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    BROMOPROPYLATE

    First draft prepared by
    A. Takanaka
    Biological Safety Research Center, National Institute of Health
    Sciences
    Tokyo, Japan

    EXPLANATION

          Bromopropylate was previously evaluated by the Joint Meeting in
    1973 when an ADI of 0-0.008 mg/kg bw was allocated (Annex 1,
    reference 20 & 21).  That meeting recommended further desirable work
    as follows: 1) studies to elucidate the effects on survival rate of
    rats in long-term feeding studies; 2) long-term studies in a second
    animal species; 3) studies on the effects of bromopropylate on the
    liver.  The results of these studies and additional data were
    submitted for the present evaluation.  This monograph summarizes the
    data that have been reviewed since the previous evaluation and
    incorporates relevant studies from the previous monograph.

    EVALUATION FOR ACCEPTABLE DAILY INTAKE

    BIOLOGICAL DATA

    Biochemical aspects

    Absorption, distribution and excretion

    Rats

          The absorption, distribution and elimination of bromopropylate
    were evaluated in rats.  [U-14C]phenyl bromopropylate was given
    orally at single doses of 0.5 mg/kg bw (at a no-effect level) or 100
    mg/kg bw (to produce some pharmacological/toxicological effect) to
    groups of 5 male and 5 female rats (Sprague-Dawley Crl: CD [SD] BR). 
    At the low dose level an additional group received 14 consecutive
    daily doses of 0.5 mg/kg bw non-labelled compound (> 95% pure)
    followed by a single dose with radiolabelled compound.  Under all
    three dosing regimens the total recoveries of radioactivity within
    168 hours past termination of dosing were 90% and higher.  Most of
    the dose was eliminated in faeces (males: 85.3-89.3%, females: 52.5-
    63.7%).  Lower amounts of radioactivity were excreted in the urine
    (males: 2.3-3%, females: 21.8-28.7%).  Excretion of radioactivity
    was essentially complete within 96 hours independent of dose level
    or pretreatment.  No radioactivity was expired in CO2.

          At the low-dose after 168 hours, tissue concentrations were low
    with highest values in liver (0.05 µg equivalents of
    bromopropylate/g tissue in male or female) and abdominal fat (0.02
    or 0.03 µg equivalents of bromopropylate/g tissue in male or
    female).  At the high dose, the tissue residue pattern was similar,
    with highest concentration of radioactivity in the abdominal fat
    (equivalent to 3.3 or 8.7 µg/g in male or female).  Pre-treatment
    with the non-radiolabelled compound did not significantly alter
    tissue residues at 168 hours post-dose over those animals receiving
    a single administration.  It was concluded that excretion rates were
    fast, and independent of dose level and pretreatment.  The routes of
    elimination were sex-dependent.  The low tissue residue levels were
    observed at 168 hours after administration (Cornelissen & Hopkins,
    1991).

          Two male and two female rats were each administered by gavage
    1.6 mg 14C-labelled bromopropylate.  Expired CO2, urine and faeces
    were collected for the next 120 hours in 24 hour periods after which
    blood and other tissues were taken for analysis.  Less than 0.2% of
    the activity was found in respired CO2.  In males, 90% of the
    activity was found in faeces and 6% in urine while in females 55%
    appeared in faeces and 33% in urine.  About 75% of the activity was

    eliminated in 48 hours but after 120 hours, 2.6% (males) and 1.5%
    (females) of the administered dose remained in tissues, mainly in
    kidneys, liver and fat (Cassidy  et al., 1968).

    Biotransformation

          The metabolic profile of bromopropylate was investigated in
    urine, faeces, and tissue extracts from male and female rats.  The
    study involved single oral administration at a low (0.5 mg/kg bw)
    and high dose level (100 mg/kg bw), and repeated oral administration
    at the low dose level.  Excreta and tissue samples generated in the
    absorption, distribution and excretion study were used in this
    experiment.

          In the urine pools, representing 1.7% to 26.4% of the
    administered dose, there were seven distinct metabolite fractions. 
    The metabolite pattern did not significantly differ between the dose
    levels or dose regimen.  However, a pronounced sex difference was
    observed: the benzilic acid was a minor fraction (10%-14%) in males
    but the major fraction (65%-72%) in females.  The metabolite pattern
    in faeces did not significantly differ between dose levels, dose
    regimen and, in contrast to urine, between the sexes.  The urinary
    and faecal metabolic patterns differed qualitatively: there was a
    non-polar fraction in the faeces, corresponding to unchanged
    bromopropylate, which represented 14 to 54% of the total faecal
    radioactivity.

          The metabolite pattern in liver tissue was not sex-dependent
    and rather simple with the two major fractions corresponding to
    bromopropylate and the benzilic acid.  The pattern in kidney tissue
    was also not sex-dependent.  It contained only one major fraction
    accounting for at least 80% of the radioactivity in kidneys and
    corresponding to the benzilic acid.  The benzilic acid accounted for
    at least 70% and 40% of the radioactivity in male and female lung
    tissue, respectively.  The fat tissue contained unchanged
    bromopropylate as a major component representing 40% and 80% of the
    radioactivity for males and females, respectively.

          Thus, within the tested dose range the metabolism of
    bromopropylate in the rat was independent of dose level and dose
    regimen.  However, a pronounced sex difference was observed in all
    groups.  The benzilic acid was a minor metabolite in males
    (approximately 6% of the dose) and the major metabolite in females
    (approximately 23% of the dose).  This parallels the sex difference
    observed for the route of excretion.  The dominant compound in
    kidney and lung tissue was the benzilic acid, in fat tissue the
    unchanged bromopropylate, and in liver tissue both were present in
    substantial amounts (Mathies, 1991).

