United States       Office of Health and     EPA-600/8-82-008
           Environmental Protection   Environmental Assessment   March 1982
           Agency         Washington DC 20460

           Raiearch and Development
oEPA     Health Assessment    DRAFT
           Document for
           Toluene

           (Part 2 of 2 parts:
           Sections 13-18 &
           References)

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          13.   PHAflMACOKINETIC CONSIDERATIONS IN HUMANS AND IN ANIMALS







13.1.  ROUTES OF EXPOSURE AND ABSORPTION



     For humans, the most  common routes of exposure to toluene are  through  the



respiratory tract and the skin.  Toluene is absorbed readily through the  respira-



tory tract.  In experimental exposures of humans to toluene conducted by Astrand



and coworkers  (1972; also  reported in Astrand,  1975),  toluene was  detected  in



arterial blood during the first 10 seconds of exposure.  Toluene was  supplied in



the inspired  air at 100 or 200  ppa  through a  breathing  valve and  mouthpiece.



Unless otherwise specified,  in  the  experiments  reported here,  human  subjects



breathed  toluene vapor from  sooe  type of  respiratory apparatus.   In  resting



subjects,  the concentration  of  toluene in  arterial  blood  increased  rapidly



during the first 10 minutes of exposure and then began to  level off,  approaching



an apparent steady state by 30 minutes. The concentration of toluene in  alveolar



air (i.e.,  an air  sample  taken  at the  end of  a normal expiration) increased



concomitantly.   ,



     Alveolar  and  arterial concentrations of  toluene were proportional to  the



concentration in inspired air.   At the end  of 30 minutes of exposure to 100  or



200 ppm  (0.375 or 0.750 mg/4) toluene, the concentration  of toluene  in  alveolar



air (mg/l) was  18$  of  that in inspired air  (mg/1),  while the concentration  in



arterial blood (mg/kg) was 270*  of that in inspired  air (mg/i) (Astrand et al.,



T972; Astrand, 1975)*  The ratio  between arterial blood and alveolar  air concen-



trations  was  15, which is similar to  the in vitro  blood/air partition coeffi-



cients (at 37°C) of 14.6,  15.6, and 15.6  reported for human blood  by  Sato et  al.



(I97"*b), Sherwood (1976), and Sato and Nakajima (1979a),  respectively.



     According to Veulemans and  Masschelein (1978a), subjects' lung clearances



(i.e., the  virtual  volume of inspired air  from which  all  available toluene is
                                      13-1

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absorbed per unit time) decreased during exposure at rest, reaching an apparent
steady state 9 to  13 minutes  from the beginning of exposure.  Lung clearance  2
(C.-C )/C, x 7 where C,  is  the concentration of toluene in inspired air  (mg/t),
C  is the concentration of toluene in expired air (mg/i),  and 7   is the respira-
 9                            .                                9
tory minute volume (Z/min).   Lung clearance varied less among individuals than
did the concentration in expired air.
     tlcniyama and Nomiyama (197Ua) measured the pulmonary  retention  ((C.-C )/C,
x TOO) of volunteers  exposed to about  115 ppm toluene for 4 hours.  The subjects
may have  been fairly sedentary  because the authors did  not mention exercise.
Setention at the  end  of 1  hour was approximately 52% and decreased to 37% at  the
end of 2 hours,  remaining  constant at that  level for the  remaining 2 hours.
These  results suggest  a slower  approach to  steady-state  concentrations  in
expired or alveolar air than was indicated  by the time  courses obtained for lung
clearance by 7euleoans  and  Masschelein (I978a) or  for alveolar air concentra-
tions by Astrand et al. (1972).  The results also suggest a  lower percentage of
uptake or retention than  was  reported by 7euleoans and Masschelein (I978a)  and
others as will be  presented subsequently.   The reasons for  these discrepancies
are unclear.
     Exercise affected the absorption of toluene through the respiratory tract.
In the  experiments of Astrand  and coworkera  (Astrand et al.,  1972;  Astrand,
T975),  exercise  greatly  increased the concentrations of toluene  in arterial
blood and alveolar air  of the  subjects during exposure, and these concentrations
did not level  off as soon  in exercising subjects as  in resting subjects.   The
concentrations of toluene in arterial blood and alveolar air were approximately
the same  at  30 minutes  of exposure to  2CO ppm during  rest as at 30 minutes of
exposure to 100 ppm during light  exercise (50 watts).   At 30  minutes exposure to
tOO or 200 ppm (0.375 or  0.750 mg/i)  toluene,  the concentrations in milligrams
                                      13-2

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per liter expressed relative to the concentration in inspired air (mg/4)  were  33$



for alveolar air and 620$ for  arterial blood at exercise of 50 watts, and 47$  for



alveolar air and 725$ for arterial blood at  exercise of 150  watts.   The  ratio of



arterial  to  alveolar concentration remained about  the  same as at  rest.   Thus,



alveolar concentrations  appeared  to  reflect arterial concentrations during  ex-



posure to 100 to 200 ppo toluene  at rest and various intensities  of exercise.



     The  inhalation of 4$ CO- by resting subjects  during  exposure to  100  ppm



toluene  increased  their  alveolar  ventilation (i/min) and the concentrations of



toluene  in their arterial  blood and  alveolar air  (Astrand  et al., 1972).   The



increased toluene concentration in blood and alveolar air were  similar  to those



obtained with a corresponding increase  in alveolar  ventilation  during exercise.



Because  exereise increased both alveolar ventilation and  heart rate while  C02



increased only alveolar  ventilation,  the effect of  exercise on toluene absorp-



tion appears to be  due to  increased alveolar (or pulmonary)  ventilation.



     In the experiments of Veuleaans  and Massehelein d978a), the  "steady state"



lung clearances of 6 different subjects during exposure to 50 ppm toluene at rest



and at  workloads  of 25  and  50 watts on a bicycle ergometer  correlated well



(r  s 0.96)  with their respiratory minute  volumes.   Lung clearance was deter-



mined from  the regression line  to be  equal  to 0.47 V  .    The uptake   rate in
                                                       C*


milligrams per minute, which equals lung clearance  times the inhaled concentra-



tion, therefore was equal to 0.47  V^C, (where C. is  expressed in mg/i) and total



uptake in milligrams equaled  47$  of  the total amount inhaled.  Lung clearances



and respiratory minute volumes doubled with an exercise intensity of 25 watts  and



tripled with an exercise intensity of 50 watts over the corresponding values at



rest (Veulemans and Massehelein,  1978a).



     Carlsson and  Lindqvist  (1977) found that  the uptake of toluene by 7 male



subjects  exposed to 100  ppm  for  30 minutes (0.375 mg/4) during rest or various
                                      13-3

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levels of exercise  (50,  100,  and 150 watts on  a  bicycle ergometer) correlated
inversely (r  a 0.72) with  the  alveolar concentration determined at the end of
30 minutes exposure, as described by the following equation:
                                        concentration (ng/£)  x 100   +• 72.9
                                 inspired concentration (mg/l)
This relationship  is logical and  applies  to other  solvents as well (Astrand,
1975; Ovrum et al.,  1978).   Percent uptake was determined on the basis of  the
total amount of  toluene inhaled and exhaled  during the entire exposure period
(i.e., the expired air was collected continuously throughout  exposure, and thus
was a mean value).   The uptake ranged from about 47 to 57 J at rest and from about
36 to 57$ at an exercise level of 150 watts.  This group of men comprised 3 thin,
1 slightly overweight , and 3 obese subjects (Carlsaon and Lindqvist,  1977).
     Ovrum and coworkers (1973), monitoring four workers exposed to toluene in  a
printing plant, found good agreement between the value for percent uptake deter-
mined directly from the total amounts  of toluene inspired' and expired during  a
sampling period and the value determined indirectly  from the  instantaneous con-
centrations in alveolar and  inspired air,  using the equation given in the pro-
ceeding paragraph.   Percent uptake determined by the  direct method was 47) and by
the indirect method was 51%.  The total uptake of toluene that would occur during
exposure  to  30 ppm (0.3 mg/1) for an  3  hour work day was calculated using  the
oean value for pulmonary ventilation of 16 l/min measured for these 4 workers  and
a  percent uptake  of  50.   The  total uptake  amounted  to  approximately 1150 mg
(Ovrum et al., 1978).
     The percent uptake values determined by Carlsson and Lindqvist (1977) and by
Ovrua et al.  (1978) are in reasonable agreement with those  previously reported in
abstracts from the foreign literature:   54? average uptake during 5 hours' expo-
sure to 271 to 1177 Mg/1 (Srbova and Teisinger,  1952) and 72$ initial retention
                                      13-4

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decreasing to  57%  retention towards the  end  of 3 hours of  exposure  to 100  to
SOO MS/! (Piotrowski, 1967).
     Another factor,  in  addition to exercise, that has been reported  to affect
the absorption of toluene through the respiratory tract is  the  amount of adipose
tissue in the body.   Carlsson and Lindqvist (1977)  found that  mean  alveolar air
concentrations were slightly higher in 3 thin  men than in 3 obese  men at the end
a? 30 ninutes  of exposure to 100 ppa (0.375 mg/Z)  toluene during rest  or  exer-
cise.  The ranges,  however, overlapped.   Conversely, the total  uptake of toluene
during 30 minutes of exposure (determined as previously described) was  lower for
the thin subjects than for the obese ones (Table 13-1). The  thin  subjects  had a
mean adipose tissue content  of 6 kg and the obese ones had a  mean  adipose tissue
content of 44 kg.  It  appears, from Figure 6 in the Carlsson and Lindqvist (1977)
paper, that the obese men inspired a greater  total  quantity  of toluene than did
the thin men.   Because the concentrations of toluene in the inspired air were the
same  for both thin  and  obese  subjects, pulmonary ventilation must have  been
greater  in the obese  ones.   Thus the differences in uptake between  the thin and
obese men may have been  at least partially due  to greater  ventilation  (respira-
tory minute volume)  in the obese subjects rather than to their adipose tissue per
se.  Veulemans and Masschelein (I978a) reported finding no correlation  between a
subject's content of adipose tissue and uptake of toluene during exposures  to 50
ta 150 ppm toluene  lasting about U hours.  Astrand  and coworkers (1972) stated
that they found no systematic differences between male subjects (N a 11, adipose
tissue  5.7 ± 1.5 kg,  mean + S.D.)  and  female  subjects (N s U,  adipose tissue
13.3 kg, mean; 9.6 to 20.2 kg, range) in alveolar air and arterial blood concen-
trations of toluene.
     Dahlmann  and  coworkers  (I963a,   196Sb)  investigated  the  absorption  of
toluene contained in cigarette smoke through the mouths and respiratory  tracts of
                                      13-5

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                                   TABLE 13-1
            Uptake of Toluene in Thin and Obese Men Curing Exposure
              to  a Toluene  Concentration of 375 ng/sr  (100 pom)  *
.- ... . ..^ . 	 - ~ • —
dumber of
Subjects
Thin (If a 3)
Mean
Range

Adipose
Tissue
(kg)
6.0
1.4-10.7


Rest
61
55-69
Uotake (mg)
Exercise
50 V 100 V
146 193
133-158 168-211


150 V
228
181-271
Slightly overweight
  (H a 1)

Obese (N * 3)
  Mean
  Range
22.8
44.0
35.1-49.0
             84
             72-73
                      179
198
183-206
            246
258
237-275
             299
319
258-358
 Source:  Carlson and Liadqvist, 1977

 The subjects were exposed during one 30 minute period of rest and three
 consecutive 30 minute periods of exercise in order of increasing intensity.
 A 20 minute pause without exposure occurred between rest and exercise.
 Expired air was collected continuously during exposure.
                                      13-6

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volunteers.  The uptake of toluene  from smoke  that stayed in the subject's south
for 2 seconds  or less and was  not Inhaled was 29?;  uptake  when  the smoke was
Inhaled into the lungs was 93?°  It is unclear whether each subject was exposed
to a single  puff of smoke, the smoke from 1  cigarette (8 puffs), or the smoke
from 2 cigarettes.
     During  inhalation  exposure  of  resting subjects,  the  concentration of
toluene in peripheral venous blood (from the  cubital vein of the ana) attained
apparent steady  state more slowly  than did lung clearance or concentrations in
alveolar air or arterial blood and was more variable among subjects than were the
above mentioned values (Veulemans and Masschelein,  I978a;  1978b; Astrand et  al.,
1972; Sato and Makajima, 1978).   Peripheral  venous concentrations appeared to
level off  during the second or third hour of exposure.  7on Oettingen (1942a,
T9*2b) had observed  that toluene concentrations in subjects' peripheral venous
blood at  the end of eight  hours of  exposure were  roughly proportional to the
concentrations of toluene (200 to  300 ppm)  in the  atmosphere  of the exposure
chamber.  Veulemans  and  Masschelein  (1978b) reported  that the steady-state  con-
centrations of toluene in peripheral  venous blood were correlated with the  rate
of  uptake   at  different  inspired  concentrations  (50,  100,  and  150  ppm)
(r2 s 0.73) and at different levels  of rest and exercise (r2 a 0.7U).  In  both
instances, the relationship between peripheral venous concentrations and uptake
rate was:
     Venous concentration (mg/i) s 0.3 min/i  x uptake rate (mg/min).
The concentration of toluene in peripheral venous blood of exercising subjects
increased more rapidly and appeared to reach  steady-state values  sooner than in
resting subjects (Astrand et al.,  1972;  Veulemans and Masschelein,  1978b).
     Absorption  through  the respiratory  tract has been studied less extensively
in experimental animals  than in humans.  The  initial  uptake of a  relatively low
                                      13-7

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concentration of  toluene was found  to be  approximately 90$  in dogs  inhaling
toluene  (Egle  and Goohberg,  1976).   Varying the  ventilator? rate  from 5  to
HO inhalations per minute,  the tidal volume from 100 to 250  o&,  or the  concentra-
tion of  toluene from 0.37  to  0.32 ug/Z (approximately  100  to 220 ppm) had  no
significant  effect on the  a"lTqlV  initial  respiratory uptake.   Toluene was
readily absorbed from the upper as wall as from the lower respiratory tract. The
dogs were  anesthetized  with sodium  pentobarbital  for  these  experiments and
breathed toluene from a recording respirometer for  1  to 2 minutes.  The percent
uptake was  calculated from the  total amounts  of toluene inhaled and exhaled
during the 1 to 2 minute exposure.
     Ton Oettingen and covorkers (19*2b) found that the concentration  of toluene
in the peripheral  venous blood of dogs  at  the end  of 8 hours of exposure was
proportional to the concentration of toluene (200,  100, or 600 ppm) in the  air  of
the exposure chamber.   As previously  described,  similar observations  had been
made with humans.
     Mice exposed  singly to  an  extremely high initial concentration  of methyl-
Tt
  C-toluene in a closed chamber for 10 minutes retained about  60*  of  the  radio-
activity when  removed from  the chamber at  the end  of  the  exposure  (Bergman,
T979).   This value La  a  rough  approximation of absorption because some of the
toluene may have been adsorbed  to the animals' fur.  A substantial portion  of the
retained dose appears to  have been absorbed,  however,  as shown  by  its  subsequent
excretion in the urine (Section 13.4.).  The initial concentration of  toluene  in
the chamber (10 jiZ evaporated in  a volume of about 30 ml,  or about 77,000 ppm)
would have been above  the  saturation  concentration even if the  temperature had
been  as  high  as   30*C   (saturation   concentration  =  43,900 ppm   at   30*C)
(Terschueren, 1977).  Bergman (1979) noted that exposure to toluene under these
conditions markedly reduced the respiratory  rate of the mice and  attributed this
                                      13-3

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reduction to irritation.   It seems more  likely  that the decreased respiratory


rate was due to narcosis.


     Absorption of toluene also  occurs  through the skin.  Dutkiewicz and Tyras


(1968a,  19680),  in  experiments with humans, measured  the absorption of liquid


toluene into the skin of the  forearm and found  the  rate of absorption to be 1U to

        2
23 mg/cm /hr.  This rate was calculated from the difference between the amount of


toluene introduced under a watch glass affixed  to the skin and the amount remain-


ing on  the  skin at  the end  of  10  to  15 minutes.    Absorption  of toluene  from


aqueous solutions during immersion of both hands  was 160 to 600 ^g/ca /hr and was


directly proportional to the initial concentration of toluene (180 to 600 mg/l).


From  these  results,  Dutkiewicz  and Tyras  d968a, I968b) calculated  that  the


absorption  of  toluene  through the skin  of both  hands  during  contact with  a


saturated aqueous solution of toluene for 1 hour could be in the same  range as


absorption through the respiratory  tract  during  3  hours of exposure to  26.5 ppm


(0.1 mg/i) toluene.


     Sato and  Nakajima  (1978)  found,  however,  that the maximum  toluene concen-


tration  (170 ng/i)  in the blood of subjects  who  immersed  one  hand  in  liquid


toluene for 30 minutes was only  26$ of  the  concentration  (650 ug/i) in  blood of


subjects who inhaled 100 ppm toluene vapor  for 30  minutes.   Blood was collected


from  the cubital vein  of the (unexposed) arm  at intervals during  and after


exposure.   Sato and Nakajima  (1978)  suggested  that  some of the toluene  that


penetrates the stratum coneum may be  subsequently  given off into the air,  rather


than entering the systemic circulation.   Toluene appears  to pass  slowly  from the


skin into the  bloodstream after  penetrating the  skin.  Guilleain et al.  (1974)


reported  that  the elimination of toluene  in  alveolar  air  sometimes increased


during  the  first  20 minutes  after the termination of exposure of both  hands to


        toluene, and Sato  and Nakajima  (1978)  noted  that  the maximum levels of
                                      13-9

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toluene in venous blood were  maintained for about  15 minutes  after the end of
exposure.
     Absorption of toluene vapor through the skin does not appear to result  in a
significant contribution to the body burden of toluene as  compared to absorption
through the respiratory tract.  In experiments conducted by Riihiaaki and Pfaffli
(1978), volunteers wearing light, loose-fitting clothing and respiratory protec-
tion were  exposed to 600 ppm toluene for  3*5 hours.   The subjects remained at
rest except for 3 exercise periods, each lasting for 10 minutes, which  occurred
at 0.5, 1.5,  and 2.5 hours of exposure.  The exercise was sufficient  to stimulate
perspiration  and raise  the skin  temperature slightly,  conditions  which are
thought to  enhance  percutaneous absorption.   The  concentration of toluene in
peripheral venous blood, measured at the end  of  1,  2,  and 3 hours of exposure,
was constant at approximately 100 ug/i.
     Riihimaki and Pfaffli  (1978)  compared total uptake through the akin (cal-
culated from the amount of toluene  exhaled  assuming  that 16 J of absorbed toluene
is  exhaled)  with theoretical uptake through the  respiratory tract (assuming
pulmonary ventilation of  10 i/min  and retention of 60%)  at  the same (600  ppm)
level of exposure.  They estimated  that uptake through the skin was approximately
11 of the theoretical uptake through the respiratory system.
     In similar  experiments conducted by  Piotrowoski (1967,  reviewed in MIOSH,
1973)i subjects exposed eternally to 1600 mg/ar (H27  ppm) toluene  for 3 hours had
no  increase  in  urinary  excretion  of a metabolite (benzole  acid)  of  toluene.
Based on this result,  Piotrowoski (1967)  concluded that  absorption of toluene
through the skin would not exceed 5J of  absorption through the  respiratory tract
under the same conditions.
     The absorption of toluene  from the gastrointestinal  tract appears  to occur
more slowly than through the respiratory tract, but appears to  be  fairly  complete
                                     13-10

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based on experiments  with  animals.   The concentration  of radioactivity in  the
blood of adult male rats reached a  maximum 2 hours after gastric  intubation of
100 (il  U-3H-toluene  in 400  ui  peanut  oil  (Pyykko et al.,  1977).   The oil  say
have  retarded absorption.    Based  on the  percentages  of the  dose  excreted
unchanged  in  the expired  air and  as  hippurie acid  in the urine of  rabbits,
toluene  appears   to   be  completely  absorbed  from the  gastrointestinal  tract
(El Masri et al., 1956; Smith et al.,  195«).

13-2.  DISTRIBUTION
     Toluene  is  highly soluble in lipid  and  sparingly soluble  in water,  as
indicated by the partition coefficients in Table  13-2.   Judging  from the  fluid/
air partition coefficients for water,  plasma, and blood,  much  of the toluene in
blood may be associated with the lipid  and  lipoprotein components,  including the
cellular elements.   The tissue/blood  partition coefficients for  fatty tissues
were  very  high  (113  for  adipose  tissue and  35  for bone  marrow);  for  other
tissues, they ranged  from about  1 to 3.
     Little is known  about the tissue distribution of toluene in humans.  During
inhalation exposure to 50 to 200 ppm toluene, the slow  approach  to steady-state
of  peripheral venous concentrations  as  compared to  arterial  concentrations
(described under absorption)  indicates that equilibration with  the  tissues  may
take at least  2  to  3  hours.   Concentrations in peripheral  venous blood do not,
however, reflect the  discharge  of toluene  to the  tissues as  fully as  would
concentrations in central  venous blood.   A teenage boy who died  from  sniffing
glue had the following levels of toluene in-his  tissues:   heart blood,  11  ag/kg;
liver, «7 mg/kg; brain, W og/kg; and  kidney, 39  mg/kg  (Winek  et al.  1963; also
reported in Winek and Collum, 1971).
                                      13-11

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                                    TABLE 13-2
                    Partition Coefficients for Toluene at 37"C
Partition Coefficient Reference
£. Fluid/Air or Material/Air
Hater
Oil, olive
Blood, Human
Fat, human, peritoneal
Oil, olive
Lard
Blood, human
Blood, human
Blood, rabbit
Plasma, rabbit
n« Tissuea/Blood (Rabbit)
Liver
Kidney
Brain
Lung
Heart
Muscle, femoral.
Bone oarow, red
Fat, retroperitoneal

2.23 Sato and Makajima, I979a
492
15.6
1296
1380 Sherwood, 1976
1270
15.6
14.64 Sato et al., 1974a, 19745
10.41
16.99
.
2.58 Sato et al., 1974a, 1974b
US*
3.06
1.92
2.10
1.18
35.43
113.16
aHbmcgenates.
 20% fat by volume.
                                          13-12

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     Several laboratories  have investigated the tissue distribution of  toluene



and its metabolites in animals exposed by inhalation to relatively high  concen-



trations of toluene.  The concentrations  of  toluene in liver, brain,  and blood of



mice exposed to  15 mg/i (3950 ppm)  toluene for 3 hours  in  a dynamic exposure



chamber rose continuously throughout the exposure period,  as  shown previously in



Ffgure 12-1.  Concentrations of toluene reached 625  mg/kg  in  liver, 420 mg/kg in



brain, and  200 mg/kg in  blood at the end  of exposure (Peterson and  Bruckner,



T973; Bruckner and  Peterson,  I98la).   Exposure of mice to 40 ing/2, (10,600  ppm)



toluene for 10 minutes resulted in lower  tissue and blood concentrations.   Inter-



mittent  exposure to  40 ag/i  in  cycles  of  5 minutes  on,  10  minutes  off  or



10 minutes on, 20  minutes off for a total of 3 hours produced  tissue  and blood



levels approximately 3 times higher  than those produced by the  single  10 minute



exposure  to  40 mg/i and  similar to  those  produced by the  3 hour exposure  to



T.CT. mg/4.  The  intermittent exposures were an attempt to  simulate solvent abuse



Cevg., glue  sniffing)  by humans  (Peterson  and  Bruckner,  1978;  Bruckner  and



Peterson, I98lb).



     After adult male  rats were exposed by inhalation to radioactively-labeled



toluene,  the highest concentrations  of radioactivity were found  in their white



adipose  tissue (Carlsson  and  Lindqvlst, 1977;  Pyykko  et al.,  1977).   In  the



experiments of Pyykko  and coworkers  (1977)  the  concentration of radioactivity



reached a maximum in all tissues but  white adipose tissue within 15 to 30  minutes



after the end of  10  minutes of exposure to 4600 ppm 4-^H-toluene.  The concentra-



tion in white  adipose  tissue reached a maximum one hour  after  the end of expo-



sure.  In the experiments of Carlsson and Lindqvist (1977), a similar increase in



the concentration  of radioactivity in white adipose tissue  occurred during the



first  hour  after  cessation  of exposure for  1  hour  to  1.950  mg/i    (550  ppm)


       14
nethyl-  C- toluene.  No  such  increase occurred  in other  tissues.
                                      13-13

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     Carlsson and  Lindqvist  (1977)  found that after  white adipose tissue, the
next highest concentrations of  radioactivity occurred in adrenals and kidneys,
followed  by liver, cerebrum,  and cerebellum,   at the end  of exposure, white
adipose tissue contained a 6-fold higher concentration of radioactivity than did
cerebrum or cerebellum.  Pyykko et al.  (1977) reported that after white  adipose
tissue, the next highest concentration of radioactivity was found in brown adi-
pose tissue, followed in order of decreasing concentrations by  adrenal, stomach,
liver and kidney, brain and other tissues, blood, and bone marrow.  The  loss of
radioactivity from adipose tissue and bone narrow appeared to  occur acre slowly
than the  loss from other tissues (Pyykko et al.,  1977).   Radioactivity in the
tissues presumably represented toluene and its metabolites.
     Bergman (1979), using three-step  whole-body autoradiography,' investigated
the  distribution of  toluene,  its metabolites,  and  covalently  bound reactive
                                                                           1U
intermediates in mice exposed to an extremely high concentration of methyl-  C-
toluene.  This work was briefly described in a previous report (Bergman, 1973).
The mice were exposed singly  to  a very high initial concentration of toluene for
10 minutes in a closed chamber,  as described in Section 13-1.,  and sacrificed at
intervals  thereafter.    Low  temperature  autoradiography,  performed  at  -80*C,
allowed the detection of both volatile radioactivity  (representing toluene) and
non-volatile radioactivity (representing  metabolites).   In a second step, sec-
tions were dried and heated to remove volatile material before autoradiography,
thus permitting detection of non-volatile metabolites only.  In the third step,
sections  that had  been dried  and heated were then extracted  to remove water-
soluble and lipid-aoluble radioactivity,  presumably  leaving  only  the  radio-
activity that was covalently bound to proteins and nucleic acids.
     Low  temperature  autoradiography  performed  immediately after  exposure
revealed high levels of radioactivity in adipose  tissue, bone marrow, and spinal

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nerves, with some radioactivity  also  present  in the brain, spinal cord,  liver,



and kidney  (Bergman,  1979).   Bergman  reported that the adrenal did not contain



high  concentrations  of radioactivity,  but he  did not discuss  whether  radio-



activity was found in the stomach.



     The only  radioactivity  visible in dried,  heated  sections appeared  in  the



liver,  kidney,  and  blood (Bergman,  1979).    This indicates  that significant



amounts of metabolites had already been formed  by  the  end  of exposure, and  that



the radioactivity  in fat and  nervous tissue was  due  to  the  parent compound.



Similarly,  as  early  as  8 minutes after  intraperitoneal  injection  of  290 ng


1U
  C-toluene/kg into mice, the majority of  radioactivity in the leidney (78?)  and



liver  (64J)  and about  half  the  radioactivity  in blood  (48J) was reported  to



represent non-volatile metabolites, while most of the radioactivity in brain and



virtually all  in  the adipose tissue  was  volatile and thus represented toluene



itself (Koga, 1978).  The methods used  in Koga's study are unclear because  the



text of the paper is in Japanese, with only the figures,  tables, and summary in



English.  Bergman  (1979)  reported that no radioactivity  was detected in auto-



radiograms  prepared  from dried,  heated,  and  extracted sections, indicating an



absence of covalent binding.



     As had been observed in  the studies of Pyykko  et al. (1977) and Carlsson and



Lindqvist (1977), radioactivity  disappeared from the tissues relatively quickly



after exposure was terminated. The distribution patterns observed in mice  killed



aore than four hours after exposure were the  same  on low  temperature autoradio-



grams as  on dried,  heated sections.  Thus,  the radioactivity remaining  in  the



tissues at this time represented non-volatile metabolites.  At  eight hours after



exposure  only  the  kidney and  the intestinal  contents  had  detectable  radio-



activity (Bergman, 1979).
                                      13-15

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     Oral administration of U-^H-toluene (100 \il toluene in 400 u£ peanut oil  by
intubation) to adult male rats produced a pattern of tissue distribution  similar
to that  produced by inhalation  exposure (Pyytcko et  al.,  1977).  Distribution
appeared to be delayed, however, by absorption from the digestive tract.   Maximum
tissue  concentrations  occurred  2  to  3 hours  after administration  for most
tissues and 5 hours after administration for adipose  tissue.
     In  summary,  toluene was preferentially accumulated in adipose tissue and
was retained in adipose tissue and  bone marrow,  which  is  reasonable on the basis
of the high tissue/blood  distribution coefficients of  these tissues.  Toluene and
its metabolites were found in relatively high concentrations in tissues active  in
its metabolism and excretion (i.e., liver and kidney).  Levels in brain relative
to those in other tissues were perhaps  lower  than'would be  expected on the basis
of the tissue/blood distribution coefficients  reported  by Sato et al.  (197Ua,
I97*tb).  Tissue distribution was similar after  inhalation  and  oral exposure.

