EPA-560/8-75-001
           ENVIRONMENTAL HAZARD ASSESSMENT REPORT
                  CHLORINATED NAPHTHALENES
                        DECEMBER 1975
               ENVIRONMENTAL PROTECTION AGENCY
                 OFFICE OF TOXIC SUBSTANCES
                   WASHINGTON, D,C,  2QwO

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                           PREFACE

     Our society uses thousands of  chemical  substances,  with  many  of
them released into the environment  in  varying  quantities as production
or handling losses, as waste materials,  or as  a direct consequence of
their intended or unintended uses.   Concern over possible effects  of
these chemicals has prompted the establishment by the Early Warning
Branch of the Office of Toxic Substances of a  program to review data on
the release, exposure, and effects  of  chemical substances in  order to
assist in setting priorities for further study or possible regulatory
action.

     Detailed analyses on every commercial chemical  are not practical.
Selected materials are initially screened with a simple literature
search; a limited number of these chemicals are selected for  more
detailed study.  Criteria for this  selection include volume of production,
manner of use, market growth potential,  exposure patterns, detection in the
environment, known toxic effects, and  functional or chemical  relationships
to known environmental pollutants.   Chlorinated naphthalenes  were  selected
for detailed study because of the serious occupational health problems
suffered by workers exposed to the compounds,  cattle poisoning incidents
in the late 1940's and early to mid 1950's, 1972 production levels of
some five million pounds, and chemical similarities to polychlorinated
biphenyls.  The early warning screening system uses diverse sources,
including opinions of experts, referrals from other units of government,
reports in. the scientific and trade literature, predictive modelling,
and public inquiries.

     These hazard assessments are prepared from reviews of the subject
substances supplemented by additional  searches and inquiries  to obtain
the most complete and recent information available.  Only data considered
pertinent to an assessment of environmental hazard are reported in this
series.


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     Although the assessments use as complete an information base as
possible, additional information may be available or may become available.
Therefore, these assessments are subject to revisions. The Office of
Toxic Substances welcomes any additional pertinent data.

     Recommendations in this document are those of the Office of Toxic
Substances and may not represent an Agency consensus.  Nor do they
represent commitment to further action by the Environmental Protection
Agency or any other organization. Tradenames and manufacturers are
mentioned in this document for purposes of clarity and specificity only
and do not constitute an endorsement of any product.
     This report was written by Frank D. Kover.  The Environmental
Hazard Assessment Series is being prepared under the guidance of Dr.
Farley Fisher, Chief of the Early Warning Branch, Office of Toxic
Substances.
     The literature review which preceded this assessment was conducted
by Dr. Philip Howard and Mr. Patrick Durkin of the Syracuse University
Research Corporation, Syracuse, New York.   That review was supplemented
by consultations with selected knowledgeable individuals both within and
outside the  Federal Government and is part of a report entitled Preliminary
Environmental Hazard Assessment of Chlorinated Naphthalenes. Silicones.
Fluorocarbons, Benzenepolycarboxylates, and Chlorophenols, available
through the  National Technical Information Service, Springfield, Virginia
22151  (NTIS  accession number - PB-238 074/AS).
                             -11-

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                               TABLE OF CONTENTS
     PREFACE	    1
     LIST OF  FIGURES	   iv
     LIST OF  TABLES	   iv
     CONCLUSIONS  AND  RECOMMENDATIONS	    1
     SUMMARY  OF TECHNICAL  DISCUSSION	    3

I.    GENERAL  INFORMATION	!	    4
II.   ENVIRONMENTAL  EXPOSURE  FACTORS	   12
III.  BIOLOGICAL EFFECTS	   19
IV.   HANDLING PRACTICES,STANDARDS,AND REGULATIONS	   32
     REFERENCES	   33
                              -in-

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                            LIST OF FIGURES
Figure 1

Figure 2


Figure 3
Monochloronaphthalenes,
Suggested Route of Decomposition of
1-Chioronaphthalene by Soil Bacteria.,

Proposed Mechanisms of Naphthalene Di-
hydrodiol Formation in Mammalian and
Microbial Systems	
 5