          The structures of eight metabolites were identified from urine
    and faeces, covering 80% and 72% of the dose for males and females,

    respectively.  The metabolic pathway is depicted in Figure 1.  It is
    concluded that bromopropylate was metabolized preferentially by
    cleavage of the isopropyl ester and to a minor extent by oxidation
    reactions attacking the phenyl ring and the isopropyl group.  The
    primary product formed after ester cleavage, the benzilic acid, was
    subject to subsequent conjugation reactions, leading to a variety of
    amino acid conjugates, or was excreted as such.  Metabolites formed
    after oxidation were 3-hydroxy-benzilate and a propylene glycol
    derivative of the parent compound (Schulze-Aurich, 1993).

    Effects on enzymes and other biochemical parameters

    Mice

          Bromopropylate (95% pure) was administered by gavage to male
    mice (Tif: MAG f) at daily doses of 0, 10, 50, 150 or 300 mg/kg bw
    for 14 days.  A dose-related increase in liver weight was associated
    with moderate induction of some enzymes known to be involved in
    xenobiotic metabolism and with a weak proliferation of smooth
    endoplasmic reticulum in hepatocytes.  Particularly, cytochrome P-
    450, ethoxycoumarin O-deethylase and styrene oxide hydrolase
    activities were enhanced at all dose levels; the activity of
    cytosolic glutathione S-transferase was increased at the two high
    dose levels, while that of UDP-glucuronyl-transferase was only
    slightly increased and that of cytosolic trans-stilbene oxide
    hydrolase was not affected by treatment.  Reversibility studies
    demonstrated that the increased liver weights as well as the
    investigated biochemical parameters fully reverted to control levels
    after 4-week recovery.  Moreover, proliferation of smooth
    endoplasmic membranes disappeared. The observed biochemical and
    morphological response pattern can therefore be interpreted as a
    reversible adaptive response to a functional overload (Waechter  et
     al., 1986).

          In a recent study, bromopropylate (94.2% pure) was given to
    groups of 6 male mice (Tif:Mag f) at single oral doses of 0, 3, 15,
    100 or 300 mg/kg bw for 14 days.  Two additional groups received
    phenobarbital (40 mg/kg bw, i.p. for 4 consecutive days) or 3-
    methylcholanthrene (80 mg/kg bw, i.p. 72 and 48 hours prior to
    sacrifice).  No symptoms and no compound-related mortalities were
    recorded. Body-weight gains were slightly reduced at 300 mg/kg bw.
    Liver weights were increased in the high-dose group and in the
    groups receiving phenobarbital or 3-methylcholanthrene.  In the
    liver, microsomal protein contents were increased dose-dependently
    in the bromopropylate-treated animals as well as in both groups
    receiving the reference compounds.  A slight to moderate dose-
    dependent increase of the microsomal P-450 content was observed.  

    FIGURE 01

    The ethoxycoumarin O-deethylase, ethoxyresorufin O-deethylase,
    pentoxyresorufin O-depentylase, and total testosterone hydroxylase
    activities were also increased.  The results of studies with
    monoclonal antibodies against rat liver cytochrome P-450 isozymes of
    four different gene families confirmed that bromopropylate shares
    properties typical of a moderate phenobarbital-type inducer and
    possibly is also a very weak peroxisome proliferator-type inducer. 
    It was concluded that bromopropylate has the properties of a
    phenobarbital-like inducer of cytochrome P-450 in the mouse liver. 
    In addition, it might act as a very weak peroxisome proliferator. 
    The increased liver weights at the high-dose and the biochemical
    changes were therefore regarded as a reversible adaptation to a
    functional overload.  At 15 mg/kg bw/day only minimal biochemical
    changes were observed and the low dose of 3 mg/kg bw/day was without
    any effects (Thomas, 1991).

          A DNA-binding study was conducted with mice (Tif: MAG f)
    pretreated for two weeks with unlabelled bromopropylate (94.2% pure)
    at daily oral doses of 300 mg/kg bw.  Radiolabelled [ bis-phenyl-
    14C] bromopropylate was then administered by gavage at a dose level
    of 300 mg/kg bw.  After 24 hours, DNA was isolated from the liver
    and purified.  No radioactivity was detected.  Bromopropylate is
    devoid of a genotoxic potential mediated by DNA-binding (Sagelsdorff
    & Heuberger, 1990).

    Toxicological studies

    Acute toxicity studies

          Bromopropylate has a low acute toxicity in rats and rabbits. 
    WHO has classified bromopropylate as unlikely to present acute
    hazard in normal use (WHO, 1992).  The LD50 and LC50 values are
    summarized in Table 1.

    Short-term toxicity studies

    Rats

          Groups of 10 male and 10 female rats received 0, 40, 200, 1000
    or 5000 mg bromopropylate/kg bw/day by gavage as a suspension in
    0.5% aqueous tragacanth on six days each week for four weeks.  The
    highest dosage level produced polyuria throughout the 21 days before
    the animals were killed and for the first eight days pale mucoid
    faeces were produced.  The rate of body-weight gain and food intake
    were reduced in the 200 and 1000 mg/kg bw/day groups.  Rats of the
    5000 mg/kg bw/day group developed a relative neutrophilia but the
    results of haematological analyses in all groups were normal.  The
    absolute and relative liver weights were increased in the three
    highest dosage groups and cytoplasmic swelling and periportal

        Table 1.  Results of acute toxicity studies with bromopropylate
                                                                                            
    Species     Sex     Route          Solvent       LD50/LC50       Reference
                                      (vehicle)      (mg/kg bw)/
                                                     (mg/m3 air)
                                                                                            

    Mouse1      M       oral              -            8000          Ueda & Kondo, 1968
    Rat1        M,F     oral              -          > 5000          Stenger, 1967
    Rat2        M,F     oral              -            6000          Drake, 1970
    Rat2        ?       oral              -          > 23 000        Fancher et al., 1968a,b
    Rat3        M,F     oral          corn oil       approx. 5000    Kuhn, 1989a
    Rat4        M,F     dermal         PEG 400       > 4000          Bathe & Sachsse, 1979
    Rat5        M,F     inhalation     ethanol       > 4458          Hartmann, 1989
    Rabbit4     M,F     oral            CMC6         > 6000          Ullmann & Sachsse, 1979a
    Rabbit3     M,F     dermal         saline        > 2020          Kuhn, 1989b

                                                                                            

    1    Purity given as Technical.
    2    Purity given as Formulation.
    3    Purity not given but known to be 90%.
    4    90% pure.
    5    95% pure.
    6    CMC = 2% carboxymethylcellulose in water.
    
    infiltration were seen.  Hepatic necrosis occurred at the highest
    dosage level.  At 40 mg/kg bw/day, the one animal which died during
    the test showed similar abnormalities in the liver; others in the
    group appeared normal (Paterson, 1967a).