13-3.  METABOLISM
     Toluene1is thought to be metabolized in humans and  in animals by the path-
ways outlined in Figure 13-1.  Some of the absorbed toluene  is  excreted unchanged
in the exhaled air, but the major portion is  metabolized by aide-chain oxidation
to benzoic acid, which  is conjugated with glycine to fora hippuric acid and then
excreted  in  the urine.   Small amounts of benzoic acid  nay be conjugated with
glucuronic acid.  Minor amounts of toluene undergo ring  hydroxylation, probably
via arene oxide intermediates, to form o-cresol and p-cresol,  which are excreted
in the urine as sulfate or glucuronide conjugates.
     Humans exposed to toluene by  inhalation exhaled about 16* of the absorbed
toluene  after exposure  was  terminated,  according   to  Nomiyama  and  Moniyama
(I971b) and Srbova and  Teisinger  (1952, 1953),  or 4%,  according to 7eulemans and
                                     13-16

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 EXHALED

UNCHANGED
                      CH3
                  TOLUENE
                                      CHjOH
                                                                 CONHCH,COOH


                                                               6
                                                            HIPPURIC AOO
                                                           /GLYC1N6
COOH
                               BENZYL ALCOHOL      3ENZOICAOO
                                                          GLUCU80NIC AOO
                                                   86N20YW GLUOJRONIO6
                                                   GLUCURONI06 AND

                                                   SULf ATS CONJUGATES
        Figure 13-1.  Metabolism of Toluene in Humans  and  Animals

                      (Adapted  from Laham, 1970)
                                  13-17

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Masschelein d978a).  Volunteers inhaling 50 to 150 ppm toluene for about  4  hours
during rest or exercise excreted 60 to 70} of the absorbed dose as hippuric acid
in  the  urine  during and after  exposure  (Veulemana and Masschelein,  1979).   A
similar  value was obtained when subjects  were exposed to toluene  (67 ppm)  and
xylene  (33 ppm)  simultaneously  for 3 hours;  68J  of the  absorbed toluene  was
excreted as urinary hippurie acid during and after exposure (Ogata et al., 1970).
Srbova and Teisinger  (1953) reported  that  although most of the benzoic  acid in
the urine of subjects who inhaled 0.271 to  2.009 mg/1 toluene (72 to 532 ppm) was
excreted as hippurie acid, 10 to 20% was excreted as a glueuronide  conjugate.
     the excretion of hippurie acid in the urine was elevated  within 30  minutes
of  the  initiation of inhalation exposure,  indicating that  the  metabolism  of
toluene is rapid  (Nomiyama and Nomiyasa,  1978; Ogata et al., '1970;  Veulemans and
Masschelein,  1979).   The maximum rate of  hippurie  acid formation  from  benzoic
acid  was reported by Amsel  and Levy (1969)  to be about  190 nmol/min,  and  it
appeared to be limited by the availability  of glycine (Amsel and Levy,  1969;
Quick, 1931).  Assuming retention of 60S of the Inhaled concentration, Riihimaki
(1979) estimated that uptake of toluene may saturate the conjugation capacity at
a  toluene  concentration of  32 omol/m  (780 ppm) during  light work (pulmonary
ventilation of 10 1/min)  or 11 omol/m  (270 ppm} during  heavy work (pulmonary
ventilation of 30 Z/min).
     £-Creaol,  a compound  which is  often not  detected  in  normal urine,  was
identified in the urine of workers exposed  to 7 to  112  ppm  toluene (Angerer,
1979; Pfaffli et al., 1979).   The concentration of oj-cresol in urine collected at
the end of exposure was  directly proportional to the time-weighted average  expo-
sure  of the  workers (Pfaffli et  al.,  1979).   Angerer  (1979)  estimated  that
approximately 0.05$  of  the retained toluene had  been  metabolized  to £-oresol.
£-Cresol may  also have been  a metabolite of  toluene  as  its  concentration  was
                                     13-18

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higher in the urine of workers exposed  to  toluene than in the urine of unexposed



workers (Angerer, 1979).  The difference,  however,  was not  significant.  Wiowode



et al. (1979) reported finding m-cresol in addition to £-cresol and £-cresol  in



the urine of workers exposed to 280  ppm toluene.  No m-cresol was detected in the



urine of unexposed workers.  No other studies of in vivo  human or aniaal metabol-



ism or _in vitro microsomal metabolism reviewed for this document have detected  m-



cresol as a metabolite of toluene.



     The concentration of phenol has been  reported  to be slightly elevated in the



urine  of exposed workers  as compared  to controls  (Angerer,  1979;  Szadkowski



et al.,  1973)°   The origin  of the increased phenol excretion was thought  to  be



the  small  amount  of benzene  present   in industrially-used  toluene  (Angerer,



1979).



     The metabolism of toluene has been  more  fully studied in animals than  in



humans.  The initial step in the metabolism of toluene to benzoic  acid appears  to



be side-chain hydroxylation of toluene  to  benzyl alcohol by the  microsomal mixed-



function oxidase system.   Toluene has  been  shown to produce  a  type  I binding



spectrum with cytochrome PU50  from rats and  hamsters, indicating  that  it  is



probably a substrate for the mixed-function oxidase system  (Canady et al.,  1974;



Al-Gailany et al., 1978).  When incubated with rabbit hepatic microsomes,  toluene



was metabolized primarily to benayl alcohol (Daly et al., 1968)  and small amounts



of benzyl alcohol  have been detected in  the urine of rats given toluene  orally



(3akke and Sheline,  1970).



     Additional  evidence that toluene is  metabolized by mixed-function oxidases



has been obtained by Ikeda and Ohtsuji (1971) who demonstrated that the induction



of hepatic  mixed-function  oxidases  by pretreatment  of adult  female  rats for



four days with  phenobarbital  increased the metabolism  of  toluene.   When  given



1.18 mg  toluene/kg  body  weight  intraperitoneally,   phenobarbital-pretreated
                                      13-19

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(induced) rats  had greatly  elevated urinary  excretions  of hippuric  acid and
decreased concentrations of  toluene in the blood  compared  to  non-induced rats
given the same dose of toluene.  Induced rats had high levels of benzoic acid in
the blood; non-induced rats had none (blood was obtained at decapitation).
     The increased metabolism of toluene by induced rats appeared to reflect an
increase in side-chain hydroxylattion of toluene, because the activity of hepatic
side-chain  hydroxylase,  assayed  in vitro  with  the  model substrate  £-aitro
toluene, was significantly increased per gram of liver.  The in vitro oxidation
of the  resultant alcohol (p-oitrobenzyl  alcohol)  to the  acid (p-oitrobenzoie
acid) was not affected.  The conjugation of benzoic acid with glycine, measured
in vivo as the total amount of hippuric  acid excreted after benzole acid adminis-
tration, was also unaffected (Ikeda and Ohtsujl, 1971).
     It has been assumed (Ikeda and Ohtsuji, 1971; Homiyama and Nomiyama,  1978;
MHC,  1960),  by analogy with the metabolism of the model substrate p-nltrotoluene
(Gillette, 1959), that benzyl alcohol is metabolized to benzaldehyde by alcohol
dehydrogenase and that  benzaldehyde in  turn  is  oxidized  to benzoic  acid by
aldehyde dehydrogenase.  These  enzymes are both found in  the  soluble fraction
from liver.   Benzaldehyde itself has not  been  detected in the urine or expired
air of  animals  given toluene  orally (Smith et al.,  1954;  3akke  and Sheline,
1970).   Metabolism of  toluene probably occurs primarily  in the  liver.   This
assumption is based on the previously  discussed tissue distribution of metabo-
lites, the demonstrated metabolism of toluene by liver mlcrosomal preparations,
and by analogy with the metabolism of other xenobiotics.
     Rabbits intubated with  300 og  toluene/kg  body  weight  eliminated approxi-
mately 18J of the dose in the expired  air (Smith  et  al.,- 1954)  and, in another
study from the same laboratory, excreted about 74$ of the dose as hippuric acid
in the  urine (SI  Masri  et  al.,  1956).   These results are  similar  to  those
                                     13-20

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obtained with humans who  inhaled  toluene.   None of  the  toluene appeared to  be
converted to benzoyl glucuronide  (Smith et al., 1954), although about  1«J of  an
oral dose of benzoic acid was  excreted by  rabbits as the glucuronide  conjugate
(Bray et al., 1951).
     Toluene metabolism appears to be  rapid in animals, as shown by  the appear-
ance of metabolites in the livers, kidneys, and blood of mice within minutes  of
exposure to toluene (Bergman, 1979;  Koga,  1978)  (discussed  in Section 13.2.) and
by the increased urinary excretion of hippuric acid in rabbits within  0.5 hour  of
the initiation  of Inhalation  exposure (Jiomiyama and Momiyama,  1978).  As was
previously mentioned for  humans,  the rate of conjugation  of benzoic  acid with
glycine may be limited in animals  by the availability of glycine.  Administration
of glycine to dogs exposed by inhalation to 200,  100,  or  600 ppm  toluene enhanced
toe rate  of hippuric  acid excretion  (Von Oettingen,  19*2b).,   At  the end  of
9 hours of exposure to 600 ppo toluene,  the concentrations of toluene in peri-
pteral venous blood from glyeine-treated dogs were lower than the concentrations
in dogs that had not been treated  with  glyeiae.  No such difference was observed
at  the two  lower exposure levels.  This  result suggests that conjugation  of
benzoic acid with glycine may have limited metabolic elimination at  the highest
level of exposure.  The level of  exposure at which glycine treatment produced a
difference in venous blood levels  of toluene is  similar  to  that  (780  ppo) calcu-
lated by Riihimaki (1979) for saturation of the glycine conjugation  capacity  of
humans.
     A  minor pathway for  the metabolism  of toluene is  ring  hydroxylation  by
mixed-function oxidases.  Incubation of toluene with rat or  rabbit liver micro-
somes resulted in the production of small amounts of £-cresol and 2-cmaol (Daly
et al., 1963; Kaubiseh et al.,  1972).   The migration of deuterium when toluene
was labeled  in the 4-position and a comparison  of the rearrangement  products  of
                                      13-21

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arena oxidaa of  toluene  with the cresols obtained  by microsomal metabolism of
toluene  indicated  that  arene oxides  are intermediates  in the  metabolism of
toluene to £- and £-cresols (Daly et al», 1963; Saubisch at al.,  1972).
     Because phenols, including cresols, are eliminated in the urine as sulfate
conjugates, thereby increasing the excretion of organic sulfates  and decreasing
the  excretion  of  inorganic  sulfate,  investigators have used  urinary sulfate
excretion after toluene administration as an indicator of cresol formation.  Oral
doses of 350 mg  toluene/leg body  weight produced no increase in organic sulfate
excretion  in  rabbits  (Smith et  al.,  195*).   In  rats,  high  doses  (2.2 and
*«3 g/kg)  of  toluene,  administered orally, resulted  in slight but significant
decreases in the ratio  of inorganic sulfate to  total sulfate is the urine, while
lower doses did not (Gerarde and  Ahlstrom,  1966).   This would  appear to be a
relatively insensitive and nonspecific assay for metabolism to eresols.
     Baklce and Sheline (1970) analyzed urinary phenols (after hydrolysis) from
male rats placed on purified diets containing aeomycin, which reduced the urinary
levels of naturally occurring phenols.  Toluene, administered orally in a dose of
TOO mg/kg body weight,  was metabolized to o-cresol  (0.04  to 0.1 U of the dose)
and £-cresol (0.4 to 1.0* of the dose).
     Metabolism  to cresols  is of  concern because  of the putative arena oxide
intermediates,  which are highly  reactive  and may  bind  to cellular macro-
molecules.  7ery little toluene is  metabolized via this pathway, however, and the
studies already  discussed in  the distribution  section indicate that binding of
toluene metabolites to proteins and nucleic acids does not occur  to any signifi-
cant extent.
     Van Doom and ooworleers  (1980)  have reported  detecting small amounts of a
mercapturic acid, tentatively identified as benzylmercapturic acid (N-acetyl-S-
benzyl-L-cysteine), in the urine of male rats  treated with toluene.  Approxi-
                                     13-22

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stately O.U  to 0.7? of  a dose of  370  mg/lcg toluene  body weight,  administered



intraperitoneally, was recovered as the mercapturic acid.  The  concentration of



glutathione in  the liver was decreased slightly  by administration of  toluene.



Benzylmercapturic  acid  would  arise  from  conjugation  with glutathione  of  an



electrophilic product of side-chain oxidation of  toluene.



     The  metabolism of  toluene appears  to result  in its detoxification.   The



length of the sleeping time produced by high doses of  toluene (1.18  to  1.15  g/fcg



intraperitoneally) was decreased in phenobarbittal-indueed female  rats  to  50$ or



less of the sleeping time of controls (Ikeda and Ohtsuji, 1971).  Similar results



were obtained with male mice  (Koga and  Ohmiya,  1968).   Phenobarbital-indueed



animals,  however,  did not  have significantly  different  mortality rates  than



controls  when given high doses  of toluene  (Ikeda and  Ohtsuji, 1971;  Koga and



Ohmiya, 1963).  Hale mice given various inhibitors of  drug metabolism  (SKF 525A,



cyanaaide, and pyrazole) 30 minutes before the injection of toluene had sleeping



times that were significantly  longer  than those of control mice and had  higher



mortality rates than did control mice  (Koga and Ohmiya,  1978).







13.*.  EXCRETION



     In both  humans and animals,  toluene is rapidly excreted  as  the  unchanged



compound in expired air  and as a metabolite, hippuric acid, in  the urine.  Most



of the absorbed toluene  is excreted within 12 hours of  the end  of exposure.



     The  concentrations  of toluene in exhaled  air and  in arterial and  venous



blood of human subjects  declined very rapidly as soon as inhalation exposure was



terminated  (Astrand et  al.,  1972;  Carlsson and Lindqvist, 1977;  Ovrum et  al.,



1978; Sato et al.,  1974b; Veulemans and Masschelein,  I978a, 1978b).  Sato  et al.



(1971b) reported that semilogarithmic  plots of  toluene  concentrations  in  alveo-



lar  air  and in peripheral  venous  blood  versus time  after the end of exposure
                                      13-23

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suggested that desaturattion  occurred in three exponential  phases:   an initial
rapid phase, followed by an intermediate phase and then a slow phase.  The data
were obtained from 3 male subjects who inhaled 100 porn toluene for 2 hours (Sato
et al., 19745; clarified in Sato and Nafcajima, 1979b).  The desaturation curves
were resolved graphically into  three components,  and constants were determined
by the least squares method.   The rate coefficients and corresponding half-lives
Ct1/2) for the decay of toluene in peripheral venous blood were 0.355 min"  ^1/2
a 1.95 minutes), 0.0197 min"1  (t1/2  a 35.2 minutes), and 0.00339 min"1 (t1/2  9
204 minutes).  Hate coefficients  and half lives for the  decay of  toluene in
alveolar  air  were  0.437 min"1   (t1/2  s   1.59 minutes),  0.0262 min"1  (t1/2
s 26.5 minutes),  and 0.00313 mia"  (t*/2 s 221 minutes).
     Because the rate coefficient for the rapid phase was derived from only  two
points (at 0 and 5 minutes), the second of which belonged with the intermediate
phase, Sato et  al.  (1974b)  noted that  the coefficient  for the  rapid phase
involved some error.  The data of Sato et al.  (1974b)  indicate that the decay of
toluene concentrations in peripheral venous  blood was more gradual than that in
expired air.  Similar conclusions  have been reported by Astrand et al. (1972),
and Veulemans and Masschelein (1978b).  Astrand et al. (1972) have reported that
peripheral venous concentrations declined more gradually than did arterial con-
centrations.
     Veulemans and Masschelein  O973a)  and Momiyama and Homiyama d974b) found
the excretion curves for toluene in expired air to  be  adequately described as  the
sum of  2 exponential  terms  rather  than  3.   Subjects for  these  studies were
exposed to 50,  100,  or 150 ppm toluene for about 4 hours.  The sampling regimens
differed from that  of Sato  et  al. (1974b),  in that Veulemans and Masschelein
(1978a) did not begin monitoring  expired air as soon after exposure ended,  and
Momiyama and Nomiyama d974b)  sampled expired air  infrequently during the period
                                     13-24

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used by Sato et al.  (1974b) to determine the first two exponential  phases.  Rate
coefficients  for  the rapid  and alow  phases were calculated  by Veulemans and
Massctieleia d978a) to be  0.340 ain~   and 0.00608 min" ,  respectively, using a
curve- fitting computer program.   These rate coefficients corresponded to half.
lives of  2.04 and  114 minutes.   Nomiyama  and Nomiyama  (1974b)  reported rate
coefficients  for the  rapid phase of 5.10 h   ^i   s 8.16 minutes) for men and
3.22 h~  (t1 ,~ = 12>9  ninutes) forewomen; the rate coefficient for the  alow phase
was 0.335 h"1-(t1/2 s 124 minutes) for both sexes.
     In the desaturation  period,  men and women  expired  17.6 and 9.4%, respec-
tively, of  the  total  amount  of  toluene calculated to have been  absorbed during
exposure (Nomiyama and Nomiyama, 1974b).  These values are close to what had been
reported previously (i.e., 161)  by Srbova and Teisinger (1952, 1953)  in abstracts
from the foreign  literature.  Veulemans and Masschelein d978a) estimated that
about 4f of the toluene  absorbed during exposure was subsequently excreted in  the
expired air.   Onlike  the continuous exposures employed  in the  other  pertinent
investigations,  however,  the  exposure  regimen  employed   by  7eulemans   and
Masschelein (1978a) was discontinuous (i.e., four 50 minute  periods of exposure
separated by  10 minute intervals of nonexposure).
     According  to  Veulemans  and Masschelein d978a)  a ouch greater variability
was observed  for  the  excretion  of toluene in expired air during the  first four
hours  after the end  of exposure  than had  been  observed for the related lung
clearances  during exposure.   This variability could  be  explained partially  by
differences in  respiratory minute volume during  the  post-exposure  period;  the
percent of absorbed toluene excreted in the expired air during the first 4 hours
after exposure correlated positively with respiratory  minute  volume  (r * 0.71).
Another  factor  that appeared to  affect excretion was the  amount of  body fat,
because  there was a  significant  (p < 0.025)  negative correlation  between  fat
                                     13-25

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content as measured by the index of  Broca and the percent excretion in expired
air  after exposure at  rest  (r  = 0.2134).   This  indicates that  less  of  the
absorbed toluene would be excreted  in the  expired  air of an obese person than in
the  expired  air of a thin person  during  the first four hours of desaturation.
Additionally, subjects who had been exposed to toluene while exercising expired
leas of the absorbed amount during the first four hours of desaturation than  did
subjects who had been exposed while resting (7euleoans and Maaschelein, 1978a).
     As previously described, 60 to 70% of the toluene absorbed by humans during
inhalation can  be  accounted for as  hippuric  acid in the urine  (Veulemans  and
Masschelein, 1979; Ogata et al., 1970).  The excretion rate of hippuric acid in
the urine of subjects Inhaling 50, 100, or 150 pom toluene increased during  the
first 2 hours, leveling off at about the third hour after  initiation of exposure
(Veulemans and Masschelein,  1979;  Somiyama and Womiyama,  1978).   Hippuric acid
excretion (mg/hr) declined fairly rapidly after cessation  of about four hours of
exposure.  tfomiyama and Somiyama (1978), treating this decline as a  monoexponen-
tial process, determined a half-life for  hippuric acid in urine of 117 minutes
for men and 74 minutes for women.  7eulemans and Masschelain (1979) reported an
initial, fairly rapid decrease with a half-life between 2.0 and 2.3 hours, fol-
lowed by a more  gradual  return to baseline excretion levels by  about 24 hours
after the start of exposure.
     The excretion rate of hippuric acid,  measured at the end of about 4 hours of
experimental exposure or 3  hours  of occupational exposure, correlated reasonably
well with  the uptake rates  (Veulemans and Masschelein,  1979)  or  total uptake
(tfilczok  and Bieniek, 1978)  during exposure.   At a  given level  of physical
activity and exposure concentration, the intra- and interindividual variability
in hippurio acid excretion was greater than that noted for uptake rates and  was
attributed to the variable baseline excretion of this compound because it was  not
                                     13-26

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explained by other factors (body weight, body fat, cardiorespiratory parameters)
(Veulemans and Masschelein, 1979).  Exercise during exposure increased the rate
of excretion  of  hippuric acid  (Veuleoans and  Masschelein,  1979) in accordance
with the increase in uptake rate.
     Hippuric acid La a normal constituent of urine derived from benzoic acid and
precursors of benzoic acid in the diet (Quick,  193D.   Concentrations of hippuric
acid in  the urine of 101 workers not exposed to toluene  ranged from 0.052 to
t.271 mg/mA (corrected to urine specific gravity of 1.024) and rates of  excretion
of hippuric acid  ranged  from  18.47 to 23.00 mg/hr for diuresis  of greater than
30 mfc/hr (Wilozok and Bieniek, 1978).  Others have  also reported great varia-
bility in the physiological concentrations  of urinary hippuric acid (Ikeda and
Ohtsuji, 1969; Luamura and Ikeda, 1973; Engstrom,  1976;  Kira,  1977;  Ogata and
Sugihara, 1977; Angerer,  1979).
     Volunteers exposed ia a chamber to 200  ppa toluene for 3 hours followed by a
1 hour break  and an additional 4  hours of  exposure  excreted  hippuric acid as
shown in Figure 13-2  (Ogata et al., 1970).  This exposure regimen was  chosen to
simulate exposure in  the workplace.    After  leveling off  after approximately
3 hours  of  exposure, excretion increased again  during the afternoon  exposure.
The rate of hippuric acid excretion  remained  elevated  for about 2 hours after
exposure was terminated and then declined almost to baseline levels by 18 hours
after the end of exposure.  The total quantity of hippuric acid  excreted during
the period lasting 26 hours from the initiation of exposure was  directly propor-
tional to the degree of  exposure  (ppm x  time) up through  the highest toluene
concentration of  200  ppm  and  could be used  to calculate exposure with a fairly
high degree of accuracy.   Less accurate for this purpose were excretion rates
during exposure (i.e., total hippuric acid  excreted during exposure *  time) and
concentrations in urine,  corrected  for specific gravity.    Concentrations of
                                      13-27

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txippuric acid in urine collected during the entire exposure period and corrected
to a  specific  gravity of  1.024 were  0.30  *  0.10,  2.55 ± 0.55,  and  5.99 *
t.20 mg/m4 (mean + standard deviation)  for control,  100  ppm,  and 200  ppm exposed
subjects, respectively.   Values for controls were  lower and more uniform than
those reported by others, as described previously.
     Spot urine samples collected  from  workers after  at  least  three hours of
exposure to toluene (and from nonexposed workers at the same time) have not given
as good a distinction between unexposed and exposed workers.  Imamura and Iksda
(1973)  have pointed out  that the  upper fiducial  limit (?  a 0.10)  of normal
oippuric acid concentrations, whether or not corrected  for specific  gravity, is
so close to the lower fiducial limit of workers exposed  to 100 ppm toluene (the
Threshold Limit 7alue) that such a measurement would not be reliable in screening
for overexposure.   This  conclusion was  based  on  data reported by Ikeda and
Qhtauji (1969).  The correlations between concentrations of toluene in workplace
air and the concentration of hippuric  acid  in  urine of individual workers have
been relatively poor  (Veulemans et al.,  1979;  Szadkowski,  1973; Ogata et al.,
T97D.  The correlation between exposure concentration and  excretion  rate during
exposure, although slightly better, was also poor:  r   s 0.096 for the correla-
tion with hippuric acid concentration (corrected for specific gravity) and r  s
0.116 for the correlation with rate of excretion of hippuric acid (Veulemans et
al.,  1979).   Some  of the  variance in  excretion rates  was accounted  for by
differences  in  lung  clearance, and,  hence, uptake among  workers  (Veulemans
et al., 1979).
                                                                111
     Mice exposed to a very high initial concentration of methyl-   C-toluene in a
closed chamber for 10 minutes excreted about 10% of the absorbed dose  as volatile
material in the exhaled air and about 68% as  unidentified compounds in the urine
within  3  hours  (Bergman,  1979).    Details  of  exposure  were  discussed  in
                                     13-28

-------
Section 13.1.  In these experiments, volatile expired radioactivity  (thought  to
represent the parent compound) was collected continuously in a  trapping  device.
The total volatile radioactivity expired during each time interval was converted
to the mean percent dose excreted per minute during that interval and plotted  at
the end of the interval.  The resultant semilogarithmic plot  of mean percent dose
exhaled per minute versus time was a curve.  Computerized non-linear regression
analysis of the data according to the method of least squares yielded 3 exponen-
tial components with rate coefficients  of 0.0659,  0.0236, and 0.0044 min'1  cor-
responding  to apparent half-lives  of  10.5,  29.4,  and 158.7 minutes,   respec-
tively.
     The  respiratory  rates  of  the mice  were,  according  to  Bergman  (1979),
"remarkably reduced" during  exposure, and hence probably were reduced during  at
least part of the post-exposure period.  If respiratory minute volumes were also
decreased,  this would,  on  the basis  of  the  observations  of  Veulemans and
Kasschelein (1978a), be expected to reduce the pulmonary excretion  of toluene.
The results of Bergman  (1979) may therefore not be relevant  to exposures at lower
concentrations of toluene.
     After inhalation  exposure of rats  or mice  to toluene,  the  disappearance  of
toluene and its metabolites  from blood and from most tissues,  including brain,
was rapid  (Peterson  and Bruckner,  1978; Carlsson and Lindqvist,  PyyWco  et al.,
1977; Bergman,  1979) as  described in Section  13«2.   The exceptions were white
adipose tissue, for which both accumulation and elimination were slow, and bone
marrow, for which elimination was very slow  (Carlsson and Lindqvist, 1977; Pyyklco
et al., 1977).  By 24 hours after exposure to radioactively-labeled toluene, the
concentration of radioactivity  remaining in most  tissues was less  than  1$ and
that remaining in adipose tissue was about  5%  of the initial  whole-body  concen-
tration (PyyWco et al., 1977).
                                      13-29

-------
     Rabbits exposed to toluene vapor at 350 ppm for 100  minutes or 4500  ppm for
10 minutes bad increased  rates  of urinary hippuric acid excretion  that  reached
Tfgy-iTiTiim values 1.5 hours  after  exposure (Momiyama and Nomiyama, 1978).   Excre-
tion rates returned to baseline levels at 7 hours after  the initiation of expo-
sure to  350 ppm  for 100  minutes  and at about  3  hours  after the initiation  of
exposure to 4500 ppm for  10 minutes.
     Deraal exposure of human subjects to toluene  liquid or vapor resulted in the
appearance of toluene in  the expired air  (Guilleman et al., 1974; Riihimaki and
Pfaffli, 1973) as  discussed in Section  13*1.   The excretion of toluene  in the
expired air of subjects  exposed to  600 ppo toluene  for 3 hours  appeared  to
consist of at least 2 exponential phases (Hiinimaki and Pfaffli, 1978). The mean
amount of toluene expired during the "quantitatively significant" portion of the
excretion curve was calculated to be 45.9 nmole  (4.23  ag) Riihiaaki and Pfaffli,
1978).   Piotrowsici (1967,  reviewed  in MIOSH,  1973)  found that  subjects  exposed
dermally  (with respiratory protection)  to  1600 ng/nr  (427 ppm)  toluene  for
8 hours had no detectable increase in urinary  excretion of benzole acid (pre-
sumably analyzed after hydrolysis of conjugates).
     Oral administration of toluene  to rabbits resulted in a pattern of excretion
similar to  that observed  after  inhalation exposure of humans.   Rabbits  (M = 2)
intubated with 350 og  toluene/kg body  weight expired  18J  of  the  dose   as  the
parent compound within  14.5 hours; less than 1$  of the dose was eliminated in the
expired air in the period from 14.5  through  35 hours after dosing (Smith  et al.,
1954).   In similar experiments from the same laboratory, rabbits intubated with
                                                                    /
274 mg toluene/kg body weight excreted an average of 74f of the dose in the urine
as  hippurlc acid; excretion  was  complete  with  24 hours of  dosing (£1 Masrs
et al., 1956).  The elimination of toluene and its metabolites  from tissues and
blood  of  rats given toluene  orally (Pyyteko  et  al.,  1977) was similar  to  the
                                     13-30

-------
pattern already described after inhalation exposure (Pyykko et  al.,  1977) except
that elimination  after  oral administration appeared  to  be delayed by a slower
rate of absorption than had been observed for inhalation exposure.
     The  excretion of  other  metabolites  of  toluene  (i.e.,  cresols,  benzyl
alcohol,  glucuronide  and  sulfate  conjugates,  benzylmercapturic acid)  in the
urine of humans and animals has already been described in Section 13-3. With the
possible exception of benzoylglucuronide  (Srbova and Teisinger, 1953), none of
these excreted metabolites  represented more than about 1$ of  the total dose of
toluene administered or absorbed (Angerer, 1979;  Bakke  and Sheline, 1970; Van
Doom et  al.,  1930;  Smith  et  al.,  1954).  Trace  amounts  of toluene were  eli-
minated in the urine of humans exposed to toluene  (Srbova  and  Teisinger, 1952).
     Biliary excretion of toluene or its metabolites appeared  to be  negligible.
                 14
Rats given 50 mg   C-toluene/kg body weight intraperitoneally excreted less  than
2%   of   the  administered   radioactivity   in   the   bile   within  24 hours
£Abou-El-Markarem et al., 1967).
     Most of the  experimental  work  on the disposition of  toluene in humans and
animals has  focused on  single  exposures.    The  elimination of toluene is rapid
enough  that  few  investigators  have  studied  its potential  accumulation  with
repeated daily exposure.  Ovrum and coworkers (1978) took samples of capillary
blood daily before work from 8 printers exposed  occupationally to 35  to 353 ppm
toluene.  No cumulative increase in blood  concentrations  of toluene was found
during the course of a 5 day work week.  Koniatzko and coworkers (1980) observed,
however,  that  toluene  concentrations in  peripheral  venous  blood  tended to
increase during the course of a 5 day work  week, although  the  ranges  overlapped
(Table 13-3).  Mean exposure concentrations, measured by  a  personal  air sampling
method, did not increase  during the week.  The  blood samples  were  taken before
work on Monday, Wednesday, and  Friday  from 8  workers exposed to 184  to 332 ppm
                                     13-31

-------
                                                    TABLE 13-3
             Toluene Concentrations in Workplace  Air and Peripheral Venous Blood of Exposed Workers  '


First week
u»
CO
IVJ

Second week


Toluene In air (ppn)
Toluene in blood
before exposure (tig/ml)
Toluene in blood
after exposure (ug/ml)
Toluene in air (ppra)
Toluene in blood
before exposure (pg/ni)
Toluene in blood
after exposure (ug/ml)
Monday Tuesday
225 233
(95-303) (153-383)
0.12
(0.09-0.211)
3.63
(2.3-1.75)
285 304
(115-173) (190-521)
0.27
(0.07-0.57)
11.60
(6.99-17.10)
Wednesday
209
(107-311)
0.51
(0.28-0.82)
6.69
(1.21-10.36)
309
(213-113)
1.00
(0.35-151)
10.19
(3.21-20.31)
Thursday Friday
212 203
(92-311) (121-309)
0.77
(0.29-1.67)
6.70
(3.99-10.67)
232 191
(125-151) (105-132)
1.21
(0.11-2.29)
5.85
(1.91-9.78)
Source:  Kometzko et al., 1980
Means and (range) of eight workers

-------
daily in a.  plastic  processing factory.  Concentrations  in blood samples  taken
after work were highly variable and did not  seem  to follow a consistent pattern.
     In an analysis of 3155 samples  of urine taken in the course of biological
monitoring from different workers on different days of the week and  in different
workplaces, Lenhert et al. (1978) observed  that  concentrations  of hippuric acid
in the  urine  did not vary with  the  day of  the week except on Monday, when  the
concentrations were significantly higher than on other days. The authors conjec-
tured that the elevation of hippuric acid concentrations on Mondays  was a  result
of different eating habits on  the weekend.
     In  experiments with  dogs,  exposure to 400 ppm  for  7 hours  a  day   for  5
consecutive days did not result  in  an increase in the total amount of hippurio
acid excreted  per day over the  period of 5 days or  change the time course  of
urinary excretion (Von Oettingen et  al.,  19*2b).  Nor did the  concentration  of
toluene in peripheral venous blood sampled  at  the end  of exposure increase with
day of exposure.

