LF-62 Toxicology of Solar Heat Transfer Fluids - Literature

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LF-62

Category: UC-48
February 1979

TOXICOLOGY OF SOLAR HEAT


TRANSFERFLUIDS: LITERATURE
SURVEY AND EVALUATION OF
MUTAGENICITY AND EFFECT ON
ARYL HYDROCARBON
HYDROXYLASEACTIVITY

C. R. Clark
T. C. Marshall
T. R. Henderson
A. Sanchez
C. H. Hobbs

LOVELACE
ENVIRONMENTAL
P,O.

BOX 5890

BIOMEDICAL
RESEARCH
Albuquerque,

and
INSTITUTE

NM 87115

Prepared for the Office of EnvironmentalResearch of the Assistant


Secretary for the Environment, U. S. Departmentof Energy,
Under Contract Number EY-76-C-04-1013

NOTICE
This report was prepared as an account of work sponsored
by the United States Government. Neither the United States
nor the United States Department of Energy, nor any of their
employees, nor any of their contractors,
subcontractors,
or
their employees, makes any warranty, expressed or implied,
or assumes any legal liability
or responsiblity
for the
accuracy, completeness or usefulness of any information,
apparatus, product or process disclosed, or represents that
its use would not infringe privately
owned rights.

The research described in this report involved animals


maintained in animal care facilities
fully accredited by the
American Association for Accreditation
of Laboratory Animal
Care.

Printed

in the United States of America


Available

From

National Technical Information Service


U. S. Department of Commerce
5285 Port Royal Road
Springfield,
VA 22161

LF-62
Category:

UC-48

TOXICOLOGY
OF SOLARHEAT TRANSFER
FLUIDS: LITERATURESURVEYANDEVALUATIONOF MUTAGENIClTY
AND EFFECTON ARYL HYDROCARBON
HYDROXYLASE
ACTIVITY

C.
T.
T.
A.
C.

Inhalation

Toxicology

Research Institute,

R. Clark
C. Marshall
R. Henderson
Sanchez
H. Hobbs

Lovelace Biomedical and Environmental

Research Institute,

P. O. Box 5890, Albuquerque, NM87115

February 1979

Research performed under U. S. Department of Energy Contract Number EY-76-C-04-1013.

ACKNOWLEDGMENT
The authors wish to acknowledge the cooperation
fluid

samples for evaluation.

of the manufacturers

who provided heat transfer

TABLE OF

CONTENTS

ACKNOWLEDGEMENTS
.............................................................................
iii

LIST OF TABLES..............................................................................
EXECUTIVESUMMARY
...........................................................................

INTRODUCTION
................................................................................

LITERATURESURVEY...........................................................................

Ethylene and Propylene Glycol ..........................................................

Hydrocarbon Oils .......................................................................

Silicone

Oils ..........................................................................

Miscellaneous

Fluids

...................................................................

EVALUATIONOF SOLARHEATTRANSFER
FLUIDS FORMUTAGENICITY
...................................
Materials

and Methods ..................................................................

A.

Heat Transfer

Fluids

B.

Preparation

and Culturing

C.

Preparation

of Liver

D.

Bacterial

E.

Controls

Mutagenicity
and Quality

Results and Discussion

..........................................................
of Tester Strains

Homogenate (S-9)
Assay ....

...................................

.........................................

...............................................

Assurance ................................................

.................................................................

INFLUENCEOF SOLARHEATTRANSFER
FLUIDS ON HEPATICARYL HYDROCARBON
HYDROXYLASE
ACTIVITY ..................................................................................
Materials

and Methods ..................................................................

5
6
6
6
6
7
7
7
7
10
10

A.

Animals and Treatment .........................................................

10

B.

10

C.

Enzyme Source .................................................................


3H-Benzo(a)pyrene Substrate ...................................................

D.

Aryl Hydrocarbon Hydroxylase Assay .............................................

12

Results and Discussion .................................................................

12

12

REFERENCES
..................................................................................

13

APPENDIX....................................................................................

16

ii

LIST OF TABLES
Page
Heat Transfer Fluids Proposed for Use in Residential

Table 2.

Mutagenicity

Table 3.

Typical

Table 4.

Mutagenicity

Testing of Heat Degraded Fluids .......................................

11

Tab1e 5.

AHHActivity

After Treatment With Solar Heat Transfer Fluids .......................

12

Testing of Heat Transfer

Solar Energy Applications

Fluids .......................................

Responses of Mutagens Used as Positive

iii

Controls

............................

.....

Table 1.

8
10

TOXICOLOGY OF SOLAR HEAT TRANSFERFLUIDS:

LITERATURE SURVEYAND EVALUATION OF

MUTAGENICITY
AND EFFECTON ARYLHYDROCARBON
HYDROXYLASE
ACTIVITY
C. R. Clark,

T. C. Marshall,

T. R. Henderson, A. Sanchez and C. H. Hobbs


EXECUTIVESUMMARY

The rapid expansion of solar


large numbers of dwellings.
industrial
closely

applications,
scrutinized

in active

technology

is resulting

While some of these materials

their

use in residential

for human health

hazards.

solar

literature

comprises the first

ethylene and propylene glycols,

include

and miscellaneous

despite the fact


salt.

fluids.

that its

from the standpoint

of acute exposure.
are the results

constructed

studies.

fluids

used

(petroleum

are more toxic

of two in vitro

screening procedures.

which had been subjected

silicone

class of fluids
glycol.

are propylene glycol-

than ethylene glycol

The ~zImone~la mutagenicity

for chemicals to induce mutations


has been suggested that mutagens de-

of producing positive

widely used in industry

toxic

energy applications

the potential

were evaluated in the Ames test

of heat trans-

distillates),

than ethylene

six times less toxic

of Salmonellatyphimurium.It

of ten of the fluids

The major categories

in rats is less than that of ordinary

category

is approximately

have a high probabiity

The assay is therefore

three commercial fluids


evaluation

for

that they be more

of the major constitu-

appears to be the most acutely

assay used to detect

strains

report.

hydrocarbon oils

being developed for solar

Propylene glycol

by the Ames test

on the toxicology

dose) oral toxicity

in the miscellaneous

of the newer fluids

(Ames) test is a bacterial

of this

Ethylene glycol

based formulations.

Also reported

portion

acute (single

Several fluids

large portion

tected

into

toxicologically

concern are heat transfer

for information

fer fluids

specially

have been evaluated

energy systems require

Of particular

ents of the fluids

table

of new materials

solar system designs.