          Groups of 12 male and 12 female rats were fed diets containing
    0, 100, 300 or 1000 ppm bromopropylate for 90 days.  Another group
    received diets containing 3000 ppm for 55 days and 4000 ppm for a
    further 35 days.  At the highest dose, the food intake and rate of
    weight gain were below normal and at autopsy the liver, kidney and
    testes weights relative to body weight were higher than in controls. 
    Swelling and loss of basophil material, pigmentation (possibly
    lipofuscin) and fatty infiltration were present in hepatocytes. 
    Mild to severe regressive changes were seen in testes on
    histological examination.  At 1000 ppm, food intake was slightly
    less than in controls although weight gain was similar.  Testes were
    lighter than in controls and similar histological changes were seen
    in the liver.  At the two lower levels, smaller numbers of rats
    showed loss of basophilic material and cytoplasmic swelling with
    focal vacuolation.  These changes were considered to be

    physiological in that they were attributed to SER hypertrophy, but
    no EM studies were carried out to confirm this.  The results of
    haematological and blood biochemistry studies and of urine analyses
    were similar in all groups (Paterson & Drake, 1967).

          Bromopropylate (94.2% pure) was applied to the shaved skin of 5
    male and 5 female rats (Tif:RAI f) per dose group for 4 weeks on a
    5-day per week basis.  The daily exposure period was 6 hours.  The
    compound was given on moistened gauze patches under occlusive
    dressing at dose levels of 0, 50, 200 or 1000 mg/kg bw/day.  There
    was no mortality, no clinical signs, no signs of local irritation
    and no body weight or food consumption changes that could be
    attributed to treatment.  At 1000 mg/kg bw/day, slightly lower
    glucose levels and a minimal increase of urea were evident in blood
    chemistry, while no changes were seen in haematology.  Organ
    weights, macro- and microscopic histopathological findings were
    similar in all groups.  The NOAEL in this study was 200 mg/kg bw/day
    in both sexes (Schneider  et al., 1989).

    Dogs

          A group of two male and two female dogs received orally, by
    capsule, 1000 mg/kg bw/day of bromopropylate for 30 days.  A second
    group received 2000 mg/kg bw/day for four days, then 500 mg/kg
    bw/day for a further 26 days.  Diarrhoea and vomiting occurred in
    dogs of both groups.  During the first week, food intake and body
    weight decreased.  The results of haematological examinations were
    normal.  Determination of organ weights did not indicate any dose-
    related changes.  In both groups, serum transaminase and alkaline
    phosphatase levels were increased by treatment and cytoplasmic
    swelling and fine vacuolation of hepatocytes were found.  No mature
    spermatozoa were found in male animals, but this may have been due
    to the age of the animals (Paterson, 1967b).

          Four groups of eight male and eight female dogs were fed for
    two years on diets containing 30, 100, 250 or 1000 ppm
    bromopropylate.  A fifth group received 4000 ppm in the diet for
    three months.  A group of 10 males and 10 females acted as controls. 
    The highest dosage level produced light-coloured soft stools after
    one week and semi-fluid stools thereafter.  Food intake was reduced
    and weight loss occurred.  Two dogs died (after four and six weeks)
    and two others were killed because they became cachectic.  In these
    four animals, increased serum alkaline phosphatase, diminished serum
    cholesterol and mild anaemia were found.  Haemosiderosis of kupfer
    cells, proximal tubular cells of the kidney, the spleen and the bone
    marrow, degenerative changes in the distal convoluted tubules of the
    kidney, hyperplasia of bone marrow and extra-medullary
    haematopoiesis were seen in these animals at autopsy.  In the other
    animals of the 4000 ppm group killed at three months, accumulation
    of haemosiderin in the macrophages of the spleen and bone marrow and

    in kupfer cells was observed.  Examination of liver by EM showed SER
    hypertrophy and an increase in numbers of lysosomes, many of which
    contained lamellar structures.  Two additional animals of each sex
    were fed for nine months on control diets following three months on
    4000 ppm diet.  Stools returned to normal consistency within a week
    and weight gain was normal.  Biochemical and haematological
    parameters also returned to normal in a short time; animals were
    indistinguishable from controls at the time of autopsy.  The 1000
    ppm diet also produced softening of stools.  Although weight gain by
    males was normal, females failed to gain weight.  Some females
    showed slight anaemia on some occasions.  The microsomal enzymes,
    biphenyl hydroxylases, showed increased activity and this was
    associated with an increase in liver weight relative to body weight
    at six months and at two years (in females only).  SER hypertrophy
    was marked at three months and numerous myelin bodies were also
    seen.  Although at two years the SER hypertrophy was not different
    from controls, myelin bodies were still present.  An increase in
    microsomal enzymes was found in the 250 ppm group together with an
    enlarged liver (relative to body weight) at six months but not at
    two years.  No adverse effects were observed in dogs fed on 30 or
    100 ppm diets (Coulston  et al., 1970a).