T3.5.  SUMMABY
     Toluene is  readily  absorbed through the  respiratory tracts of humans  and
experimental animals, as would be expected  from  its blood/air  partition coeffi-
cient of approximately 15  (Sato and Nakajima,  1979; Sato et al., 197«a,  I97«b;
Sherwood, 1976).  The amount of toluene absorbed  (uptake) is proportional  to  the
concentration  in inspired air,  length of  exposure,  and pulmonary ventilation
(respiratory minute volume) (Astrand  et al., 1972; Astrand, 1975; Veul'emans  and
Masschelein, 1978a).
     The  uptake of  toluene by  humans was about 50% of  the amount inspired
(Veulemans and Masschelein,  1978a;  Carlsson and Lindqvist, 1977, Ovrum et al.,
1978).   Total  uptake  (absorption)   can  be approximated  as  follows:    Uptake
                                      13-33

-------
s 0.5 ^  C, t, where  7  13 the  respirator? minute volume in  i/min,  C^ is the
inspired concentration in mg/i, and t is the length of exposure  in minutes (Ovrum
at al.,  1978; Teulemaiu  and Masachelein,  1978a).   Because of its dependence on
respiratory minute volume, the uptake of toluene  is affected  by the subjects'
level of physical activity (Astrand  et al., 1972; Astrand, 1975; Veuleoans and
tfasschelein, 197da;  Carlsson and Lindqvlst, 1977).  A subject's content of adi-
pose tissue had  little or oo effect  on the uptake of toluene during exposures
lasting four hours or less  (7eulemans and  Masschelein,  1978a;  Astrand et al.,
1972) except in the  case of extremely obese individuals  (Carlsson and Lindqvlst,
I977)t and even then the increased uptake  my have been at least partly due to
greater pulmonary ventilation in  the  obese subjects than in the thin ones.  Under
•steady state* conditions, peripheral venous concentrations of toluene corre-
lated roughly with exposure concentrations.  Inter- and intraindividual varia-
bility were high enough to make this  an insensitive estimate of exposure concen-
                                                                               )
tratlon or uptake (Von Oettingen  et al., 19*2a,  I942b; Taulemans and Masschelein,
T978b).
     Although toluene appears to be absorbed less  readily through the skin than
through the respiratory tract, percutaneous absorption of liquid toluene may be
significant.  The maximum  toluene concentration  in peripheral venous blood of
subjects who immersed one hand in liquid toluene for 30 oinutes was about 26f of
the concentration in peripheral venous  blood  of  subjects who inhaled 100 ppo
toluene vapor for 30 oinutes  (Sato and Nakajlma,  1978).  Absorption of toluene
vapor through the skin in humans,  however, probably amounts to less than 5% of
the total  uptake through the respiratory  tract  under  the same  conditions of
exposure  (Rilhiaakl  and Pfaffli,  1978;  Piotrowski,  1967; reviewed  in MIOSH,
1973).  Absorption of  toluene through the gastrointestinal tract appears to be
fairly complete, based on the amounts of toluene and its metabolites excreted by
                                     13-34

-------
experimental  aninala  after  administration of  toluene  (Pyykko  at  al.,   1977;
El Masri et al., 1956; Smith et al., 1954).
     Toluene appers to be distributed in the body in accordance with  the tissue/
blood distribution  coefficients and its  metabolic and  excretory  fate.    Thus,
toluene itself is found in high concentrations in adipose tissue and bone marrow,
and toluene and its metabolites are found in moderately high  concentrations  in
liver and  Icidney (Peterson  and Bruckner, 1978; Bruckner  and Peterson,  198la;
Carlsson and  Lindqvist,  1977;  Pyykko at  al.,  1977; Bergman,  1979).   The  time
course of  toluene concentrations  in the brain appeared  to correlate with beha-
vioral effects (Peterson and Bruckner,  1978; Bruckner and Peterson,  1981a).
     The major  portion of inhaled  or ingested  toluene is metabolized by side-
chain oxidation to benzoic acid, conjugated with glycine to  form hippuric acid,
and excreted in the urine.   Regardless  of the route of administration, dose,  or
species, 60 to 75% of the absorbed (inhalation) or administered (oral) toluene
could be accounted for as hippuric acid in the urine (Veuleaans and Massehelein,
1979; Ogata et al.,  1970;  SI Masri et al.,  1956).  Much of the  remaining toluene
(9  to  18%)  was exhaled  unchanged (Nomiyama and  Somiyama,  I974b;  Srbova and
Teisinger, 1952, 1953; Smith et al., 1954). Two percent  or less appeared  in the
urine as  cresols  and benzylmercapturie acid; these metabolites are of concern
because they indicate formation of reactive intermediates that potentially could
bind to tissue  macromolecules.  Mo evidence of covalent binding to  tissue com-
                                                                            14
ponents has been detected, however, by autoradiography of mice that inhaled   C-
toluene (Bergman, 1979).
     Most  of the toluene absorbed  by humans or  animals after inhalation or oral
exposure is excreted within 12 hours of the end  of exposure (Ogata  et al., 1970;
7eulemans  and Massehelein, 1979; Nomiyama and Nomiyama, 1978; Smith at al., 1954;
Bergman,   1979).   In experimental  animals,  elimination of  toluene  and its
                                     13-35

-------
metabolites from most tissues, including brain, was rapid; elimination front fat
and bone narrow was slower (Peterson and Bruckner, 1978; Bruckner and Peterson,
t98la; Pyykko et al., 1977; Carlsson and Lindqvist, 1977).
     In humans, the  time course of desaturation  after  cessation of inhalation
exposure appeared to consist  of 3 exponential phases with  half -lives of 1.95,
35.2, and 204 minutes for toluene concentrations in peripheral venous blood and
1.59, 26.5,  and 221  minutes  for  toluene concentrations in  alveolar air (Sato
et al., 1974).  Toluene concentrations in expired  air or peripheral venous blood
after the  end of  inhalation  exposure  were not reliable  indicators  of toluene
uptake or  of exposure  concentrations because of the  great variability among
individuals  (Teuleoana  and Masschelein,  1978a, 1973b;  Astrand  et  al.,  1972).
Some of this  variability,  particularly in expired air concentrations, could be
explained by differences in exercise load during exposure, in respiratory minute
volumes after exposure,  and in adipose tissue content (7eulemans  and Masschelein
?978a, 1978b).  Similarly, although the excretion of hippuric acid in the urine
is roughly proportional to the degree of exposure to toluene, inter- and intra-
individual variations  in the physiological excretion  of hippuric  acid render
quantitation of exposure or uptake  from urinary hippuric acid concentration or
excretion  rates unreliable (lamamura and Dceda,   1973;  Veulemans et al., 1979;
Teulemans and Masschelein, 1979; Ogata et al., 1971; Wilczok and Bienick, 1978;
and others as reported in Section 13.4.).
                                     13-36

-------
             1U.   CAflCINOGENICITY,  MUTACEMICITY,  AND  TERATOGENICITY






1U.1.  CARCINOGENICITY



     In the 2U aonth chronic inhalation study described  In Section  12.2.2., CUT



(1980) concluded  that exposure  to toluene  at  concentrations  of 30,  100,  or



300 ppm did  not  produce  an increased incidence  of  neoplastic, proliferatlve,



inflammatory, or degenerative lesions  in Fischer 3^ male or female  rats relative



to unexposed  controls.    It  should be noted, however,  that  the design of this



study has been deemed inadequate in that the rats were not exposed to a utaximyg



tolerated dose (MID) of toluene (Powers, 1979).



     The Md/NTP Carcinogenesis Testing Program has initiated bioassays of com-



mercial toluene in rats and alee exposed via inhalation and savage (NTP,  1981).



Preohronic testing is currently in progress.



     Toluene has been utilized extensively as a solvent  for lipophilio chemicals



being tested  for their  carcinogenic  potential  when applied topically  to the



shaved skin of animals.   Results  of control experiments with pure toluene have



been uniformly negative.  Poel (1963), for example, applied toluene (volume not
       •


stated) to the shaved intersoapular skin 3 times a week throughout the lifetime



of 5* male SWR,  C3HeB, and A/He mice and found no carcinogenic response.   Coombs



et al. (1973) treated the dorsal  akin  of 20 randomly bred albino mice with  1 drop



of toluene (6 u£) twice a week for 50 weeks.  There was no evidence of squamous



papillomas or carcinomas in the mice one year following  termination of exposure,



although survival was only 35} (7 of 20).  Ooak et al.  (1976) applied estimated



toluene volumes of 0.05 to 0.1 mi/mouse to the backs of CF1, C.3,  and CSaH mice



(approximately 25 mice of each sex of each strain) twice  weekly for 56 weeks, and



failed to elicit  skin tumors  or a significantly increased frequency of systemic



tumors over  untreated controls.    It  is not  clear in  these  studies,  however,
                                      1U-1

-------
whether  the  toluene  was  applied  under an  occluaive dressing or  allowed  to
evaporate.  lijinsky and Garcia (1972)  did  report a skin papilloma In 1 mouse and
a skin carcinoma in a second mouse In a  group of 30 aniaals that were subjected to
topical applications of 16 to 20 u£ of toluene twice a week for 72 weeks.
     Frei and Singsley (1968) examined the promoting effect of toluene in Swiss
nice following  initiation with 7,12-dimethylbenzCal anthracene  (DMBA).  In  this
study, the ears of the nice were topically  treated once with 0.1 aSL of 1.5$  DMBA
in mineral oil  and subsequently,  beginning a week later, twice a week with the
same volume  of  100J  toluene for 20  weeks.  Results showed that  11  of 35  mice
developed  tumors (6 permanent,  5 regressing)  compared  with  8 of 53  negative
controls treated with  100* mineral oil (Table 14-1).  In 14  mice painted  with
1001 toluene but no DMBA initiator, 2  developed tumors (1 permanent,  1  regress-
ing) .  In another study with  an identical experimental design,  Frei and Stephens
(1968) similarly found that 100$ toluene promoted a yield of tumors no different
from that found  in the controls (Table  14-1).  In this study, a total  of 7 tumors
were found in 35 surviving mice treated with toluene following initiation  with
DMBA;  the  negative control  group (DMBA  followed  by biweekly applications  of
mineral oil) had 3 skin tumors in 53 survivors after the 20 weeks.

14.2.  MOTAGEHICITT

14.2.1.  Growth Inhibition Tests In Bacteria.  The ability of  toluene to Induce
DNA damage was evaluated In two studies by comparing its differential  toxicity to
wild-type and DNA repair-deficient bacteria (Fluck et al., 1976; Mortelmans and
Rlocio, 1980).   Two species were tested with negative results:   Ssefaeriahia  coll
W3110 (ool A*)  and p3478 (pol O  and Salmonella typhiaurium SL4525'(rfa) Crec"")
and SL4700  (rfa)  (rec").    In the  first study, Pluck  et al.   (1976-)- applied
                                      14-2

-------
                                                              TABLE 14-1

                                        Epidermal Tumor Yield in 20 Week Two-Stage Experiments2
DMBA Promoting Agent
* None
+ 5$ oroton oil
* 100$ toluene
+ 100$ mineral oil
5$ croton oil°
100$ toluene
+ None
* 5$ croton oll°
+ 100$
+ 5$ croton oil
5$ croton oil°
100$ toluene
No. Surviving
Mice
23b
33b
35b
53b
25b
I4b
23d
35d
. 53°
20d
I4d
Tumor
bearing
survivors
NR
NR
NR
NR
NR
NR
4$
88$
11$
11$
5$
0$
Number of Tumors
Permanent
0
381
6
8
"l
1
NR
NR
NR
NR
NR
0
Regressing
0
70
5
0
2
1
NR
NR
NR
NR
NR
0
Total
0
451
11
8
3
2
1
352
7
6
1
0
Tumors
per
Survivor
0
13.7
0.31
0.15
0.11
0.14
0.04
10.7
0.2
0.15
0.05
0
Regressing
Tumors
($) Reference
0 Frei and Kingsley,
1968
15.5
45.4
0
66.6
5.0
NR Frei and Stephens,
1968
NR
NR
NR
NR
0
 Ears of Swiss mice treated once with 0.1 m£ of 0.5$ DMBA and subsequently, beginning 1 week later, twice a week with the
 promoting agent.
 Not specifically stated whether this is the number of surviving nice.  Also, the number of mice at the start not stated.
 In mineral oil
 .30 mice at the start
160 mice at tlie atart
Nit ™ not reported

-------
toluene  (25 (in/plate)  without metabolic  activation directly  to wells  in the
center of culture  plates containing the JS.  eoli  and found ao zones of growth
inhibition with either strain.  In the Mortalmans and Hiccio  (1980) study> growth
inhibition was also found  to  be   comparable with both the repair competent and
deficient strains of  the S.  coli and £. typhimurium when sterile filter discs
inoculated with 0.001  to 0.01  [il toluene  were  placed in the centers of culture
plates; these assays were performed both with and without metabolic activation.
Mortelmans and Riccio (1960)  further found that  toluene (0.001  to O.OT (jJl/plate)
was not differentially toxic to either strain of the S. eoli  or £. typhimurium  in
quantitative growth inhibition tests.   In th«  quantitative assays, the toluene
was preincubated in liquid suspension with the  bacteria, with and without S-9
activation, prior to plating; following plate incubation,  the numbers of surviv-
ing cells were counted (instead of recording measurements of diameters of zones
of growth Inhibition).

14.2.2.  Tests for Gen» Mutations

     14.2.2.1.  ASSAZS USING BACTERIA AND YEAST  — Toluene has been reported  to
be non-outagenic in the  Ames  Salmonella assay  when tested with strains TA1535,
TA1537, TA1538, TA98,  and  TA100  (Litton Bionetics, Inc.,  1978a; Mortelmans and
Riccio, 1980;  Mestaann at al.,  1980; Bos at al.,  1981; Snow et al.,  1981), and  in
the S.  coli VP2  reversion to trp* prototrophy assay (Mortalmana and Riccio,
1980).  The details of these  studies  are  summarized in Table  14-2.  All assays
were performed  in  the presence and in  the absence of Aroclor 1254-induced rat
liver homogenate (5-9) and employed positive and negative controls.  It should  be
noted that there  way  have been  significant  losses of toluene from the culture
media during  incubation in  all  but  one  of the aforementioned  studies (Snow
                                      14-4

-------
                                                                              TABLB l»-2

                                                                    HlorobUl Hutagenlolty aoaaya
4=
in
Type
of taaay
Strain
Metabolic
Activation8
Dose
Application Response Reference
Reverse Mutation
3.


3.


3.


5-


3.


3.


£•

3.
typhlBurtuai


typhlaurluai


tvphlaurlua


typhlaurluai


typlilaurlujl


typhlajurluB


coll

cerevlalae
TA 98.
1535.
15)8
TA98.
15)5.
1538
TA98.
15)5.
15)8
TA98,
15)5.
15)8
T»98.
15)5.
15)8
T»98.


UT2

07
100,
15)7.

100.
15)7.

too,
15)7.

100,
15)7.

100.
15)7.

TalOO





yea


yea


yea


yea


yea


yea

yea
yea

yea
and no


and no


and no


and no


and no


and no0

and no°
and no

and no
0.001 to S.Oui/
plat*

0.004 to 0.0)11"


0.01 to 10|it/pUt*


5 tit/plat*


0.115 to 2.) |ift/
plat*

0.) |>1 to 100 |it/
plat*
11 to 3764 ppa
0.01 to 10 pi/
plate
0.001 to 0.5»f
rut*


Liquid


ruta


rut*


rut*


rut*

Inoorporatlon


•uapenaton


incorporation


incorporation


Inoorporatlon


Inoorporatlon

Litton Blonetloa, Ino..
197Ba




Hortelaans and Rloolo,
1980

Heataann et al.. 1980


Boa et al., 1981


Snow et al.. 1981

Vapor exposure"
rut*

Liquid
Incorporation

suspension
Hortelaana and Rioolo.
1980
Hortelanna and Rlcolo,
Hltotlo (Jen* Conversion

  S. oerevlala*         M


  S. oerevlalae         P7
            Hltotlo Groaalne-Ocer

              3. caretlalan         07
                                                  yea and no

                                                  yea and no
                                                  yea and no
yea and no
                0.001 to S.0|ii/
                plat*
                0.1)8 to I.IS

                0.001 to 5.0fr
0.001 to 5.0>'
                      riat* Incorporation

                      Liquid auapenalon

                      Liquid luapenalon
Liquid suapanalon
                                    1980



                                  Litton Dlonetloa, Inc.,

                                    I978a
                                  Mortela)ana and Rloolo.
                                    1980
                                                                                                              Hortelaiana and Rloolo,
                                                                                                                1980
              A roo lor  I25*l-Induoed  rat  liver hoaogenata 3-9  f riot Ion
             bWt arartaUly at  the  alftheat doae
              The  toluene uaa teated with toluene-Induced  3-9  aa welt  aa with aroolor Induoed 3-9.
              The platea were Inoubated In aealed plaatlo  baga or ahaabera  for part  of a 72-hr  Incubation period)  In the  arooIor-Induoed
              3-9  teats, the platea Mere reoovod from the  baga after 48  hr,  countad, Incubated  en addition 24  hr.  and recounted!  In the
              experUenta with  toluene-Induced 3-9  the platea  «er*  reaoved  after 21  hr to prevent oolature and spreading  problems,  and then
             ^incubated an additional 18 hr before  counting.
             •The assays ware run In a  aealed Incubation chamber with  a  second glaaa plate (open) trtiloh  contained  the toluene;  after
             .2$ hr  the chaiabers were opened and the  plates  Incubated  for an additional  48 hr.  •
             'lOOf mortal 11 jr at O.lf and 0.5}

-------
at al.,  1981),  particularly at the  higher doses  tested.   Snow at al.  (1931)
conducted plate incorporation assays in sealed plastic bags and chambers as  well
as Taper exposures in desiccators to prevent excessive evaporation.  The design
of  the Snow et al.  (1931)  study is  also noteworthy, because the toluene was
tested with  toluene-induced rat liver  S-9 fraction  as  well  as with  Aroclor-
induced S-9.
     Toluene,  with and  without metabolic  activation,  was  also  tested in £.
cerevisiae for  its ability to induce reversions  to isoleuoine independence in
strain 07 (Mortelaans and Hiccio,  1930),  mitotic gene conversion  to tryptophan
independence in strains 04 (Litton Bionetio,  Inc.,  1978a) and 07 (Mortelaans and
Hiccio,  1980), and aitotic  crossing  over at  the  ade2  locus  in  strain 07
(Mortelaans and  Riceio,  1980).   Toluene did  not elicit  a positive mutagenic
response in any of these tests (Table 14-2).

     14.2.2.2.  TZ MUTATION IN L5178Y MOOSE LDffHOMA  rgr.T-S  —  Litton Bionetics,
Inc. (1978a) reported that toluene failed to induce specific locus  forward nuta-
tion in the L5173y Thymidine Kinase  (TK) mouse  lyophoma cell assay.  Toluene was
tested at concentrations of 0.05 to 0.30 \ii/mi, with and without mouse liver S-9
activation.

14.2.3*  Test for  Chromosomal Mutations

     14.2.3*1   MXCKONUCLEas TEST  IN MICE —  It was recently reported  by SRI
International  (Zirkhart,  1980)   that  the   intraperitoneal administration of
toluene to male Swiss mice  failed to cause an increase in micronucleated poly-
chrooatophilic  erythrocytes in  the  bone  marrow.   Doses  of  250,  500,  and
1000 mg/kg were administered  to  groups  of 32  mice at  0 and 24 hours,  with
                                      14-6

-------
sacrifices 30, 48, and 72 hours  after the first dose (3 mice/sacrifice).  Five
hundred polychromatic erythocytes per animal were evaluated for  the  presence  of
micronuclei.  The highest dose tested (1000 tag/kg) approximated the LJX-  for male
mice (Koga and Ohmiya, 1978).
     14.2.3.2.  MOOSE DOMINANT LETHAL ASSAI — Toluene was recently evaluated for
its ability to induce dominant lethal mutations in sperm cells of  CD-1 male  mice
(Litton Bionetics, Inc., 1981).  Test nice (12  per dose) were exposed via inhala-
tion to targeted exposure levels of  100 and 400 ppm 6 hours  per day, 5  days per
week for 8 weeks.  Twelve negative control mice were exposed to filtered air in
an identical exposure regimen, and 12 positive  control mice were injected intra-
peritoneally  with  0.3 mg/kg triathyleneaelamine  (TSM)  on day  40  of the dosing
schedule.  Following  treatment,  the  males were aated sequentially to 2  females
per week for  each  of 2 weeks; 14 days  after the  midweek  of  mating,  each female
was sacrificed using  CO.  and the number  of living and  dead implantations  were
counted.   The  results of  this study  showed  that  toluene did  not cause  any
significant reduction  in the  fertility  of the  treated males, and did not cause
increases in either pre- or post-iaplantation loss of embryos when compared  with
the negative controls.  A significant induction of dominant lethal mutations was
observed in the positive control mice.

     14.2.3.3.   CHROMOSOME  ABERRATION  STUDIES — Two  reports  from  the  Russian
literature concluded  that toluene induced chromosomal  aberrations in rat  bone
marrow  cells following subcutaneous  injection  (Dobrokhotov,  1972; Lyapkalo,
1973).  In an analysis of 720 metaphases from the  bone marrow of 5 rats  that had
been subcutaneously injected  with 0.3 g/kg/day toluene  for 12 days,  Dobrokhotov
(1972)  found that 78  (13J)  showed aberrations.   Sixty-six  percent  of  the
                                      14-7

-------
aberrations were  chromatid  breaks,, 24*  were chromatid  "fractures",  7$ were
chromosome "fractures1*, and 31 involved multiple aberrations.  The frequency of
spontaneous aberrations in  600 marrow aetaphases from  5  control rats injected
with vegetable oil  averaged 4.16* (65.3* were breaks  and 32.4$ were chromatid
aberrations; no "fractures"  or multiple injuries were recorded.).  It was further
found that similar administration of 0.2  g/kg/day of benzene  induced a frequency;
of chromosomal damage (13.61) comparable  to  that  of  0.3  g/kg/day of toluene, and
that when a mixture of 0.2 g/kg benzene and 0.3 g/kg toluene was injected daily
for 12 days,  the  damage was approximately additive (33*33$  aberrations),  the
significance of the positive clastogenie effects attributed to toluene is dif-
ficult to assess,  however,  because the purity of the  sample  employed  was not
stated, and because the distinction between chromafcid  breaks  and fractures is
unclear.
     Lyapkalo  (1973)  administered 1 g/kg/day toluene  to  6 rats and 1 g/kg/day;
benzene to 3 rats by subcutaneous injection  for 12 days. Treatment with toluene
reportedly resulted in chromosome aberrations in 11.61  of the bone marrow cells
examined (34  aberrant metaphases/724 cells)  compared  with  3.37*  (40/1033)  in
olive oil injected  controls.   The types  of aberrations that were observed con-
sisted of  "gaps'* (60.17%),  chromatid breaks  (38.37$)  and  isocromatid breaks
(1.16*).  Benzene caused a greater degree of chromosome damage than the toluene
(57.21 of the cells examined had aberrant chromosomes (573/1002)), and the dis-
tribution of  aberration types  was different (44.721  "gaps",  50.94$ chromatid
breaks, 4.341 isochromatid breaks).  The purity of the toluene used in this study
was also not stated.
     In a third Russian study,  Dobrokhotov and Sinkeev  (1975) reported that rats
exposed  to  30 ppm  (610 mg/ar)   toluene via inhalation,   4  hours  daily  for
4 months, showed damaged metaphase chromosomes in-21.6* of the  bone marrow cells
                                      14-3

-------
analyzed.  The percentage of metaphaaes with damaged chromosomes  in  bone  marrow
cells from  air-exposed  control rats was  U.025.   Inhalation of 162  ppm benzene
caused damage to chromosomes in 21.56%  of the narrow cells, and a  mixture  of the
toluene  and benzene (30 and  162 ppm,  respectively) damaged  chromosomes in  an
additive manner (41.21$ of the cells were involved).  Chromosome damage was  also
observed in all  of the  groups 1  and 2.5 months after  the  initial exposure,  and
one month after the end of exposure, the frequency of chromosome damage was still
elevated.  A total  of 96 rats were used in this study,  but the number of rats in
each group was not stated;  it  should also be  emphasized that the number of cells
scored and  the purity of the  toluene used were not reported.
     In  contrast  to  the aforementioned  Russian cytogenetics studies,  Litton
Bionetics, Inc. (1978) found that intraperitoneal injection of pure toluene  into
Charles River rats  did not induce bone marrow chromosomal  aberrations.  Toluene
was injected at dose levels of 22, 71,  and 214  mg/kg in 2 different experiments.
In 1 study, 5 rats ware  sacrificed at 6,  24,  and 48 hours following injection of
each dose;  in a second study, 5 rats were dosed dally  at each  level  for 5 days,
and the rats were sacrificed 6 hours after injection of the last dose.  Approxi-
mately 50 cells  per animal  were  scored for damage.  Dimethyl  sulphoxide  (DMSO;
the solvent vehicle) administered intraperitoneally at 0.65 mi/rat was used  as a
negative control,  and triethylenemelamine  (TEM) in saline  at 0.3  ag/kg was  used
as  a  positive control.   The  results  of the bone  marrow  cytogenetic analyses
following sacrifice are summarized in Table 14-3.   It was also  noted that none of
the observed aberrations differed significantly in frequency or type from  either
concurrent  or historical spontaneous values.
     Gerner-Smidt  and Priedricb  (1978)  reported that  toluene  at  concentrations
of  1.52, 152, and  1520 us/mi  did not influence the number  of structural  chromo-
somal aberrations in cultured human lymphocytes.   Benzene and xylene at  the  same
                                      14-9

-------
                                                                             f ABU 11-1
                                          •at Bon* Harrow Call Aberrations following Intraperltopaat  Indention of Toluaae*
o
Treatamnt Doae
DM30 0.69 ait/rat
(Solvent)


Trletbylano 0.3 ag/kg
Helaalna
Toluene 22 ag/kg



Toluene ?t ag/kg



Toluene 214 eg/kg



TIM or
Saorlfloe
6 b
24 b
46 b
6 b (3A)°
24 b

6 b
24 b
46 b
6 b
6 b
24 b
46 b
6 b
6 b
24 b
46 b
6 b UA)"
No. or
Anlaala
5
5
S
S
S

S
5
S
S
S
S
3
9
S
S
S
S
Total No.
or Calla
225
250
250
22?
250

250
242
250
236
239
, 22?
ISO
212
250
250
250
250
Typa and frequency
ef Aberration*
4
2r.ttd
-- —
itb.tr
ttd
lltb.2ab.Sar.4Sr. 2pp
26t.tr. tOtd.t2>(>
..
» —
.. • „
3r
ttd tpp
2td. tar.tr
« —
—
tr 2pp

Itb.ltd
Itd.Jar
Mo. or Calla
Hltb One or Nora
Abarratlona
3 (t.3»)
0 (0.01)
2 (0.6f)
t (0.4*)
72 (20.a»
•
0 (O.Of)
0 (0.0|)
0 (O.Of)
2(0.6*)
2 (0 «*)
* (t.'ei)
0 (0.0»)
0 (0.0|)
3 (1.21)
t (0.4»
2 (o.af )
2 (0.6|)
No. or Aolnala
Hltbout
Abarratlona
3
9
k,
»
0

S
9
S
3
«
3
3
9
3
4
3
3
Hltotla
Inda*
3.6
£.0
6.1
9.0
1.4

3.4
9.9
7.0
6.3
2.5
4.3
5.?

4.5
3.6
S.4
5.4
"souroat  Litton Blonottoa,  loo.,  I978«
blh« toluana uaad waa 99.96  Mt.  %  pura (atbylbanzana. 0.03I| £-Bylanac   polyplold} pu B pulvarlsad ohroa>oao«a| ^r • Quadrlradlalf r • ring] ab • ohroanaoM braak;
       t » tranalooattoni tb > ohroaatld break)  td • ohroaatld dalatlon| tr « trtradlal{ > • graatar than 10 abarrattona
             on a count of at laaat 500 o«lla per anlaial

-------
concentrations  also had  negative  clastogenic  effects  but  toluene  (152  and



1520 tig/mi) and xylene (1520 ng/mi) caused a significant cell growth  inhibition



which was not observed with  benzene.   The data  from  this  study cannot be ade-



quately evaluated, however, because the source  and purity of the toluene were  not



stated, no positive control experiments were perforated, no metabolic  activation



system was employed, and the  type of chromosome damage scored was not  specified.



     Peripheral blood  lymphocytes of  toluene-exposed rotogravure workers have



also been  examined for chromosome aberrations with  negative  results.  In  one



study, Forni  and  cowortcers (1971) examined  the lymphocyte chromosomes from 3"



workers from  a  single  plant  and 3" controls from outside  the plant matched  for



age and sex.  Ten  of the workers were exposed daily  to nrtpl"T"ffi concentrations of



131  to  532 ppm benzene  for  2  to 7 years and subsequently to toluene in  the



general range of 200 to 400 ppm  for 14 years; 2U of the workers were exposed only



to toluene  for  7  to 15  years.   (The ink solvent used in this plant was changed



from benzene to toluene which contained some xylene,  but reportedly no benzene,



after an outbreak of benzene  poisoning  in  1954.)  No significant  differences were



found  between the  toluene and control groups  in  frequencies of  stable  and



unstable chromosome aberrations or in  chromosome counts (Table  14«4).  Approxi-



mately 100 metaphases from each subject or control  were scored.  The  proportion



of   chromosome   changes   were   significantly   higher  statistically  in   the



benzene/toluene group compared  with controls,  and in  the benzene/toluene  group



relative to the toluene group.



     Maki-Paakkanen  et al. (1980) recently found no  evidence of clastogenieity



in cultured peripheral blood lymphocytes  from  32 printers and assistants  from 2



different rotoprinting factories who had  a history of exposure to pure toluene



(benzene concentration, <0.05X;  average benzene concentration,  0.006?) at 8 hour



time-weighted average (TWA) concentrations of  7  to  112 ppm.  The average  age of
                                      14-11

-------
                                                          TABLE 14-4

                              Frequency of Unstable and Stable Chromosome Changes and Chromosome
                                   Counts in Subjects  Exposed to Benzene  or Toluene or Both



1
to
Expaoure Subjects

Benzene (•*• toluene)
Toluene
Control subjects
No. of Age
Cases Range

10
24
34

36-54
29-60
25-60
Total
Cells
Counted

964
2,400
3,262
t Cells
cb
u
1.66(1.87)d'e'f
0.80(0.83)d
0.61(0.67)

C°
s
0.62e'f
0.08
0.09
% Cells
<46

13.1
14.3
10.2
With Chromosome Number
46

86.0
85.4
89.5
>46
(Polyplold)
0.9(0.52)
0.3(0.29)
0.3(0.3)
 Source:  Fornl et al.,  1971
 Cells with "unstable" chromosome aberrations (fragments,  dicentrios,  ring chromosomes).   The presence  of each
 fragment was considered as one break,  the presence  of a dioentrio or  ring chromosome  as  two breaks.