A survey of the scientific

oils

i~ the introduction

results

as an initial

in animal carcinogenesis

toxicological

screen.

Twenty-

and none were found to be mutagenic. Further


to temperatures reached in solar

collectors

were also negative.


Six of the fluids
for their

ability

which contained aromatic components as their

to induce hepatic aryl

way for some chemical carcinogens.


pathway. The results
currently
studied.

reported

in progress will

Two of the six fluids


input

enhanced this

were evaluated
metabolic

systems

assessments for the materials

most likely

path-

metabolic

developed in whole animal test

for developing risk

consider the materials

of the material

major constituent

(AHH), an important

significantly

here as well as information

provide

This assessment will

and the toxicity

hydrocarbon hydroxylase

being

to be used, the population

at risk

being evaluated.
INTRODUCTION

Solar energy is expected to be particularly

useful

for the heating and cooling

of residential-

sized buildings.
The current use of solar energy to heat and cool residences is very limited.
However, it is expected to increase markedly over the next few years. One report I estimates that solar
energy could provide

up to 20% of the nations

to Congress on April

21, 1977, President

energy source for the heating and cooling


these systems and by setting

of this

Carter placed heavy emphasis on the development of this


of houses by proposing tax credits

a goal of using solar

To meet these projections


rapid introduction

energy needs by the year 2000. In his Energy Address

and goals,

new technology

energy in 2.5 million

for installation

homes by 1985.

a rapid expansion of the technology


will

many of which are not now used in homes, into

be associated

is necessary.

with the introduction

large numbers of dwellings.

of

The

of materials,

Thus, there is the

potential
for

for exposure of large numbers of people to materials

toxicity

tial

under normal or abnormal conditions.

effects

on human health

the widescale introduction


The objective
ing of buildings
materials

of materials

is essential

that an evaluation

of the poten-

used in the systems be evaluated and determined prior

to

of this new technology.

of this

study is to identify

are the most acceptable

proposed for

It

that may not have been characterized

which materials

from a standpoint

use, the heat transfer

proposed for solar

heating and cool-

of hazard to human health.

Of the

and storage media appear to have a relatively

high

potential
for hazard to man. Information
from industrial
research and development groups and from
a solar energy handbook published by Sandia Laboratories 2 aided us in identifying
heat transfer
fluids

which would most likely

in Table I. A list

find

of manufacturers

solar

applications.

and the individuals

Samples provided

by manufacturers

are listed

contacted is contained in the Appendix.

Table 1
Heat Transfer

Fluids Proposed for

Commercial Name
Silicone

Use in Residential

Solar Energy Applications

Manufacturer

Composition

Oils
General Electric
Dow-Corning

Polydimethylsiloxanes

Mobiltherm Light

Mobil Oil

Paraffinic,

high aromatic

Mobiltherm 603

Mobil Oil

Paraffinic,

neutral

Suntemp

Resource Technical Corporation

Paraffinic,

low aromatic

Exxon Corporation

Paraffinic,

low aromatic

Exxon Corporation

Naphthenic mineral oil

DowChemical

Ethylene glycol

and inhibitors

UCARThermofluid-17

Union Carbide

Ethylene glycol

and inhibitors

Dowfrost

DowChemical

Propylene glycol

and inhibitors

Solar Winter Ban

Camco

Propylene glycol

and inhibitors

Freeze Proof

CommonwealthChemical

Propylene glocol

and inhibitors

UCARFood Freeze 35

Union Carbide

Propylene glycol

and inhibitors

Nutek 835

Nuclear Technical Corporation

50% propylene glycol

Sunsol60

Sunworks

Propylene glycol

UCON50-HB-280X

Union Carbide

Polyalkylene

glycol

UCON500

Union Carbide

Polyalkylene

glycol

SF-96
DC Q2-1132

Polydimethylsiloxanes

Hydrocarbon Oils

Caloria

HT-43

Process Oil 3029

oil

Glycols
Dowtherm SR-I

and inhibitors

and inhibitors

Miscellaneous
Nutek 876

Nuclear Technical

Corporation

Concentrated inhibitors

for aqueous systems

Virco Pet 30

Mobil Chemical

Butoxyethyl acid phosphate


diethylamine adduct

Therminol 66

Monsanto

Terphenyls mixture

Dowtherm A

DowChemical

Diphenyl/diphenyl

Drewsol

Drew Chemical Corporation

Polyhydroxy-organic

Solargard G

Daystar Corporation

Glycerol/water

oxide

The likelihood

of exposure of these fluids

tenance procedures and contamination


required

that tests

these tests

ical

portion

information

at this

of this

of aryl

time.

report

on the materials.

screening procedures including


tion

water (via

for skin and eye irritation

are incomplete

The first

to the skin and eyes during installation

of potable

for more extensive

bacterial

mutagenicity

contains

findings

Also included

in this

(AHH) activity.

toxicological

assay utilizing

evaluation

specially

both frameshift

normally surrounding

wild type cells


sive,

rapid,

of the strains
deficient

agar plates

capable of synthesizing

reproducible

and yields

results

histidine

results

Those fluids

containing

ability

lase is a monooxygenase (microsomal)

enzyme responsible

excision

genes (R-factors)

Incubation

of the histidine

is inexpen-

potential,

i.e.,

are also mutagenic in the

major constituent
(AHH) activity.

with most

auxotrophs to

The Ames test

well with carcinogenic

repair

further

of the strains

scored.

capa-

Loss of the protective

deficient

in animal studies

hydrocarbon hydroxylase

and induc-

pathway provide strains

wall,

in the reversion

which correlate

of in vitro

(Ames) test

is a
5
of 5~Imonellatyphi~rium.

resistance

and are easily

aromatic components as their

to induce aryl

cell

events.

most chemicals which have demonstrated carcinogenicity


Amestest. 5

for their

of a series

type mutations.

antibiotic

to mutational

for toxicolog-

systems. The Ames test

biosynthetic

the bacterial

mechanisms and the presence of plasmids carrying


mutagens on histidine

literature

were used as an aid in selecting

strains

and base pair substitution

Results of
3,4

elsewhere.

are results

in animal test

constructed

blocks in various steps of the histidine

increase the sensitivity

report

These tests

ble of detecting

barrier

are published

a review of the scientific

Mutation-induced
lipopolysaccharide

be performed.

