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    GLYCEROL ESTER OF WOOD ROSIN
    (food and beverage grade)

    First draft prepared by
    Dr G.J.A. Speijers

    Section on Public Health of the Advisory Centre of Toxicology,
    National Institute of Public Health and Environmental Protection
    (RIVM), Bilthoven, Netherlands

    Explanation

    Biological data

    Comments

    Evaluation

    References

    1.  EXPLANATION

         Glycerol esters of resin acids of wood rosins used as food
    additives in beverages and chewing gum are those prepared from wood
    rosin that is harvested from the stumps of the longleaf pine  (Pinus
     palustris) and purified to a beverage-grade ester gum. The resin
    acid composition of wood rosin can vary considerably; however, the
    main resin acids in ester gum are abietic acids, with smaller contents
    of dehydroabietic and neoabietic acids; pimaric acids, including
    isopimaric and sandaracopimaric acids; and palustric acid. The
    toxicology of glycerol esters of wood rosins harvested from the stumps
    of the pine tree is different from that of glycerol esters from
    tall-oil and gums, which are not used for the preparation of food
    additives. The latter are therefore not reviewed or evaluated in this
    monograph addendum.

         Resin acids of wood rosins can react on their carboxylic acid
    group with salts, by esterification to ethylene glycol, diethylene
    glycol, glycerol, and pentaerythrol, by reduction to alcohols and
    aldehydes, and by decarboxylation; and also on their double bonds by
    isomerization (to abietic, norabietic, palustric, and levopimaric
    acids), by hydrogenation (dihydro- and tetrahydro- products), by
    dehydrogenation or disproportionation (dehydroabietic and di- and
    tetrahydro- products), Diels-Alder adducts (maleic anhydride and
    fumaric acid), oxidation and polymerization. The carboxylic group of
    the resin acids in wood rosin is attached to a tertiary carbon which
    is sterically hindered. In order to esterify this type of hindered
    carboxyl, higher temperatures and generally more drastic conditions
    are used than for other carboxylic acids. These steric effects are
    also responsible for the resistance of the resin acid ester linkage to
    cleavage by water, acid, and alkali.

         Glycerol ester of wood rosin was previously considered by the
    Committee at its eighteenth, twentieth, thirty-third, and forty-fourth
    meetings (Annex, references 35, 41, 83, and 116). At its twentieth
    meeting, the Committee noted that in view of the stable ester bond and
    the anticipated stability of this material, studies of long-term and
    reproductive toxicity should be performed on the specific substance,
    as opposed to unmodified resin, before further evaluation.
    Specifications for food-grade material were adopted at the thirty-
    seventh meeting of the Committee (Annex 1, references 94 and 96),
    which described the material as a complex mixture of tri- and
    diglycerol esters of resin acids from wood rosin with a residual
    fraction of monoglycerol ester varying from 1 to 3%. At the forty-
    fourth meeting of the Committee, a full monograph was prepared on
    glycerol ester of wood rosin (Annex 1, reference 117). On the basis of
    the results of studies of faecal excretion by rats of unlabelled
    glycerol ester of wood rosin (identified as 'beverage-grade ester
    gum'), the authors concluded that hydrolysis was minor; however, the
    low sensitivity of the analytical chemical method used did not allow a

    conclusion about the stability or non-bioavailability of glycerol
    ester of wood rosin. The Committee was unable to establish an ADI
    until studies became available demonstrating the metabolic stability
    and non-bioavailability of glycerol ester of wood rosin under
    conditions resembling those present in the human gastrointestinal
    tract.

    2.  BIOLOGICAL DATA: Absorption, distribution and excretion

         Ester gum 8BG was fed in the diet to groups of six male and six
    female Fischer 344 rats either for 24 h at concentrations of 7000
    or 28 000 mg/kg diet or for 10 days at concentrations of 14 000 or
    28 000 mg/kg diet. Food consumption was measured during the treatment
    period, and ester gum 8BG intake was calculated for each treatment
    group. Faeces were collected during each 24-h treatment period and for
    subsequent 24-h periods until no ester gum 8BG was detected.
    Analytical validation showed that the limit of detection of ester gum
    8BG in rat faeces was about 25 mg/ 7 g of faecal material. Studies of
    the recovery of ester gum added to rat faecal samples resulted in
    recoveries of 94-118 % of the nominal concentration, with an overall
    relative standard deviation of less than 10%.