°Cella with "stable" chromosome changes (abnormal monooentrio chromosomes due  to deletions,  translooationa,  etc.,
 trisomies)
 Numbers in parentheses show percentage of calculated breaks.

^Difference from toluene group was significant (P <  0.05)

 Difference from control was significant (P < 0.01)

-------
the workers was 34.2 years and Che average length of employment was  14.6 years.
Results of analyses showed that when frequencies of chromosome aberrations were
compared with those of  15 unexposed research  institute  workers,  there were no
significant differences (Table 14-5).  Similarly,  no significant deviations were
observed in the frequencies of aberrations in  relation to duration of  exposure.
     In  a  report  on  chromosome  aberrations  of  women  in  laboratory  work,
Funes-Cravioto at al. (1977) also presented data on 1U workers who were exposed
to toluene in a rotogravure factory.  Exposures ranged from  1.5 to 26  years and
air measurements of toluene showed TWA  values  of 100 to 200 ppm, with occasional
rises up to 500 to 700  ppm;  the exposures  were sufficient in most cases  to elicit
frequent headaches and fatigue, and occasional vertigo, nausea, and  feelings of
drunkenness.  The workers had been exposed to  toluene since  approximately 1950;
before 1958, it was stated that the toluene was probably contaminated by a "low"
percentage  of benzene.   Results  of lymphocyte  analysis showed an excess of
chromosome  aberrations  (abnormal  chromosomes and breaks)  in the  14  toluene-
exposed workers relative  to a control  group of 42 adults.   It should  be noted,
however, that only a small number of subjects were examined in this study and the
exposure background (e.g., extent of exposure to benzene  and  other chemicals) of
the group was not  well characterized.  The results of this study are presented in
Table 14=6.  The results of chromosome analyses of 8 other workers with definite
exposure to benzene (concentration not measured) for 2 to  10 years  prior to 1950,
and subsequently  to toluene as stated above,  are included  for  comparison.

     14.2.3.4.  SISTER CHROMATID  EXCHANGE — Gerner-Smidt and Friedrich (1978)
reported that Jjn  vitro exposure  to toluene at concentrations  of  15.2, 152, and
1520 iig/mi had no  effect  on the  number of sister-ohromatid  exchanges  (SCEs) in
cultured human  lymphocytes, but  no positive control experiments  were  performed
                                      14-13

-------
                                                                       TABLC 11-5
                     Effect of Occupational Toluene Bnpoaure and Socking on Chroaoaaoal Aberrations and Slater Chroaatld Biahangaa




Cella »
ilth Cbroaosoaal Aberrations (I)
Qapa gxolndad
Occupational
Toluene Exposure
(yr)
Total Worker
No. of
Subjects
32
Mean
Age Cella Chroaatld Cbroaoaoaa Oapa Included
(yr) Analysed" type Type Total Total
34.2*
— _
1.0
0.5 1.5
2.5
Slater Cteroaat^d Exchanges (SCBs)
Cells Mean per Subject
Analysed4 per Cell"
— —
a.s
(14.6 yr average exposure)
Total Control
0 (controls)
Noneaokera
Saokera
Total
1-10 (aean, 8.0)
Honaaokara
Saokera
Total
>IO (aean, 19.3)
Honaaokora
Saokera
Total
15

4
II
15

3
10
13

II
a
19
34.2«

31.0
35.5
3«.3

21.1
28.2
28.1

38.5
35.9
31.5
--

800
1100
1900

300
1000
1300

1 100
800
1900
0.1

0.5
0.9
0.1

0.1
0.1
0.1

o.a
i.a
1.2
0.9 1.*

o.a
8.0
0.9

0.3
0.3
0.3
.3
.a
.6

.0
.0
.0

0.5 1.4
o.a 2.5
0.6 i.a
2.1

2.3
3.1
2.1

2.3
1.9
2.0

2.5
3.1
2.8
~

234
3ia
552

19
295
314

330
205
535
8.9

8.0
9.1"
9.2

1.9
j.giaa
a.a

1.5
9.6«"
a.3
'Sources  Hakl-Paakkanen et al..  1980
bIOO cells analysed per Individual
°JO oolla analysed per Individual
 Calculated froa Individual aaana
aHean value
 SCBa uare analysed froa 1 aubjectai  "P < 0.01  and •••  P  < 0.001 ooapared to nonaaokarc  In the group, one-tailed Student's £-
yr z year

-------
                                   TABLE 14-6

             Chromosome Aberrations in Rotoprinting Factory Workers3

Ho. of Subjects
Age (year)
Range
Mean
Ho. of Cells Analyzed
Total
Abnormal
Total
Frequency range ($)
Mean frequency ($)
Ho. of Chromosomes Analyzed
Total
Breaks
Total
Range (per 100 cells)
Mean (per 100 cells)

Control
49

0.16 to 63
24.4

5000

217
0 to 20
4.3

230,000

233
0 to 22
5.1
Group
Toluene
1tt

23 to 5*
37.2

1,400

106
2 to 15
7.7

64,400

124
2 to 17
8.9


Benzene/Toluene
8

54 to
61.3

800

76
4 to
9.5

36,800

95
6 to
11.9


65





17





17

Source:  Funes-Cravioto et al., 1977
Exposure details provided in accompanying text.
                                        14-15

-------
and no  metabolic activation system  was employed.   Twenty-six cells/dose were
scored  for SC2a  and cytotoxicity was observed  at the highest doae.  Evans and
Mitchell (1930) concluded that toluene did not alter SCZ frequencies in cultured
Chinese hamster  ovary  (CHO)  cells.   In the latter study, CHO  cells without rat
liver 3-9 activation were exposed to  0.0025 to 0.04$  toluene for 21.4 hours, and
CHO cells with activation were exposed to 0.0125  to  0.21$ for  2 hours.
     In an analysis of cultured peripheral blood lymphocytes from 32 rotogravure
workers with daily chronic exposure to 8 hour TWA concentrations of 7 to  112 ppm
pure toluene, Maki-Paakkanen at al.  (1980) found no increase in SCSs relative  to
a group of  15 unexposed control  subjects*   The average age of the workers was
34.2 years and their  average  length of  employment was  14.6 years.    The SCS
analysis was part of a study examining chromosomal aberrations in these workers;.
the exposure history of the subjects is described in more detail with the  summary
of  the  aberration  findings (Section  14.2.4.1.), and  the  results of  the SCS
analyses are included  in Table 14-5.
     Funea-Cravioto et al. (1977) studied SCS formation in groups  of 4 rotogra-
vure printers, 12  laboratory technicians, and  4  children of  female laboratory
technicians.  The printers had been exposed to benzene during the 1940'a for 2  to
10 years and subsequently to  toluene; exposure to benzene and toluene ranged from
2  to  26 years.   TWA  concentrations  of toluene  generally  ranged from  100  to
200 ppm (occasionally  to  500 to 700 ppm),  but  benzene  concentrations were not
measured.  The technicians also had a  history  of exposure  to toluene,  but the
exposures were poorly characterized  (duration and concentrations not stated) and
each had considerable  concurrent exposure to other  solvents  as well, particu-
larly  benzene and  chloroform.    Results  of  peripheral  lymphocyte  analysis
(20 cells/individual scored) showed  a statistically significant increase  in SCZs
in the laboratory technicians and the children of female technicians, but not  in
                                     14-16

-------
the exposed printers; however, due to the nature of the exposure,  the  increases
noted cannot be exclusively attributed to toluene.

14.3.  TEHATOGEHICITY

14.3.1.   Animal  Studies.    Toluene was  reported in  a recent  abstract to  be
teratogenic  to  CD-1 nice  following  oral exposure (Nawrot and Staples,  1979).
Toluene was administered by gavage from days 6-15 of gestation at levels of  0.3*
0.5, and 1.0 ml/kg/day and  from days 12 to 15 at 1.0 mi/kg/day.  The vehicle  used
was  cottonseed  oil  (0.5J  of  maternal  body weight  per dose).   A  significant
increase in embryonic lethality occurred at all dose  levels when administered  on
days 6 to 15, and a significant reduction in fetal  weight was measured in the 0.5
and  1.0 mi/kg groups.   Exposure to  1.0 mi/kg toluene  on days 6  to 15  also
significantly increased the incidence of cleft palate;  this effect reportedly
did not appear to be due merely  to  a  general retardation  ia growth  rate.   When
toluene was administered  at  1.0 mi/kg  on  days  12  to  15» however,  decreased
maternal weight gain was the only effect observed.   Maternal toxicity was not
noted after exposure to toluene  on days 6 to 15 at any dose level.  It  should  be
emphasized that the numbers of mice exposed and the numbers of fetuses examined
were not stated in  the available abstract of this study;  a complete copy of  this
report is not available for review but has  been submitted  for publication.
     Hudak and  Ongvary (1978) recently concluded  that toluene was  not  terato-
genie to CFLP mice or CFT rats when  administered via inhalation according to the
following schedule:
                                      14-17

-------
                       Doaa           ,     Days of Pregnancy    Duration
       CFPL mica     133 ppm (500 mg/ar3}          6-13           24 hours/day
                     399 pom (1500 mg/nr)         6-13           24 hours/day
       OFT rata      266 ppm (1000 mg/nc)         1-21            3 hours/day
                     399 ppm (1500 og/nq)         1-3            24 hours/day
                     399 ppm (1500 ng/m3)         9-14           24 hours/day
16 waa found that the entire group of mice exposed to 399 ppm toluene died within
24 hours.  Toluene administered to rata  at 399 ppn alao had an effact on maternal
survival, but none of the exposures adversely affected  the  incidence of external
or  visceral malformations in  either species relative  to  air-exposed controls
(Table 14-7).  An  increased  incidence of skeletal anomalies (fused sternebrae,
extra ribs)  was observed,  however,  in the rata exposed continuously  to  399  ppm,
toluene on days 9  to  14,  and signs of retarded skeletal development  (including
poorly ossified sternebrae, bipartite vertebra centra,  and shortened  13th  ribs)
were found  in  the  rata  exposed on days 1  to 3  (399 ppm) and during  the entire
period of pregnancy  (days  1  to 21) at 266 ppm for 3 hours/day.  An embryotoxic
effact of toluene waa further indicated  by low fatal weights in the mice, and in
the rata  exposed  on days  1  to 3  of pregnancy.  Fetal loss (percent of  total
implants), mean litter size, mean placental weight, and maternal weight gain were
unaffected by exposure in aither species.
     In a more recent teratogenicity study, groups of 20 CFY rata were  exposed to
266 ppa (1000 mg/sr) toluene,  125  ppm (400 ng/nr)  benzene, or a combination of
these concentrations of toluene and  benzene vapor for 24 hours/day on days 7 to
14 of gestation  (Tatrai at al., 1930).   A group of 22 rats inhaling pure  air
served as controls, and  the  fetuses were examined on day  21 of  pregnancy.  The
results of the toluene exposures in this study are consistent with those of  Hudak
and dngvary's continuous 399 ppm toluene exposures with rats on  days  9 to  14 of
gestation.   Tatrai et al.  (1930)  concluded that continuous  exposure  to  266  ppm
toluene was not  taratogenic (no external, internal,  or skeletal malformations
                                      14-18

-------
                           TtBL8 14-T




Teratogenlolty Evaluation of Toluene la Cfl Data and CFI.P Htoe*





No. pregnant anlnala enaialned
Ho. pregnant anlaula died
Maternal weight gain6 ($)
Ho. live fetuses
Ho. reaorbed fetuses
Ha. dead fetuaaa
Fetal loss (*)
Mean Utter alze
Mean fetal Height (g) '
Maan placental Height (g)
Weight retarded fetuses0 ($)
External nalfarmaltona
Ho. fetnaea dissected8
Internal aal forma lions
Anophthal«la
llydroceplialua
llydronnphoroal a
Ho. of Alizarin-stained
fetuses
Skeletal retardation algna'

>lr Inhalation

Daya 1 to 21
B h/d
10
0
46.6
III
8
0
6.7
M.I
3.8
0.5
7.2
0
51

0

1

57
0


1 Toluene
266 ppa
Daya 1 to 21
8 h/d
10
0
44.1
133
3
0
2.2
13-3
3.6
0.5
16
0
64

0
-_
6

69
17"
399 ppai
Daya 1 to
24 b/d
9
5
44.0
95
6
0
5.9
10.6
3.3»
0.5
46"
0
49

0
4
4

42
7"
Hata
*lr Inhalation

a Daya 9 to 14
24 h/d
26
0
46.9
348
15
0
4.1
13.4
3.a
0.5
6.9
0
179

1
.-
16

169
II.

Toluene
399 pp»
Daya 9 to
24 h/d
19
2
41.8
213
ia
0
7.B
11.2
3.8
0.5
17.3
0
no

0
—
4

102
24"

Mr inhalation

14 Daya 6 to 13
24 h/d
14
0
—
124
6
1
6.1
9.0
I.I
—
6.5
0
64

0
—
1

60
3
Mice

133 t
Daya 6

Toluene
•V* )99 ppa
to 13 Daya 6 to 13
24 h/d 24 b/d
M
0
—
112
10
0
a.
10.
i.
—
27.
0
sa

0
—
3

54
1
0
IS

0
0
0
2 0
2
0*
—
6*>
—
0

	
--
--

—
—

-------
                                                                TABU  8H-7 (oont.)
                                                                                                                     Mlo«


ilr fpha|atj

|on Toluene
266 ff»
399 MM
Daya 1 to 21 Daya 1 to 21 Daya 1 to

Skeletal anoeallea
Fitted ataraabraa
Bitra rlba
Skeletal Mirorawtlona"
Hlaalng vertebrae
BraoblMtlla
8 l»/d

0
0

0
0
I b/d

0
0

0
0
2* b/d

0
0

0
0
Jlr fnhafa.tloa folu^na
J99 M*
0 Daya 9 to II Day* 9 to
2* b/d 2% b/d

2 ?••
0 221**

0 2
0 0
Air fnnalatton Toluene

U) wa>
II Daya 6 to 1) Daya 6 to 1)
2% b/d

0
0

0
1
21 b/d

0
0

0
0
399 wei
Daya 6 to U
21 b/d

__
—

__
"•
*Souroo>  Uudak and Ungvary. 1978
 feraaut of at art Ing body might
 Paroant of living fatuaaa weighing <).] g (rata) or 0.9 g (•!<)•)
d«gnatbla. braotalaMlla, Biasing tall
 Tha rata wera aaorlftoed on day 21 of pregnancy, tba aloa on day 18
 Thyaua hy|X»laa!a alao looked for
'inoludlng poorly oaalflod ataroebraa, bipartite vartabra centra, and anortanad l)tb rlba
S'loaura atarnl and agaatbla alao looked for
•r < 0.01 (t-taat)t •• f < 0.05 (Hann Whitney U Taat)i ••• P < 0.01 (Mann Hbltnay U Teat)
b « hourj d » day

-------
were reported), although the exposures were associated with evidence of skeletal



retardation (not detailed) and an increased incidence of extra ribs (Table 14-3).



It was additionally  found that the  incidence  of extra ribs  was  higher in  the



group exposed to toluene in combination with benzene  than  in  the  groups exposed



to toluene alone.  Maternal loss, maternal weight gain, number of litters, mean



implantation/dam, placental weight,  fetal  loss,  and fetal weight  loss  were  not



significantly affected by the  toluene exposures.  Exposure to 125  ppm benzene  did



cause decreases in maternal weight gain, placental  weight  and fetal weight,  but



these effects appeared to be inhibited by concurrent exposure to 266 ppm toluene.



Further,  it was reported that post-implantation fetal loss (the  number of dead



and  resorbed  fetuses  relative to  the  number of  total implantation  sites  in



percent)  was significantly increased in the group exposed to benzene in combina-



tion with toluene;  fetal loss was not, as indicated earlier, affected by exposure



to the toluene (or benzene) alone.



     In  a  third inhalation study,  Litton  Bionetics,  Inc. (1978b)  reported  no



evidence of teratogenicity in  the 20 day old fetuses  of Charles  River  rats that



were exposed to 100 or  400 ppm toluene vapor for 6  hours/day  on  days 6 to  15 of



gestation.  Histological examinations revealed no unusual  incidence of visceral



or  skeletal  abnormalities   (Table  14-9);  unusual  skeletal variations  were



observed in a small but  comparable  number  of fetuses from both the exposed  and



control groups, but these changes were in most cases attributed  to retarded bone



ossification and were not considered to  be malformations as such.   It  was also



noted that  there were  no  maternal  deaths  during this  study, and  that  the  sex



ratio of the offspring  did  not differ  significantly between  the  treated  and



control groups.



     In  a brief abstract,  Roche and  Hine  (1963)  noted  that  toluene was  not



teratogenic to either  the  rat  fetus  or the chick embryo.   Parameters  evaluated
                                     1U-21

-------
                      TABLE  14-8

Taratogenio  Effects  of Exposure  to Toluene,  Benzene,
and a Combination of Toluene and Benzene in CFY Rats

rnhaXation on days
T ta T* of pregnancy
2,* b/d
Number of females
treated
died
non pregnant
total resorption
Number of liters
Mean implantation/dam
Maternal weight gain
la % . of starting body
weight
ReladTO liver weight
(•$}•
Mean; placenta! weight
(gO;
Number of fetuses
li.ve
dead
resorbed
Mean fetal weight (g)

Weight retarded
fetuses in % of living
fetuses
External malformations
Fetal loss/total
implantation sites (J)
Scv Alizarine-stained
fetuses
Skeletal retarded
fetuses in % of
*T Irar1n*t— •'^t nnd
fetuses
Toluene
Air 266 ppo.
dOOOmg/m-3)
21
1
21
14
68
+2

4
±°
0
^
294
280
0.
14
3
±P
2


—
4

142

13





.0
.32
.40

.25
.08
.58
.006




.94
.02
.3



.7







20
2
18
14
65
+2

4
+0
0
^
259
239
-0
20
3
±°
3


—
7

121

31





.4
.82
.13

o37*
.07
.60
.006




.91
.02
•3



.7







Benzene
125 ppffl.
(400 ng/nr)
20
3
1?
14.6
46.74***
±a.69

4.67*
*0.12
0.48***
^0.006
248
236
2
10
3.16***
±0.03
57. 6»*


—
4.3

122

77»»»



Toluene/Benzene Significance
266 ppn ••• 125 ppo of.
(1000 og./400 og) Interaction
20
1
... 19
13.
" 53.
+1.

4.
±°*
0.
±°'
262
234
„.
28
3.
±°*
9.


~
10.
-
118

39*

- - -


—

3
94*»» p < 0.05
3ft .

10 P < 0.01
09
54*«» p < 0.05
004




79** p < 0.001
02
a*



7*








                           14-22

-------
                                    TABLE 14-3 (cont.)
Inhalation on days
7 to 1* of pregnancy
2* h/d
        Toluene       Benzene     Toluene/Ben  ene   Significance
Air     266 ppm       125 ppm.   266 ppm +  125 ppm       of
      (lOOOag/or3)   (400 mg/ar3)   (1000 mg^UOO rag)  Interaction
Skeletal anomalies
  sternum misaligned      U
  asymmetric vertebra     1
  extra ribs              1

Skeletal malformations   ~
                          5
                          3
                          1
 1
 1
19*»
Ho. fetuses dissected
Internal malformations
polycystic lungs
pyelectasia
dystopia renis
Tesica giganta
sticropbthaloia
anophtnalmia
oydrocephalus
internus
138

1
2
—
—
~
—

-•"
118

—
5
1
3
«—
0»

""*
114

...
—
—
1
<—
2

3
116

—
1
~
1
1
—

™™
Source:  Tatrai et al.,  1980

"*" * p < 0.1; »ap< 0.05;  *•  s  p  <0.01;  ••«  s p < 0.001;  * s SEM
                                              14-23

-------
                                    TABLE  14-9

                    Teratogenicity and Reproductive Performance
                      Evaluation  in Rats Exposed  to  Toluene



Pregnancy ratio
(Pregnant/Bred)
Ho. pregnant rats that died
Live litters
Implantation sites
(Left Horn/Hignt Horn)
Resorptions
Litters with resorptions
Dead fetuses
Litters with dead fetuses
Live fetuses/implantation site
Mean live litter size (fetuses)
Average fetal weight (g)
Number of fetuses examine for soft
tissue (visceral) changes
Somber of fetuses examined for
skeletal changes
ftimber of fetuses with normal
skeletal examinations
Fetuses with commonlx encountered
skeletal changes3 'r
Fetuses with unusual skeletal
variations '*


0

26/27
0
26
152/194
26
13
0
0
320/3*6
12
3.6
108(51/57)

212

139
67(20)
6(4)

Dose (pom)
100

27/27
0
27
181/177
28
20
1
1 -
329/358
12
3.5
105(47/58)

221

150
62(20)
9(4)


400

27/27
0
26
179/190
41b
17
0
0
328/369
12
3.8 .
104(51/53)

224

158
58(20)
3(6)

"^Source:"  Litton Bionettics,  Inc., 1978b
  The increase in total resorptions at this dose was attributed to the total
  resorption of the litter of one particular female.
 ^Numbers  of male/females examined in parentheses.
 °Four specimens from one litter were not examined (missing).
 8A qualitative examination of the observations recorded for the fetuses indicates
  that bilateral ribs, unilateral ribs, and reduced ossification of various bones
  were the most frequently encountered changes.
  Number of litters in parenthesis.
 *rhese were generally cases of acre severe and extensive retarded ossification.
                                         14-24

-------
included  body  weight,  bone  length,  and  gross abnormalities,  but no  dose  or
exposure information or other quantitative data were provided.
     Elovaara et al. O979b) injected  toluene into the air space of developing
chicken eggs at doses of 5, 25, 50, and 100 umol/egg on the 2nd and 6th days  of
incubation.   Survival incidence  after 14  days  of  incubation appeared  to  be
influenced only after injection of toluene on  day 6 at 100  umol/egg;' the "approx-
imate LD-0" for toluene was Judged to be in excess of 100 umol/egg.  Macroscopic
examination on day  14  indicated  that only 3 of 46 of  the chick embryos treated
with 5 to 100 umol/egg of toluene were  malformed;  1 displayed profound edema and
3 had skeletal abnormalities (musculoskeletal  defects  of the lower extremities,
but not wings).
     McLaughlin et al. (1964)  injected toluene at dose levels of 4.3, 8.7, and
17.4 mg  into  the yolk sac of  fresh   fertile  chicken  eggs  before incubation.
Following incubation, the percentages of batch at the 3 doses were, respectively,
85$, 259, and Of. Teratogenic  effects  were not observed in either the eggs  that
failed to hatch or in the chicks  that  did hatch.

14.3.2.   Human  Reports.   Holmberg (1979) gathered  information  on exposure  to
noxious agents during the pregnancies of 120 mothers  of children with congenital
CNS defects and their matched-pair controls.   The matched-control mother is the
mother whose delivery  immediately preceded  that  of the case mother in the  same
Finnish  maternity welfare district.   Results showed  that  14  of  the  120  case
mothers  had  been exposed  more often  than  control  mothers  (3/120)  to organic
solvents during the first trimester of  pregnancy.   Among the 14 exposed mothers,
2 had been exposed to toluene.  One of the toluene-exposed mothers  (age 13) had
reportedly been  exposed  in  the metal products manufacturing industry (no other
details of exposure given),  and gave birth to a child that died after 2 hours and
                                      14-25

-------
showed internal congenital hydrocephaly and agenesis of the corpus callosum upon
autopsy;  other  findings  included  pulmonary  hypoplasia  and  a diaphragmatic
hernia.  The other mother  was  exposed  to toluene concomitantly with other sol-
vents  (xylane, white spirit, methyl  ethyl ketone) during rubber products manu-
facturing; her child was hydranencephalic and died 24 days after birth.  It was
noted that in this case parental age (maternal, 42 years; paternal, 44 years) and
a previous child with brain injury (born 20 years previously,  died at age 4) were
more likely than the recent exposure  to have predisposed the more recent child to
the defect.
     Toutant  and Lippman  (1979)  described the  birth of • a  child  with "nearly
classic" fetal alcohol syndrome to a 20 year old  primigravlda whose  major addic-
tion was to solvents (reportedly, primarily toluene).  This woman had a 14 year
history of daily heavy solvent abuse (no details provided) and a 3  year history
of  alcohol intake  of  about  a  six-pack of  beer weekly.   On  admission,  she
exhibited .signs  compatabile with severe solvent  and/or  alcohol abuse (ataxia,
resting and intention tremors, mild diffuse sensory deficits, short-term memory
loss, and poor intellectual functioning).  The child was born at term, was small
(10th percentile in weight, 5th percentile in head size), and exhibited abnormal
features that included microcephaly,  a  flat nasal bridge, hypoplastic mandible,
short palpebral fissures, mildly low-set ears, pronounced sacral dimple, sloping
forehead, and uncoordinated arm  movements.  It  was  noted that although solvent
abuse rather than alcohol  predominated in this  mother's addiction  pattern, the
case seemed no different from reports of fetal alcohol syndrome.

14.4.  SUMMARY
     CUT  (1930)  concluded that, exposure to 30,  TOO, or  300  ppm  toluene for
24 months did not produce  an increased incidence of neoplastic, proliferative,
                                     14.26

-------
inflammatory, or degenerative  lesions in rats relative  to unexposed controls;



the highest  dose tested was  not,  however,  a minimum toxic dose.  Other studies



indicate that toluene is not carcinogenic  when applied topically to the shaved



skin of  mice (Poel,  1973; Linsky and Garcia, 1972;  Coombs  et al., 1973; Ooak



et.al., 1976), and that it doea not promote the development of epidermal tumors



following  initiation  with DMBA  (Frei and  Kingsley,  1968; Frei  and Stephens,



T968).



     Toluene has yielded negative results  in a battery of microbial, mammalian



cell, and whole organism test  systems.   The microbial assays conducted include



differential toxicity testing with wild-type and  DMA repair-deficient strains of



E. eoli and  S.  typhimurium  (Fluok et al.,  1976; Mortelaans and Riccio, 1980),



reverse mutation tasting with various strains  of S. typhiaurium. E.  coli  WP2,  and



S. eerevlsiae D7  (Litton Bionetics,  Inc.,  1978a;  Mortelaans  and Riccio,  1980;



Sestman et al.,  1980), and aitotic gene conversion and crossing-over evaluation



in S. cerevisiae W  and D7 (Litton Bionetics, Inc.,  I978a;  Mortelaans and Riccio,



1980).   Toluene also failed  to  induce specific locus  forward mutation in  the



L5178Y  Thymidine  Kinase mouse lymphoma  cell assay  (Litton  Bionetics,   Inc.,



!978a), was  negative in the micronucleus test  in mice (Kirkhart, 1980), and  was



negative  in  the mouse  dominant   lethal  assay (Litton Bionetics,  Inc., 1981).



Sister-chromatid exchange (SCE) frequencies were not altered in Chinese hamster



ovary cells  (Evans and Mitchell,  1980) or in human  lymphocytes  (Gerner-Smidt  and



Friedrich, 1978) cultured  with toluene, or in the peripheral lymphocytes cul-



tured from workers with a history  of chronic exposure to toluene (Funes-Cravioto



et al., 1977; Maki-Paakkanen et al.,  1980).