the salmonella~mammalian microsome mutagenicity

hydrocarbon hydroxylase

materials

and acute oral toxicity

Preliminary

and main-

leaks in hot water tank heat exchangers)

were further

evaluated

Aryl hydrocarbon hydroxy-

for the activation

of polynuclear

aromatic

hydrocarbons (PAHs) to biologically


reactive arene oxides, an obligatory
first
step in the induction
of cancer by PAHs.6 The activity
of AHH, as well as most microsomal enzymes, can be significantly
increased by exposure to a wide variety
drugs and pesticides,
non specific,
may result

cigarette

i.e.,

the activity

in either

by the inducer.

chemical carcinogenesis

it

certain
is usually

of enzymes is increased concomitantly.

or detoxification

Induction

of a chemical depending upon the spectrum

Because of the demonstrated importance of the AHH pathway in

was of interest

aromatic constituents

PAHs and other aromatics,

This phenomenon, known as enzyme induction

of a wide variety

increased activation

of enzymes affected
taining

of chemicals including

smoking, etc.

to evaluate the ability

to induce this

of the heat transfer

fluids

con-

enzyme.

LITERATURESURVEY
This section
cological

summarizes information

information

on the heat transfer

commercial preparations
studies
materials

relevant

fluids.

no information

is available

found. Their widespread use in industrial,

data is available

for toxion the

Only those

to be encountered from the use of these

energy systems are considered here. Ethylene and propylene

have mandated that toxicological

manufacturers

Practically

literature

themselves so the search centered on the major constituents.

to probable routes of exposure likely

in solar

bulk of the information


plications

gathered in a survey of the scientific

evaluations

on the hydrocarbon oil

glycol

food processing

comprised the
and medical ap-

of the two chemicals be made. Only limited


heat transfer

fluids;

the silicone

oils

have been well studied.


Ethyleneand PropyleneGlycol
Solar heat transfer
comprise a major portion

fluids

containing

of the projects

pounds have been the subject

ethylene

or propylene glycol

under investigation

of considerable

toxicological

as the major constituent

in the present studies.


inquiry

due to their

These two com-

past or present use

as drug solvents,

food additives

and anti-freezes.

78 Of the two, ethylene

glycol

is more toxic

both acutely and chronically.


It has a rat oral 24-hour LD50 (that dose which is lethal to 50% of
the animals exposed) of 5840 mg/kg, although death has been reported in humans from doses as low as
1500 mg/kg.9 Large doses of ethylene glycol to man and other animals cause a severe metabolic
acidosis

and renal failure,


the latter of which is due, at least in part, to oxalate crystal formation in the kidneys. I0~11 This chemical has demonstrated some eye irritation
in rabbits,
although
12
for both single and repeated applications
the maximumnon-damaging concentration was 20%.
Chronic studies

in which rats and mice were exposed to ethylene

glycol

as a I to 4% dietary

supplement for their life span have demonstrated that the compound is more toxic to males than
females. 1314 This difference is most likely
due to a variance in the metabolic disposition
of
ethylene glycol centering around the extent of oxalate formation. 15 A similar explanation of the
observed interspecies
susceptibility
to ethylene glycol poisoning
by experimental evidence. 1116 The most notable histopathological

has been proposed and is supported


effects following long term expo-

sure in rats and monkeys was marked kidney damage, with the former species also demonstrating slight
lung and liver anomalies. 1317-19 The highest no-effect level of ethylene glycol in the diet of
rats was reported as 0.2%. 18 None of the above-mentioned chronic studies, as well as a lifetime
exposure to subcutaneous injections
Repeated and continuous
been conducted in rats,

of this

inhalation

rabbits,

glycol

to rats,

have indicated

any carcinogenic

potential.

aerosols (I0 to 57 mg/m3) have


monkeys. 21 Repeated exposures (40

exposures of ethylene glycol

guinea pigs,

dogs and squirrel

hours per day for 6 weeks) resulted in mild to severe eye irritation
in rodents and spleen congestion
in dogs, but no deaths in any species. Ninety-day continuous exposures (12 mg/m3) caused moderate
to severe eye irritation
and inflammatory

in rodents and apparent blindness

changes in lungs were observed in all

Humanvolunteers

exposed to a mean concentration

in two of 15 rats after


21
species.

of 28 mg/m3 ethylene glycol

8 days. Deaths

vapor for 4 weeks

(actual lengths of exposure per day was not stated) complained of mild headache and backpains and
22 At concentrtaions
throat irritation.
of 250-300 mg/m3 volunteers could not tolerate
a single
3
3
breathing cycle. A threshold limit
valve (TLV) of i0 mg/m for the mist and 250 mg/m of the vapor
has been set. 23 These values represent
workers may be repeatedly

time weighted average concentrations

to which nearly

exposed for a normal 8-hour workday or 40-hour workweek without

all

adverse

effects.
The maximumconcentration to which workers can be exposed for a period of up to 15 minutes
(short-term
exposures limit or STEL) has been set at 20 mg/m3 for the mist and 325 mg/m3 for the
vapor. 23 The value of 325 mg/m3 for the vapor does not appear adequate in view of the inability
of
3.
the volunteers in the above study to tolerate
an atmosphere of 250-300 mg/m The low vapor concentration

of ethylene glycol

perature;

(0.06 mmHg at 20C) prohibits

excessive exposure to vapors at room tem-

however, escape of vapors or mists from leaks or pressure relief

is possible

at the high operating

Propylene glycol

valves in solar systems

temperatures encountered.

is much less toxic

than ethylene glycol as evidenced by an acute oral 24-hour


LD50 in the rat of 21,000 mg/kg body weight. 9 Such large doses can be tolerated by animals since
propylene glycol is rapidly elminated pez, ~ or metabolized to lactate and pyruvate allowing it to
be utilized
as an energy source. 8 In standard tests conducted on rabbit skin, propylene glycol was
24 Two chronic toxicity
not irritating.
studies in which propylene glycol was incorporated into the
diet of rats at levels ranging from 0.6 to 5.0% revealed no significant
body weight or mortality
1325
differences
compared to controls.
Neither of these investigations
nor a lifetime
skin painting
26 When propylene glycol was administest in rats demonstrated any indication
of carcinogenicity.
tered to Beagle dogs at concentrations
level.27
slight

At the 20% level


increase in total

an increase
bilirubin,

of 8 and 20% in the diet,


in the rate of erythrocyte

however, no histopathological

no effect

was observed at the 8%

hemolysis was noted along with a


abnormalities

were found.