         After dietary intake for 24 h, most of the ingested ester gum
    was excreted in the faeces after 48-72 h. Of the dose of 7000 mg/kg,
    75% was accounted for in the faeces, and total recovery at the
    28 000 mg/kg dietary level was 95% of the amount ingested. The author
    postulated that the lower recovery from the 7000 mg/kg diet was due to
    the fact that the concentrations in faeces were near the detection
    limit; the low recovery can thus be attributed to the lack of
    sensitivity of the analytical method.

         After repeated intake of ester gum 8BG over 10 days, total
    recovery was about 102% of the amount ingested at the 14 000 mg/kg
    dietary level and about 91% at the 28 000 mg/kg level. The author
    concluded that at these doses, the total faecal recoveries were
    essentially equal to the amounts ingested. As the mouth-to-anus
    transit time in this experiment was not long, it was concluded that
    enterohepatic cycling of ester gum 8BG did not occur and that no
    measurable hydrolysis of ester gum 8BG took place in the rat intestine
    (Blair, 1995).

         In a pharmacokinetic study with [1,3-14C]glycerol ester gum
    8BG, Fischer 344 rats received a single dose of about 200 mg/kg bw by
    gavage after one (five male and five female rats) or 10 days (five
    male rats) of dietary administration of unlabelled compound. The
    degree of absorption of ester gum was determined by quantifying the
    amount of radioactivity eliminated in expired carbon dioxide, urine,
    and faeces during the 120-h interval after administration and by
    assessing the residual radioactivity in the carcass 120 h after
    treatment. In a separate investigation with five male rats, radiolabel
    was determined in bile and blood at 4- and 12-h intervals for 24 h
    after administration of 14C-ester gum. The extent of hydrolysis of
    the ester gum was assessed by reverse-phase high-performance liquid
    chromatography (HPLC) of extracts of faeces.

         In both male and female rats fed ester gum for one day, 1% or
    less of the administered radiolabel was excreted either as expired
    carbon dioxide or in urine within 120 h. Most of the dose (> 95%) was
    recovered in faeces and cage rinses. Only traces (< 0.2% of the
    total dose) of radiolabel were detected in eight of 15 carcasses
    obtained 120 h after treatment. According to the author, the traces
    may have been unabsorbed 14C-ester gum remaining in the gut, since
    the gastrointestinal tract was not removed before radioanalyses of the
    carcasses. Similar results (< 1.1% in expired carbon dioxide or
    urine) were obtained for male rats given the labelled ester gum after
    a 10-day dietary administration of unlabelled ester gum. HPLC analysis
    of the faeces of male rats collected during the first 48 h after
    administration of 14C-ester gum showed that they contained a higher
    percentage of a radioactive peak that eluted at the approximate void
    volume of the column than did a standard solution of 14C-ester gum,
    with 0.8% of the administered dose in samples collected at 0-12 h,
    2.2% at 12-24 h, and 0.8% at 24-48 h after treatment. Two small peaks
    of radioactivity that were present in 14C-ester gum and eluted at
    the approximate retention time of monoglycerol esters of ester gum
    were not detectable in faeces, indicating that only a very small
    percentage of the administered 14C-ester gum, probably monoglycerol
    esters, was hydrolysed.

         In a separate study, five male rats with jugular vein and biliary
    duct cannulas excreted 1.6-2.9 % of the dose into bile during a 24-h
    interval after oral administration of 14C-ester gum. In HPLC
    analyses conducted on two bile samples obtained 0-4 h after treatment,
    all of the radioactivity eluted at the approximate void volume of the
    column, indicating the presence of hydrolysed components, which may be
    the same as those eliminated in faeces. The maximal total blood
    content of radioactivity at 4, 8, 12, or 24 h after administration of
    the labelled ester gum accounted for < 0.1% of the dose. In livers
    collected from the same rats 24 h after treatment, radiolabel
    represented 0.1-0.2% of the dose. These results indicate that only low
    levels of radioactivity were absorbed; they also indicate that
    14C-ester gum undergoes little hydrolysis or degradation in the
    gastrointestinal tract. The author concluded that the metabolism of
    14C-ester gum may involve hydrolysis of the monoglycerol esters
    present in the formulation (Noker, 1996).