16



17
Table I.


Table II.
        LIST OF TABLES

     Comparative Properties of Halowax
     Chioronaphthalenes	

     Uses of Chlorinated Naphthalenes..
  6

 11
                              -TV-

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     Appreciation is expressed to the many individuals  who  provided
information and reviewed drafts of this  report.   Special  appreciation
is expressed to the Office of Toxic Substances  Staff, and to  Dr.  J.G.
Vos of the Institute of Veterinary Pathology, University  of Utrecht, the
Netherlands, for valuable comments and information concerning European
work on chlorinated naphthalenes and related chlorinated  hydrocarbon
compounds.  Comments and suggestions incorporated into  this report were
contributed by Guy Nelson, U.S. EPA/NERC-Corvallis; Dr. Donald I.
Mount, Director, EPA-National Water Quality Laboratory, Duluth;  Dr.
Gilman Veith, EPA-National Water Quality Laboratory, Duluth;  Dr.  Gerald
Bowes, California Water Resources Board, Sacramento; John P.  Lehman,  EPA
Office of Solid Waste Management Programs, Hazardous Waste  Management
Division, Washington, D. C.; George B. Morgan,  EPA/NERC-Las Vegas; Dr.
Charles F. Jelinek, FDA, Bureau of Foods, Division of Chemical Technology,
Washington, D.C.; and Daniel F. McCarthy, U.S.  International  Trade
Commission (formerly U.S. Tariff Commission).
                              -v-

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               CONCLUSIONS AND RECOMMENDATIONS

     The largest use of the chlorinated naphthalenes  employs  the lower
chlorinated compounds in a temporarily "closed"  system (automobile
capacitor).  The extent to which these compounds leach out or are
otherwise released from the capacitor to the environment has  not been
determined; should release occur, they are likely to  be readily decomposed.

     The more toxic higher chlorinated members of this class  are produced
at the rate of a half million pounds per year.  Whether or not these
compounds persist in the environment is unknown, but  their chemical
similarities to polychlorinated biphenyls (PCBs) arouse some  suspicion.
In addition, traces of higher chlorinated naphthalenes have been detected
in one species of water fowl in the Netherlands.  Only two reports of
chlorinated naphthalenes in U.S. environmental samples have been cited.
Amounts of these compounds released to the environment as a result of
their use seem low.

     Overall, the available information on the chlorinated naphthalenes
suggests that the potential environmental hazard associated with these
compounds warrants a moderate level of concern.   The  available monitoring
data from limited U.S efforts could represent just some isolated
contamination or indicate a more widespread problem that is just beginning
to be detected.

Recommendations

1.   The environmental hazard posed by these chemicals should be reassessed
if:  (a)  chlorinated naphthalenes are detected with  greater frequency
in environmental samples by FDA  (food), EPA, or others; (b) production
levels of penta- and hexachloronaphthalenes double; or (c) new use(s) of
these compounds with higher exposure potential is proposed.
                             -1-

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2.   The environmental persistence of the higher chlorinated naph-
thalenes should be determined.

3.   Monitoring should be undertaken in the vicinities of electro-
plating activities discharges,  waste oil  discharges,  electronic parts
manufacturing wastes, landfill  disposal activities, as well  as effluent
from the production plant.   Samples should be taken from water sediments
since these compounds are water insoluble. Some of this monitoring might
be carried out in conjunction with future monitoring programs for PCBs
and chlorinated hydrocarbons, and particularly pesticides.

4.   Further investigation to determine the environmental fate of the
penta- and hexachloronaphthalenes will be necessary if monitoring data
indicate their presence near electroplating activities.

5.   The potential for chlorinated naphthalenes to undergo epoxi-
dation similiar to dieldrin has led to some concern about carcinogenic
implications.  The metabolic fate of these compounds with regard to
epoxide formation should be determined.
                              -2-

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               SUMMARY OF TECHNICAL DISCUSSJON