          Bromopropylate (95% pure) was administered in the diet at
    concentrations of 0, 100, 400 or 2000 ppm to groups of 6 male and 6
    female beagle dogs for one year.  After completion of the treatment
    period, subgroups of 2 animals per sex were kept for one month on
    compound-free (control) diet to determine reversibility of potential
    toxic effects.  There were no compound-related mortalities and no
    clinical signs.  Body-weight gain was decreased markedly at 2000 ppm
    in both sexes and slightly at 400 ppm in females from week 28
    onwards.  Food consumption was not affected and there were no
    ophthalmic, haematological or urinary changes.  The only relevant
    change in blood chemistry was a slight reversible increase of
    alkaline phosphatase activity in the females at 2000 ppm.  At the
    end of the 12-month treatment period, liver weights were slightly
    increased and there was a slight hypertrophy of hepatocytes.  These
    changes only occurred at 2000 ppm and were not present after the
    one-month recovery period.  The NOAEL in this study was 100 ppm,
    equal to 2.7 mg/kg bw/day (males) and 2.8 mg/kg bw/day (females)
    (Gretener  et al., 1989).

    Long-term toxicity/carcinogenicity studies

    Mice

          In an oncogenicity study, mice (Charles River CD-1, 50 males
    and 50 females per group) were given bromopropylate (98.7% pure) in
    the diet during 18 and 20 months for males and females,
    respectively, at concentrations of 0, 30, 300 or 1000 ppm.  Similar
    reduction in body weight was noted for the control and test groups

    after 12 months of testing, males losing an average of 6 to 7 grams
    and females 2 to 3 grams.  This generalized reduction in body weight
    occurred following alterations in both the method of feeding and the
    standard diet fed.  However, no statistically significant
    differences in mean body weights were noted for any treatment group. 
    Meaningful evaluation of body-weight gain cannot be made since body
    weights were not measured during the first 6 months of testing. 
    Negative body-weight gains were recorded for the observation period
    for all groups.  The mean survival time of males in the 1000 ppm
    group was significantly reduced.  Significantly increased
    mortalities in the 30 and 1000 ppm groups were observed, which were
    considered coincidental.  No treatment-related findings were seen at
    gross pathological examination.  Histopathology revealed dose-
    related centrilobular hypertrophy of hepatocytes in the two higher
    doses.  Additional sporadic histopathological findings were not
    considered as related to treatment.  The compound did not show an
    oncogenic potential in this study (Charles  et al., 1979).

          Bromopropylate (95% pure) was administered to male and female
    mice (Tif: MAGf (SPF), hybrids of inbred MIG x NIH mice) in the diet
    at levels of 0, 30, 150, 1000 or 3000 ppm (60 males and 60 females
    per group) for 24 months.  Appearance and behaviour were not
    affected by treatment.  Lower body-weight gain was recorded for the
    3000 ppm group over the first 12 weeks for males and the first 25
    weeks for females.  Thereafter, mean body weights remained 5-7% and
    15-18% lower than control values, for males and females,
    respectively.  Food consumption was slightly lowered in females in
    the 1000 and 3000 ppm groups during the first year.  Water
    consumption was increased at 3000 ppm.  Haematological parameters
    were not significantly affected by treatment.  Absolute and relative
    liver weights were significantly increased in both sexes at 1000 and
    3000 ppm.  Macroscopic examination revealed dose-related increase of
    masses and nodules in the livers of male and female mice from these
    two groups.  Kidney weights at 3000 ppm were lower than in the
    control group.  On microscopic examination, hepatocellular
    neoplastic lesions, i.e. benign hepatomas and hepatocellular
    carcinomas, accounted for most of the macroscopically observed
    masses and nodules in the liver.  The frequency of these lesions was
    significantly increased in both sexes at 1000 and 3000 ppm.  Animals
    of both sexes of these two groups also showed a frequent hypertrophy
    of hepatocytes.  The only other compound-related finding was an
    increased incidence of reactive hyperplasia of splenic white pulp in
    female mice of the high dose group (3000 ppm).  The NOAEL in this
    study was 150 ppm, equal to 16 mg/kg bw/day in both males and
    females (Basler  et al., 1990).

    Rats

          Groups of 50 male and 50 female rats were fed diets containing
    0, 15, 30 or 100 ppm bromopropylate for two years.  Five male and

    five female rats from each group were killed after six months or one
    year and autopsies performed.  No changes in appearance or behaviour
    occurred.  Food consumption and weight gain were similar in test and
    control animals throughout the test and survival rates were similar
    for the first 18 months.  Approximately half of the control female
    animals alive at 18 months survived to 24 months while only a third
    of test animals at 30 and 100 ppm survived over this period.  No
    alterations attributable to bromopropylate were observed in the
    haematological examinations in test animals.  No changes in organ
    weights or gross or microscopic abnormalities attributable to
    ingestion of the pesticide were observed in animals examined at any
    time.  However, EM studies on the livers of animals of the 100 ppm
    group surviving two years showed slightly less glycogen, focal
    enlargement of intracrestal space in the mitochondria, focal
    dilatation of SER and more prominent lipid accumulations than livers
    of control animals.  These differences were not considered to be
    significant pathological alterations in cell ultrastructure.  The
    number of tumours and their location were similar in control and
    test groups (Coulston  et al., 1970b).