          The possible metabolic fate of ester gum 8BG was also studied
     in vitro. [1,3-14C]Glycerol ester gum 8BG was incubated at a
    concentration of 4.4 or 0.5 mg/ml with human faecal extract, simulated
    gastric fluid, or sterile water (as a negative control) for 24 h.
    Samples collected 0, 6, and 24 h after incubation were analysed
    in a HPLC-radiodetector system. The elution patterns on the
    radiochromatogram were similar. Since ester gum is a mixture, further
    analysis was based on changes in radioactivity in seven regions
    related to the peaks of radioactivity on the radiogram. With the
    negative control, no significant changes were observed at either

    concentration. With human faecal extracts, occasional, minor
    differences were seen in regions containing small peaks. With the low
    concentration of ester gum in simulated gastric fluid, there was no
    significant change in the peak regions after 24 h; however, with the
    high concentration, a slight decrease was seen at 24 h in one peak
    region which is associated with the triglycerides of rosin in
    comparison with the 6-h sample; but there was no significant
    difference in that peak region at 6 h relative to 0 h. Since the
    emptying time of the stomach is normally about 4h, changes occurring
    after that time will have no effect on the stability of ester gum in
    the stomach  in vivo. These studies showed no substantial change with
    the longest incubation, indicating that beverage-grade ester gum is
    stable in the human gastrointestinal tract (Tsu-Han Lin, 1996).

    3.  COMMENTS

         The present Committee reviewed new studies with 14C-labelled
    glycerol ester of wood rosin administered to rats and  in vitro,
    which indicate that the food-grade material is quite stable in the
    gastrointestinal tract and that only a minor fraction, most likely the
    monoglycerol ester fraction, undergoes partial hydrolysis. The
    Committee therefore based the present evaluation on the new studies
    showing the metabolic stability of glycerol ester of wood rosin and
    the toxicological data available for food-grade and non-food-grade
    material and wood rosin evaluated at the forty-fourth meeting (Annex
    1, reference 116). From these studies, it was concluded that glycerol
    ester of wood rosin has no genotoxic properties; wood rosin at doses
    up to 434 mg/kg of body weight (bw) per day did not induce any
    treatment-related histopathological changes in a long-term study of
    toxicity and carcinogenicity in Sprague-Dawley rats; and the food-
    grade material was less toxic than the non-food-grade material in
    13-week studies of toxicity.

    4.  EVALUATION

         Although there were no long-term studies of toxicity or
    reproductive toxicity available, the Committee considered that the
    data from previously reviewed studies and the new studies confirming
    non-bioavailability were adequate to establish an ADI. Therefore, on
    the basis of the 13-week toxicity study in rats with food-grade
    material, in which the effect level was 2500 mg/kg bw per day, the
    Committee allocated an ADI of 0-25 mg/kg bw, applying a safety factor
    of 100. The Committee did not round the ADI to one significant figure,
    because such rounding would have resulted in a decrease in the value
    of the ADI of 20%.

    5.  REFERENCES

    Blair, M. (1995) A dietary excretion study with Ester Gum 8BG in
    Fischer 344 rats. Report No. 3352.2 from Springborn Laboratories,
    Inc., Spencervile, OH, USA. Submitted to WHO by Hercules Inc.,
    Wilmington,DE, USA.

    Noker, P.E. (1996) Pharmacokinetic study of Ester Gum 8BG in rats.
    Report project No. 8801 from Southern Research Institute, Birmingham,
    AL 35205, USA. Submitted to WHO by ILSI North America, Washington DC,
    USA.

    Tsu-Han Lin (1996) Metabolism study of Ester Gum 8BG in human faecal
    extracts and simulated human gastric juice. Report Project No. 8871
    from Southern Research Institute, Birmingham, AL 35205, USA. Submitted
    to WHO by ILSI North America, Washington DC, USA.
    


    See Also:
       Toxicological Abbreviations
       Glycerol ester of wood rosin (WHO Food Additives Series 35)
       GLYCEROL ESTER OF WOOD ROSIN (JECFA Evaluation)