double-crested                  Mexicali Valley, Baja California, 
    cormorant                       Mexico                                Liver           4.2 (2.9-8.2) ww          Mora & Anderson (1995)
    (Phalacrocorax auritus)

    Duck species                    Grassland water district,             Egg             3.07-6.17 dw              Hothem & Welsh (1994)
                                    California, USA

    Wading bird species             Grassland water district,             Egg             2.2-3.45 dw               Hothem & Welsh (1994)
                                    California, USA

    Aquatic mammals                 Precambrian Shield lake,              Muscle          7.9 ww                    Wren et al. (1983)
                                    Ontario, Canada
                                                                                                                                             

    a    ww = wet weight; dw = dry weight; aw = ash weight; concentrations are given as means or ranges of means; ranges are given in parentheses.
    b    Exposed to tile drainage water.
    
    0.0627 mg/litre. The mean tissue concentrations of boron in the five
    fish species ranged from 3.23 µg/g for lake whitefish to 12.44 µg/g
    for white sucker.

         Wren et al. (1983) reported boron concentrations in freshwater
    fish and clams from a Precambrian Shield lake in Ontario, Canada. The
    lake was free from direct human impact. Boron levels in the
    undeveloped and protected muscle tissue of the fish were generally
    lower than those observed in fish from the Cold River drainage area in
    western Canada. The mean concentrations (wet weights) in the fish
    ranged from 1.8 to 2.9 µg/g. The boron concentration in the soft
    tissue of the clam  (Elliptio dilitata) was 2.6 µg/g.

         In contrast, boron levels were only slightly elevated in
    whole-body samples of bluegill  (Lepomis macrochirus) and common carp
     (Cyprinus carpio) from the San Joaquin River and two tributaries
    that receive agricultural subsurface drainage water. The highest boron
    concentrations (dry weights) measured were 14 µg/g (approx. 3.5 µg/g
    wet weight) in bluegills and 20 µg/g (approx. 5 µg/g wet weight) in
    carp (Saiki & May, 1988). Ohlendorf et al. (1986) reported similar
    values for mosquitofish  (Gambusia affinis) from the San Joaquin
    River Valley. However, Saiki & May (1988) reported that the elevated
    boron levels may also result from natural boron deposits in adjacent
    soils or from sand-and-gravel mining operations in the area.

         Paveglio et al. (1992) analysed boron concentrations in livers of
    aquatic birds collected from the Grassland Water District of
    California, USA, during 1985-1988. The use of subsurface agricultural
    drainage water for marsh management resulted in trace element
    contamination of components of the food-chain in this region. During
    the breeding and wintering periods, livers of birds from northern and
    southern areas of the grasslands contained high concentrations of
    boron (1.7-40 mg/kg dry weight).

         A number of studies have investigated the accumulation of boron
    in aquatic food organisms, such as plants, insects, and fish (Saiki &
    May, 1988; Hothem & Ohlendorf, 1989; Smith & Anders, 1989; Paveglio et
    al., 1992; Saiki et al., 1993). The results of these studies suggest
    that aquatic plants bioaccumulate boron, but that boron does not
    biomagnify in aquatic food-chains.

    5.1.6  Terrestrial biota

         Concentrations of boron in terrestrial biota are summarized in
    Table 9.

         The studies discussed in section 4.2.3 suggest that plants grown
    in boron-rich soil often contain high levels of boron in their
    tissues. Another source of boron