     The chlorinated naphthalenes enjoyed large scale use  prior to  and
during World War II.  Capacitor and cable manufacturers  used  them as
dielectrics and water repellents superior to paraffin wax.  Other industrial
applications of that era included use as additives  for high-pressure
lubricants, as wood preservatives, and as synthetic waxes  and impregnants.
Today their major uses are confined to use as a paper impregnant in
automobile capacitors (dielectric), and as an oil  additive to clean
sludge and petroleum deposits from engines.  Two minor uses of potential
environmental significance are in the electroplating industry (stopoff
compounds) and in the fabric dyeing industry.
     Available production and market information on these  compounds
indicates that total production has declined somewhat over the last
decade and a half, probably at least in part due to severe occupational
skin problems (chloracne) associated with the higher chlorinated compounds,
especially the penta- and hexachloronaphthalenes.  The lower chlorinated
naphthalenes (mono-, di-, tri-, and tetrachloronaphthalenes)  form the
bulk of today's market and are not associated with severe  toxic manifestations.
     The levels of chlorinated naphthalenes which are important from a
toxicity standpoint show rather wide variation in toxic response from
species to species.  In general it is somewhat useful to consider the
toxicity of the chlorinated naphthalenes to increase with  the degree of
chlorination.  The penta- and hexachloronaphthalenes elicit the most
severe toxic responses.  Mono- and dichloronaphthalenes have relatively
low toxicity.  One of the most susceptible animals is the  cow.
     The lack of homogeneity in human response has prevented the establishment
of a no-effect level.  Industrial hygiene standards of 0.5 mg/m  in air
                                       3
for pentachloronaphthalene and 0.2 mg/m' for hexachloronaphthalene are
designed to minimize the incidence of chloracne and to prevent liver
damage.
     A foreign report of traces of chlorinated naphthalenes in one
species of fish eating birds appears to demonstrate a potential for
bioaccumulation.  Only two reports of detection in environmental samples
from the U.S. are known.
                                   -3-

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I.    GENERAL INFORMATION
Physical  and Chemical  Characteristics

     In general, the chlorinated naphthalenes are water insoluble waxy
solids exhibiting a high degree of chemical  and thermal stability.  Their
physical  properties vary with the degree of chlorination.   The mono- and
dichloronaphthalenes are liquids at room temperature whereas the higher
chlorinated compositions are solids.  As the chlorine content increases,
the specific gravity,  boiling point, melting point, fire point and flash
point all increase while vapor pressure and water solubility decrease.
     The structure of the chlorinated naphthalenes consists of the
naphthalene double ring where any or all of the eight hydrogen atoms can
be replaced with chlorine (C-mH/c)  \C1 ) (Figure 1.). The commercial
products are generally mixtures with different degrees of chlorination
and the dominant species is indicated by the percent chlorine content
attributed to the product (Table I).  No data from manufacturers are
available on the ratios among the structural isomers in the commercial
products.  The commercial products are sold as refined chloronaphthalenes
(Table I)  and as chloronaphthalene crudes.  The product bulletin (Koppers,,
a) describes the crudes as having essentially the same physical properties
as the refined products, but "not held within close limits".  It suggests
they are suitable for many applications where dark colors are acceptable.
Amounts of the crude forms produced are a minor portion of the total
production (Hoy, 1975).   Possible impurities of these products are
chlorinated derivatives, corresponding to the impurities in coal tar, or
petroleum-derived naphthalene feedstock which may include biphenyls,
fluorenes, pyrenes, anthracenes, and dibenzofurans (Hunt and O'Neal, 1967).
Koppers'  Research Department analyzed the company's naphthalene feedstock
(refined coal tar base) and did not detect any trace of biphenyls or
dibenzofurans (Hoy, 1975).
                              -4-

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       FIGURE 1
MONOCHLOROHAPHTHALENES
             Cl
 1-chloronaphthalene
 2-chloronaphthalene
       -5-

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                      Tfl8LE E
COmPRRRTiVE PROPERTIES OF HflLOWflX CHLORONRPHTHflLENES
      j              (KOPPERS.a)
PRODUCT NUMBER

1 COMPOSITION |
2 PHYSICAL FORM ' \
3 CHLORINE CONTENT, % (Appioximate)
!@ 25°C
4 SPECIFIC GRAVITY >
!@ 60°C
!@- 30 MM
5 INITIAL BOILING POINTS, ~@ 100 MM
!>' 700 MM

.6 DISTILLATION RANGE!

7 SOFTENING POINT(Melting Point), °C(Approx.)
C.O.C •
9 Flii POINT, °C, C.O.C. •
10 SPECIFIC HEAT, Gm. Cal./Gm./°C
11 LAT!"tJT HEAT OF VAPORIZATION, Cal,/Gm.
12 COLOR
13 ACIDITY, MAXIMUM (Mg. of KOH/Gm.)
14 VISCOSITY, SAYBOLT UNIV. SEC. (APPROX.
200 Cms. with Surfr.ee! 9.5 Sq.
15 VOLATILITY '" '" 1° L"1V"?> Ro°m Tt"Ilp-
Gms./Sq. In/Hr. G>10r>°C'
1G PENETRATION, 200 Gm., 5 Sees. @> 25°C(Approx.)
8 FLASH POINT, °C
1 7 DIELECTRIC CONSTANT ! @~60 CYCLE'S/SEC.
t> i666cYci.es/sEc.
®> 60 CYCLES/SEC.
IB POWER FACTOR 	 '"" 	 "
(B> 1000 CYCLES/SEC.
19 RESISTIVITY, MEGOHM CENTIMETERS .
! 1031