     In the Russian literature, chromosome  aberrations were reported in  the bone



marrow cells of rats exposed subcutaneously (Dobrokhotov,  1972; Lyapkalo,  1973)



and via inhalation  (Dobrokhotov and Einkeev,  1977) to toluene.  These  findings
                                      14-27

-------
were not corroborated, however,  in a Litton Bionetics, Inc. (1978b) study in rats
following intraperitoneal  injection,  in cultured human  lymphocytes exposed  to
toluene jLn  vitro  (Gerner-Smidt  and Friedrich,  1978),  or  in lymphocytes  from
workers  chronically  exposed  to  toluene (Forai  et al.,  1971;   Maki-Paakkanen
et al., 1930).  Funes-Cravioto et al.  (1977)  did report an excess of aberrations
in the lymphocytes from 14 printers exposed  to 100  to 200 ppm toluene for  1  to
16 years,  but  it  is probable   that  part  of  the exposure  was  to benzene-
contaminated toluene.
     Toluene was reported in a recent abstract  from MIEH3 to induce cleft  palates
at a  level  of  1.0 out/kg  following oral  exposure  to nice  on days 6  to 15  of
gestation (Nawrot  and Staples,  1979);  significant increases in  embryolathality
and decreases in fetal weight were noted as well at doses as low  as  0.3 a/kg/day
and  0.5 m/kg/day,  respectively.    The  teratogenic  effect reportedly  did not
appear to be due merely to the general retardation in growth rate.  Three  other
studies concluded  that toluene  is not  teratogenic  in mice (Hudak  and Ungvary,
1978) or rats  (Hudak and  Ongvary, 1978;  Litton Bionetics,  Inc., 1978b; Tatrai
et al.,  1980)  following inhalation  exposure.    Embryotoxic effects  (increased
incidence of skeletal anomalies and signs of retarded skeletal development, low
fetal weights) and increased maternal mortality were noted, however,  in  some  of
the rats and mice exposed via inhalation.  Injection of toluene into the yolk sac
(MeLaughlin et al.,  1964)  or air  space (Slovaara et al.,  1979b)  of  chicken eggs
before incubation or during development,  respectively, did not result  in  terato-
genic effects.
                                     14.28

-------
           15.  SYNEBGISMS AND ANTAGONIST AT THE PHSIXOGXCAL LEVEL

T5.1.  BENZENE AND TCLOENE
     Animal studies have  shown  that benzene and toluene may be  metabolized by
similar enzyme systems  in  parenehymal cells of the  liver.   In the studies of
Pawar and Mungikar (1975), the activities of hepatic aminopyrine N-demethylase,
HRDPH-linked  peroxidation,  and  ascorbate-induced   lipid   perorLdation  were
reduced, while acetanilide hydroxylase was increased  by either benzene pretreat-
ment  or   toluene  pretreataent  in  male   rats.     Induction  of  aminopyrine
N-demethylase and components of the electron transport system was seen when the
animals were given phenobarbital (Pawar and Mungikar, 1975;  Mungikar and Pawar,
1967a, 1967b).  When phenobarbital  was coadministered with  benzene or toluene,
the changes ia the activity of these enzymes  produced  by single administration of
the xenobiotics were attenuated  (Pawar and  Mungikar, 1975).  That induction of
hepatic enzymes by phenobarbital affects metabolism  of toluene is indicated by
the reduction of  toluene  toxioity  (decreased narcosis) ia  female rats or male
mice given  phenobarbital  prior  to intraperitoneal injection  of  toluene (Ikeda
and  Ohtsuji,  1971; Koga  and Obmiya, 1978) and  the accelerated  excretion of
toluene metabolites from female  rats  as  described in Sections  12.3.  and 12.U.
(Ikeda and Ohtsuji, 1971).
     The following studies indicate that toluene has  the potential for altering
the bioaotivity of benzene  when  given in sufficiently large  quantities.  When
benzene was given in combination with  toluene, the conversion of benzene to its
metabolites (phenols) was suppressed  in  rats (Ikeda  et al.,  1972)  and in mice
(Andrews et al., 1977).  Ikeda et al.  (1972) administered a mixture of benzene
and toluene (equivalent to  110 mg  benzene/kg and  430 tag toluene/kg) intra peri-
toneal ly to female rats and observed a reduced excretion of  total  phenols.  When
                                      15-1

-------
a mixture of toluene and benzene  (110  mg toluene/kg and 440 mg benzene/kg) was
administered, hippuric acid excretion was reduced up to  4 hours after injection.
Induction of hepatic microaooai enzymes by phenobarbital prior to administration
of the mixture alleviated the suppression.
     Andrews  at al.  (1977)  co-administered  440  or  380 ng/kg  benzene  and
1720 ng/kg toluene intraperltoneally to nice  and found a significant reduction
in urinary excretion of benzene metabolites and a compensatory increase of pul-
monary excretion of unmetaoolized benzene.  When toluene and benzene were coad-
ministered by subcutaneous  injection,  toluene did not significantly change the
total amount of benzene found in fat, liver, spleen, blood, or bone marrow, but
it did  reduce  significantly the accumulation of metabolites  in these tissues.
Coadministration of toluene and benzene also counteracted benzene-Induced reduc-
                  eq
tion of red cell J7Fe  uptake  in developing  erythrocytes,  suggesting that the
oyelotoxicity of benzene might be attenuated by toluene-inhibition  of benzene
metabolism  in  the  bone marrow.   In  an in vitro  study  of a  liver microsome
preparation, Andrews and coworkers (1977) determined that toluene is a competi-
tive inhibitor of benzene metabolism.
     In the studies of  Ikeda et al.  (1972)  and Andrews et al. (1977), however,
benzene and  toluene  were  given intraperitoneally  in large amounts.   Sato and
Nakajima d979b) used doses in the  range of 24.2 to 390.6 mg/kg of benzene and
23.6 to 460.3 mg/kg of toluene to assess concentrations which might be found in
the workplace.  They found that when benzene was given to rats in the range of
24.2 to 97.7 mg/kg, there  was  no  significant difference in the  rate of disap-
pearance of benzene from the blood whether the benzene was administered singly or
in combination with an  equimolar amount of toluene.  At a  dose of 390.6 mg/kg
benzene, an equioolar dose of toluene delayed the disappearance of benzene from
blood, and the excretion of phenol was  reduced.  A dose-dependent inhibition of
                                      15-2

-------
the metabolism of benzene by toluene was  found.   In a study of human exposure,
inhalation of a mixture of 25  ppm benzene  and 100 ppm toluene for 2 hours did not
exert any influence on  the disappearance  rate  of benzene and toluene in either
blood or  end-tidal  (alveolar)  air as compared  to inhalation of  either  solvent
singly.  Desaturation curves (concentration versus  time) for blood or end-tidal
air obtained  for each  solvent  after inhalation of the specified mixture were
virtually superimposable on desaturation curves obtained after  inhalation of the
same  solvent  (25 ppm  benzene or  100  ppm toluene)  by itself.   These  results
indicate  that  in  the  range  of  threshold  limit  value  "the pharaacokinetic
processes ...   of absorption, distribution, excretion, and metabolism of either
benzene or  toluene  are not influenced  by simultaneous  exposure  to the other"
(Sato and Nakajima, I979b).  The data for the single-solvent exposures  had been
published  previously  (Sato  et al.,  197Ub);  details  of  the  experiment  with
toluene were discussed  in Section  12.U.

15.2.  XYLENES AND TOLOENE
     When 0.1 mi/kg or  0.2 ml/kg toluene  was co-administered with similar doses
of  m-xylene intraperitoneally  into male rats,  the  amounts  of hippuric and
m-methylhippurie acid  excreted  in urine over a  period of 24  hours  were not
different from the amount of metabolites formed by single injection of toluene  or
n-xylane.   The  velocity  of  excretion  of metabolites  in  the  simultaneously
injected group was slightly delayed  in  comparison with that in singly  injected
groups.   Thus,  simultaneous administration of  the  compounds does not  signifi-
cantly interfere with the metabolism of either  compound (Ogata  and Fujii, 1979).
     To  study  the excretion  kinetic interactions  between  toluene and  xylene,
Riihimaki (1979) determined the conjugation and urinary excretion of  metabolites
of  toluene  and  m-xylene,  benzoic acid  and methylbenzoic acid, respectively,  .in
                                      15-3

-------
vivo in one  nan.   Forty-one oillimoles benzole  acid  or 7.4 omol aethylbenzoic


acid was ingested singly or in combination by one adult human male.  In the 25 to


30 hours that urine  was collected after  ingestion,  the total  recovery of the


ingested compounds with the exception of one sample (dose excreted in  that  case:

84 J) indicated  that  all excretion  took place via  the  kidneys.   The combined


intake of methylbenzoic acid and benzoic acid did not significantly affect conju-


gation or  excretion  of either metabolite.   This  study indicates  that during
                                                            *
simultaneous exposures to toluene and a-rylene,  even at a relatively  high  level


of  occupational exposure,  conjugation and  excretion of  metabolites  are not


likely to be rate-limiting steps except under conditions  of  Halted availability


of glycine.




t5.3.  TOLUENE AND OTHES SOL7ENTS                                  :


     Simultaneous intraperitoneal injection of 1.18 g/kg toluene with 0.91 g/kg


nt-oexane into female rats did not affect  the  concentrations of n-hexane in the


blood nor was excretion of hippuric  acid affected by eoadninistraton of jt-hexane


(Suzuki et al.,  1974).

     Coadminlstration  of ethanol  by  ingestion  and  of toluene  by   inhalation


(4000 og toluene/or,  6 hours dally,  5 days a week for 4 weeks) into rats did not


change  the electrocardiogram, hematocrit values,  or hlstological  and histo-


chemical structure of  the heart.  Toluene increased vascular resistance of the


myocardium and  reduced  cerebral  blood flow,  while alcohol  ingestion reduced

arterial blood pressure, the  cardiac index, and blood  flow to the myocardium,


kidney, skin, and carcass.  Myocardial and cutaneous vascular resistance, as well


as cerebral blood flow, increased after alcohol ingestion. It was concluded that


combined exposure to the two substances produced additive effects on  myocardial


vascular resistance  (Morval and (Jngvary,  1979).   During subchronic exposure of
                                      15-4

-------
rats to  toluene  and ethanol, there  is  a potentiation  of  microsomal and  nito-
chondrial changes in the liver (Hudak et al., 1978).
     In  their study of joint toxic action,  Smyth  et al.  (1969) suggested  that
perchloroethylene is capable of  enhancing the toxicity of toluene administered
orally in rats.  Withey and Hall (1975) observed that administration by  intuba-
tion into rats of trichloroethylene and toluene in combinations of  mixtures at
five different dose levels  revealed a departure from an  additive model.   They
concluded that  the effect  of co-administration  of the solvents  could not  be
described in terns of synergism or potentiation  until further studies were  made.
     Ilceda  (197U)  observed  that  ooadminlstration  of  trichloroethylene  and
toluene  (730 mg/kg  and 430 ing/kg,  respectively)  by  the  intraperitoneal  route
into rats  reduced  the amounts of  metabolites  of  both solvents compared  with
amounts  excreted after administration of either solvent alone.
                                      15-5

-------
                        . 16.   ECOSYSTEM CONSIEERATIONS







16.1.  EFFECTS ON VEGETATION







16.1.1.  Introduction.  Toluene volatilizes rapidly  from  solutions  (Mackay and



Wolkoff, 1973).   Most  studies investigating the phototoxieity  of toluene  have



been with  algae.   Of  these  studies,  only one (Dunstan et al.,  1973)  was  done



under conditions that maintained a nearly constant concentration of toluene in



the  culture  medim throughout  the  experiment.   Other studies  were  done  with



culture vessels capped  with metal caps or with cotton plugs, allowing the toluene



to volatilize and escape from the exposure solutions.  Even though steady-state



concentrations  are lacking,  these  studies do approximate  situations in  the



environment where  a  point source of  toluene  exists  to a body  of  water.   The



discussion of these studies  will, therefore, be  under the headings  of "closed"



and "open11 experimental systems.







16.1.2.  Effects of Toluene on Plants.







     16.1.2.1.  ALGAE







     16.1.2.1.1.   Closed  System Studies — Dunstan  et al.  (1975) exposed  4



marine  algal  species  to  toluene concentrations ranging  from   1 to  10* ug/i,



Axenic algal cultures were inoculated  at  18*C and grown with a 12-hour light/dark



cycle  under  cool-white fluorescent  light (4000 uW/cm , 380   to  700 on)  in



filtered enriched  seawater.   To minimize loss of  toluene by vaporization, the



125 mi Erlenmeyer  flasks were made airtight with rubber stoppers.   Experiments



were never run beyond a cell  density at which C0_  limitations might limit growth.
                                      16-1

-------
the four species used were the diatom, Skeletonema coatatun; the dinoflagellate,
ftmphi'Unium earterae; the cocolithophorld, Crieoaohaera earterae; and the green
flagellate, Dunaliella tertiolecta.
     To  illustrate  the difficulty of establishing  absolute concentration when
working with toluene, Dunstan et al. (1975) observed the toluene concentrations
at three intervals in stoppered flasks (Table 16-1).  Eighty-four percent of the
theoretial initial  concentration was lost  at the beginning  of the experiment
during the  handling and dispensing of the toluene into culture flasks, even when
the toluene was rapidly dispensed under sterile conditions.
     Figure 16-1 shows how toluene can  both stimulate and inhibit algal growth
depending on the species and the concentration of toluene.  The dinoflagellate,
Amphidiniua  earterae was  inhibited at  all  concentrations--o£~toluene—(1  to
to5 tig/I) from 20 to 50$.  The other three species however, were stimulated by 1
      H
to  10  ug/l,  but  higher  concentrations  of  toluene either had  no  effect
CDunaliella  tertiolecta)  or  became   inhibitory   (Skeletoneaa-—oostatum  and
Crieoaphaera earterae).   This  work indicated that  one of-the most significant
environmental effects was in the  short-term  selection of certain phytoplanktonic
species  by the  growth  stimulation  brought  about  by  low levels  of toluene.
Dunstan et al. (1975) concluded that the differential growth of phytoplanktonic
species within the phytoplankton population ultimately determines the community
structure, its succession, and its trophic relationship.
     Potera (1975)  evaluated the effect of toluene on saltwater phytoplankton
dominated by Chlorella  sp. using Warburg manometry.   Toluene inhibited—photo-
synthesis 29% at 34  tog/1 and 35} at  342 ng/1 (at 20«C).  Respiration (at 20*0
was inhibited 62$ at 3« mg/1 and 16$ at 342 ag/l.
                                      16-2

-------
                                   TABLE  16-1
                 Concentrations  of Toluene  in Stoppered Flasks*
        Time of Measuraaent                        Percent of Theoretical
                                                        Concentration
        Theoretical initial concentration                100
        Measured initial concentration                    16
        Concentration after 3 days of growth
           Stoppered flask                                14
           Cotton*plugged flask                            1
aSource:  Dunstan et al., 1975
                                     16-3

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-------
     16.1.2.1.2.  Open Studies — Illustrative of the "open"  type  of  experiment



Is that of Kauss and Hutchinson (1975).  The freshwater alga, Chlorella vulgaria.



was exposed  to toluene  for 10 days  in 125 mi cotton-plugged  Erlenmeyer  flasks.



Each flask was agitated to resuspend the cells daily.  The concentrations listed



in Figure 16-2 are nominal  initial concentrations.   In this open experiment,



toluene was  less toxic to  the alga  because  the toluene concentration  diminished



by volatilization  during  the experiments.  Comparison  with controls revealed



that  a lag  phase  that  lasted  for  one day existed  between  inoculation  and



commencement  of  growth  for  50  and  100 mg/i.   Recovery  was less  rapid  with



250 mg/i.  At concentrations approaching  toluene  saturation (i.e.,  505 mg/1),



toluene was  lethal to the  cells.



     Table 16-2 summarizes the toxic  effects of  toluene  on algae.  In assessing



the toxlcity of toluene to algae, both  the  inherent toxicity  of  toluene  and the



exposure  time need to be considered.  The no-effect concentration for  most algal



species studied appears to be at  the 10 mg/1 level.  The evaporation rate from



solution  (fresh or saltwater) however,   rapidly  diminishes the exposure  concen-



tration of toluene (Dunstan  et al.,  1975).  The  toxicity of  toluene  is  more



closely approximated by levels of 100 mg/i  in "open" systems, as shown by Kauss



and Hutchinson (1975).







     16.1.2.2.   EFFECTS   ON  HIGHER  PLANTS — Currier   (195D  exposed  barley,



tomatoes, and carrots to toluene vapor.   Air at a flow rate of 11.5 i/min passed



through a small vaporizing chamber  containing the toluene and into the top of a



bell  jar  containing the  plants.    The  concentration of toluene  in  the  vapor



chamber was varied by changing the temperature of the toluene. The concentration



of vapor  in the air was determined by measuring the  amount of  toluene  evaporated



per  unit  of  time.   Three  tomatoes,  20 carrots, and  12 barley seedlings  were
                                      16-5

-------
6———A SOppm

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                                    TABLE 16-2

                        Toxic Effects of Toluene to Algae
Species
Concentration
Effect
Reference
                                    FRESHWATER
Cnlorella vulgaria       2U5 mg/i


Chlorella vulgaria       250 mg/i


Mierocyatia aeruginoaa   105 mg/i


Scenedeamua quadricauda  >400 mg/i
                 2U h EC
                 (cell number)

                 96 h no-effect cone.
                 (cell number)

                 3 d no-effect cone.
                 (chlorophyll a)

                 3 d no-effect cone.
                   (chlorophyll a)
                    Kauas and Hutchinson,
                      1975

                    Kausa and Hutchinson,
                      1975

                    Bringfflann and Kuhn,
                      1978

                    Bringmann and Kuhn,
                      1978
                                    SALTWATER
Afflphidinium earterae     <0.001 Bg/2,
Dunaliella tertiolecta   10 mg/i
Skeletonema eoatatum     10 og/l
Cricosohaera earterae    10 mg/i
                 2 feo 3 d  no-effect
                 cone, (cell number
                 and chlorophyll)

                 2 to 3 d  no-effect
                 cone, (cell number
                 and chlorophyll)

                 2 to 3 d no-effect
                 cone, (cell number
                 and chlorophyll)

                 2 to 3 d no-effect
                 cone. (cell number
                 and chlorophyll)
                    Dunatan et al.(
                      1975
                    Dunatan et al.,
                      1975
                    Dunstan et al.,
                      1975
                    Dunatan et al.,
                      1975
Ectocarpua sp.
anteromoroha ap.
1730 mg/i
1730 mg/i
inhibits asexual
spore germination
inhibits asexual
spore germination
Skinner, 1972
Skinner, 1972
h 9 hour; cone, a concentration; d = day.
                                       16-7

-------
tasted 32, 32, and 14 days respectively after planting.  Plants were exposed  in
the gas chamber for 1/4,  1/2,  1, and 2 hours.  The type and extent of injury were
recorded after one month to allow for a  recovery period.   Temperature of the
plants was held at 25*C.
     Results showed that toxic effects of toluene vapor were influenced by  expo-
sure period  and dosage  (Table 16-3).   Toluene  was observed  to be  toxic  at
concentrations of 6.4 to 12.0  mg/1 after  15  minutes  of exposure  (Currier, 1951).
Fifteen minutes of exposure at 12 ag/Z, toluene produced a 50, 0,  and 60% injury
to tomato, carrot,  and barley, respectively.   The  effects of the exposures  on
flower and fruit  development  were not determined.   For lethality  to occur  at
T2.0 mg/i, barley required 1 hour, tomato 2 hours, and carrot over 2 hours. The
toxicity  appeared  to  vary  markedly within  a narrow  limit.   By lowering the
concentration  of  toluene from 12.0 to-  6.4 og/l,  the percentage of  injury  to
barley after  a two hour exposure  was reduced  from 100*  (lethal) to  15}.   At
21.1 mg/i, toluene was only twice as  toxic to barley seedlings as at  12.0 mg/.l
after a 30 minute exposure.
     Toluene entered the plant rapidly through the cuticle and stomata.   Symptoms
of injury included a darkening of  the  tips of the youngest leaves, presumably  as
a  result  of  leakage  of sap  into the cellular  spaces (Currier,  195O.    This
darkening spread to the older  leaves.  There was a  loss of  turgor, with draping
stems and Leaves.  In  bright sunlight, the chlorophyll was  destroyed.
     Toluene  is  classified as a  contact poison  that quickly  kills  the  plant
tissue with  which it  comes in contact (Currier, 1951).   This  material is not
accumulated in plants nor is it translocated.  The mechanism of toxicity involves
disorganization of the outer  membrane of the cell due to solvent action on the
lipoid constituents,  resulting in  disruption of  photosynthesis,  respiration, and
turgor pressure.
                                      16-8

-------
                                     TABLE  16-3
          Toxic Effects of Toluene Vapor on Carrots, Tomatoes, and Barley3
Percent Injury
Material
Tomato
Carrot
Barley
Barley
Barley
Concentration
12.0 og/1
12.0 mg/i
12.0 ag/1
6.4 mg/i
24.1 ng/Z
Exposure Tiae (h)
1/4
50
0
60
0
ND
1/2
60
50
50
25
100
1
75
75
98
15
100
2 •
100
75
100
15
ND
Source:  Currier, 1951
 0% s no effect; 100} s lethal 1 month after exposure.
h s hour; ND a not determined.
                                      16-9

-------
16.2.  3IOCCNCEOTHATION, BIOACCOMuLATION, AND BIOMAGHIFICATIOM POTENTIAL
     Limited infonaation is available concerning toluene's potential for accumu-
lating  in aquatic organism  and aquatic  food  chains.   Possible pathways  of
toluene uptake are directly from water (tioconcentration) and from both water and
food (bioaccunulation).  Bicmagniflcation occurs if toe concentration of a coo-
pound in an organism increases  with its trophic Level as a result  of passage
through food chains.
     Huoes and Benville (1979) studied the uptake and depuration of toluene and
other nonocyclic  aromatic  components  of the water-soluble  fraction  (>5F)  of
Alas Ion Cook Inlet crude  oil  in  Manila class (Tapes aeaideeussata).  Clans were
exposed  for  eight days to  a  constant VSF concentration under continuous-flow
exposure conditions.  The toluene concentration in water was measured daily.  The
toluene concentration in a pooled sample of 10 clams was measured at 2, 4, 6, and
3 days.  At the end of the exposure period, remaining clams  were transferred to
clean-flowing seawater and pooled tissue samples were analyzed for toluene after
7, 7, and 12 days of depuration.   The data are provided  in the following tabula-
tion:
                                        Toluene Concentration (ppm)
Exposure
Depuration
           Days
1
2
3
4
5
6
7
8
1
7
                        Water
                                      1.2
                                      1-3
                                      1.7
                                      1.4
                                      1.2
                                      0.9
                                      1.0
                                      1.1
Tissue

 2.3
 2.2
 0.87
 2.0
 3.30
 0.30
 1.10
                                     16-10

-------
The  mean  water  concentration during  the uptake  period was  1.2 ppo  toluene.



Tissue concentrations  reached a marl'W"  by two days of exposure and  remained



relatively constant  except for a  temporary decline  on day six.   The  average



tissue concentration  during the exposure period was 1.5 ppm.   The  calculated



bioconeentration factor (BCF) is 1.25  (which is  equivalent  to  1.5  ppm in tissue



and 1.2 ppm in water).   The depuration study showed that toluene was lost rapidly



during the first  week  of  depuration,  but that  a  significant concentration  of



toluene remained in the clams by two weeks after beginning  depuration.



     Hansen et al. (1978)  investigated the uptake and depuration of   C-toluene



by blue mussels  (Mytilus  edulis) .   Groups of mussels were  exposed under static


                                     1U
conditions to four concentrations of   C-toluene for up  to eight hours,  followed


                                                                     14
by exposure to clean recirculatiag seawater for up to 192 hours. The   C-toluene



concentration in water and tissue (pooled sample from four mussels) was measured



by liquid  scintillation counting  at  1,  2, 4,  and  3 hours  after  beginning  the



uptake phase and periodically in tissue during the depuration  phase.


         14
     The   C-toluene concentration in tissue exceeded the water concentration by



one hour at  all exposure  concentrations  except the highest  (40  til/kg  s  ppm),



which was toxic as shown by closure of the mussels at this concentration (Hansen



et al., 1973).  Equilibrium was  reached by four hours  in all  groups.   The  BCF



values at eight hours, expressed as the tissue concentration divided by the mean



water concentration, were  as follows:




                      Water concentration

                                               . BCF
                              0.05                3.8

                              0.4                 5.7

                              4.0                 3.6

                              4.0                 3.6



     The BCF values,  which averaged 4.2, seemed to be independent of the exposure



concentration,  indicating that  accumulation was proportional  to the  level  in
                                      16-11

-------
                                                                 T4
water (Hansen at al., 1978).  More than half of the accumulated   C-toluena  was



eliminated by one hour after the depuration phase began at all exposure concen-


                                           14
trations.  The depuration time by which no   C-toluene was detectable in  tissue


                                                 14
was one hour  in  the mussels exposed to 0.05  u&    C- toluene/kg,  four hours  for



those exposed to  0.4 uA/kg,  120 hours for those exposed to  4 (ill/kg, and 192 hours



for the animal ft exposed to 40 u£/kg.



     Lee et al. (1972) reported that the same  species of mussel (Mytilus edulis)



took up 3 to 10 ug of  C-toluene per mussel (average dry  weight  tissue a  0.3 g)



during static  exposure  for an unspecified period of  time  to 0.1  to 0.5 og/i.



Using tissue toluene concentrations of  10  to  33  ug/g, the BCF la calculated to



have been  between 66 and  100.   Because these values are based on dry  tissue



weights rather than wet weight, they are considerably higher  than those reported



by Sunes and Benville (1979) and Hansen et: al. (1973).



     Berry  (1980)  investigated the uptake  of   C-toluene by bluegill sunfish



(Laponis naerochirus ) and  crayfish (Qrconectas rusticus ) ..   The exposure solu-


                                     14
tions were prepared by adding 1 m&  of    C-toluene to  100 t of water for the fish


                                14
experiment  and by  adding  1 mi   C-toluene to 10  I of water for  the crayfish
experiment.  A group of 40 animals was added after thorough mi^ng of  t&e  solu-



tions.  Duplicate water samples and 2  to 4 animals were taken at 0, 0.5, 1,  2,  4,


                                                                     14
8,  12,  16, 20,  24,  and  48  hours  after beginning  exposure.    The    C-toluene



concentration, expressed  as  nanograms per milligram (= ppm) ,  was determined  in



water and in 7 (crayfish) or 9 (fish) tissues or organs by liquid scintillation



counting.   The 3CF  for each  tissue  was also  calculated.    Analysis of  water



samples  showed  that the  toluene concentration  in  water  decreased at  a  much



greater  rate  in  the crayfish  experiment  than in the bluegill experiment  (39%



versus 51 % loss by 48 hours).  The  maximum  BCF 'of bluegill tissues  ranged  from



about 3  for brain  to 45  for  spleen.  Fish muscle tissue was not analyzed.  The
                                     16-12

-------
maximum 3(7 for moat fis.h tissues was  reached by eight hours.  The maximum BCF of



crayfish tissues ranged from about 3 for muscle to 140  for hepatapancreas.   The



3GT  values increased  throughout  the 48 hour exposure  period for all  tissues



except testes  and muscle.   These results indicate  that  toluene is accumulated



above the water concentration by many tissues in these  two species.  The BC? of



sight in the edible portion  (muscle)  of crayfish is considered to be a minimum



value because  of the  rapidly decreasing toluene exposure  concentration during



this experiment.



     Berry et al. (1978) also measured the uptake of %-toluene by fed and unfed



mosquito (Aedes aegypti) larvae and the uptake  of  %-toluene by fed larvae in the



presence or absence  of benzene.   The larvae were exposed to an initial concentra-



tion of 0.5 nl %-toluene/J, water.   Duplicate water samples and 2 to  5 larvae



were taken at  1, 2, 4,  3,  12,  16, 20, and  24  hours and counted individually by



liquid scintillation counting.  Maximum %-toluene counts per minute  (cpm)  were



equal in fed and  unfed larvae, but  were reached more  quickly (one hour versus



four hours) by  the  fed animals.   The %-toluene counts  per minute values  in



larvae, expressed as the percentage of initial water counts, were greater during



the  first  four hours  in the benzene and toluene mixture than in  the  solution



containing toluene alone.  BCF  values  cannot  be  calculated because the authors



ezpresssed %-toluene uptake as counts per  minute per larvae rather than counts



per minute per gram.  The weight of the larvae was not provided.  Interpretation



was  also complicated  by rapid loss  of  ^H-toluene  (half-time  about four hours)



during the  uptake period.   It is  likely, however,  that  uptake by ingestion of



toluene adsorbed to  food particles can be a significant route of accumulation in



aquatic organisms.



     Ogate and Miyake  (1973)  identified toluene as the cause of offensive odor in



the  flesh of grey mullet (Mugil japanieus)  taken from a harbor receiving efflu-
                                     16-13

-------
eats from  refineries  and petrochemical industries.   Toluene was identified  in

seawater and  fish  tissue by gas' chromatography,  infrared (IH) and  ultraviolet

(07) absorption, and mass spectrometry.  The toluene concentration in most  fish

was not quantified; however, the flesh of one mullet with an offensive odor  con-

tained 5 ppo  toluene.   Additional experiments  showed  that toluene  was  accumu-

lated by caged  eels kept for ten days in several locations  in the harbor to  an

average of 2.4 times the water concentration.  These eels had the  same offensive

odor as mullet collected from the harbor.   In  another experiment,  four eels  were

exposed in seawater to which a mixed solution of benzene, toluene,  and  xylenes

was added  daily for  five days.  The concentration of  each chemical  was  then

measured in  seawater, muscle,  and  liver.   The  results with  toluene  were  as

follows:



                                Toluene Concentration
                  Pish Mo.      	(pom)	      BCF

     Muscle           1
                      2
                      3
                      4

                   Mean

     Liver            1
                      2
                      3
                      4

                   Mean

     Water           —


The results indicate that BCF  in muscle was equal to or  greater than the BCF  in

liver and that tissue concentrations  rarely exceeded the water concentration.

     In later  experiments,  Ogata and Miyake  (1978) found that eels (Anguilla

japoniea)   accumulated toluene  to  whole-body  concentrations-  greater  than  the

water concentration  in freshwater.   For this  study,  the  authors  studied  the

uptake and elimination  of toluene by  eels  exposed  in freshwater to crude  oil.
                                     16-14
11.2
2.6
5.1
30.8
12.4
9.0
2. '5
5.2
2.5
4.8
16.1
0.70
0.16
0.32
1.91
0.77
0.56
0.16
0.32
0.16
0.30
_^

-------
The animals were exposed for ten days to a recireulating oil  suspension  (50  ppm,



w/v) which was renewed every day.  During this period,  the toluene concentration



was  measured in  pooled groups  of  5 eels  taken on  1,  5,  and  10 days after



beginning exposure.  The concentration of toluene in water was measured  each day



at 1, 3,  6, 9, 14.5, and 24 hours after preparing the crude oil suspensions.   The



remaining eels were  then  transferred to clean seawater  and  sampled  after 3.  5,



and 10 days of depuration.  The average toluene concentration in water during the



uptake period was 0.130 ppm.    The  concentration in  eels was 0.641 ppm after



1 day, 1.547  ppm after 5 days, and 1.718  ppm  after  10  days.   The  respective BCF



values were  4.9,  11.9, and  13.2.    A semilogarithmic  plot of the logarithm  of



tissue concentration versus  time indicated that equilibrium had  not  quite  been



reached  by ten days.  The depuration phase of the experiment shoved  that tissue



concentration decreased rapidly from 1.718 ppm at the beginning of depuration to



0.315 ppm after 3 days, 0.121 ppm after 5 days,  and 0.035 ppm after  10  days.   A



semilog  plot  showed  that  toluene was eliminated in 2 phases.  The  elimination



half-time during the first phase, lasting from 0 to 5 days, was 1.4 days. About



93* of the accumulated  toluene  was eliminated by the  end of this period.   The



remaining toluene was eliminated at  a somewhat slower rate, with about 2? of the



accumulated toluene remaining after  ten days  of  depuration.



     The  only information  found concerning  food-chain  transfer  of  toluene  is



provided by Berry and Fisher O979)i  who exposed mosquito larvae (Aedes  aegypti)



to    C-toluene  for  3 hours  and then  fed them to  bluegill sunfish  (Lepomis



macrochirus).  In duplicate  experiments,  each of 25  fish in.-separate containers



were  fed with 10 contaminated  larvae.   The  mean level of  radioactivity in  10



larvae was 736 cpm in the first experiment and 3196 cpm in the second experiment.



Internal  organs  (spleen,  gall bladder,  liver, stomach,  intestine,  and kidney)



from 5 fish, sampled at  each  interval of 1, 4,  8, 24, and 48 hours after  feeding,
                                      16-15

-------
were analyzed for radioactivity by liquid scintillation counting.  Radioactivity
was expressed as counts per minute per organ rather  than on a weight basis.  The
only organ that  had  counts  per  minute values significantly greater  than back-
ground levels was the stomach at  1,  4,  and 3 hours  after feeding.  The authors
concluded that an insignificant  amount of toluene, if any, leaves the digestive
tract  to be  accumulated  la other  organs  of  sunfish.   The  validity of  this
conclusion is unlmown  because the dose was so low  that  absorption,  if  it  had
occurred, could not have been differentiated from background counts and because
the counts were not expressed on a tissue weight  basis, even in the stomach.
     In  summary,  the available  information indicates that the  primary path of
toluene  uptake  in aquatic  organisms is  direct   absorption  from  water.   The
reported or  calculated  BO?  values for edible portion  or  whole organism ranged
between  <1  to about 14,  indicating  that  toluene  has  a low  bioconcentration
potential.  These BCF values are lower than the value predicted on the basis of
the relationship established between octanol-water partition coefficient (?) of
lipophilic compounds and steady-state 8(7 (Veith at  al.,  1979).  This relation-
ship, expressed by the equation "log BCF s (0.35 log P) - 0.70," would predict a
3
-------
goli  and  Pseudomonas   fluereseens  within  2U hours  with  1000 mg/i  toluene.