2O

Hydrocarbon Ogl;~
Heat transfer

fluids

in this

naphthenic (40% or greater


greater
tion

paraffinic

is complicated

of crude oil.

category are petroleum products that are further

classified

naphthenic content such as Exxon Process Oil 3029) or paraffinic

content such as Suntemp I).


by the fact

that their

Acute oral toxicity

Detailed

characterization

composition will

as
(40%

and toxicological

evalua-

vary somewhat depending on the source

does not appear to be a significant

problem, since the manufac-

turers 24-hour oral LD~n values in rats for Mobiltherm light,


Mobiltherm 603 (paraffinic
oil) and
Suntemp I are 20,000, 2 57,0002 and > 45,00028 mg/kg body weight, respectively.
In addition,
data
28
on Suntemp I demonstrated that it was not irritating
to rabbit skin.
At present, no chronic
toxicity

data are known to be available.

SgZ.icone
Oils
Silicone

oils

used as heat transfer

fluids

are linear

polydimethylsiloxanes

(PDMS). Rat oral

24-hour LD50s are reported by the manufacturer to range from 30 to 50 ml/kg and higher, indicating
low toxicity. 29 The rat i.v. 24-hour LD50 for Dow-Corning 200 (a PDMS)is 500 mg/kg, which is about
0.5 ml/kg. 30 The large discrepancy between oral and systemic toxicities
can be accounted for by
data which show that PDMSis poorly absorbed from the gastrointestinal
tract. 30 Polydimethylsiloxanes
caused a temporary conjunctival
irritation
when instilled
into the eyes of rabbits, a response also
observed in humans.31 When applied to intact and abraded rabbit skin, a series of PDMSwere not
irritating

and apparently

were not absorbed. Guinea pigs tolerated

hexamethyldisiloxane

at a vapor

concentration of 25,000 ppm for 30 minutes, but died of respiratory


failure at 40,000 ppm within
this time frame. 31 However, it is unlikely that prolonged exposures to concentrations of this
magnitude would occur in man since amounts above 4,000 ppm have a distinctly
variety

of PDMSsubchronic

and chronic studies

(1.0-2.5% dietary

disagreeable

exposure to mice for

odor. A

80 weeks; 1%

exposure to rats for 90 days; 30 intraperitoneal


injection
of rats with 10-29 cc over a 40030
day period;
oral intubation
of rats with I, 2, 5, I0 and 20 g/kg over a 28-day period 31) revealed
dietary
little

or no observable

toxicity

or pathology.

No fetotoxicity

or teratogenicity

was reported

among

the offspring of rats and rabbits administered 200 to I000 mg/kg of a PDMSpreparation for 2 to 3
weeks. 32 The toxicity
of PDMSvapors is of limited interest
because of their low vapor pressure
but much attention

has been given to inhalation

of their

use in cosmetic,

extensive

valves in active

solar

with aerosols and generated mists because

household and industrial

of PDMSmay be generated by conditions


release

studies

spray formulations.

Vapors or mists

of high pressure and subsequent release through pressure

systems. Rabbits exposed to 15 one-second bursts

of a 5% aerosol

over a 7-i/2 hour period (mean chamber concentration


was 65 mg/L) showed no observable symptoms
29 Exposure to a similar aerosol (two 15-second bursts daily, 5 days/week for 13 weeks)
toxicity.
29
did not produce any gross effects or histopathologic
changes in rabbits.
Due to the stability

of PDMSand their

high resistance

concern has been expressed over the influx

of PDMSinto

to biodegradation

the environment.

that PDMSdegrades via reactions with various components in soils


33
course of these processes was not elucidated.

by microorganisms,

A recent report

and water,

stated

however, the time

MiscellaneousFluids
Several heat transfer
cations.

fluids

Therminol 66 is described

do not readily
by its

fit

into

manufacturer

any of the previously


as a modified

exposure (350 mg/kg/day for 235 days) of a commercial mixture


caused irreversible

kidney damage (interstitial

nephritis),

terphenyl

mentioned classifipreparation.

Chronic

of terphenyls

(Santowax OM) to
anemia and weight loss. 34 Exposure of

mice to an aerosol of ortho-, para- and meta-terphenyls mixture (mean concentration 0.5 mg/L, particle size 8 4 pm) produced no gross lung injury. 35 Many Type II epithelial
cells showed central

vacuolation of mitochondria but the succeeding generation of epithelial


cells showed no abnormalities.
In another study, inhalation
exposure of rats to a terphenyls mixture (OMRE, 2.55 g/m3) for 14 days
36
resulted in mortality
of one of the eight rats.
Symptomatology included pulmonary edema, bronchopneumonia and small pulmonary hemorrhages. The same terphenyls

mixture was irritating

to the

conjunctiva in rabbits and produced sensitization


and chemical necrosis following intracutaneous
injection
(guinea pigs). 36 Studies in BALB/c mice of a hydrogenated terphenyls mixture (Monsanto
37
HB-40) demonstrated that the fluid was not oncogenic when applied to the skin daily for 13-59 weeks.
The toxicity

of terphenyls

mixtures appears to be related

to their

composition of ortho,

meta and

para isomers since these possess rat oral LD50s of 1900, 2400 and greater than 10,000 mg/kg, respectively. 38 Inhalation
exposure of eight rats each to mean concentrations of about 3.5 g/m3 for I
hour resulted
14 36
days.

in 5/8, 4/8 and 0/8 deaths for

Dowtherm A is a mixture

of diphenyl

the ortho-,

meta- and para-isomers,

(26%) and diphenyl

respectively

oxide (74%). Chronic diphenyl

after

exposure

(0.5% in diet for 4 days, rat) caused polyuria and irritation


of the kidney (probably caused
deposition of insoluble crystals of the p-hydroxybiphenyl
metabolite in the tubule). 39 Inhalation
exposure of diphenyl dust (0.3 mg/l, 7 hours/day x 54 days) of rats led to an irritation
of the
40
nasal mucosa.
Repeated inhalation
exposures of rats, rabbits and dogs to diphenyl oxide vapors
41 Eye
(4.0 ppm, 7 hours/day, 5 days/week for 4 weeks) produced no signs of toxicity
or irritation.
and nasal irritation
vapors.41

were observed in rats and rabbits,

but not dogs at I0 ppm diphenyl

oxide

24-hour oral LD50 of diphenyl oxide was reported to be 3.37 g/kg and acute
dermal LD50 as > 5 g/kg. 42 In humans, exposure to 7-10 ppm of a eutectic mixture of diphenyl/diphenyl
oxide vapors was extremely nauseating and painful to the eyes and upper respiratory
tract. 43 It is
not likely

The acute rat

that excessive exposure to vapors would go unnoticed because the striking


as low as 7 ppm.41

odor of Dowtherm

A is apparent at concentrations

Virco Pet 30 is a butoxyethyl

acid phosphate diethylamine

adduct. Manufacturers

data lists

the rat 24 hour oral LD50 at 6830 mg/kg, and states that rats tolerated an inhalation exposure of
44 Irritancy
23 mg/L for i hour without lethality.
studies in rabbits generated an eye score of
29/110 at 24 hours and primary
44
irritant.

skin score of 2.5/8.0,

classifying

Virco Pet 30 as a moderate

EVALUATION OF SOLAR HEAT TRANSFERFLUIDS FOR MUTAGENICITY


Matertalsand Methods
A.