Mono-Chlor
LIQUID
122
jl.20
—
;144°C
;IBO°C
250°C
. 654 Mux. 255°C
9656 Min. 26B°C
989i Mln. 275°C
1-25
\135

—
	
While to Pale Straw
0.05
35@25°C
1.0%
	
	

	
	
	
	

; 1000

Mono-+Di.Chlor
LIQUID
26
1.22
	
;144°C
; i8o°c
! 250°C
	
80% Mln. 282°C
90S Iviin. 300°C
'-33
130

0.40E> 50°
0.42& 100°

Whrto to Pali Straw
, 0.05
34 @ 25°C
'1.5%
	
	
	
	
	
	
	

• 1001

Trl-+Totra-Chlor
FLAKES
50
1.58
	
200°C
234°C
308°C
	
	
	
93
'200 •
1 Nono to Boiling
0.22<5> 15°
o.cr, 


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                     TflBLEI (CONT.)
COmPflRflTIVE PROPERTIES OF HflLOWflX CHLORONfiPHTHflLENES~
                      (KOPPERS.a)
PRODUCT NUMBER
1. COMPOSITION
2. PHYSICAL FORM
3. CHLORINE CONTENT, %(Approximate)
• • 1© ?'~>°r
4 SPECIFIC GRAVITY ../,, .7
1 @ 60°C :
I@!':30MM
5. INITIAL BOILING POJ NTS! (@ 100 MM.
!@ 760MM

6. DISTILLATION RANGE

7. SOFTENING POINTlMelting Point), °C(Approx.)
B. FLASH POINT, °C, C.O.C.
*
,9. FIRE POINT, °C, C.O.C.
1
10. SPECIFIC HFAT, Gm. Cal./Gm7°C
11. LATENT HEAT OF VAPORIZATION, Cal./Gm.
12. COLOR'
13. ACIDITY. MAXIMUM (Mg. of KOH/Gm.)
14. VISCOSITY, SAYBOLT UNIV. SEC.IApprox.)
, 200'Gms. with Surface 9.6 Sq.
15 VOLATILITY '" "" '° D"V' * R°°m T<""D'
Gm«./Sq. In/Hr. S> 105°C
16. PENETRATION.200 Gm,5 Sec. @ 25°C(Approx.) '

17. DIELECTRIC CONSTANT '' , o 60 CVCLES/SEC.
e> 1000 CYCLES/SEC.
if 60 CYCLES/SEC.
18 POWER FACTOR ""
E> 1000 CYCLES/SEC.
19. RESISTIVITY, MEGOHM CENTIMETERS
,1013
'Tatra-tPanto-Chlor
IFLAKES
:56
1.67

:222°C
'258°C
328°C
•


1120
1 230
, Nono to Boiling •


! Light Yellow
.0.05
;33@>130°C

0.005

25°C' i!30°C
4.8 '3.81
4.8 3.8
0.002 0.45
0.0003 0.04
'Over1x10B| ilx10B
il014
Penta.+HCKO-Chlor
IFLAKES
'62
11.78

i242°C
!278°C
i344°C



(137
250
None to Boiling
0.19 0> 16°
10.489 100°

I Light Yellow
10.05
35@150°C

!0.001;

25°C: il50°C
!4.4 3.7
4.4 .3.7
0.0009 0.99
: 0.0002 , 0.44
Over 1«10B |1x10B
11051
Octa-Chlor
POWDfc'R
i70
1 2.00

i310°C



''

I185
i None to 430
None to BollinQ


1 Light Yellow
,0.1










2141
Blunct
•; CAKES
M
11.G3







'.135




I Grnv White
i 0.05 .
;183@160°C

:0.06@ 140°C
24 1
r25°
13.8
'3.8
! 0.0006
! 0.0002 ,
| Our 1»108
                     -7-

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     Reactivity with environmental  chemical  species and potential
complex formulations have not been  studied.   However,  as discussed  below
some insights might be drawn from the chemical  similarity of these
compounds to polychlorinated biphenyls (PCBs).