Threshold concentrations for toluene have been established by Bringmann and Kuhn



(1959,  1976,  1977,  1980)   for  various  microorganisms.    These  investigators



reported values of 29 mg/i for P..  putida. 200 mg/i for E. coli. and greater than



450 mg/i for the ciliated protozoan Oronema parduezi.   Partial sterilization of



soil was achieved by adding toluene to the soil (Pochon and Lajudie, 1943).



     The effects  of toluene on bacterial  activity and  growth have  also  been



studied.  As measured by methane evolution rates,  20 mg/i toluene increased the



growth rate of  bacteria in sewage sludge  deposits, while 200 mg/i  produced  a



toxic effect (Sarash, 1957). Similarly low levels of toluene allowed good growth



of £.  putida and Hoeardia sp.,  while saturation levels (515 mg/i at 20°C) were



to*ie (Gibson,  1975).   Depending  on the concentration  (173  to 17,300 mg/i),  a



rotifer (Dieranopnorus  for el pat us) was unaffected, or  temporarily" inhibited, or



permanently inhibited  by toluene  (Erben,  1978).   Death and  disintegration of



rumen ciliates  occurred between U60 and 6U5  ing/2- of toluene (Sadie et al., 1956).



At  sublsthal  concentrations  (1000  and 6000 mg/i),  toluene caused  a negative



chemotactic response or totally inhibited the chemotatic response of all marine



bacteria tested (Mitchell et al.,  1972;  Young and Mitchell, 1973).  Although the



effects were reversible, the authors of the  1972-paper expressed concern that the



inhibition could  seriously undermine  the capacity of  the marine microflora to



control  the  self-purification processes in the sea.   Seek  and Poschenrieder



(1963) found that high concentrations of toluene (50  to 100,000 mg/g of soil)



suppressed soil microflora activity.  In addition, they found that gram-positive



bacilli sporeformers, streptomycetes,  and cocci  were especially resistant, while



gram-negative bacteria were sensitive.



     Toluene has  been  shown to  affect .the  integrity of the microbial cell wall



and cytopiasmic membrane (Dean, 1978).  Thompson and  Macleod (1974) reported that
                                     16-17

-------
marine pseudcmonad cells washed and suspended in 0.5 M MaCl were lysed by treat-
nent with  20,000 mg/i toluene  and released 959  of the cells'  alkaline phos-
pnatase.  Because  the  cells remained intact with 0.05 M MgSO^  and 20,000 mg/1
toluene, the  authors concluded that Mg ions  prevented cellular  disruption by
strengthening the integrity of the cell wall.  tfoldringn (1973) established that
a  2500 mg/i  solution  of  toluene partially  dissolved  the  inner  cytoplasmic
membrane of Z. coli and displaced  nuclear material to the periphery of the cell.
DeSmet  at al. (1978)  reported that at  100,000  mg/l toluene,  the cytoplasmic
membrane was completely disorganized.  The presence of Mg ions at lower toluene
concentrations (up  to  10,000  mg/i),  however, prevented  extensive  damage to the
cytoplasmic membrane and  loss of intraoellular  material; thus,- permeability
depended on the integrity of the outer membrane (OeSmet et al., 1973).  Oeutscher
Ct-971) found  that  the  effects  of toluene  treatment were  dependent  on various
cultural conditions including pfl,  temperature,  Mg ion concentration, and age of
the  culture.   Temperature-dependent effects  of toluene  treatment were  also
reported by Jackson and  OeMoss  (1965).   Toluene changed  the  asymmetric unit
membrane profile to a symmetric profile in vegetative cells of Bacillus aubtilis
and  caused  gaps  in the  membrane to  appear  (Silva  et al.,  1973).    Fan and
Gardner-Sekstrcm (1975)  found  that  toluene-treated Bacillus aegaterlum cells
liberated a membrane protein essential for peptidoglyca synthesis and that this
protein could be added back to the membrane to reconstitute peptidoglycan syn-
thesis.    Toluene  at  36,000 mg/i  induced  the  autolysis  of  Saeeharemyeea
cerevlsiae.  the  release  of 07 absorbing substances  from- the  cells,  and the
deacylation of phosphopllpids  (Zshida,  1973).   At saturation  concentrations of
toluene, however,  no cytolysis of yeast occurred  (Lindenberg et al.,  1957).
Scholz et al.  (1959)  noted that  toluene-treated  yeast  cells  accumulated hexo-
sephosphates.  Bucksteeg (1942) found that the concentration of toluene and time
                                     16-18

-------
of exposure determined its affect on Cytophaga sp. and Azotobacter ehroecocgun.
The lower the concentration,  the longer the contact time needed to produce lethal
effects.   Azotobaeter was oore resistant  than  the  Cytophaga sp.   Bucksteeg
theorized that  toluene  affected the physical and  chemical  constitution of the
cell.   An  alteration in  plaque morphology  ia  two  coliphages  (Tgrt  and T.)
occurred with 1% toluene (Brown, 1957).
     The ability  of toluene to  disrupt  cell membranes led to the use of this
compound as an unmasking  agent in microbial research to  assay  a  variety  of
enzymes (Herzenberg,  1959; Dobrogosz and DeMoss, 1963; Levinthal et al., 1962).
The in vitro assays using toluene have been  used  to make  enzymes  within a cell
accessible  to  exogenous substrates  (Jackson and DeMoss,  1965;  DeSmet et al.,
1978).  Generally, toluene treatment makes the cells permeable to low molecular
weight  compounds  (such  as   deoxynueleoside  triphosphate dNTP)  and  several
macrcmolecules while-remaining impermeable  to proteins larger than approximately
50,000 daltons  (Deutscher,  197U; DeSmet et  al.,  1978).   Several  investigators
have  used  these  findings  to study DNA  replication in  bacteria  (_&•  coli.  ,3.
subtilis).   bacteriophage  (E. eoli.  Tj.),  and diatoms (Cylindrotheca fusifonais)
after treating the organisms with 0.1 to 1% toluene in solution (Miller et al.,
1973; McNicol  and Miller,  1975; Moses and  Richarson,  1970; Matsushita et al.,
1971; Winston and Matsushita, 1975; Sullivan and Valeani, 1976).   Other uses of
toluene  treated  cells are in studying the synthesis of heteroribonucleotides,
SNA, and peptidoglycan  and the  repair synthesis  of DNA  (DeSmet  et al.,  1978;
Moses and Richardson, 1970;  Segev  et  al.,  1973;  Winston and Matsushita, 1975).
Burger (1971) showed  that  toluene-treated  _E. eoli  cells continued DNA replica-
tion,  but   only  in that  chromosomal  region  that  was  about  to  be  replicated
_in vitro.  Toluene-treated cells  can also be used to study the  effects of various
                                     16-19

-------
antibiotics in cell growth and DMA  replication (Hein,  1954;  Burger and Glaaer,
1973).
     Although the  exact  aechanisos of toluene-induced  disaggregration of cell
aenbranea are not known, Jackson and DeMoss (1965) state that the mechanisms fall
into  two  classes:    (1)  a dlsaggregrating (autolytio)  anzyne(s)  perhaps syn-
thesized in the presence of toluene or (2)  a direct denaturation of cell membrane
constituents such as phospholipids;  a condition inhibited by stabilizing factors
such as divalent cations (e.g., Mg).
                                     16-20

-------
                        17.  EFFECTS ON AQUATIC SPECIES




17.1.  GUIDELINES FOR EVALUATION

     Evaluation of the available  information concerning the effects of toluene

on aquatic organisms  oust take into account  several factors.   A primary con-

sideration for evaluation of toxicity test results is toluene's high volatility.

The half-life for volatilization  of toluene  from  a water column one m deep has

been reported to be between approximately 30 minutes (Mackay and Wolkoff,  1973)

and 5 hours (Mackay and Leinonen, 1975).  Benville and Korn (1977) analyzed the

toluene concentration in  test  containers  during a 96 hour static toxicity test

and showed  that the  percentage  of toluene  lost  was  48? by 24  hours,  53* by

48 hours, and greater than 99* by 72 hours.   Korn et al. (1979) reported that

toluene was .lost at a  greater rate from  bioassay containers at 12°C (99? loss by
                                                       •
72 hours) than at 8*C (>99t loss  by 96  hours) or at U*C  (75% loss by 96 hours).

Potera (1975)  found that the observed half-life of toluene in bioassay containers

was 16.5 ± 1.13 hours.  The rate  of volatilization of toluene from water varies

with the amount of mixing, temperature, surface area to  volume ratio, and  other

factors.  Adsorption to sediments and suspended particles may decrease evapora-

tive loss and result in greater persistence of toluene.   Although adsorption nay

lower the  concentration  of  dissolved  toluene in  the  water column,  binding to

sediment and suspended matter may increase the  effective exposure concentration

to benthic and filter-feeding organisms.

     Most  of  the  reported  aquatic  toxicity  studies with  toluene  have  used  a

static exposure technique.   In most cases, the  LC=Q has been calculated on the

basis of initial nominal  (unmeasured)  or  initial  measured concentrations.  The

test  organisms  in  these  static  experiments however,  are exposed  to rapidly
                                      17-1

-------
decreasing toluene concentrations.   Most  of the reported acute static toxicity
studies show little or no change in  the LC.Q value between 24 and 96 hours.  This
lack of change indicates  that most, if not all,  of the mortalities  in these tests
occurred during the first 24 hours when toluene concentrations were highest.  In
contrast, those flow-through studies that reported acute LC-Q values at more than
one exposure period showed that LC_0 values decreased significantly with time.
     Numerous  other  factors  may affect  the  results   of  toxicity  tests  with
toluene.   It  has been shown that the  acute toxicity of toluene is  affected in
some  cases by  temperature  and  salinity  (Section  17.3*)•    These  effects  on
toxicity nay be due to effects on the test organisms (metabolism, uptake, stress,
etc,,), effects on the physioochemical behavior  of toluene (solubility, volatili-
zation, etc.),  or interactive  effects  of both.  For  example,  toluene is less
soluble in saltwater than in freshwater and is both more soluble and more vola-
tile at higher  temperatures.  Laboratory  results may also be influenced by the
loading ratio (gran  organism per liter water); dissolved oxygen concentration;
age, health,  and species  of test organisms; and other exposure conditions, all of
which nay interact to affect the results in an unpredictable manner.
     Prediction of  environmental  effects  from laboratory results oust consider
the influence  of the variables associated  with laboratory tests  and  with the
natural variability  intrinsic  to the  aquatic  environment.    Results of static
acute toxicity tests with volatile compounds such as  toluene nay approximate the
acute toxic effects  that nay occur  in  nature  to the same species  during acci-
dental spills,  because toluene  concentrations rapidly  decrease  In both situa-
tions.   Plow-through acute  toxicity tests  nay provide some  insight  into the
expected effects of a short-tera but constant release of toluene into the aquatic
environment,   as  night  occur   in  areas  receiving  refinery  or   petrochemical
effluents.  Neither static nor flow-through  acute toxicity tests can predict the
                                      17-2

-------
received refinery  and  petrochemical effluents,  the effects of  such low  level
chronic pollution in natural aquatic habitats are unknown.

17.3.  LABORATORY STUDIES OP TOXECITY

17.3.1.  Lethal Effects.   The  lethal effects of toluene have been reported  for
numerous species of freshwater and marine fish and invertebrates.   The acute LC-0
for 22  species  of freshwater and marine  animals ranged between 3 and  1180  ppm
(Table 17-1).  All but four of the LC-0 values were determined in static  tests.
Of the four flow-through LC-. tests, only two utilized measured  toluene concen-
trations.   Mo  information was  found  concerning  the  effects  of  toluene   on
amphibians.

     17.3.1.1*    PRESHWAT2H  PISH — The  earliest  investigation   of  toluene
toxicity to freshwater  fish was conducted by Shelford et  al.  (1917). who  reported
that one hour of exposure to 61 to 65 mg/i toluene was lethal to orange spotted
sunfish (Lapemis hymilia).  This test  was conducted under static conditions at
20*C in freshwater of unspecified temperature and composition.
     Oegani (1943) conducted static  toxicity tests with  15  day old lake  trout
(Salvelinus namayeush)  fry and  1.5  g moaquitofish (Gambusia  affinis)  in  dechlor-
inated capwater at 17 to 18°C using 3 to 5 fish  per container (2 liter  volume).
The  time  to death  at  a nominal exposure concentration of  90  ppm  toluene  was
390 minutes for trout  and  47 minutes for  oosquitofish.  The  time to  death of
trout fry exposed to 50 ppm toluene was 253 minutes.
     Wallen et al.  (1957)  also conducted  static acute  toluene  toxicity  tests
with female mosquitofish (Gambusia affinis)  of unspecified size in  turbid pond
water  (150  ppm  turbidity as measured  by Jackson turbidimeter,  pH 7.5  to 3.5,
                                      17-4

-------
:nronic effects  of low level  toluene  pollution.    In  addition,  acute  toxicity
sests usually determine the concentration of toxicant which kills or affects  50?
of the test population.  LC~Q or EC-0 values,  therefore, represent concentrations
which are toxic to half the population and provide no information concerning  the
concentration which will have  no  adverse effects  during acute or chronic expo-
sure.

17.2.  EFFECTS OF ACCIDENTAL SPILLS
     No information  was found  concerning the effects of  accidental spills of
toluene per se  on aquatic  organisms; however,  toluene  is  one of the major
aromatic components of  crude oil  and such refined petroleum products as diesel
fuel, gasoline, and jet  fuel, all of which have been released in large amounts to
the aquatic environment during spills.
     The long term ecological impact of accidental spills of toluene is  unknown.
In spill situations,  most of the toluene would probably evaporate rapidly.   For
instance,  McAuliffe (1976) reported  that toluene, benzene, and xylene  could be
found in the water under crude  oil slicks only during the first 30 minutes after
spillage.    In  contrast, spills in areas of shallow water and restricted water
flow, such as in  certain portions  of estuaries,  lakes,  and streams,  have a
greater potential  for  causing  acute mortalities  because  the toluene may reach
higher dissolved  concentrations and may persist  longer through adsorption to
sediments.  Toluene is an acute toxic  to many aquatic species at concentrations
veil below its  water solubility, and lethal exposure may well occur during spills
in shallow water.
     Although  chronic,  low-level  pollution  by  toluene has  been reported  in a
Japanese river (Funasoka et al., 1975)  and a harbor (Ogate and Miyake, 1973) that
                                      17-3

-------
                        T»W-6 11.1



Acute ToKlolty of Toluene to Plate and  Aquatic  Invertebratea
Spec lea
FISH
Frealiwater
Ide

(teuclacua Idua
aelanotua)



Hoaqulloflah
(Oaabuala afflnla)

_. Ooldflah
-4 (Caraaatua euratua)
VJI
Uoldflah
(Caraaalua auratua)


Qoldflah
(Caraaalua auratua)









Fathead alnnou
(Plaaphalea propel aa)


Fathead alnnow
(Plaephalea prooelaa)


Teap. Type 2* It
(*C) Teat


20»t SU

20.1 SU




17 to SU 1310
22

20»l SH 58


25 SU 57.7
(18.9
to
68.8)
17 to FH 41.6
19 (32.0
to
71.7)







25 SU *6.3
(37.0
to
59.*)
25 SU 56.0
(1*.7
to
67.1)
I.C50
18 n 72 b


70

*22




1260


	 	


57.7
(18.9
to
68.8)
27.6 25.3
(21.6 (20.1
to to
36.0) 31.9)







*6.1
(37.0
to
59.*)
56.0
(16.7
to
67.1)
96 h


...

	




1180


	


57.7
(*8.9
to
68.8)
22.80
(17.1
to
30.0)







3*. 3
(22.8
to
*5.9)
*2.3
(33.5
to
53.5)
Ho Effect Reported
Concentration Concentration Coauenta Reference
Unlta


52 atg/t Lab 1, lOOf kill at Juhnke and
88 ag/t. Ludeaann. 1978
365 Lab 2, 1001 kill at
*70 ag/t.
Teata were auppoaedly
oonduoted under
Identical conditions.
560 ppa Teata were oonduoted Hallen et al..
In aerated turbid 1957
pond uater.
	 ag/l Teat uaa conducted Bridle et al..
In tap uater (|>ll 1979
7.8)
— ag/l Teat uaa oonduoted Pickering and
In aoft uater. Henderaon, 1966


— ppa Teata were oonduoted Brenntaan et al.,
under flow-through 1976
to eondlttona In aoft
deoblorlnated tap
uater. The teat uaa
continued to 720 h
(30 d) at uhloh
tlae the LC (and
951 confidence Inter-
val) uaa 14.6 (10.7
to 20.0) ppa.
	 ag/l Teata were conducted Pickering and
In aoft water. Henderaon, 1966


	 ag/t Teata were conducted
In hard walor.



-------
TABU ll-t (ooot.)
Spool aa
aiueglll aunrtob
(tepcmla aaprooMrua)


eiuegtll aunriah
(Lepoylq lUorooMrual


Uupplaa

-------
Species
Pink saloon
(Oncorhimchua Mautoh)








Teap. Type 2* h
(*C) Teat
t SH



6 SH


12 SH


tc
«B b *°72 to 96 b
	 6.M
(5.71
to
7. IB)
	 7.6J
to
8.«B)
8.09
to
8.78)
Ho Effect Reported
Conoentratlon Concentration CoMenta Reference
Unita
|ii/l Teata were conducted Korn et al . , 1979
ultb sal son fry
cool luted to 28°/oo
aeawater at dlf-
	 ferent temperatures.


	


Striped baaa
  (Horono aanatllla)
                            16
Sheepaliead alnnou          HR
  (Cyprloodoti »arlegatua)
         SH   7.}
                                   SU   >277    >277
7.1
                                      >277
             277
|ift/i       Teat* tier* conducted     Beavllle and
           In 25°/oo aallnlty         lorP. 1971
           aaawater with juvenile
           flab.
ppa        Data only olted In       U.S. SPA.  1976
           U.S. IH, 1980.
IHVEHTEDHUE3

frealmater

Water flea
          Teat waa conduoted
                                      with dlatllled
                                      water.
                                                                 •g/i       Teat waa  conducted
                                                                            with artiriolal  aea-
                                                                            water.
                                    LeBlano,  I960
                                    Brlngoann and Kubn,
                                       1959

                                    Berry and
                                      BraMter.  1977
                                                               Price et al..  197*

-------
TABU 17-1 (ooat.)
Speoloa
Bay aliriap
(Crago franqlauorui))



Shrlap
(Eualiis app.)










Oraaa ahrlap
(Pagieajoqataa puglo)













Qraaa alirlap
(Paoae«oiieti»j puglo)






Taap. Typa 24 It 18 b
(•« Taat
16 SH 12
(10
to
13)

1 SH 	



6 SH 	



12 SH



20 SH 20.2
(16.)
to
22.5)
20 SH 17.2
(11.9
to
19.1)
10 SH 37.6
(35.0
to
10 SH 36.1
(36.1
to
39.6)
20 SH 30.6
(21.3
to
11.5)
20 SH 25.6
(16.0
to
31.6)
M72 h 96 b
*.|
(}.t
to
9.6)

21.1
(19.5
to
2).S)
20.2
(17.9
to
22.6)
11.7
(13.1
to
16.6)
... ...



... ...



... ...


... ...



... ...


-
.-_ ...



No Bffaot B*port«4
Conoantratlon Coooaotrttloa Coamaat* B*f*rano«
Unit* .
— |it/t Taata Mera oooduoteiJ Banvili* ami
Mith 25°/oo Korn, 1971


••Unity •aaiMtar.
lift/t Corn «t •!., 1919


,
|U/ft Korn at •!., 1919



H»/l Korn at •!., 1919



•ft/ft aOulta at !5°/oo Potar*. 1975
••Unity.


— »g/i Adult* »t 2S°/oo Potara, 1975
••Unity.


•f/i Adults at !5°/oo Potara. 1975
••Unity.
•.
•«/! Adult* at 25°/oo Potar*. 1975
••Unity.


HH UrvM *t l5°/oo Potara, 1975
••Unity.


•tg/t Larvaa at 25 /oo Potara, 1975
••Unity.



-------
                                                                         TaBLB 17-1 (cent.)
vO
Spec lea
Gi'dflS stiriiip
(Palaeaonotoa pugto)
Hyal
NB

HI



Ni

M




20



20
to
21.5
LC No Bffeot Reported
Typa 24 b 48 h 72 b 96 b Concentration Conoantratlon Coananta •efaranoa
Taat Uotta
3d 	 	 ... ... a, 5 ... *g/t — - lleff at al 1976

SU 64.6 56.} 56.1 56.] 27.7 ppa Data only oltad In U.S. BTA, 1978
(50.9 C43.0 (4J.O (»J.O U.S. BPa. 1980.
to to to to
62.5) 70.6) 70.6) 70.8)
FU — 170 	 26 — Kg/I Larvae. Cat dwell at al.,
1976
SM ?a 2 /t l5°/nn nail Ito B 1 IO.71

(19-8
to
30.2)

(52.0
to
100.5)
SU — 1050 — — 	 a«/t Larvaa. Legore, 197*


     Tcnp. * tenperaturei  h •  hour;  d B  day| MM  * not  reported.

-------
methyl orange alkalinity < 100 ppa, temperature 17 to 22*C).  For these toxioity

testa,  ten fish  per  concentration  were added  immediately  after addition  of

different amounts of toluene to the bioassay containers  (15 liter volume).   The

test solutions  were constantly aerated and mortalities were  recorded  daily for

96 hours.  The  21, 43,  and 96 hour LC^Q values  were 13*0, 1260,  and  1180  ppm,

respectively.   These values  were  estimated on the basis of the  initial nominal

toluene concentrations.  Because the test containers were vigorously aerated, it

is probable that the actual toluene concentrations decreased rapidly during the

exposure period.  It was also  observed that the turbidity  of the  toluene solu-

tions decreased from 150 to 100 ppm over the 96 hour  exposure  period.  At concen-

trations of 560 ppm and  below,  all fish appeared to be unaffected.  The  remainder

of the test results are presented below:


          Concentration                  Percent Mortality (M * 10?.
              (ppm)                         24 h      43 h     96  h

              < 560                           0        0        0
              T,000                          20       30      40
              1,300                          30       30      100
              3,200                          80       90      100
              5,600                         100       100      100
             10,000                         100       100      100

     Pickering  and Henderson  (1966}  investigated the acute toxicity of toluene

to   fathead   minnows    (Plmephales   promelas),   bluegill   aunfish   (Lepomis

macroehirua), goldfish  (Carassius auratus), and  guppies  (Labiates  retieulatus

s Poecilia reticulata).  The length and weight of the fish used for testing  were

3.3 to 6.4 ca and 1 to  2 g for the first 3  species and 1.9 to 2.5 cm and 0.1 to

0.2 g for guppies.  Each test utilized 10  fish per  concentration or control in

either 10 1 (minnows,  sunfish, goldfish) or 2  i  (guppies) of soft water (pH  7.5,

alkalinity 13 og/1, ETTA hardness 20 mg/l) made by mixing 5 parts of hard natural

spring water  with 95  parts  of distilled  deninerallzed water.    In  addition,

fathead ainnows were tested (10 fish/concentration) in the hard spring water (pH
                                      17-10

-------
3.2, alkalinity 300 mg/i, EDTA  hardness 360 mg/i)  to investigate the effect  of
these water  characteristics  on toluene toxicity.   All tests were conducted  at
25*C.  The test solutions were not aerated, and dissolved oxygen concentrations
were measured but not  reported.   The 24,  48, and 96 hour LC_Q values and  their
95 J confidence limits,  as calculated by the moving average-angle method of Harris
(1959)  using   initial  nominal  toluene   concentrations,   are  presented   in
Table 17-1. The 96 hour LC-g  values  increased in the order of bluegill  sunfiah
(2U.O mg/1), fathead minnow (34.3 mg/1  in soft water,  42.3 mg/i in hard  water),
goldfish  (57.7  mg/1),  and guppies (59.3 mg/l).   The  96 hour  LC^Q  for  fathead
minnows in soft water was not significantly different  from the 96 hour LC-fl  for
the same species in hard water.  Comparison of the  95$ confidence limits of  the
96 hour LCe0 values in soft  water for the 4 species indicated  that the LC~0
values were  not significantly  different  between fathead minnows  and bluegill
sunfish or between goldfish  and guppies.   Both fathead minnows  and bluegill
sunfish had  96 hour LC-Q  values significantly lover than goldfish and guppies.
The 96 hour LC-. was not significantly different  from the 24 hour LC-. for any of
the species  tested in soft water.
     Static acute LC.Q values for bluegill sunfish have also been reported by  the
O.S. EPA (1978,  cited in O.S. EPA, 1980). The 24, 48, 72,  and  96 hour  LC5Q values
were 16.6, 13«3> 12.7, and 12.7 ppm, respectively.  No effects were  observed at
or below  10  ppm.  Additional  information  concerning these tests was not avail-
able.
     Berry (1980) mentioned that the upper  non-lethal  tolaene  concentration  for
bluegill sunfish (Lepomis maeroehirus)  was  3.7 mg/1.  The duration  of exposure
and lowest lethal concentration were not specified.
     Bridie  et  al.  (1979) and  Brenniaan et al.  (1976)  also  investigated  the
acute toxicity  of  toluene to goldfish.   Bridie  et al. (1979) used  goldfish of
                                      17-11

-------
slightly greater  weight (mean 3*3 S,  range 2.3  to 4.3 g)  than Pickering  and
                                                                       ; .  .5 ij «i j7 •;

Henderson (1966) to determine the static 24 hour LC_Q.  In this test,  6  fish per


concentration were  exposed without  aeration to  a toluene  series  in  25  I  of


tapwater that had a pH of 7.8 and contained  (in milligrams per liter):  Cl~ = 65;


H02"s 0; M03" * 4; SO^2" a 35; P0ft3" a 0.15; HC03" s 25; SiOj a 25; MH^* * 0;  Fe s


0.05;  MB s  0;  Ca2* a  100; Mg2"* s  3;  and  alkali as Ha*  a 30.   The toluene


concentration was measured at  the beginning and end of  the test.  The 24  hour


LC-Q, obtained by interpolation  from a graph of the logarithm  of concentration


versus percent mortality, was  58  mg/l, which is  the same  as  the  24 hour  LC-Q for


goldfish reported by Pickering and Henderson (1966).


     Much larger goldfish (length,  13 to 20  cm;  weight, 20 to 30 g) were used by


Brenniman et al.  (1976)  to determine the acute toxicity of  toluene under  flow-


through exposure conditions.   The LC.Q values were determined by exposing 6  fish


per 38 1 aquarium to three toluene concentrations  (and a control) in  dechlorin-


ated soft tapwater (methyl orange alkalinity s 34  ppm as CaCO-;  phenolphthaline


alkalinity  = 37 ppo  as CaCO-;  total  hardness a  30 ppm  as  CaCO-;  calcium a


21.6 ppm; magnesium a  5.3 ppo; SiO, a 3 ppm; chromium a <0.002 ppm; pH  7.0  * 0.3;


temperature  17  to 194C) at a flow  rate calibrated to  renew  the test chamber


volumes every 1.5 hours.   This flow rate was  sufficient to maintain dissolved


oxygen concentrations at >7 ppm and  to maintain  constant  toluene concentrations,


as measured by continuous monitoring at 210 am by spectrophotometer.  The 24, 48,


72, and  96  hour LC_Q  values,  calculated'by probit  analysis,  were 41.6,  27.6,


25.3, and 22.3 ppm, respectively.    Although most of  the  fish died during the


first 24 hours, the 96 hour LC-Q was significantly lower than  the 24  hour  LC-Q.


These  LC.Q  values  are somewhat lower  than  those  reported by  Pickering  and


Henderson  (1966)  and  Bridie  et al.  (1979) for  goldfish  tested under  static


conditions.   In addition,  the LCQ  values  reported  by Pickering and Henderson
                                     17-12

-------
(1966) did not decrease significantly from 24 to 96 hours.   These differences are

probably due to a rapid decline in the  toluene concentration through evaporation

in the static tests in contrast to constant toluene concentrations  in  the  flow-

through  test.   Brenniman  et al.  (1976) continued  their flow-through  exposure

test  for 30 days,  at which time  the  LC.Q had  decreased  to  11.6  ppm.   These

results  emphasize the fact that static acute toxicity tests may seriously under-

estimate the  acute  toxicity of toluene  and  that chronic  effects  may  occur  at

concentrations  which  are  considerably lower  than  those  which  cause  acute

effects.

     Juhnke  and Ludeaann   (1978)  investigated  the  static acute  toxicity  of

toluene to the ide (Leueiseus idus melanotus)  using comparable  procedures in two

different  laboratories.    The  toxicity  tests  were conducted  according to  the

methods  of Mann (1975,  1976),  i.e.  48  hours  of exposure  with  10  fish (1.5  *

C.3 g, 5 to 7 cm) per concentration in tapwater (pH 7-3,  hardness 268 + 54  mg/1)

at 20 *  1*C.  The 48 hour  LCQ  (OJ mortality), LC-0, and LC1QO  (100$  mortality)

values determined at each  laboratory were as  follows:


                                  48 Hour Lethal  Concentration Values  (ng/g.)

                                       LC0             LC50            LC100


          Laboratory 1                 52             70               88
          Laboratory 2                 365             422              470

     Although  it  was stated  that these tests were conducted under  comparable

conditions, the results were clearly different.  The concentration that caused no

deaths of  fish in laboratory  2  (365  mg/1) was  about 4  times higher  than  the

concentration  that killed  all  fish in laboratory 1 (88 mg/i).   The authors did

not discuss the reasons for  the difference in  results.