          Bromopropylate (95% pure) was administered in the diet to rats
    (Tif: RAlf, 80 males and 80 females per dose group) at levels of 0,
    100, 700 or 5000 ppm.  The study duration was 119 weeks for males
    and 131 weeks for females.  Average intakes of bromopropylate were
    3.7, 26 or 217 mg/kg bw/day for males and 4.4, 32 or 270 mg/kg
    bw/day for females.  In the 5000 ppm group, males maintained mean
    body weights 20% lower than control values from 15 weeks onwards,
    whereas females showed a progressive divergence, attaining a 37%
    difference from control values at 95 weeks.  Food consumption was
    decreased in males and females at 5000 ppm, and water consumption
    was increased in both males and females at 5000 ppm and in males at
    700 ppm.  Calculated red blood cell indices (MCV, MCH) were
    decreased in males (from 80 weeks) and in females (from 27 weeks) at
    5000 ppm, suggesting a tendency to microcytosis and hypochromoasia
    of red blood cells.  Increased prothrombin times were recorded in
    males at weeks 12, 27, and 80, and in females at all investigated
    weeks at 5000 ppm.  Blood samples were collected at 12, 27, 53, 80,
    105 and 131 weeks.  A non-progressive lowering of blood glucose was
    recorded at weeks 12 to 80 for males and at weeks 27, 53 and 80 for
    females at 5000 ppm.  A hyperproteinemia resulting from
    hyperglobulinemia was observed in the males and females at 5000 ppm. 
    Females of the 700 ppm group showed a similar trend, but to a lesser
    degree between weeks 27 and 105.  Higher levels of cholesterol and
    phospholipids were recorded at week 53 for males and on all
    occasions for females at 5000 ppm.  In the 700 ppm group, high
    levels of cholesterol were observed in females at weeks 12, 27 and
    80.  Also, high levels of phospholipids were recorded in females at
    12 and 80 weeks.  Both sexes of the 5000 ppm group showed a marked
    increase in gamma glutamyl transpeptidase activity at each
    investigation.

          At the interim sacrifices during weeks 53 and 105 and at the
    termination of the study, relative liver weight for males and
    females of the 5000 ppm group were significantly increased.  In
    addition, the relative liver weights for rats at 700 ppm were
    significantly increased at week 53 for females and at termination
    for males.  Significantly increased relative kidney weights were
    recorded for males and females of the 5000 ppm group at week 53 and
    for females at week 105.  Relative thyroid gland weights in males at
    700 and 5000 ppm were significantly increased at week 53 and the
    relative weight in males at 5000 ppm was also increased at
    termination of the study.  Macroscopic examination revealed an
    increased number of rats with edema of the testes and an increased
    number of females with liver cysts at 5000 ppm.  In
    histopathological examinations, increased incidences of focal
    hepatocellular hypertrophy and fatty changes and pigmentation of
    hepatocytes were also observed in both sexes at 700 and 5000 ppm. 
    Incidences of biliary cysts and cholangiofibrosis were increased in
    females at 5000 ppm.  Occurrence of lung alveolar foam cells were
    increased in females at 5000 ppm.  An increase in the number of rats
    with testicular tubular atrophy and an associated edema and nodular
    hyperplasia (Leydig cells) was observed at 5000 ppm.  Numbers of
    rats with follicular cystic dilatation and thyroid gland hyperplasia
    were increased in both sexes at 5000 ppm.  Incidence of rats with
    thyroid gland adenoma was increased at 5000 ppm in males.  The NOAEL
    in this study was 100 ppm (equal to 3.7 mg/kg bw/day for males and
    4.4 mg/kg bw/day for females) (Basler  et al., 1989).

    Reproduction studies

    Rats

          Groups of 20 male and 20 female rats in the first generation
    and groups of 25 male and 25 female rats in the second and third
    generations were used in a three-generation test (two litters being
    produced in each generation) and fed diets containing 0, 2.5 or 5
    ppm bromopropylate.  In a second test, groups of 25 male and 25
    female rats received diets containing 0, 30 or 100 ppm
    bromopropylate.  Throughout the tests no abnormalities attributable
    to bromopropylate were found in the reproductive physiology of male
    or female rats and there was no evidence of gross abnormalities in
    the offspring throughout the studies.  The number of young in each
    litter and their growth and survival were normal.  The weights of
    liver, kidneys and spleen were comparable with controls in the rats
    of the F3b generation whose parents received 2.5 or 5 ppm diets
    while spleen and liver weights of the F3b young of parents fed 30
    or 100 ppm diets were slightly higher than controls.  No
    histological abnormalities were found in these animals at any dosage
    level (Coulston  et al., 1971).

          In a two-generation reproduction study, rats (Sprague-Dawley-
    served, Tif:RAI f) were administered bromopropylate (93.5% pure) in
    the diet at concentrations of 0, 165, 750 or 2250 ppm (28
    rats/sex/dose level).  Approximate daily intakes of bromopropylate
    were 12, 54 or 170 mg/kg bw for parental males and 16, 72 or 218
    mg/kg bw for parental females.  The administration started 10 weeks
    prior to mating of the F0 parents and was continued throughout the
    mating, lactation and weaning periods of the F1 and up to weaning
    of the F2 generation.

          F0 parental animals showed reduced body-weight gain and food
    consumption at 2250 ppm and, to a lesser extent, in the 750 ppm
    group.  The females of the F1 parental generation showed some
    depression in food consumption at 750 and 2250 ppm prior to mating
    and only at 2250 ppm during lactation.  Histological changes
    consisted of a dose-related slight to severe hepatocellular
    enlargement at 750 ppm and 2250 ppm corresponding to liver weight
    increases in the F1 animals; in addition, some of the males in the
    high-dose group showed hepatocyte necrosis.  Reproductive parameters
    (concerning mating, fertility, pregnancy, parturition and rearing)
    were not affected by the treatment.  With respect to the offspring,
    the F1 pups of the 2250 ppm group showed an increased mortality
    rate.  For both F1 and F2 young rats of the 2250 ppm group, a
    diminished body-weight gain was recorded from weaning onwards. 
    Exploratory locomotion was depressed in the young F1 rats at 750
    and 2250 ppm and in the F2 rats at 750 ppm only.

          Histopathological examination of the F1 rats revealed changes
    in the liver, as indicated by slight to severe hypertrophy of
    hepatocytes in about two-thirds of the males and females at 750 ppm
    and in all animals at 2250 ppm.  In the males, necrosis (8/24 at
    2250 ppm) or other structural alterations of hepatocytes (11/23 at
    750 ppm, 22/24 at 2250 ppm) were noted.  Parallel to these results,
    absolute as well as relative liver weights were found to be
    increased in a "positive trend" from the control to the high
    concentration.  The lowest mean daily compound intakes during the
    various study periods were calculated to be approximately 9, 40 or
    128 mg/kg body weight.  The NOAEL in this study was 165 ppm (equal
    to 9 mg/kg bw/day) (Fritz  et al., 1986).