Heat Transfer Fluids


Comercially

and diluted

available

heat transfer

in dimethylsulfoxide

fluids

(DMSO, spectral

were obtained from the manufacturers

quality)

sealed in evacuated pyrex tubes and heated at 232C for


encountered in closed-system
fluids

as obtained per test


B.

Preparation

collectors.

Concentrations

for

evaluation.

10 days to simulate
tested

stagnation

were

conditions

ranged from 1 to 10,000 ~Jg of the

plate.

and Culturing

of Tester Strains

Top agar (0.6% Difco agar/O.5% NaCl) was autoclaved just


0.5 mMhistidine/O.5

(Table 1)

Ten of the fluids

mMbiotin

added after

cooling

prior

to use and 10 ml of sterile

top agar in a 45~C water bath. Minimal agar

plates contained 1.5% Bacto-Difco

agar in Vogel-Bonner E medium (0.03% MgSO


4 7H20, 0.3% citric
acid H20, 1.5% K2HPO
4, 0.525% NaNH4PO
4 4H20) with 2% glucose. Nutrient agar plates (2.3%
nutrient agar, 0.5% NaCI) were used for evaluation of bacterial
cell suspension population and cytotoxicity.

SalmonelLa typhim~ri~n

strains

TA-1535, TA-1537, TA-1538, TA-98 and TA-IO0 (provided

Bruce Ames, University of California,


Berkeley) were grown in nutrient broth (0.8% nutrient
broth/0.5% NaCl) for 16 hours prior to use in a 37C shaking water bath.

by

C.

Preparation

.of Liver

Homogenate(S-9~

Livers from male Fischer-344


Aroclor

1254 (500 mg/kg, ip)


in small vials

colony) treated

with

were excised and homogenized in ice cold 1.15% KCI 5 days after

ment. Homogenates were centrifuged


distributed

rats (250-300 g, from the Institutes

for

and quickly

I0 minutes at 9000 X g and the supernatant


frozen (-70C).

The S-9 was thawed just

(S-9)

prior

treat-

collected,

to use and

mixed with an appropriate amount of cofactor solution (8 mMMgCl2, 33 mMKCl, 5 mMglucose-6phosphate, 4 mMNADP) in 0.2 M phosphate buffer (pH 7.4) and filter
sterilized
(0.45 ~m Millipore
filter).

To determine the amount of S-9 required

for mutagens requiring

metabolic

activation,

per ml cofactor

(0.04 ml S-9/ml cofactor

D.

Bacterial

Mutaqenicity

Maximumreversions

were obtained at 20 ul S-9

solution).
Assay
by Ames ~t al. 5 Test tubes containing

The assay was conducted as described

agar were kept in a 45~C water bath. To 2 ml of the agar, 0.1 ml bacterial
test

compound and 0.5 ml sterile

poured onto a petri


per dose level

E.

tested.

Controls

saline

dish containing
After

manually or with a Fischer

strains:

it

suspension,

incubating

at 37C in the dark for

top

0.I

or S-9 mix were added in sequence, then mixed gently

and Quality

ml

and

were evaluated

48 hours colonies

were counted

Assurance
controls

N-methyl-N-nitro-N-nitrosoguanidine

(9-AA; I0 l~g/plate

2 ml soft

automatic colony counter.

and TA-IO0); 2-aminofluorene


mutagenicity,

cell

minimal glucose agar. A minimum of two plates

Known mutagens were used as positive


tester

to maximize reversions

varying amounts of s-g were tested using TA-IO0,

TA-1538 and TA-98 exposed to I0 ug 2-aminofluorene.


per plate

solution

(2-AF, I0 ug/plate

in ethanol,

to confirm the reversion

(MNNG,10 ~ig/plate

properties

dissolved

of the

in DMSO,TA-1535

in DMSO,TA-1538, TA-98, TA-IO0); and 9-aminoacridine

TA-1537). Since 2-AF requires

metabolic

also served to confirm the enzymatic activity

activation

to express

of the S-9 mixture.

Spontaneous (background) reversion rates were determined by substituting


DMSOfor the test
-6
compound in the assay. Bacterial cell populations used in the test were determined by adding 10
dilutions
(0.i ml) to 2 ml top agar and layering on nutrient
agar plates. Cytotoxicity
to the tester
strains was determined by adding 0.I ml of the 10-6 cell suspension to 2 ml top agar, 0.I ml test
compound and 0.5 ml sterile

saline

and layering

to controls

(DMSOsubstituted

The saline,

S-9, DMSOand heat transfer

plates

for test

on nutrient

agar plates.

Decreased growth compared

compound) was taken as an indication


fluids

of direct

cytotoxicity.

used in the assay were streaked on nutrient

agar

to ensure they were not contaminated with bacteria.