Production Levels and Trends

     The production process generally involves  the chlorination of
naphthalene in the presence of a ferric and  antimony chloride catalyst.
Foreign manufacturers of chlorinated naphthalenes are Bayer in Germany
(Nibren waxes) and the Imperial Chemical Industries Ltd. in the United
Kingdom (Seekay waxes).  Crow (1970) has stated that in the United
Kingdom only chlorinated naphthalenes with four chlorines or less are
produced and sold.  Personal communications  with the International  Trade
Commission (formerly the U.S. Tariff Commission) revealed that the  last
reported imports of any chlorinated naphthalenes were 53 pounds (24 kg)
of 1-chloronaphthalene in 1963 and  12,231 pounds (5,560 kg) of the  same
in 1964.  Since that time no imports of chlorinated naphthalenes (by
trade name or chemical name) have been reported.

     The only U.S. manufacturer of chlorinated  naphthalenes is the
Koppers Company which produces them under the trade name of Halowaxes at
a plant in Bridgeville, Pennsylvania, a few miles from Pittsburgh.  In
1956, the total output was about 7  million pounds (about 3.24 million
kilograms)  (Hardie, 1964).  Hardie (1964) suggested that the decline in
use evident at the time was due to  their serious disadvantages, such as
their toxic nature in handling.  In 1972 the market for chlorinated
naphthalenes was less than 5 million pounds  (2.27 million kilograms)
(Koppers, 1973). Recent indications are that the market has continued
to decline slightly over the last two years  (Hoy, 1975).
                               -8-

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Past and Present Use Patterns

     Historically, the chlorinated naphthalenes  were  used  in  the  1930's
and 40's as electrical cable insulating materials  where  they  serve  water
repellant and flame resistant functions.   This  use led to  recognition
of the chlorinated naphthalenes as a serious occupational  health  problem
during cable manufacture.   Use of the penta- and hexachloronaphthalenes
in cable manufacture was discontinued due to occupational  health  problems
and the introduction of plastics as substitute  materials after World War
II (Hardies 1964).  Use as electrical insulating material  in  certain
applications remains today mostly for capacitors where  lower  chlorinated
members of th£ group, which exhibit a low order of toxicity,  are  employed.
Uses as lubricant additive associated with feed pelletizing machinery
and wood preservatives, both popular in the 40's and  50's, have been
discontinued largely due to serious cattle poisoning  incidents associated
with those uses in the early 1950's.
     Table II lists the various commercial mixtures presently marketed
as Halowaxes and indicates the number of chlorines, the  approximate
percentage of the market and the current principal commercial uses.  The
tri- and tetrachloronaphthalenes (Halowax 1001  and 1099) are  solids and
make up more than half of the United States market.  .They are used
almost exclusively as the paper impregnant in automobile capacitors.
The second largest part of the market is the mono- and  dichloronaphthalenes
(Halowax 1000 and 1031 liquids), most of which  are used  as an oil additive
to clean sludge and petroleum deposits in engines.  These products find
some use in the fabric dyeing industry, specifics about  which are
considered trade secrets by producers and users.  The manufacturer's
product bulletin indicates that monochloronaphthalene (Halowax 1031) is
about 96% pure, containing predominantly 1-chloronaphthalene, and is
used as a raw material for production of dyes.
                               -9-

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     The highly chlorinated naphthalenes  (Halowax  1013  and  1014) are
used mainly as electroplating stopoff compounds  in relatively  small
quantities.  Some specialized minor uses  as  an additive in  automobile
and industrial gear oils and cutting oils are also mentioned  in  the
manufacturers product bulletin (Koppers9  a).  The  product bulletin also
mentions other possible minor applications of Halowax  1000  as  solution
polymerization solvents, gauge fluids, inert liquid seals for  instruments,
and photoelastic immersion fluids.   Halowax  1001  is said to have applications
in the paper coating and precision  casting industries.
                               -10-

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                                      TABLE II
                        USES OF CHLORINATED NAPHTHALENES
                                  (KOPPERS, 1973)
HALOWAX % OF CHLORINATED % MARKET*
ISOMERS (1972)
1000 60%
1031 95%

1000 60%
1031 95%
1001 ( 10%
1099 (40%
1013 10%
1014 20%




MONO
MONO

MONO
MONO
01
TETRA
TRI
TETRA




40% Dl 15-18%
5% Dl

40% Dl 10%
5% Dl
40% TRI 65-66%
10% PENTA
50% TETRA 40% PENTA 8%
40% PENTA 40% HEXA




USES
ENGINE OIL ADDITIVE
TO DISSOLVE SLUDGE
AND DEPOSITS
PROPRIETARY
USES IN FABRIC
IMPREGNANT FOR AUTO-
MOBILE CAPACITORS
MOSTLY AS ELECTRO-
PLATING STOPOFF
COMPOUNDS, ALSO
IMPREGNANT FOR CARBON
ELECTRODES USED FOR
CHLORINE PRODUCTION
       1051
10%  HEPTA   90% OCTA
.5%
UNKNOWN
•BASED ON MARKET OF LESS THAN 2.27 x 108a (5 MILLION LBS.)
                                 0