    Dogs

          Groups of three male and three female dogs were fed diets
    containing 0, 30 or 100 ppm bromopropylate.  After an unstated time,
    the females were mated with males of the same group.  All matings
    resulted in pregnancy and delivery of normally sized litters.  The
    only deformed pup was found in a control litter.  All others were
    normal in appearance, behaviour and development.  Increases in the
    body weight of the pups in most of the litters of groups receiving

    bromopropylate were similar to those of control pups.  The reduced
    growth rate of one litter of the 100 ppm group was attributed to the
    results of poor maternal care (Coulston  et al., 1970a; Coulston &
    Benitz, 1972).

    Special studies on embryo/fetotoxicity

    Rats

          Bromopropylate (90% pure) was administered orally by gavage to
    three groups of pregnant rats (CRL: COBS CD[SD]BR, 26 females/group)
    at doses of 0, 50, 300 or 700 mg/kg bw once daily during days 6
    through 15 of gestation.  A control group of 26 female rats received
    an equivalent volume (10 ml/kg bw) of aqueous 3% corn starch with
    0.5% Tween 80.  All surviving animals were sacrificed on day 20 of
    presumed gestation.  Evaluations were conducted on clinical signs,
    maternal body weights, food consumption, necropsy and skeletal
    abnormalities.  Compound-related effects were noted at 300 and 700
    mg/kg bw/day.  These changes included: an increased incidence of
    salivation and alopecia accompanied by skin irritation; transient
    body-weight loss and slight reductions in daily food consumption at
    700 mg/kg bw/day and of body-weight gain at 300 mg/kg bw/day; slight
    decreases in mean male and female fetal weight at 700 mg/kg bw/day;
    and an increased incidence of skeletal variations of fully formed
    14th ribs and rudimentary 14th ribs at 300 and 700 mg/kg bw/day and
    in forepaw metacarpals not ossified at 700 mg/kg bw/day.  The fetal
    findings were considered to be slight treatment-related effects
    associated with the compound-induced maternal toxicity.  There was
    no evidence of embryo/fetotoxicity or teratogenicity at doses up to
    and including 700 mg/kg bw/day.  The maternal NOAEL in this study
    was 50 mg/kg bw/day (Singh & Yau, 1990).

    Rabbits

          Bromopropylate (90% pure) was administered orally by gavage to
    three groups of pregnant rabbits (New Zeeland white, 20
    females/group) at doses of 0, 20, 60, or 120 mg/kg bw once daily
    during gestation days 7 through 19.  A control group of 20 pregnant
    rabbits received an equivalent volume (5 ml/kg bw) of the vehicle. 
    All surviving animals were sacrificed on day 29 of presumed
    gestation.  Evaluations were conducted on clinical signs, maternal
    body weights, food consumption, necropsy, reproductive parameters,
    fetal weights and fetal gross, visceral and skeletal observations. 
    Treatment-related maternal effects were observed at 60 and 120 mg/kg
    bw/day.  These changes included: mortality/moribundity of two
    animals at 120 mg/kg bw/day; clinical signs of lethargy at 120 mg/kg
    bw/day and anogenital staining at 60 and 120 mg/kg bw/day;
    reductions in mean body weight at 120 mg/kg bw/day, mean body-weight
    gain at 60 and 120 mg/kg bw/day, and reduction of food consumption
    at 120 mg/kg bw/day; and the necropsy finding of distended stomach

    with viscous/gelatinous material at 120 mg/kg bw/day.  There was no
    evidence of embryotoxicity, fetotoxicity or teratogenicity at any
    dose level.  The NOAEL for maternal toxicity was 20 mg/kg bw/day
    (Sing  et al., 1990).

    Special studies on genotoxicity

          The results of genotoxicity studies conducted with bacteria,
    mammalian cells  in vitro and with intact animals  in vivo are
    presented in Tables 2a, b and c.  In all studies, bromopropylate was
    devoid of mutagenic potential.

    Special studies on inhibition of cell-cell communication and liver
    tumour promotion

          Bromopropylate was investigated  in vitro for its ability to
    inhibit gap junctional intercellular communication in the Chinese
    hamster fibroblast cell V79 metabolic cooperation assay and in the
    scrape-loading/dye-transfer assay in WBF344 rat liver epithelial
    cells, and  in vivo altered hepatic foci assay and hepatic drug
    metabolizing activity in male Sprague-Dawley rats.  Technical grade
    bromopropylate (94% pure) induced a dose-dependent increase in the
    recovery of 6-thioguanine-resistant mutants within the same dose
    range as reported earlier for the analytical grade (Wärngard  et
     al., 1985).  In the scrape-loading assay, intercellular
    communication was abolished at non-cytotoxic concentrations both
    with technical and analytical grade bromopropylate.  There was a
    gradual decrease in dye transfer from the lowest concentration (20
    µM) up to the dose inducing complete blockade of dye transfer.

          Bromopropylate was shown to cause hepatomegaly and induction of
    cytochrome P-450b-related O-dealkylase enzyme activities in hepatic
    microsomes when fed to rats at 1000 ppm for 11 weeks, indicating a
    phenobarbital-type induction of hepatic metabolism.

          The rats were initiated by partial (2/3) hepatectomy and 24
    hours later received a single intraperitoneal dose of 30 mg
    nitrosodiethylamine/kg bw.  From week 2 after initiation until
    termination at week 13, the animals were fed a diet containing 1000
    ppm bromopropylate.  A group of non-hepatectomized, non-
    diethylnitrosamine-treated rats was also fed the bromopropylate-
    containing food.  Appropriate control groups received the control
    diet.  Bromopropylate enhanced the incidence of GGT-positive foci
    and the percentage of liver occupied by foci's tissue in initiated
    rats (Flodström  et al., 1990).