~esuIL.sand Discussion
Despite a certain
generally

from mutagenic events.


tion

amount of controversy

rates of the tester

For this

reason, it

strains

Solar heat transfer


activity.
strains
within

is extremely

important

can result

of Ames test

reported

in an initial

fluids

were evaluated

in Table 2, indicate

the range of variability

it

controls

different

sensitivity.

or loss of the

For substances with low


to demonstrate reproducible

at doses ranging from I to i0,000

ug/plate.

as tested produced significant

confirmed the revertant

for the laboratory.

is

from the historical

properties

The remutagenic

of the tester

of the S-9 mix (Table 3), and spontaneous reversion

established

it

results

to monitor the spontaneous muta-

is desirable

that none of the fluids

The mutagens used as positive


and the enzymatic a~tivity

screen,

results,

number of revertants

from poor growth of the culture

plasmids (TA-98 and TA-IO0) which can decrease their

or questionable mutagenic activity


5
dose-response relationships.

sults,

interpretation

to ensure they are not significantly

background. Low background revertants


R-factor

surrounding

agreed that a response of twice the spontaneous (background)

rates were

Table 2
Mutagenicity

Heat Transfer Fluid

~_~te~

Testing of Heat Transfer

Fluids

Number of Revertants
(Without-With Metabolic aActivation)
S. typhimur<~zStrain
TA-1537
TA-1538
TA-98

TA-1535

135-111
111-112
110-128
145-128

SF-96

0
10
100
1000

22-13
7- 7
12- 7
8- 7

7-18
5-10
7-10
5- 7

9-33
9-38
9-35
7-36

18-57
11-39
20-41
22-50

Mobiltherm Light

0
I
10
100
i000

12-16
7- 9
6- 0
O- 0
O- i

12-15
2- 2
3- 2
3- 2
O- 3

9-18
3~23
2- 5
O- 0
5-16

11~17
23-46
0-19
13- 0
26-28

Mobiltherm 603

0
1
10
100
1000

19141277-

8-10
4- 7
6- 7
4- 7
8- 9

6-42
6-33
16-30
9-31
8-12

12~39
16-50
15-46
21-40
16-22

7
9
5
5
5

11-36
12-27
9-34
14-17
25-14

15-45
20-48
21-37
13~25
26-21

i17-121
134-122
143-130
102-120
127-120

9-33
7-45
7-37
3-39

18-57
11-40
16-34
16-37

135-111
101-109
97- 96
85- 96
117-121
133-133
121-151
116-132
98-136

Suntemp

7
5
8
8
4

5101169-

0
10
100
I000
i0000

22-17
20- 9
28-11
20-10
-

0
10
i00
I000

22-13
17- 5
21-12
12- 6

7-18
8- 5
6- 4
5- 7

0
10
100
i000
10000

22-17
19-10
26- 9
24-10
13-11

59566-

7
8
9
4
6

11-36
10-38
10-27
9-14
9-17

15-45
19-37
20-36
17-27
16-13

Dowtherm SR-1

0
I
10
i00
1000

12-16
7- 5
7- 3
5- 4
3- 7

12-15
2- 8
5- 5
2- 5
5- 7

9-18
8-31
8-45
8-29
7-23

11-17
20-55
31-46
25-35
17-40

UCARThermofluid-17

0
1
10
i00
I000

19- 7
16- 8
10-12
6-10
9- 7

8-10
8-11
7- 5
8- 8
6- 5

6-42
5-41
8-24
6-33
9-21

12-39
7-18
6-40
9-45
13-54

Dowfrost

0
1
10
i00
I000

12-16
7- 5
8- 6
8- 8
i0- 5

12-15
4- 5
3- 9
O- 0
O- 6

9-18
3-22
5- 8
3- 0
7-24

11-17
23-59
18~50
24-42
8-37

Solar Winter Ban

0
100
1000

7- 6
4- 2
8- 8

3- 7
3- 4
4- 5

6-12
2-12
10-13

9-24
14-28
19-15

Freeze Proof

0
100
1000

7- 6
8- 4
6- 5

2- 7
3- 3
1- 2

6-12
5-10
4- 6

9-24
13-18
13-17

Caloria HT-43

Process Oil 3029

Table 2 (Continued)
Number of Revertants
a
(Without-With Metabolic Activation)
s. typhim~ium Strain
TA-1537
TA-1538
TA-98

ug/Plate b

TA-1535

UCAR-35

0
1
10
I00
1000

19- 7
13- 7
9- 6
14-10
16-12

8-10
44 4
6- 4
9-11
5- 7

6-42
9-36
9-28
9-46
12-45

12-39
18-50
19-54
21-64
19-59

Nutek 835

0
10
100
i000

10-12
13-13
16-13
13-12

17-39
19-15
13-35
17-33

25-63
30-58
32-62
31-57

174-156
173-169
185-171
174-173

Sunsol 60

0
100
1000

7- 6
5- 4
8- 6

3- 7
3- 2
24 2

6-12
6-12
3-13

9-24
10-22
7-17

126-142
127-137
143-143

UCON-50

0
10
100
1000

UCON-500

0
1
10
100
I000

19- 7
17- 7
18-11
12- 7
ii- 7

8-10
7- 7
9~ 7
6- 5
i- 5

6-53
14-43
12-30
8-32
15-17

23-39
20-54
19-49
21-42
18-26

Nutek 876

0
10
100
1000

10-12
15-18
10-18
14-11

17-39
20-42
11-37
11-58

25-63
24-57
21-55
14-50

Heat Transfer

Fluid

9-33
10-20
6-36
4-12

TA-IO0

135-111
97-105
95- 58
113- 97

174-156
172-172
167-179
176-182

Virco Pet-30

0
100
1000

7- 6
7- 4
8- 8

3- 7
5- 4
3- 5

6-12
5- 7
5-11

9-24
7-10
13-22

Therminol 66

0
10
100
I000

22-13
27~ 8
27- 8
I0- 8

7-18
9- 7
8- 7
10- 9

9-33
7-45
9-21
16-23

18-57
11-28
12-28
16-28

135-111
127-134
107-139
111-113

7
6
5
5
0

11-36
10-29
13-26
4-16
O- 0

15-45
17-39
11-36
12-24
O- 0

117-121
135-124
96-130
66- 62
42- 53
126-142
133-138
128-143

Dowtherm A

0
10
I00
I000
I0000

5743O-

Drewsol

0
100
1000

7- 6
10- 4
12- 5

3- 7
4- 2
3- 2

6-12
6-16
3-12

9-24
12-16
10-12

Solargard G

0
100
1000

7- 6
6- 5
8- 8

3- 7
3- 5
1- 3

6-12
2- 5
I- 4

9-24
13-17
ii-II

aMetabolic

activation

bDosage indicated

by Aroclor

was delivered

1254 induced rat liver


in 0.I ml DMSO.

microsomal preparations.

Table 3
a
Typical
Spontaneous
Revertants

Responses of Mutagens Used as Positive

Number of Revertants
Salmonella
ty,ph<rr~r<um
Strain
TALl537
TA-153B
TA-IOO

TA-1535
20

160

25

175

MNNG(10 ~g)

> 2000

> 2000

9-AA (I0 ~Jg)

200
> 1000

Saline
b
s-g

2-AF (I0 ug)/saline


2-AF (I0 ~Jg/S-9
aused to confirm
bLiver

reversion

properties

microsomal preparations

Controls

of tester

T--AZ-g~-.