     Slooff (1978, 1979) reported, that the 48  hour  LC_Q of toluene  to sebrafish

(Brachydanio  perio)  was 25  to 27 mg/1.   This test  was  conducted  under  flow-
                                     17-13

-------
through (6  i/hr)  exposure conditions using  10 fish  per  concentration in  10 i
sealed aquaria and dechlorinated tapwatar (20 * 1*C;  pH 3.0 * 0.2; hardness T80 *
T.3 as/I as CaCOj).
     The acuta effects of toluene on parasitized and unparasitized coho  saloon
(Oncornynchua Icisutefa) fry were studied by Moles  (1980).   The parasitized  fry
were artificially infected before toluene exposure with glochidial larvae  of the
freshwater mussel, Anodonta oregonensis.   Toluene exposure was conducted under
flow-through  conditions,  using  five measured  concentrations and  20 fish  per
concentration.  The teoperature  and  characteristics  of the water used were  not
specified.    The  96 hour  LC»g,  as  calculated  by  probit  analysis,   was
9.36 uZ/i (ppn) for unparasitized fish and 3.08 ui/i  for fish  parasitized  with a
mean number of 69 glochidia per fish.  The LC-Q values were  significantly  dif-
ferent, indicating that parasitized  fish  were less resistant to the  effects of
toluene.
     Stoss  and  Raines (1978)  investigated the  effects  of static exposure  to
toluene on the survival of fertilized eggs and newly  hatched  fry of the nedaka,
Qryzias latipes.  Groups of ten eggs or fry were exposed in  loosely capped vials
containing 20 mi  of the  exposure medium (synthetic  rearing  medium:   pH  7.6;
akalinity 99 mg/i as CaCO-) at 23 * 2°C.  Toluene concentrations were prepared by
diluting a water-soluble extract  of  10 ai toluene/I medium.   In order to  deter-
mine the sensitivity of different stages of embryo  development,  tests  were begun
with eggs of various  ages after fertilization.  Tests with fry were all begun
within  24 hours  after hatching,   nominal, initial toluene  concentrations  were
used for calculation  of LC-Q  values.  The LC~Q  values for  embryos varied  with
length of exposure and the age at time of  introduction.   The mean 24, 48,  and
96 hour LC-_ values for all ages of embryos were 30, 63, and 54 mg/i.  The range
of E.Cj0 values was 20 to  135  mg/Z at 48 hours and  23 to 110 mg/i at 96 hours
                                     17-14

-------
(Stoss, personal communication).   Early (j<3.5 hours  old)  and late  (£192  hours



old) embryos had  significantly lower LC_Q  values  at each exposure  period than



embryos of  intermediate age  at tine  of introduction.    The  24, 48,  96,  and



168 hour LC-. values for fry were 44, 36, 32, and  23  mg/i, respectively  (Stoss,



personal communication).   These values  were lower  than  the  mean embryo  1C,-,,



values for the same exposure period; however, fry  LC_Q values  were greater than



the LCcQ values for the susceptible early and late stage embryos  and lower than



most of the LC_Q values for intermediate stage embryos.  Stoss and Haines (1978)



also investigated the sublethal effects of toluene on hatching time and induction



of  developmental  abnormalities.    These  sublethal  effects  are discussed  in



Section 17.3.2.U







     17.3.^.2.   MABINE  FISH — Morrow  et  al.   (1975)  studied  the  effects  of



toluene on young coho salmon (Oneorhynehus  ieisuteh)  that had been acclimated to



artificial seawater (30 °/oo (parts per  thousand)  salinity;  8*C;  pH  3.1) for up



to 2 weeks.   A static exposure technique was used  in which toluene was  added



directly to exposure  aquaria  containing fish and 73  i of  seawater (_<1 g fish/2,



water) to give nominal concentrations of 0,  1,  10,  50, and  100  ppm toluene.  The



average weight of  the fish used during triplicate  tests  ranged from  5 g/fish in



the fall of the year to  nearly 40 g/fish  in  the spring.   The  mortality data



provided in the paper are given below:





                                                     Percent  Mortality
Concentration No. of
(pom)
0
1
10
50
100
Tests
3
3
3
1
3
No. of Fish per
Concentration
30
30
30
10
30

0 h
0
0
0
0
0

24 h
7
7
0
90
93

48 h
7
7
0
100
100

72 h
13
13
3
100
100

96 h
13
13
10
100
100
     Using 2x2 contingency table analysis, the authors determined that mortal-
                                      17-15

-------
ity was significantly different from control mortality at 50 and 100 ppm,  but not
at 10 and  1  ppm.   The reasons for control mortality were  not  discussed  but may
have been due to salinity stress; the authors mentioned  that smaller fish  adapted
less easily  to seawater than  larger  fish.   In order to incorporate  these  data
into Table 17-1, the LC-.  values were calculated as the geometric mean of 50 ppm
(mortality 3  100$) and  10 ppm  (mortality corrected  for control mortality «  0$).
This value for the 46, 72, and 96 hour LC-Q was 22.4 ppm. The authors  state  that
fish exposed to 50  and 100 ppm toluene exhibited  rapid,  violent, and  erratic
swimming within 15 to 20  minutes,  followed by "coughing,* loss  of equilibrium,
and death of  most  fish  within  the  first few hours.
     The acute  effects  of toluene  on another  species of salmon in  seawater  were
investigated  by Corn  et al.  (1979).  Pink salmon  (Onefaorhynehus gorbuscna)  fry,
weighing about 0.35 g each,  were acclimated to natural  seawater (6  to  3*C; 26 to
28 °/oo salinity).  Groups  of fry were then acclimated to 4,  8, or 12*C for
determination of  the 96 hour LC__ at  3  temperatures.    Each toxicity test was
conducted with 10 to 15 fry per concentration (<1 g fisn/i water).   Fish  were
added to the  test  containers after addition of an appropriate  amount  of  toluene
in water stock  solution.  The  containers were not aerated  until after the first
•48 hours of exposure  to  minimize evaporative loss.  Even so, analysis showed  that
toluene decreased  to  nondetectable levels by 72 hours at 12°C and by 96 hours at
8°C and to 25} of  the  initial concentration by 96 hours at 4*C.   The 96 hour  LC.Q
values,  estimated by  probit  analysis using initial  measured concentrations
expressed as microliters per liter toluene (s ppm),  were 6.4  at 4*C, 7.6  at  3*C,
and 8.1 at 12°C.  The 95* confidence intervals of the 4*C and 12*C LC-Q  values did
not overlap, indicating that temperature affected  the toxicity of toluene. There
was no significant difference  between  24 and  96 hour LC,Q  values because almost
all deaths  occurred  within the first 24 hours  of exposure.   The  effect  of
                                     17-16

-------
temperature nay have been caused by greater sensitivity of the  fish  at  the  lower



temperature and/or by the longer persistence of toluene at the lower  temperature.



     Thomas and  Rice (1979) used  the previously described  techniques of  Korn



et al.  (1979)  to determine  the static  24 hour LC_Q  of toluene with  somewhat



larger (1 to 2  g, 4.5 to 5.5 cm) pink salmon fry at 12°C in seawater.   The 24  hour



LC5Q (and 95$  confidence interval) was 5.4 (4.4 to 6.5)  ppm,  which is signifi-



cantly different from the 96 hour LC-. value of 3.1  ppm (7.5  to 8.8)  obtained



with younger fry at  12°C by Korn et al. (1979).   The reasons  for this difference



cannot be determined from  the information  provided.



     A similar static exposure technique was used by Benville and Korn  (1977)  in



their study of the  acute toxicity of  toluene to  juvenile striped  bass (Morone



saxatilis)  in  seawater  (25 °/oo  salinity, 16*C).   The  test  was  initiated  by



adding different amounts of saturated toluene in water stock solution to the test



aquaria, each  containing 10  fish.   Toluene concentrations were  measured at the



beginning of the test and every 21  hours  thereafter  to  the end  of the test.   The



24 and  96 hour LC5Q values  were  both 7.3  i£/l  (ppm).  Almost  all mortalities



occurred  within  6  hours.   The average  percent loss of  toluene   was  40?  by



2U hours, 53* by 48 hours, and  >99J  by 72  hours.



     The  only  other  information  available  concerning  the  lethal effects  of



toluene on marine fish is  provided in  a U.S. EPA unpublished study  (1978,  cited



in U.S.  EPA,   1930).   The 24,  48,  and  96 hour static  acute  LC-0 values  for



sheepshead minnows  (Cyprinodon  variegatua) were all reported to be  greater than



277 ppm and less  than 485 ppm.  The no-effect  concentration  was 277  ppm.   Mo



other information concerning these results was available.







     17.3.1.3.      FRESHWATER    INVERTEBRATES  — Berry   and    Brammer   (1977)



investigated the acute static toxicity of toluene to fourth-instar larvae  of the
                                      17-17

-------
mosquito,  Aedea  aegygti.   The  larvae  were reared  from  eggs  and  tasted' 'in
distilled water at 25 ± 1*C.  For each of four replicate tests, duplicate groups
of 20 larvae each were exposed to 14  toluene concentrations. The mortality  data
were pooled  (160  larvae/concentration)  to calculate the 24 hour LC__ by probitt
analysis.    Initial  exposure concentrations were  determined  by gas-liquid
chrooatography.  The 24 hour LC-- (* standard error) was 21.52 > (7.16 ppm.  The
highest  concentration (*  standard  error)  that  caused  no mortality  over the
24 hour exposure period was 9.95 * 1.30 ppm.
     Berry (1980) mentioned that the upper non-lethal toluene concentration for
crayfish  (Orconetes rustieus) was  104.4 mg/fc.    The duration of  exposure and
lowest lethal concentration were not specified.
     The acute toxicity of toluene has also been  determined with the cladoceran,.
Daphnia aagna, by Brlngmann and Sunn (1959) and by LeBlane-M980).   Bringmann and
Sunn (1959) reported a 48 hour LC_Q of 60 mg/i.  This static test  was conducted
with first instar  (<24 hours  old) Daohnia magna in natural freshwater  (pH  7.5;
hardness 214 mg/i) at 23*C.
     LeBlanc  (I960)  conducted static  tests with first  instar (<24 hours  old)
animals in deionized well water reconstituted to  a total  hardness of 72  * 6  mg/1
as CaCO- and a pH of 7.0 > 0.2 at 22 * 1*C.  Three groups of 5 daphnids each  were
exposed to each of at least five  toluene concentrations and uncontaminated water
in covered 250 mi beakers containing 150  mi of test  solution.  The 24 and 48  hour
LC-0 values (and 95} confidence intervals), based on initial nominal concentra-
tions, were both  310  (240  to  420) mg/1.   The "no discernible effect concentra-
tion" was 28 mg/i.  This LC5Q  value is considerably  higher  than that reported  by
Brlngaann and Kuhn (1959).  The reasons for this  difference cannot  be determined
from the data provided.
                                     17-18

-------
     17. 3. 1.4.    MAfllNE  INVESTEBRATES — Price  et al.  (197*)  determined  the



static  24 hour  LC-0 of  toluene to  brine  shrimp  nauplii  (Artemia  salina)  in



artificial  seawater  (27.87 g/i  MaCl;   1.36 g/i  CaSOu;   3.17 g/i  MgSO^^HjO;



8.42 g/4 MgCl2;  0.79 g/i  KC1; 0.16 g/i Mgflr2«6H20) at 24.5°C.  Groups of 30 to 50



newly hatched brine shrimp were exposed to  5 toluene concentrations  in  100 mi



seawater.  The estimated 24 hour LC-Q, based  on  initial nominal  concentrations,



was 33 mg/i.



     Bay shrimp (Crago franeiseorum) were shown by Benville and Korn (1977) to be



somewhat more sensitive  to toluene.   The 24 hour static  LC-Q, determined  in



natural seawater (25 °/oo salinity)  at 16°C, was  12 ui/i (ppm).  The  96  hour LC_.



for this species (4.3 uA/i) was significantly lower than  the  24  hour LC--  (non-



overlapping 95) confidence  limits).   These  values were calculated from initial



measured toluene concentrations.



     Korn et al.  (1979)  investigated the  effects of  temperature  on  the  acute



toxicity of toluene to another genus of shrimp  (Sualus  spp.).  Shrimp (0.8 g;



6 cm long)  were acclimated to the  test temperatures  in  natural 26 to 28 °/oo



salinity seawater for 4 days and then exposed in  groups of 10  to  15 animals to a



series  of toluene  concentrations,  prepared  by  dilution of  a. saturated  water



solution.  The tissue loading  in the test containers was  less than  1 g/l.   Mea-



surement by (TV spectrophotometry showed  that  toluene concentrations  decreased to



nondetectable levels by 72 hours at  12°C and  by  96 hours  at 8°C, and  to  25 J of



the initial concentration  by 96 hours at 4*C.   The 96 hour LC-. values,  calcu-



lated  from  initial  measured   toluene concentrations, were  21.4 (ii/1 at  4*C,
20.2 ui/i at 8*C, and 14.7 uVl at 128C.  The 96 hour LC5Q values at 4*C and 8'C



were not  significantly different  (overlapping 95$ fiducial  limits) from  each



other, but both  were  significantly higher "than the 96 hour LC-.  at 12°C.   This



trend of greater toxicity at higher temperatures was opposite to the relationship
                                     17-19

-------
 found by these authors  for pink saloon fry  (Section 17.3« 1.2.) and  by Potera
 (1975)  for grass shrimp (see below).  The reasons for this difference could not
 be established but may have been due to some combination of effects of tempera-
 ture on persistence of  toluene in water, altered  toluene  uptake and metabolic
 rates,  and possible interaction of toluene tozicity and temperature stress.  The-
 authors concluded  that  temperature  affected the  toxieity of toluene  to these
 species of shrimp  and saloon  but that it would  be  impossible to  predict the
 effects of temperature change on the toxicity of toluene to other species.
      Potera  (1975)  investigated  the  effects  of  temperature  (10  and  20*C),
 salinity (15  and 25  °/oo),  and life stage  (larvae  and adults) on  the static
 24 hour LC.Q of toluene to  the grass shrimp, Palaemonetes pugio.   The 24 hour
 LC_Q values,  based on  measured initial  concentrations,  ranged  from  17.2  to
 38.1 ag/l.
      As shown by  overlapping 95} confidence intervals (Table 12-1), there was no
 significant difference  in  LC_Q values between  adults and  larvae at  the same
 salinity and  temperature, or between adults tested at the same temperature but at
 different salinities.   The  LC-- was  significantly lower at 20 *C, however,  than
 at 10 *C for adults tested  at either 15 °/oo or 25 °/oo  salinity.   The time to
 produce narcosis  in at least 50* of adult shrimp at 20*C was less than 30 minutes
 at initial exposure concentrations of  19.3 mg/i and greater.   Recovery of more
 than 90% of exposed shrimp could occur if shrimp were transferred to clean water
 after exposure to up  to 30  ng/i for  30  minutes.
      Potera (1975) also determined  the 24 hour LC-.  for  the copepod,  Mitocra
 spinipes.  at  a temperature  of 20*C  and at  salinities - of  either  15 °/oo  or
 25 °/oo.  The  24 hour LC-Q  values  from  replicate tests were  24.4 at  15 °/oo
 salinity and 74.2 mg/i  at  25 °/oo salinity.   These values were  significantly
»
 different (non-overlapping  95J confidence intervals).  Potera  (1975)  suggested
                                      17-20

-------
that the lower salinity may have stressed the copepods, resulting in a lower LCe0
value.
     Neff et  al.  (7976)  also determined the  static  96 hour LC_Q of  toluene  to
grass shrimp, Palaeaonetes ougio.  This value, based  on  initial  nominal  concen-
trations, was 9*5 ag/i, which is lower than the 24 hour  LC-. values reported  by
Potera (1975).
     Caldwell  et  al.  (1976)  determined the  48 and 96 hour LC_Q of  toluene  to
larval stages  of  the  dungeness  crab (Cancer magister) under flow-through  expo-
sure conditions.  The IS  and 96 hour LC_Q values were 170  and 28 mg/i,  respec-
tively.
     Static  acute LC_0 values  for oysid  shrimp (Myaidopsis  bahia) have  been
reported by  the U.S.  EPA (1978, cited  in O.S. SPA,  1980).  The  24 and 48  to
96 hour  LC_0 values  were 64.3  and 56.3 ppo,  respectively.   The "no  effect"
concentration was 27.7 ppa.  Additional information concerning this test was not
available.
     The  48 hour  static  LC-Q  of  toluene  to  larvae  of  the  Pacific oyster
(Crasscstrea gigas) was reported to be 1050 mg/i  (Leflore, 1974).  This  test was
conducted with  filtered  seawater (25.3 to  30.8  °/oo  salinity) at  20 to 21.5*C
using 30,000 larvae per exposure concentration.

17.3.2.  Sublethal Effects.

     17.3*2.1.   FISH — Very  little information is  available  concerning the
sublethal effects of toluene exposure on fish. Morrow et al. (1975) studied the
effects of several aromatic hydrocarbons,  including toluene, on the levels of Ma*
and fC*  in  the blood' of young  coho salmon  (Oneorhynehus kisuteh)  in seawater.
Static exposure to 30 ppm toluene caused a small increase in these blood  cations,
                                      17-21

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reaching a <*»*4**u* at about two hours after beginning exposure.   The Ma  concen-
tration returned to the control level by three hours.  Blood  EC* decreased after
two hours but was still elevated at  four  hours,  the last sampling  period.   The
toluene  exposure  concentration   of  30  PPn  was  sufficient   to   cause  some
mortalities  and  behavioral  effects.    The authors suggested  that  toluene
increased membrane permeability, particularly in the gills.  In the hypertonic
seawater medium, this  change  would result in ion influx  and  water loss  in the
fish, perhaps accounting for  the initial rise in blood ion  concentration.
     Brenniman et al.  (1979)  conducted a series of  experiments  to determine the
effects of toluene exposure on blood gas physiology,  hippuric acid content, and
histopathology of goldfish (Carassius auratus).  The  fish used  in these experi-
ments were  exposed to two or  more  toluene  concentrations under  flow-through
conditions using dechlorinated tapwater.
     For the pathology study, groups of six  fish were exposed for up to 30 days
to 0, 5, 10, and 21 ppm toluene (Brennlman et al.,  1979).   Ho  gross  or  micro-
scopic lesions were observed  in fish during the first week of  exposure.   After
the first week, ascites developed in 3 fish at 21  ppm and in 2 fish at 10 ppm.  In
exposed fish that survived 15  to 30 days, about 50$ had a white epidermal exudate
of unknown origin,  and some fish at all toluene concentrations had gross lasions
in gill,  liver,  or gall bladder.  Excessive mucus production in gills occurred in
all fish at 21 and 10 ppm and in 50J of the  fish at 5 ppm.  Microscopic lesions
were found in gills (fusion), liver (decreased cytoplasm!c nuclear ratio), and
kidney (tubular vacuolizatlon)  of many exposed  fish but not in control fish.
Exposed fish did not  eat  food and  had livers which were  paler  and smaller than
control fish.
     For the blood gas study,  groups of 3 or 4 fish were exposed for 4 hours to 0,
60, or 30 ppm toluene  (Brenniman et al.,  1979).   The blood samples were analyzed
                                     17-22

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for pH,  percent oxygen saturation, partial pressures of carbon dioxide (p»  )  and
                                                                        C02
oxygen (p. ), and bicarbonate.  The results are presented below:
Mean Values
Toluene Cone.
(ppm)
0
60
30
•\
*2.33a
16.253
15.63*
'CO,
11.50
23.25a
19.27
PH
7.56
6.90a
6.96a
O.-Saturation
U8.67
27.00a
20.33a
Bicarbonate
9.33
5.10
M.17a
  P < 0.05 when compared to control.

     Toluene exposure  caused significant  changes  in all parameters  (Brenniaan
et al., 1979).   The authors suggested that the decreased p. ,  increased pM ,  and
                                                         °2             W2
resultant acid-base imbalance may have been due to lowered 0. and CO. exchange at
the gills.   Two  proposed mechanisms  for  impaired  gas  exchange  were  lowered
respiratory rate  and gill damage.   The former mechanism  is  less likely because
sublethal toluene exposure  has  been shown  to  increase the respiratory  rate  in
fish  (Slooff,   1978,  1979;  Thomas  and  Rice,  1979).   The  latter  mechanism  is
supported by the  authors' observation that toluene caused excess mucus produc-
tion and fusion of gill lamellae in gills.
     The whole-fish  content of hippuric  acid was measured  in fish  exposed  in
groups of 6 fish to 0, 5, 10, or 21 ppm toluene  for  96 hours (Brenniman et al.,
T979).  This experiment was conducted to determine whether the fish were able to
metabolize  toluene  ultimately  to  hippuric   acid,   as  occurs   in   mammals
(Chapter 12.).  The  results,  presented below,  indicated  that hippuric  acid  was
elevated at all the toluene concentrations tested and that this metabolic pathway
occurs in goldfish.
                                      17-23

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     Toluene Concentration            Mean Hippuric Acid Concentration
             (ppn)                                 (ppm)
               0                                   1539.50,
               5                                   3608.67*
              10                                   3536.67*
              21                                   2829.17*
*? < 0.05 when compared to control.
The pattern of decreasing hippuric acid  concentration with increasing  toluene
concentration was attributed to increasing stress and  lower metabolic  efficiency
as toluene concentration increased. Hippuric acid  was elevated above the  control
levels, however,  evea at the highest toluene concentration.
     The only other information available relevant to  toluene metabolism  in fish
is provided by Ohaori at al. (1975),  who investigated the comparative in  vitro
metabolism of a toluene analog, £-nitrotoluene,  by liver homogenates of rats and
eels.   The  species of  eel was  not  specified.   Both species  were able  to
metabolize £-oitrotoluene (PNT) to £-nittrobenzoic  acid (PUB acid),  via oxygena-
tion of PUT to £-nitrobenzyl alcohol (PUB alcohol), to £-nitrobenzaldehyde (PNB
aldehyde), and finally to PNB acid. The rate of  the overall reaction (PNT to PNB
acid) in eel liver,  however,  was only 3** (at 25*C) to 46*  (at  37 *C) of the rate
in rat liver.  The rate of formation of PNB alcohol from PNT in eel liver  was 29$
(at 25*C) to 16*  (at  37*C)  of  the rate in rat liver.  This  step  was the  rate-
limiting step for the overall reaction  because the  formation of PNB acid from PNB
alcohol was faster in eels than in rats.
     Thomas  and  Rice (1979)  measured  the  effects  of flow-through   toluene
exposure  on  the  respiratory   rate and   oxygen  consumption   of  pink  salmon
(Oncorhynehua gorbuscfaa)  fry at  two temperatures (U°c, 12*C) in aeawater.   The
fish were placed in sealed chambers fitted with  a water inlet and  outlet,  mesh
electrodes (for measuring opercular breathing rata), and oxygen electrodes (for
measuring oxygen  concentration  of inflowing  and outflowing  water).     After

-------
determining  the  2U hour LC5Q  (5.38 ppm),  the  authors exposed  fry  to  several
toluene  concentrations,  expressed  as  percentages of  the LC__.   Significant
increases in  opercular  breathing rate at  12°C  occurred at exposure concentra-
tions of 94 and 69$ of the LC5Q,  but not  at 45 or 30* of the LC^.  The  breathing
rate remained elevated throughout the 15 hour exposure period  only at 94% of  the
LC.Q, at which concentration 6 of 23 fish died.  The breathing rate at  a  toluene
exposure concentration of 69} of the  LCeQ  reached a maximum at  three  hours  and
returned  to control  level  by  15  hours.   Additional  experiments showed that
exposures to 71J of the  LCcQ  increased oxygen consumption.  The percent increase
in both oxygen consumption and  breathing rate was greater at U°C than at  12*C.
The authors suggested that these effects were due to the energy requirements  for
metabolism of toluene and that this requirement was greater at the lower tempera-
ture.  The threshold for an effect  on  breathing rate at  12*C was  estimated  to be
about U6J of the LC~g> or about  2.5 ppm.
     Slooff  (1978,  1979) conducted similar experiments to determine the sensi-
tivity of  a biological monitoring  system using fish  respiratory rates as  an
indicator of water pollution  by  toluene and other chemicals.  Adult rainbow  trout
(mean weight  56  g)  were acclimated to  dechlorinated  tapwater at  20  +  1*C  and
tested individually in  sealed   flow-through  chambers  equipped  with  stainless
steel mesh electrodes for measuring breathing rate.   After the normal  breathing
rate for a fish over a three  day  period had been determined,  toluene contaminated
water was added continuously  and  the breathing rates were monitored over a period
of U8 hours.   Measurements  were taken  at  the same time of day  during the pre-
exposure and exposure periods.  A toxic effect was considered to have occurred if
the respiration  frequency of at  least 75% of the  test  fish exceeded the prede-
termined individual normal frequencies measured at the same hourly interval.   The
lowest toluene  concentration that  caused  an increase  in  respiratory rate  was
                                      17-25

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2.5 mg/i.  This concentration is identical to the  estimated  threshold concentra-
tion for an effect on breathing rate in pink salmon (Thomas and Rice,  1979).
     Leung and Bulkley (1979) investigated the effects of 1QO |i£/l toluene on the
rate of  opercular movement  by  eight day  old embryos of the  Japanese medaka,
Orysiaa  rnedaka.   The basal  (unexposed)  rate was determined  for each of  three
embryos  and  then  toluene was added  to  the culture medium  to  obtain  a nominal
concentration of 100 nA/l.  The rate was then determined for each embryo at about
five minute intervals for 40 minutes. The average rate before  exposure was zero
movements/minute.  The average of 8 counts (each  1 minute long) over 40 minutes
after beginning exposure was 2.28 movements/minute.  The standard deviation was
so great, however,  that this increase was not statistically significant.
     The sublethal effects of toluene on nedaka were also investigated by Stoss
and Haines (1978).  The exposure techniques and  lethal effects  reported by these
authors  have been discussed in Section 17.3.1.1.   Static  exposure of eggs to
initial nominal concentrations of 41 and 32 mg toluene/1 resulted in a signifi-
cant delay in time to hatching and a decrease in  the proportion of embryos that
hatched successfully.  Exposure to 41 mg/i and greater caused  numerous develop-
mental abnormalities,  including disruption of  cell  cleavage  patterns,   defor-
mation of eyes, appearance of isolated blood islands in the circulatory system,
and abnormal heart  structure,  tail flexures, and visceral  organ formation and
placement.  No  abnormalities  were observed in embryos exposed to 16 mg toluene/Z.
     The only other information  available concerning  sublethal toluene effects
on fish  is provided in  a U.S.  SPA unpublished study  (1978, cited in U.S.   EPA,
1980).  An embryo-larval subchronic test with the sheepshead minnow (Cyprinodon
variegatus) in  seawater showed that  toxic effects were observed at  a toluene
concentration of 7.7 ppm, but not at 3.2 ppm.  The type(s) of toxic effects were
not specified in the U.S. EPA (1980)  report, which was simply a  data compilation.
                                     17-26

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The   96 hour   LC50    tor   this   species   was   between   277   and  U85  ppm
(Section 17.3.1-2.).   The  ratio  between acute  and sub-chronic  toxicity  was
between 36 and 152,  indicating that chronic effects occur at  concentrations such
lower than acute effects.
     In  summary,  the  lowest  toluene concentration  shown  to  cause  sublethal
effects in fish was  2.5 ppm,  the concentration which caused an increased breath-
ing rate in trout (Slooff, 1978, 1979) and salmon (Thomas and Rice, 1979).  This
value is somewhat below the lowest acute LC-Q  value reported for  any fish species
(3.08 ppm for coho salmon, see Table  17-1).  An embryo-larval test with sheeps-
head minnow  (0.5. SPA,  1960)  showed  that subchronic toxic effects occurred at
7»7 ppo but  not at  3«2 ppm and  that  the  ratio between the acute  LC5Q and sub-
chronic toxic!ty for this species was between 36 and 152.   Although  acute-chronic
ratios may vary greatly among species, this  information suggests  that chronic
toxic effects may  occur in coho salmon and other sensitive species  at  concentra-
tions well below 3 ppm.

     17.3.2.2.   INVERTEBRATES — Berry  et al.  (1978)  conducted   a  series  of
experiments to determine the effects of 21 hours of exposure to sublethal concen-
trations of  water-soluble fractions  (VSFs) of gasoline, benzene,   xylenes,  and
toluene on oxygen consumption by fed and unfed larval stages of  the  mosquito,
Aedes aegypti.  Control experiments with untreated animals showed that there  was
no  significant difference  in  0- consumption between  fed  and  unfed larvae.
Treatment  with the  WSF  of  1  mi/I gasoline,   however   caused  an   increased 0,
consumption  in fed,  but  not unfed,  larvae  relative  to  untreated  controls.
Treatment  of  fed  larvae  with individual  WSFs  of benzene  (1 ml/2,), xylenes
(0.3 mi/i), or toluene (0.1 to 0.5  mi/Z) had no effect on 0. consumption relative
to fed controls.  A  WSF mixture of benzene, xylenes,  and  toluene and a mixture of
                                      17-27

-------
benzene and toluene (0.2 ai/i for each compound)  caused significant increases, in
0. consumption.  Exposure to a WSF mixture of benzene and xylenes  or  toluene  and
xylenes (0.2 oi/Z for each compound) bad no effect.  The authors  also conducted
experiments on the uptake of %-labeled toluene in fed and unfed animals,  as well
as uptake  of %- toluene by fed  larvae in the presence  or  absence  of  benzene
(Section 15.3.).  Marlonim ^H-toluene counts were equal in fed and unfed  larvae,
but were reached more quickly  (one hour versus  four hours)  by the fed animals.
The ^H-toluene  counts  in larvae,  expressed as the  percentage*  of the  initial
water  counts,  were  greater in  the benzene  and toluene mixture than  in  the
solution containing  toluene alone.  The authors concluded  that  the effects  of
gasoline on  0- consumption  were due  to the  enhanced  uptake  and synergistic
effects of toluene and  benzene, two of the major aromatic  components of gasoline.
They also suggested that the presence of food accelerated the uptake of  toluene
through absorption of toluene  to the consumed food particles.
     Blundo (1978) investigated the effects of toluene on the swimming activity
and survival of  barnacle (Balanus  eburneus)  larvae.   Groups of  larvae were
exposed for one hour in specially  constructed tubes  to  10,  20,  30,  40,  50,  60,
70, 30, and 90f of the water soluble fraction (WSF)  nade by saturating seawater
with toluene.  The tubes  were  designed so that actively swimming photopositive
larvae would  be  attracted to  light at  the  top of  the tube.   After one  hour  of
exposure, the inactive  larvae  were collected from the bottom,of  the tubes  and
stained with a vital  dye (neutral red)  to determine percent  mortality.    The
remaining portion, containing the active larvae,  was  then  collected and counted.
The interpolated concentration that immobilized  50%  of the larvae was 12.5H  of
the WSF.  All larvae were immobilized at 30%  WSF and higher. About  33*1/3$ of  the
larvae were immobilized at 10J  WSF,  the lowest concentration tested.   The  percent
mortality of the immobilized larvae ranged from about 3J at 10* WSF to a  maximum
                                     17-28

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at 12$ at 90$  WSF.   The author also measured  the  effects  of WSFs  that had been

aged in covered containers  for one day in a refrigerator or exposed to air for up

to 3 days.  The percent WSF that immobilized 33-1/3$  of the larvae was 10$ in the

fresh solution, 37.5$  in the refrigerated  solution,  and 90$ in the  evaporated

solution.  Additional experiments showed that  aeration of  the WSF  for six hours

lowered the toxicity to  the same extent as  three days  of exposure  to  air.