        Table 2a.  Mutagenicity tests in bacteria  in vitro
                                                                                                                          
    Test                   Test object     S-9 mix    Concentrations         Purity     Results    Reference
                                                                                                                          

    Escherichia coli       WP2hcr            +/-      10-5000 µg/plate        99.7%        -       Shirasu et al., 1979

    Escherichia coli       B/r WP2 try-               500-2000 µg/disc          ?          -       Toyoshima et al., 1977
                           SD-4

    Bacillus subtilis      rec+(H17)                  20-2000 µg/disc         99.7%        -       Shirasu et al., 1977
                           rec-(M45)

    Bacillus subtilis      rec+(H17)                  50-2000 µg/disc           ?          -       Toyoshima et al., 1977
                           rec-(M45)

    Salmonella             TA98              +/-      10-5000 µg/plate        99.7%        -       Shirasu et al., 1979
     typhimurium           TA100             +/-                                           -
                           TA1535            +/-                                           -
                           TA1537            +/-                                           -
                           TA1538            +/-                                           -

                           TA98              +/-      313-5000 µg/0.1 ml      94.2%        -       Deparade, 1989
                           TA100             +/-                                           -
                           TA1535            +/-                                           -
                           TA1537            +/-                                           -

                                                                                                                          

    Table 2b.  Mutagenicity tests in mammalian cells  in vitro
                                                                                                                            
    Test              Test object              Concentrations           Purity               Results       Reference
                                                                                                                          

    Chromosomal       Chinese hamster          3.13-25 µg/ml            Batch op.               -          Strasser, 1990
    aberrations       ovary cells with                                  406162                             
                      and without S-9                                   94.2%                              
                      mix

    DNA repair        human fibroblasts        0.5-60 µg/ml             Batch op.               -          Meyer & Puri,
    (UDS)                                                               406162                             1987
                                                                        95%                                

    DNA repair        rat hepatocytes          0.4-40 µg/ml             Batch op.               -          Hertner & Puri,
    (UDS)                                                               406162                             1987
                                                                        95%                                

                                                                                                                          

    Table 2c.  Mutagenicity tests in mammalian cells  in vivo
                                                                                                                          
    Test              Test object              Dose levels              Purity               Results       Reference
                                                                                                                          

    Chromosomal       Mouse                    five times and           batch P 43/78           -          Hool & Müller,
    aberrations       spermatocytes            3000 mg/kg               90%                                1989a
                                               within 10 days                                              

    Chromosomal       Mouse                    five times and           batch P 43/78           -          Hool & Müller,
    aberrations       spermatogonia            3000 mg/kg on            90%                                1989b
                                               five consecutive                                            
                                               days

    Nucleus           Chinese                  2500, 5000 and           batch P 43/78           -          Hool et al., 
    anomaly test      hamster,                 10 000 mg/kg             90%                                1980
                      bone marrow              twice on two 
                                               consecutive days

    Dominant          Male mice                single oral doses        batch Mg.               -          Hool & Müller,
    lethal test                                of 0, 1100 or            68/77                              1981
                                               3300 mg/kg               91.5%                              

                                                                                                                          
    

    Special studies on skin and eye irritation

          A primary eye irritation test on bromopropylate (90% pure) was
    performed by using 3 male and 3 female New Zeeland white rabbits. 
    Irritation observed after the application of 100 mg of undiluted
    test material into the conjunctival sac consisted of reversible
    redness, chemosis and discharge in all rabbits and iridal
    involvement in one rabbit.  The compound was given a descriptive
    rating "mildly irritant" in non-washed eyes and in washed eyes, with
    maximum average irritation scores of 9.3 and 3.3, respectively. 
    However, the mean values of the scores calculated from the 24, 48
    and 72 hour readings over all tested animals were 0.07 for iris
    lesions, 0.6 for redness, and 0.3 for edema of conjunctiva. 
    According to the EEC Directive 83/467 the test substance is
    therefore classified as "non-irritant" to eyes (Kuhn, 1989c).

          A primary skin irritation test on bromopropylate (90% pure) was
    performed using 3 male and 3 female New Zeeland white rabbits. 
    Irritation observed on the skin after the application of 500 mg of
    test material moistened with 0.4 ml of saline consisted of grade 1
    erythema in 5 out of 6 rabbits at the 1 hour reading time.  The
    compound was given a descriptive rating "slight irritant".  However,
    the mean values of the scores calculated from the 24, 48 and 72 hour
    readings over all tested animals were 0 for erythema and 0 for
    edema.  According to the EEC Directive 83/467 the test substance is
    therefore classified as "non-irritant" to skin (Kuhn, 1989d).

    Special studies on skin sensitization

          A sensitization assay with bromopropylate (90% pure) using
    Freund's complete adjuvant during the induction period (optimization
    test) was conducted at a concentration of 0.1% in propylene glycol
    as vehicle in guinea-pigs (Pirbright white strain, 10 males and 10
    females/group).  Significant differences between the test group
    (14/20) and vehicle-treated controls (4/20) were seen only after
    intradermal challenge application, i.e. when the skin barrier was
    intentionally by-passed.  No difference between the test (0/19) and
    the control (0/20) groups was seen after epidermal challenge
    application.  It was therefore concluded that, in artificially
    sensitized guinea-pigs, exposure of intact skin does not provoke
    contact dermatitis (Ullmann & Sachsse, 1979b).

    Observations in humans

          No information available.

    COMMENTS

          After oral administration of [U-14C]phenyl bromopropylate,
    most of the radioactivity was eliminated in the faeces, with lower
    amounts of radioactivity excreted in the urine.  The routes of
    elimination were sex-dependent.

          Bromopropylate was metabolized preferentially by cleavage of
    the isopropyl ester, and to a minor extent by oxidation reactions
    attacking the phenyl ring and the isopropyl group.

          Bromopropylate has the properties of a phenobarbital-like
    inducer of cytochrome P-450 in the mouse liver.  In a DNA-binding
    study conducted with mice, no radioactivity was detectable in liver
    DNA, indicating that bromopropylate is devoid of genotoxic potential
    in this tissue.