25

40

40

55

> I000

70

90

> 2000

> 2000

7
I0

strains.

from Aroclor-1254

induced rats.

Virco Pet-30, Mobiltherm Light and Dowtherm A were toxic to the tester strains at the higher
-6
doses. Mobiltherm Light and Dowtherm A caused 75% and 100% cell death to the tester strains (10
dilution),
respectively,
at I000 ~g/plate.
No mutagenicity was observed at doses which were not
44
toxic. Virco Pet-30 was reported to be negative in the Ames test by other investigators.
Ten fluids
not flowing

were subjected

to heating

at 232C to simulate

through the system (pump failure

changes occurred in many of the fluids

indicating

were mutagenic (Table 4). Mobiltherm Light


Studies are in progress to characterize
with collector
transfer
~ically

materials

fluids

(copper,

temperatures

reached when fluid

or normal occurrence in draindown systems).

is

Color

some chemical decomposition but none of the fluids

and Dowtherm A were again cytotoxic

changes in chemical composition

aluminum, etc.)

and it

is anticipated

used in Department of Energy Solar demonstration

at the higher doses.

of the fluids

when heated

that samples of solar

projects

will

heat

be evaluated chem-

and toxicologically.
The results

reported

here for 24 heat transfer

for lack of mutagenicity

(or carcinogenicity).

events which are not necessarily


formulations

fluids

Salmonella

induced by all

cannot be considered unequivocal evidence


systems detect

mutagens. In addition,

such as these may not detect trace quantities

highly

specific

Ames testing

mutational

of complex

of mutagens which might be present.

INFLUENCE OF SOLAR HEAT TRANSFERFLUIDS ON HEPATIC ARYL HYDROCARBON


HYDROXYLASEACTIVITY
Materialsand Methods
A.

Animals and Treatment


Male Fischer-344

vided food and water ad lib


shavings.

Roomtemperature

rats (COB CD F/Crl


(Lab-Blox,

Allied

Br, 220-300 g) from the Institutes


Mills,

Chicago, IL),

was maintained at 70 2C and lighting

and kept on sterilized


schedule was constant

In all studies, animals were sacrificed


between 0900 and i000. Six heat transfer
obtained from the manufacturers were evaluated. Three animals each were injected
between 0900 and 1000 with either

heat transfer

AHHinducer),

Animals were sacrificed

B.

or saline

(0.2 ml).

fluid

colony were pro-

(500 mg/kg), Aroclor


3 days after

aspen
(12L:12D).

fluids (Table 5)
intraperitoneally

1254 (500 mg/kg, a known

treatment

by decapitation.

Enzyme Source
Livers were excised,

weighed and homogenized in 3 volumes of ice cold 1.15% KCI and centri-

fuged (9,000 x g x 10 min) in an ultracentrifuge.


The supernatant was removed and protein
tration
determined. 45 Supernatants were stored in glass vials at -70C until used.

10

concen-

Table 4
Mutagenicity

Heat Transfer

~g/Plate c

Fluid

Testing of Heat Degradeda Fluids

TA-1535

Number of Revertants
b
,(Without-With Metabolic Activation)
s, typhimu~uln Strain
T--A~-i53~/
TA1538
TA-98

TA-IO0

UCON500

0
1
10
i00
I000

45-14
31-13
60-12
41-14
51-10

16-15
17-17
24-16
20- 8
15-14

13-37
12-56
17-46
14-37
15-14

23-53
19-60
19-56
29-54
17-40

187-116
150-113
144- 86
136-114
139- 91

UCON5O

0
I
10
I00
i000

45-14
43-16
47- 9
49-15
49-11

16-15
20-19
16-14
27-14
16-11

13-37
6-25
14-33
8-31
17-20

23-53
24-54
26-53
28-44
18-34

187-116
139-124
148-120
145-122
160-124

Suntemp

0
1
i0
i00
I000

45-14
44-14
51-17
46-15
46-16

16-15
12-14
32-13
24-12
25-10

13-37
13-31
16-35
8-36
12-17

23-53
27-46
27-43
30-55
24-38

187-116
151-123
150-143
170~I02
125- 97

Mobiltherm 603

0
1
10
I00
I000

45-14
46-14
32-10
37-13
35-14

16-15
27-9
24-12
25- 9
17- 9

13-37
13-30
12-44
11-37
12-22

23-53
19-53
21-50
27-50
27-33

187-116
157- 91
134- 87
161-120
148-122

0
10
100
I000
I0000

9122OO-

7
9
5
0
0

10-13
7-10
2- 8
O- 0
O- 0

7-40
8-41
11-27
O- 0
O- 0

9-37
8-39
8-31
4-26
O- 0

152-141
118-119
73- 72
17- 41
O- 0

Mobiltherm Light

0
10
100
i000
I0000

9595O-

7
5
3
i
0

10-13
8- 9
5-10
6- 7
O- 0

7-40
10-21
11-23
7-41
O- 0

9437
12-34
10-37
8-39
O- 0

152-141
90-150
73-159
53-108
O- 0

Therminol 66

0
i0
100
1000
10000

8- 7
10- 4
8-11
ii- 5
6- 2

10-13
5- 5
6-11
6- 3
3- 3

7-40
6-30
9-22
10-14
7-12

9-37
13-32
12-16
11-18
5-23

152-141
125-130
117-154
123-116
132-161

UCAR-17

0
I0
100
i000
i0000

14-10
24-11
15-11
17-15
20-10

14-33
14-33
15-33
13-31
12-43

185-111
116- 92
128- 97
103- 88
119- 99

Process Oil 3029

0
10
100
1000
10000

19~I0
17-14
20-15
13-13
16-10

14-33
13-31
16-34
11-19
11-26

185-III
126-123
119-110
114-118
120- 73

0
10
i00
I000
I0000

19-10
19-18
24-23
17-22
25-26

14-33
15-36
16-45
16-40
14-37

185-111
121- 84
127- 30
111-115
113-117

Jowtherm A

SF-96

aFluids

heated in evacuated pyrex tubes at 232C for 10 days.

bMetabolic activation
CDose indicated

by Aroolor 1254 induced rat

delivered

liver

in 0.I ml DMSO.

11

microsomal preparations.

Table 5

C.

AHHActivity
After Treatment with Solar
a
Heat Transfer Fluids

A stock solution
was diluted

n moles
product/min/mg
Protein
Mean s.d.