     Baklce and Skjoldal  (1979)  investigated the effects of toluene on activity,

survival, and physiology of the isopod,  Cirolana borealis.  For  determination of

median effective  times  (ET5Qf  partial  or  complete narcotization  as  endpoint),

groups of 15 isopods were exposed in duplicate to nominal initial concentrations

of 0, 0.0125,  1.25, 5.7, 12.5, 25, and 125 ppm toluene for 4  days.   The exposure

medium (33.5  to 34.5 °/oo  salinity seawater  at 9 to  10°C) was changed every
                                                12
2 days.  The interpolated or extrapolated ST50 values  were as follows:
                                                 3
                  Toluene                       -«
               Conflfe«tioa                    (hours)


                  0.0125          -               	
                  1.25                           	
                  5.7                            100
                 12.5                              69
                 25                                28
                125                                3


     No effects on activity were observed in animals  exposed  to  1.25 ppm or less

CBaklce and  Skjoldal,  1979).    The authors also  investigated  the recovery  of

isopods after exposure for varying periods to 12.5  or 125 ppm toluene.  Exposure

to 125 ppo  for one hour caused complete  inactivity, but  all animals recovered

within 12 hours after transfer  to clean water. Exposure for 2  or  more hours to

125 ppm caused partial  or  complete mortality.  All  isopods  could  recover after

exposure to 12.5 ppm for 30 hours but not longer.   Additional experiments showed

that  there  was no  significant  effect of  4 days  of exposure  to up  to 5.7 ppm
                                      17-29

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toluene on oxygen consumption, ATP concentration, or energy charge.   Exposure to
12.5 ppm resulted in a progressive decrease in ATP level and energy  charge over
eight days of exposure, at which time all organisms had died.  Exposure to  the
rapidly lethal concentration of 125 ppm toluene showed no effect on ATP level or
energy charge.  These results with 12.5 and 125 ppm wore essentially  the same as
those reported by the authors in a previous paper  (Skjoldal  and 3akke, 1978).
Bakke and Skjoldal  (1979) concluded that the effect of toluene on activity  was
ouch more  sensitive as an  indicator  of aublethal  toluene toxlcity  than  its
effects on respiration, ATP level, and energy charge.
     In  summary,  the lowest  toluene  concentration  shown to cause sublethal
effects in invertebrates was 5.7 ppm, the concentration which caused narcotiza-
tion of  isopods  (Bakke and Skjoldal, 1979).   This  concentration  is somewhat
higher than the 96 hour LC_Q of 4.3 ppm for bay shrimp (see Table  17-1) reported
by Benville and Corn (1977)*   The latter  concentration is the lowest  reported to
have toxic effects on freshwater or marine invertebrates.   Although  the chronic
toxicity of toluene  to aquatic invertebrates has not been studied,  it  is probable
that chronic effects could occur in sensitive invertebrate  species at concentra-
tion below  4.3 ppm.  This  conclusion  is  supported  by the fact  that chronic
effects in fish occurred at concentrations well  below  the  acutely toxic concen-
trations (Section 17.3.2.2.).
                                     17-30

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                          18.  HEALTH EFFECTS SUMMARY



18.1.  EXISTING GUIDELINES AND STANDARDS



13.1.1.  Air. The Occupational Safety and Health Administration (OSHA) currently

limits occupational exposure  to  toluene to 200 ppm as an 8 hour time-weighted-

average   (TWA),   with  an   acceptable   ceiling   concentration   of   300  ppa

(40 CFR 1910.1000); the acceptable maximum peak above the ceiling concentration

is 500 ppm  for  a maximum  duration of  10  minutes.   The National Institute  for

Occupational Safety and  Health (NIOSH, 1973)  currently recommends  an  exposure

limit of  100 ppm as an  8  hour TWA with  a ceiling of  200  ppm.   An 8 hour  TWA

concentration of 100 ppm  is also  recommended by  the American  Conference  of

Governmental  Industrial  Hygienists  (ACGIH,   1980)  as a Threshold  Limit  Value

(TL7) for toluene; the short-term  (15 minute)  exposure  limit  recommended by  the

ACGIH is 150 ppm.  ACGIH (1980) has further noted that  there  may be significant

contribution to the overall exposure by the cutaneous route.

     Threshold limit values that have been established for occupational  exposure

to toluene in other countries are  listed as follows  (Verschueren, 1977):

     USSR                      13  ppm  (50  mg/m3!          1972
     Czechoslavakia            52  ppm  (200 mg/ne)         1969
     West Germany (BDR)       200  ppm  (750 mg/m^)         1974
     East Germany (DDR)        52  ppm  (200 mg/nc)         1973
     Sweden                    98  ppm  (375 mg/m3)         1975

     There .are no standards for general atmospheric  pollution by toluene in  the

United States, although  a  National Ambient Air Quality Standard specifies that

nonmethane  hydrocarbons  shall  not exceed 0.24 ppm  (160 pg/nr)  as  a  maximum

3 hour average concentration  (6 to 9 a.m.), more than once per year  (40  CFR 50).

Ambient air quality standards have,  however, been  promulgated  for toluene in
                                      18-1

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other  countries.     These  foreign   standards  are   summarized  as   follows
(7erschueren, 1977):
     Vest Germany (3RD)

     East Germany (DDR)

     Bulgaria

     Hungary
     Hungary (protected areas)
     Yugoslavia
   Concentration
0.15 ppm (0.6 og/oc)
0.15 ppat (0.6 og/or)
15 ppm (60 og/ar)
 5 ppm (20 og/nr)
 0.5 ppm (2.0 ng/nrl
 0.15 pom (0.6 og/ar)
 0.15 ppm (0.6 ng/ar)
 0.15 ppm (0.6 og/ar)
13.3 ppm (50.0 og/rn^}
 5.3 ppm (20.0 og/ac)
 0.16 ppm (0.6 og/sc)
 0.16 ppm (0.6 og/nr)
 0.16 ppm (0.6 og/ac)
 0.16 ppm (0.6 og/or)
Averaging Time
    20 tola
    24 or
    30 min
    24 hr
    30 oin
    24 hr
    20 aia
    24 hr
    30 aln
    24 hr
    30 fflln
    24 hr
    20 oin
    24 hr
13.1.2.  Water.  The Committee on Safe Drinking Water of the National Academy  of
Sciences concluded in 1977 that toluene and its oajor metabolite, benzoic acid,
were relatively  nontoxic,  and that  there was insufficient  toxicological data
available to serve as a  basis for  setting a long-term ingestion standard (MAS,
1977).  It was  recommended that studies be conducted  to produce relevant informa-
tion.  Toluene has recently  been considered for a second time by a reorganized
Toxicology Subcommittee  of the Safety  Drinking  Water Committee of the National
Academy of Sciences  (U.S.  SPA, 1980), but  the  results  of the deliberations  of
this group have not yet  been made public.
     The U.S.  EPA (1980) has recently  derived an ambient water criterion level
for toluene of 14.3 ag/4.  This criterion is intended to protect humans against
the  toxic effects  of toluene  ingested  through water and  contaminated aquatic
organisms,  and is based  on an Acceptable Daily Intake (ADI) calculated from the
                                      18-2

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maximum-no-effect dose reported in the Wolf et al.  (1956) subchronic  oral study

in rats and an uncertainty factor of  1000.  The criterion level  for toluene can

alternatively be  expressed  as 424 ng/i if exposure is assumed  to be from the

consumption of fisn and shellfish products alone.



18.1.3.  Food.  Toluene has been approved by the Food and Drug Administration for

use as a component  of articles intended for use in contact  with food (i.e.,  an

indirect food additive).  Articles that contain residues of  toluene may  be used

in   producing,   manufacturing,   packing,   processing,   preparing,   treating,

packaging,  transporting,  or  holding food.   The  use  of  toluene  in the  food

industry is summarized as follows:

     Component of adhesives                               21  CFH 175*105

     Adjuvant substance in resinous and
       polymeric coatings for  polyolefin films
       used as food contact surfaces                      21  CFH 175*320

     Component of the uncoated or coated
       surfaces of paper and paperboard
       articles intended for use with
       dry foods                                          21  CPU 176.180

     Used in the formulation of semirigid
       and rigid acrylic and modified acrylic
       plastic articles                                   21  CFH 177.1010

     Additive for cellophane (residue limit
       0.1*)                                              21  CFH 177.1300

     Additive for 1,4-cyclohexylene dimethy-
       lene terephthalate and  1,4-cyclo-
       hexylene diaethylene isophthalate
       copolymer                                          21  CFH 172.1240

     Solvent for 4,4'-isopropylidenediphenol-
       epichlorohydrin resins  with a  minimum
       molecular weight of 10,000 (residue
       limit ^1000 ppm in the  finished resin)             21  CFR 177.1440

     Solvent for polysulfide polymer-polyepoxy
       resins                                             21  CFR 177.1650
                                      18-3

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     Solvent for poly(2,6-dimethyl-1,4-
       phenylene)oxide resins (residue limit
       0.2* by weight)                                    21 CFH  177.2460
     Blowing agent adjuvant used In the manu-
       facture of foamed polystyrene (residue
       limit 
-------
Somiyama and Nooiyaffia,  1978).   Although most  of these reports  do not  provide
quantitative exposure  estimates,  glue sniffers  are  probably exposed to  nearly
saturated  air-vapor mixtures of  about 30,000 ppm  toluene.   The occupational
report of Longley et al. (1967) indicated that a loss of consciousness  occurred
within minutes after  exposure  to  atmospheres  estimated to contain  10,000  ppm
toluene at waist level and 30,000  ppm toluene at  floor level.  The  acute inhala-
tion toxicity  data  on experimental mammals, summarised  in Table  12-1,  suggest
that exposure periods of  several  hours to  toluene levels greater  than  4000  ppm
may  be  lethal.  Based  on the results of  longer term  human studies discussed
below, short exposures to concentrations of  up to 1500 ppm  are not likely to be
lethal (Wilson, 1943; Ogata et al., 1970, see following discussion).   The single
report by  Gusev (1965)  of effects on SEG activity in  4 individuals  exposed to
0.27 ppm for 6 minute intervals may be a subtle  indication  of the  perception of
toluene  at  this  low  level  but  does  not  have  any  apparent  toxicologic
significance.
     For single  exposure periods  that approximate a normal  wortcing day  (7 to
3 hours),  von Oettingen  et al.  (1942a,   1942b) and  Carpenter  et  al.  (1944)
provide relatively  consistent  information  on sublethal dose-response relation-
ships.  As summarized previously  in  Table  10-1, von  Oettingen et al.  (1942a,
1942b) noted a range of subjective complaints from 8 hour  exposures  to toluene
concentrations  ranging from  50 ppm  (drowsiness)  to 300 ppm  (severe  fatigue,
nausea, incoordination, etc., with after effects lasting at least several days).
Although the terminology  used  by  Carpenter et al. (1944) is somewhat different
from  that  used by  von Oettingen,  the effects  noted seem  comparable  over  the
common exposure range (200 to 300 ppm).  Although the consistency  between these
two  studies  is reassuring, it should be noted  that even combined both studies
involve  exposures  of  only  five  individuals  who  were   placed on  multiple
                                      18-5

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exposure/recovery schedules*   The  impact that  such multiple  exposures could
potentially have on the results cannot be determined. Given the small  number of
individuals involved in the exposures  to toluene,  an attempt to generalize  for
the human population a detailed  dose-response gradient  comparable to  that pre-
sented in Table  11-1  does not seem  Justifiable.   When these  studies  are con-
sidered along with  the results of Ogata and coworkera (1970) and Gamberale  and
Hultengren (1972) however, it seems reasonable to conclude  that  exposure  periods
of 3 hours or  less  to toluene concentrations  below 100 ppm may result  in adld
subjective complaints (fatigue or headache)  but are not  likely to induce  observ-
able effects.   Concentrations above  100 ppm may  cause  impaired reaction time
(200 ppm x  3 hours, Ogata  at al.t  1970; 300  ppm  x 20 minutes,  Gamberale  and
Hultengren,  1972).  At concentrations of 300  to 300 ppm and above, gross signs of
iacoordlnation may  be  expected (von Oettingen  et  al.,  1942a,  1942b;  Carpenter
et al., 1944).
     Accidental acute overexposure to  toluene  nay  be limited to some  extent by
the organoleptic or irritant  properties  of  the compound.   Gusev (1965)  reports
ranges of maximum imperceptible  concentrations and minimum perceptible  concen-
trations of  0.35  to 0.79 ppo and 0.40  to 0.35 ppm, respectively.   May  (1966)
reports a minimum perceptible concentration of 37 ppm.   The  reasons  for this
discrepancy between the Russian and American values are not apparent.  Although
the Russian study entailed  a  total of 30 subjects and 744 observations  and  the
American report involved  16 individuals  (number of observations not  specified),
it is  unlikely that  the difference in  the reported detectable  levels  is  due
simply to sample size.  In any event,  toluene appears to  be  detectable in  the  air
at levels  below  those causing  impaired coordination  (i.e.,  >100 ppm).    In
addition, Carpenter and  coworkers (1944)  reported that  toluene  caused mild
throat and aye irritation at 200 ppm and also caused lacrlaation at  400  ppm.
                                      13-6

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     In summary, the estimated dose-response relationships for the  acute effects

of single short-tens exposures to toluene are presented below:


     10,000 to           :    Onset of narcosis within a  few minutes.  Longer
     30,000 ppm               exposures may be lethal.

     >4,000 ppm          :    Would probably cause rapid  impairment of reaction
                              time and  coordination.   Exposures of  1  hour or
                              longer might lead to narcosis and  possibly death.

      1,500 ppa          :    Probably not lethal for exposure periods of up to
                              8 hours.

        300 to 800 ppm   :    Gross  signs  of incoordination  may  be expected
                              during exposure periods up  to 8 hours.

        400 ppm          :    Lacrimation and irritation to the eyes and throat.

        100 to 300 ppm   :    Detectable signs of incoordination may be expected
                              during exposure periods up  to 3 hours.

        200 ppa          :    Mild throat and eye irritation.

         50 to 100 p(pm   :    Subjective  complaints  (fatigue  or headache)  but
                              probably no observable impairment of  reaction  time
                              or coordination.

        >37 ppa          :    Probably perceptible to most humans.


From the above  discussion,  it should be  evident  that these approximations are

crude composites and contain several areas of uncertainty and overlap.
T8.2.2.   Effects of  Intermittent Exposures  Over Prolonged  Periods.   Limited

information  is  available on  the effects  of subchronic  or chronic continuous

exposures to  toluene  on humans or experimental  aniaals.   Most  of the studies

either  involve  occupational  exposures or  are designed  to mimic  occupational

exposures.  Consequently, while the data described below may be directly applic-

able to estimating effects from occupational exposures,  an additional element of

uncertainty  must be  considered  in  any  attempt  to estimate  the  effects  of

continuous exposures that may occur from ambient  air.
                                      18-7

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     Wilson (1943) provides the only acceptable data on the effects of repeated
occupational exposures to toluene over a period of weeks (Section  11.1.1.2.).   In
this  study,  the  workers were classified  into three  groups  by  the  levels  of
toluene to which they were exposed:  50  to  200 ppm,  200 to 500 ppm, and 500  to
1500 ppm.  The effects noted at the various levels were essentially the same  as
those seen  in single  exposures.   In  the low  exposure group,  the  reports  of
headache and lassitude are  consistent  with symptoms noted by von Oettingen and
coworkers (1942a, 1942b)  over the same range of exposure. Although Wilson (1943)
did not attribute  these  effects  to toluene exposure, his failure to include  an
unexposed  control  group makes  this  judgment  questionable  in  view of the
von Oettingen data.   In the  middle and  high exposure groups,  the reports  of
headache,  nausea,  and   concentration-related  impairment  of  coordination and
reaction time are also consistent with  the symptoms reported by von Oettingen and
coworkers  (1942a,  1942b) and  Carpenter  and  coworkers (1944)  for short-tarn
single exposures.  The major discomforting feature of the Wilson (1943) report  is
that it involved only 100 out of a  total of 1000 workers.  It is unclear whether
the remaining 900 workers evidenced any symptoms of toluene exposure.
     The only other study that reports effects of repeated exposures to toluene
for relatively short periods of time is that presented by Greenburg and coworkers
(1942).  In this study,  repeated occupational exposures to toluene at levels  of
100 to 1100 ppm for periods of 2 weeks to 5 years were associated with enlarged
livers in 13 of 61 airplane painters.  This incidence of liver enlargement was
reported to be  3 times  that of  a  control group of  430  workers  not exposed  to
toluene. Because Greenburg and coworkers (1942) were not able to associate  liver
enlargement  with  clinical  or laboratory  evidence  of  disease,  because the
painters were also exposed to significant  quantities of  other  volatile  paint
components (Table 11-9),  and because the liver effect has not been corroborated
                                      18-8

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by other  Investigators (e.g.,  Parmeggiani and  Sassl,  1954; Suhr,  1975), the
hepatomegaly reported  by Greenburg  should  be  given relatively little weight in
risk assessment.
     Other reports of repeated occupational exposures to toluene  involve periods
of several years.  For mean exposure levels above 200 ppm, all of the available
studies except  that  of Suhr (1975) report  some evidence of neurologic effects
(Capellini and  Alessio,  1971;  Paraeggiani  and Sassi,  195*;  Munchinger,   1963;
Rouskova,  1975).
     The Suhr  (1975)  study involved a group  of 100 printers exposed to 200 to
400 ppm toluene for  over  10  years.   Compared  to  a group  of  100 non-exposed
individuals, no significant differences were seen in symptoms of  central nervous
system  (CHS)  depression or Sphallpgraph  tests, which  are  designed to measure
muscular coordination.  An interpretation of the significance of  the Suhr (1975)
study is  confounded,  however,  by  several factors.   As  discussed  in Sections
T1.1.1.2.  and 11.3«,  the limitations of this  study  include an undefined control
group,  uncertainties  involving  the time of  reflex  reaction  and  sphallograph
testing (i.e.,  blood  toluene  levels  may have  declined significantly  if the
workers were  examined before  or after  the  work  shifts),   and  the use  of an
apparently ^invalidated device (sphallograph) for the detection  of slight distur-
bances of muscular coordination.
     The  other studies that  do report  effects at  equal or higher  levels of
exposure can be challenged for  various reasons.  The report of  "nervous hyper-
excitability"  in  6 of 11  exposed   to  200  to 800 ppm toluene  for "many years"
(Parmeggiani and  Sassi,  1954)  does not seem to be  characteristic of toluene
intoxication.   This report is from the Italian  literature,  however, and a full
text translation has  not yet  been made  available for this  review.  The Capellini
and  Alessio  (197D study, which associated  stupor,  nervousness, and insomnia
                                      18-9

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with occupational exposure  to  250  (210 to 300)  ppm toluene for several  years,

involved  only a  single  worker.    The  "organic psychosyndrome"  diagnosed  by

MuBchinger  (1963)  in workers  exposed to  300 and  430  ppa toluene  for  Id  and

T2 years,  respectively,   is  supported by  the results  of  Rorschach tests  and

Enoepfel's  13-Srror  tests*   Because  Munchinger did  not use  a control  group,

however, the utility of  this study is limited.  The changes in SEG  response to

photic stimulation that were reported by Rouskova (1975) in workers exposed to
                                                             *
>250 ppa toluene for an average of 13.5 years also involved exposure  to unspeci-

fied levels of 1,1,1-trichloroethane.   Thus,  the interpretation of the  dis-

crepancies between the study by Suhr (1975) and these other reports is problema-

tic.  Considering the relatively well  documented CSS effects of single exposures

to toluene  at  levels above 200 ppa (Section 13.1.1.)  and  the  effects noted by

Wilson (19^3) at comparable levels for much shorter  periods  of time, it would

seem imprudent to accept the. Suhr (1975) data as a "no-observed-offeet level1* for

Roman risle assessment.

     An alternative approach could be to use the study  by  Capellini  and  Alessio

C1971) in  which  no  CSS or  liver  effects were  aoted  in a  group  of  17  workers

occupationally exposed to 125  (30  to  160) ppm toluene for  "diverse   years."  In

addition to the problems  of small  sample size,  failure to  precisely define the

duration of exposure,  and  lack of a control  group,  the  use  of this study is

compromised by reports of effects  in two  other groups of workers at lower levels

of toluene  exposure.   Matsushita  and coworkers  (1975)  reported impaired  per-

formance in  neurological  and muscular function  tests  in a group  of 33  female

shoemakers  who  had  been  exposed   to  15  to  200  ppa toluene for  an  average of

1 years and 4 months.  In addition,  19  of 33 exposed women, compared to 3  of 16 in

the control group, complained of dysmenorrhea.   The second  group of  workers was

composed of 100 car painters who had been occupationally exposed to an average of
                                     18-10

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30.6 ppm toluene  for an average  of 14.8 years.   As reported  by Hanninen  and


eoworkers (1976) and Seppalainen and coworkers (1978), the exposed workers had a



greater incidence of CHS symptoms and impaired performance on tests for  intelli-



gence and memory, as well as for visual and verbal ability.  Both of the studies


on  this  group of workers  used control  groups of  approximately  100 unexposed



individuals.  The major problem with the reports of adverse effects on the female



shoemakers  and  male car  painters  is  that  both  groups were exposed  to  other
                                                      /

potentially toxic agents.  The female shoemakers were exposed to "slight" levels



of gasoline (Matsushita et al.,  1975)  and,  as detailed in Table  11-3,  the male



car painters were exposed to several other  organic  solvents.


     The suochronic and chronic data on experimental mammai« are of only limited



use  in  helping to  resolve  the uncertainties  in  the human  data.  Jenkins  and


coworkers (1970), and CII7 (1980) report no-observable-effect levels  (NOELs) in



experimental mammals 1085 ppm (8 hours per day, 5 days per week for 6  weeks) and



300 ppn  (6 hours  per day,  5 days per  week for 24  months),  respectively.   For



reasons discussed in detail in Section 12.1.2., the CIIT study is not  considered


appropriate for human  risk  assessment; interpretation of this  study  is compli-


cated by the  absence of quality  assurance  throughout the study,  the use of an



inappropriate strain of rats for study of myelotoxicity, and the fact  that the


highest  level  tested was not a  maximum tolerated dose.  As  discussed  above in



this section, a NOEL of 1085 ppm is  contradicted by  human experience,  suggesting



that humans  are more sensitive  than  experimental mammals to toluene exposure.



Similarly, the continuous-exposure  NOEL of 107 ppm for 90 days in rats, guinea


pigs, dogs, and monkeys  (Jenkins et al., 1970) does  not,  in itself,  negate the



concerns with effects reported  in humans at lower levels.
                                      18-11

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18.3.  ORAL EXPOSURES
     Vary littla information  la  available on the acute, aubchronic, or  chronic
effects of toluene in experimental mgmniaT?-  As summarized in Table  12-1, acute
oral LDg03 In adult  rats  range from 5500 mg/kg to 7530 mg/kg.  Using  the cubed
root of the  body weight  ratios  for intarspecies conversion  (U.S. EPA, 1980c;
Freireich et al., 1966; Rail,  1969),  an approximate lethal dose for humans can be
estimated at 983 ag/kg (5500  mg/kg  • (70 kg  •  0.4  kg)1/^).    The conversion
factor, as used here, assumes  that humans are more sensitive than rats,  which, as
discussed above, is  consistent with  the  available data on Inhalation  exposure.
This estimate of the approximate lethal dose is also consistent with the report
by Prancone  and Braier  (1954) that  leukemia patients  were able to tolerate
cumulative doses of  up  to 130,000  mg of toluene  given over a  3 week period
(approximately 38 lag/kg/day).
     The  only subchronic oral  data  are  reported in  the  study by  Wolf  and
covorkers (1956), indicating a NOEL in rats at 590  ag/kg/day,  given five days per
week for six months.

T8.4.  DERMAL EXPOSURES
     Studies on the dermal toxicity of toluene are not adequate for quantitative
risk assessment.  Qualitatively,  the little information that is available  sug-
gests that moderate dermal contact with liquid toluene  (i.e., exposure of human
forearm 3kin to toluene for 1  hour on 6  successive  days) may cause  akin damage
but does hot result in overt signs of toxicity (Maitan et al., 1963).  Similarly,
the acute and subchronic data  on  toluene  exposure  in experimental mammals do not
suggest that toluene  is  a potent  toxicant on dermal  contact.    A method  for
quantitatively using such data to estimate equivalent human dose-response rela-
tionships, however, has not been fully formulated or validated.
                                     18-12

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As discussed in Section  13.1.,  exposure  to toluene vapor results in  relatively



little dermal absorption compared to absorption across the lungs.







18.5.  RESPONSES OF SPECIAL CONCERN







18.5.1.   Carcinogenieity.   CUT (1980)  concluded  that exposure to 30,  100,  or



300 ppo  toluene  for  24 months did  not  produce  an  increased  incidence  of



neoplastic, proliferative, inflammatory, or degenerative  lesions in Fischer 3^4



rats; however, the high spontaneous incidence (16}) of mononuclear  cell leukemia



in aging Fischer 3^4 male rats has  been reported by Coleaan and coworkers (1977),



suggesting that this strain say  be inappropriate for the study of a  chemical that



might be ayelotoxic.  Also, the design of the study has been deemed  inadequate in



that the highest level tested was not a  minimum lethal dose  (Powers,  1979).



     Other studies  suggest that toluene  is not carcinogenic when applied  topi-



cally to the shaved skin of animals.  Toluene is used extensively as a solvent



for  lipophilic  chemicals  being  tested  for  carcinogenic  potential;  negative



control studies  employing  100?  toluene  have not elicited carcinogenic effects.



Also, no evidence of a promotion effect was noted when toluene was painted on the



skin of mice twice weekly  for 20 weeks following initiation  with 7,12-dimethyl-



bens- [a] -anthracene  (Frei  and Stephens,  1968; Frei and Kingsley, 1968).



     The above data are not adequate for  assessing  the potential carcinogenicity



of toluene with great assurance and they cannot be used  for  supporting carcino-



genicity as a valid biologic endpoint in quantitative risk assessment.







13.5.2.   Mutagenicity.  Toluene  has yielded negative  results in a  battery of



microbial, mammalian cell, and  whole  organism test systems  as  indicated in the



following:
                                     18-13

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          Differential Toxioity/DNA Repair Assays
               Saeherichia coli
               .Salmonella typhimurium
          Reverse Mutation Testing
               Salwnalla typhimurium (Ames test)
               Sscfaerichia ooli WP2 assay
               Saecharomyees cercvisiae 07
          Mitotic Gene Conversion/Crossing Over
               Saecharomyces cerqvisiae D4, 07
          Thymidine Stnase Assay
               L5178T mouse lymphoma cells
          Mieronucleus test
               mouse
          Dominant Lethal Assay
               aouse
          Sistar-Caromatid Exchange
               cultured CHO cells
               human lymphocytes: in vitro
               human lymphocytes in vivo (workers)
     In the Russian Literature,  chromosome aberrations were reported in the bone
marrow cells of rats exposed subcutaneously (Dobrokhotov,  1972; Lyapkalo, 1973)
and via inhalation  (Dobrokhotov and  Sinkeev,  1977) to toluene.  These findings
were not corroborated in a Litton Sioneties, Inc.  (1973b)  study in rats  following
intraperitoneal  injection,  in  cultured human  lymphocytes exposed  to  toluene
in vitro  (Gerner-Smidt  and Friedrich,  1978),  or  in  lymphocytes  from  workers
chronically exposed to toluene (200 to 400 ppm,  Forni et  al.,  1971;  7 to 112  ppm
toluene,  Maki-Paakanen at al.,  1960).    Differences  in  doses  employed   gay
account, at least in part,  for these  conflicting  results.  Funes-Cravioto et  al.
(1977) did report an excess of  aberrations  in  the lymphocytes from  14 printers
exposed to TWA  concentrations of 100 to  200 ppm for  1  to  16 years, but it  is
probable that part of the exposure was  to benzene-contaminated toluene.  Also,
the number of workers was small in this study.
                                    18-14

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tS.5.3.  Teratogeoicity.  Toluene was reported in a recent abstract from MIEHS to
induce cleft palates at a level of 1.0  mi/leg (approximately  366 mg/kg) following
oral exposure  to mice on  days  6 to 15 of gestation  (Nawrot  and Staples,  1979).
This effect reportedly  did  not appear  to be due merely to a general retardation
in growth  rate.  Levels of  0.3 and 0.5 mi/kg (approximately  260 and 433  mg/kg)
toluene had no teratogenic  effect,  but the number of mice exposed and number of
fetuses  examined were  not  stated.    Nawrot and  Staples  (1979)  also noted  a
.significant increase in embryonic lethality at all dose levels and a significant
reduction  in  fetal  weight  at  the two  higher  dose  levels.   No  frank  signs of
maternal  toxicity  were seen at any dose  level;  however, at  the highest dose,
decreased  maternal weight gain was  reported in  mice exposed on days 12 to 15 of
gestation.  A  complete copy of this report has not been made available for review
but has been submitted  for  publication.
     Three other studies  have  concluded that toluene is not teratogenic in mice
CHudak and Ungvary,  1978) or  rats  (Rudak and Ungvary,  1978;  Litton Bionetics,
T978b; Tatrai  et al.,   1980) following inhalation exposure.   Hudak and Ungvary
(1978) and Tatrai et al.  (1980) have noted, however,  an increased incidence of
skeletal  anomalies  and  signs of retarded skeletal  development in the rats that
were not considered malformations as such.  Eabryotaxicity was also indicated by
low fetal  weights in mice and  some  rats (Hudak  and Ungvary, 1978).  At the high
exposure  levels in the study  by Hudak  and Ungvary  (1978),  increased maternal
mortality  was  noted  in  rats  (399  ppm, 21 hours/day,  days  1  to 8)  and mice
(399 ppm,  24 hours/day, days 6 to 13).   No increased  maternal mortality was noted
by  either Hudak and Ungvary  (1978) or Tatrai  et al. (1980)  at lower exposure
levels  in rats (266 ppm,  3 hours/day, days 1  to  21;  266 ppm,  24 hours/day,
days 7  to 14)  or mice  (133 ppof 24 hours/day,  days 6 to 13).   In the study by
Litton Bionetics, Inc.   d978b), no  signs of maternal toxicity were noted in rats
exposed to 100 or 400 ppm,  6 hours/day,  on days 5 to 15 of gestation.

                                     18-15

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     The extrapolation  of these  results  to define  potential Human risk  Is  an
uncertain process.  The dose that produced cleft palates in mice on oral  expo-
sure, 366 nig/kg, Is oul? slightly higher than the NOEL  In rats,  590 tag/kg/day.
     Although Inhalation  exposure to toluene have  not been  shown  to be  tera-
togenic, embryotoxicity is an endpoint of concern.  The  effects noted in rats and
nice at  the high exposure  level (400 ppm)  in  the  study by  Hudak  and  Ongvary
(1978) nay be of limited use in human risk assessment because of the occurrence
of natarnal mortality.   The lowest  effect level not  associated with maternal
mortality was  133 PP»f  24 hours/day, on  days 6 to  13, which caused low  fetal
weights in nice.  Ho fetal effects were noted in the study by Litton Bionetics,
Inc. (1978b),  however, when rats were exposed to  100  ppa or 400 ppa, 6 hours/day,
on days 6 to 15 of gestation, or in the Tatrai et al. (1980)  study when rats were
continuously exposed  to 266 ppm  toluene on  days 7  to  14.   As is the case with
oral exposure studies,  a  quantitative approach  for  using this  type of  data  in
human risk assessment has not been validated.
                                     18-16

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