          Bromopropylate has a low acute toxicity in rats and rabbits. 
    WHO has classified bromopropylate as unlikely to present acute
    hazard in normal use.

          In a one-year study in dogs at dietary concentrations of 0,
    100, 400 or 2000 ppm, the NOAEL was 100 ppm (equal to 2.7 mg/kg
    bw/day), based on depressed body-weight gain at 400 ppm and above.

          In a study in mice using dietary concentrations of 0, 30, 150,
    1000 or 3000 ppm for 24 months, the NOAEL was 150 ppm (equal to 16
    mg/kg bw/day), based on increased absolute and relative liver weight
    and hepatocellular neoplastic lesions at 1000 ppm and above.

          Long-term toxicity/carcinogenicity studies in rats were
    reviewed.  The study considered by the 1973 Joint Meeting was found
    to be unacceptable.  In a new study at dietary concentrations of 0,
    100, 700 or 5000 ppm, the NOAEL was 100 ppm (equal to 3.7 mg/kg
    bw/day), based on increased water consumption and increased relative
    liver and thyroid weights at 700 ppm and above.  Increased
    incidences of focal hepatocellular hypertrophy and fatty changes and
    pigmentation of hepatocytes were also observed at 700 ppm and above.

          In a reproduction study in rats using dietary concentrations of
    0, 165, 750 or 2250 ppm, the NOAEL was 165 ppm (equal to 9 mg/kg
    bw/day), based on increased liver weight and hypertrophy of
    hepatocytes in F1 animals at 750 ppm and above.

          Teratogenicity studies were conducted with rats and rabbits. 
    In the study in rats at doses of 0, 50, 300 or 700 mg/kg bw/day,
    depressed maternal body-weight gain and an increased incidence of
    skeletal variations of fully formed 14th ribs and rudimentary 14th
    ribs were recorded at 300 mg/kg bw/day and above.  The maternal
    NOAEL in this study was 50 mg/kg bw/day.  There was no evidence of

    embryo/fetotoxicity or teratogenicity.  In the study in rabbits at
    doses of 0, 20, 60, or 120 mg/kg bw/day, mean body-weight gain was
    depressed at 60 mg/kg bw/day.  The NOAEL for maternal toxicity was
    20 mg/kg bw/day, and no embryo/fetotoxic or teratogenic effects were
    found.

          After reviewing the available genotoxicity data, the Meeting
    concluded that bromopropylate was not genotoxic.

          An ADI was established based on the NOAEL of 2.7 mg/kg bw/day
    in the one-year study in dogs, using a 100-fold safety factor.

    TOXICOLOGICAL EVALUATION

    Level causing no toxicological effect

          Mouse:       150 ppm, equal to 16 mg/kg bw/day (two-year study)

          Rat:         100 ppm, equal to 3.7 mg/kg bw/day (two-year study)

          Dog:         100 ppm, equal to 2.7 mg/kg bw/day (one-year study)

    Estimate of acceptable daily intake for humans

                       0-0.03 mg/kg bw

    Studies which will provide information valuable in the continued
    evaluation of the compound

          Observations in humans.

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    Unpublished report from J.R. Geigy Ltd., Basle, Switzerland.

    Strasser F. (1990). GS 19'851 tech.: Chromosome studies on Chinese
    hamster ovary cell line CCL 61  in vitro. Proj. No: 891515.
    Unpublished report dated July 4, 1990 from Ciba-Geigy Ltd., Basle,
    Switzerland. Submitted to WHO by Ciba-Geigy Ltd., Basle,
    Switzerland.

    Thomas, H. (1991). Inductive effects of GS 19'851 on mouse liver
    cytochromes P-450 and associated monooxygenase activities. Proj. No:
    CB 90/28 BY. Unpublished report dated September 16, 1991 from Ciba-
    Geigy Ltd., Basle, Switzerland. Submitted to WHO by Ciba-Geigy Ltd.,
    Basle, Switzerland.

    Toyoshima, S., Fujita, H. & Satoh, R. (1977). GS 19'851 tech.:
    Recombination assay and reversion test. Unpublished report dated
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    Ueda, K. & Kondo, T. (1968) Report on experiment of acute toxicity.
    Unpublished report from Tokyo Dental College, Hygienics Laboratory,
    Tokyo, Japan. Submitted by Geigy Chemical Corporation.

    Ullmann, L. & Sachsse, K. (1979a). GS 19'851 tech.: Acute oral LD50
    in the rabbit. Proj. No: 790968. Unpublished report dated September
    5, 1979 from Ciba-Geigy Ltd., Stein, Switzerland. Submitted to WHO
    by Ciba-Geigy Ltd., Basle, Switzerland.

    Ullmann, L. & Sachsse, K. (1979b). GS 19'851 tech.: Skin sensitizing
    (contact allergenic) effect in guinea pigs. Proj. No: 790972.
    Unpublished report dated September 5, 1979 from Ciba-Geigy Ltd.,
    Stein, Switzerland. Submitted to WHO by Ciba-Geigy Ltd., Basle,
    Switzerland.

    Waechter, F., Bentley, P. & Staeubli, W. (1986). The effect of GS
    19'851 on mouse liver drug metabolizing enzymes. Unpublished report
    dated September 19, 1986 from Ciba-Geigy Ltd., Basle, Switzerland.
    Submitted to WHO by Ciba-Geigy Ltd., Basle, Switzerland.

    Wärngard, L., Flodström, S., Ljungquist, S. & Ahlborg, U.G. (1985).
    Inhibition of metabolic cooperation in Chinese hamster lung
    fibroblast cells (V79) in culture by various DDT-analogs.  Arch.
     Environ. Contam. Toxicol., 14: 541-546.

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    Health Organization, Geneva, Switzerland.


    See Also:
       Toxicological Abbreviations
       Bromopropylate (WHO Pesticide Residues Series 3)