Treatment

3H-Benzo(a)pyrene Substrate

tivity

of 3H-BAP (= 25 Ci/mM)

with unlabeled BAP to a specific

of 30 mCi/mmol, dissolved

and extracted

five

KOH/DMSO
(15/85;

times with 50 ml aqueous 1M

v/v)

to eliminate

contaminants.

The hexane was evaporated under nitrogen


Saline

0.8 0.I

Dowtherm A
Mobiltherm 603

1.0 0.3
b
2.9 0.7
b
1.2 0.I

Suntemp

0.8 0.I

Caloria HT-43

0.9 + 0.2

Therminol 66

0.9 0.I
b
3.1 0.3

Mobiltherm Light

Aroclor 1254
(positive control)

and the

residue resuspended in acetone such that I0 pl


acetone resulted in a BAP concentration
mMin the 1.0 ml incubation system.
D.

Aryl Hydrocarbon l~droxylase

of 0.08

Assay

The method used to determine AHHactivity


46
was basically that of Van Cantforts.
Activity
was determined by incubating

enzyme preparation

(corresponding to approximately 0.5 mg protein)


with the 3H-BaP substrate for 10 minutes. Dupli-

a500 mg/kg, ip, 3 days before sacrifice.


bsignificantly
greater than control
(p < 0.005, students t test).

cate incubations

of each liver

homogenate were

conducted. Total incubation volume was 1.0 ml and


contained NAD(0.43 mM), NADP(0.37 mM), glucose-

6-phosphate (2.5 mM), glucose-6-phosphate


MgCI2 (5 n~I),
enzyme protein

ac-

in i00 ml hexane

dehydrogenase (1.0 l.U./ml),

Tris

buffer

(50 mM, pH

3H-BaP (0.08 mMdissolved in I0 ul acetone), bovine serum albumin (0.8 mg/ml) and
in 0.1 ml KCI. Blank values were obtained by running the assay in the absence of

enzyme.
The reaction was stopped by the addition of I ml KOH(0.15 M in 85% DMSO)and the unmetabolized
3H-BaP was extracted (3 x 5 ml with hexane). The aqueous phase (0.5 ml) was transferred
to a scintillation

vial

containing

0.5 ml 1N HCI and I0 ml Instagel.

The cpm obtained

by liquid

tion counting of the samples for I0 minutes were converted to nanomoles total metabolite
specific activity
of 3H-BaP substrate) and expressed as nanomoles formed/min/mg protein.

scintilla(based on

Resultsand Discussion
The six commercial heat transfer
oils

(Mobiltherm

Caloria

Light,

fluids

tested included

Mobiltherm 603 and Suntemp) and three synthetic

HT-43 and Therminol 66). The doses used produced no toxic

The AHHactivity

measured in liver

microsomal preparations

mals is summarized in Table 5. The AHH activity


603 and Mobiltherm Light
controls.

were significantly

Treatment with Aroclor

and confirmed the inducibility


The results
two positive

of this

fluids,

in preparations

from petroleum crude

aromatic

from the treated

(Dowtherm

resulted

animals.

and untreated

from animals treated

ani-

with Mobiltherm

measured in untreated

in the highest

AHH activity

of the rats used in the study.

study do not imply the presence of PAHs or carcinogenic


to enhance the hydroxylation

activation

Whether the net effect

of some PAH carcinogens

of the induction

of a PAH is dependent upon the chemical,


is beyond the scope of this

fluids

symptoms in the test

higher (p < 0.005) than activity

1254, a known AHHinducer,

only an ability

role of AHHin the metabolic


monitor.

three distilled

of aryl
makes it

potential

hydrocarbons.
an important

demonstrated would be activation

of the

The key

enzyme to

or detoxification

extent of exposure and animal species being considered and

study.

12

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15

APPENDIX
MANUFACTURERS
PROVIDING HEAT TRANSFERFLUID SAMPLESFOR TOXICOLOGICAL EVALUATION

CAMCO
MANUFACTURING,
INC.
2804 Patterson Street
Greensboro, NC 27407
(Mr. Don Caine)
SOLARWINTERBAN

GENERAL
ELECTRICCOMPANY
SILICONESDIVISION
Waterford, NY 12188
(Dr. John Nair)
SF-96

COMMONWEALTH
CHEMICAL
1052 Gorham Street
Lowell, MA 01852
(Mr. Marry Paulson)
FREEZEPROOF

MOBIL OIL CORPORATION


P. O. Box 240
Edison, NJ 08817
(Dr. T. Ellison)
VIRCO PET 30
MOBILTHERM
603
MOBILTHERM
LIGHT

DAYSTAR
CORPORATION
90 Cambridge Street
Burlington,
MA 01803
(Mr. Jim Hall)
SOLARGARD-G
DOWCHEMICAL,USA
2020 Dow Center
Midland, MI 48640
(Dr. Paul J. Moses)
DOWEROST
DOWTHERM
SR-1
DOWTHERM
A

MONSANTO
INDUSTRIALCHEMICALS
COMPANY
1401 Dove Street
Newport Beach, CA 92663
(Mr. Ken Brakebill)
THERMINOL
66
NUCLEARTECHNOLOGY
CORPORATION
P. O. Box 2, Rt. 85
Amston, CT 06231
(Dr. Dennis Jakiela)
NUTEK835
NUTEK876

DOWCORNINGCORPORATION
Biological Services
2020 Dow Center
Midland, MI 48640
(Dr. Charles L. Groh)
DC Q2-1132

RESOURCE
TECHNOLOGY
CORPORATION
151 John Downey Drive
New Britain,
CT 06051
(Mr. Don Caine)
SUNTEMP

DREWCHEMICALCORPORATION
1 Drew Chemical Plaza
Boonton, NJ 07006
(Dr. Elliott
J. Levi)
DREWSOL

SUNWORKS,
DIVISION OF ENTHIONE,INC.
P. O. Box 1004
New Haven, CT 06508
(Ms. Ruth Smith.)
SUNSOL-60

EXXONCORPORATION
Marketing Technical Services
P. O. Box 2180
Houston, TX 77001
(Dr. Thomas G. Lipscomb)
PROCESS
OIL 3029
CALORIAHT-43

UNIONCARBIDE
17 Executive Park Drive
Atlanta, GA 30359
(Dr. Sam Livengood)
UCARFOODFREEZE35
UCARTHERMOFLUID
17
UCON50-HB-280-X
UCON5OO
PROPYLENE
GLYCOL,USP

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