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II.  ENVIRONMENTAL EXPOSURE FACTORS

     The potential for environmental  exposure may be significant when
these compounds are used as oil  additives, electroplating stopoff com-
pounds, and in the fabric dyeing industry.  With the latter two uses,
effluent discharges from point sources may release these compounds to
the environment, while with the former, more widespread non-point
sources would be involved.  The largest use (about two-thirds of the
market) of these compounds is as an impregnant for automobile capacitors.
Automobile capacitors can be considered disposable items since they are
often changed during engine tune-ups.   This use is in a temporarily
"closed" system, and the extent to which chlorinated naphthalenes will
leach out or be released has not been determined.  Previous use in
products as insulation., e.g., old cables, could allow entry to the
environment as a result of general waste disposal and physical breakdown
of the products.
     Chlorinated naphthalenes, like PCBs, exhibit a high degree of
chemical and thermal stability as indicated by their resistance to most
acids and alkalies and resistance to dehydrochlorination (Koppers, a).
Although a number of researchers have recognized the similarity between
the physical and chemical properties and uses of PCBs and chlorinated
naphthalenes (Armour and Burke, 1971; Goerlitz and Law, 1972) and have
developed analytical procedures for low level detection in environmental
samples, only two reports of chlorinated naphthalenes contamination of
the environment in the U.S have been reported.  In addition, Koeman ejt
aj_. (1973) detected traces of chlorinated naphthalenes during PCB and
DDE residue analysis in cormorants (fish-eating birds) that were found
dead in various parts of the Netherlands.  In most cases the analytical
procedures were developed to assure that chlorinated naphthalenes were
not interfering with analysis for PCBs or organochlorine pesticides such
as DDT.  Some of the analytical techniques developed, especially gas
chromatography-mass spectrometry (GC-MS), would allow detection and
quantification of chlorinated naphthalenes in environmental samples.
                              -12-

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     The Food and Drug Administration (FDA),  in their monitoring
program for pesticides and other industrial  chemicals, such as  PCBs,
in agricultural  products, is able to determine the presence of  chlorinated
naphthalenes in  food (grain, fruits, vegetables, milk, eggs, cheese,  fish,
etc.).  This capability has been available since 1970.  To date,  no findings
have been reported by FDA District Laboratories.  This surveillance
program is carried out on a continuing basis  and would be in a good
position to determine whether or not chlorinated naphthalenes become  a
significant contaminant of agricultural  products (FDA, 1975).

     Similarly,  a personal communication with the EPA National  Hater
Quality Laboratory in Duluth, Minnesota revealed that they have been
monitoring samples of fish from the Great Lakes as well as many major
rivers in the U.S. and have found no chlorinated naphthalenes as of
February, 1975.   The analytical chemist did indicate that some tentative
findings of chloronaphthalenes had been made which, upon confirmatory
analysis, proved to be other chlorinated hydrocarbons.  For example,  a
tentative tetrachloronaphthalene identification was later found to be a
compound with the same molecular weight, pentachlorophenol.  Another
tentative identification of octachloronaphthalene was later determined
to be a pentachloroterphenyl with nearly the same molecular weight.  One
other tentative finding  in Great Lakes herring gull extract awaits
confirmation at the California Water Resources Control Board.  The type
of analytical procedures involved in identifying chlorinated naphthalenes
seems to make their detection by those doing routine analyses for chlorinated
hydrocarbons unlikely unless chlorinated naphthalenes are specifically
sought.
     A study of the distribution of polychlorinated biphenyls in the
aquatic environment by Crump-Wiesner et^ aj_. (1973) led to the first
report of chlorinated naphthalenes  in an environmental sample in the
United States.  In analyzing sediment samples from a south  Florida
                              -13-

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drainage ditch, mixtures of chlorinated naphthalenes ranging from 1.25
to 5 mg/kg were found.  Water samples overlying the sediments averaged
5.7 jjg/1.  Identification was confirmed by both microcoulometry and GC-
MS.  Discussions with the authors revealed that the drainage ditch was
in the vicinity of an airport overhaul hangar.
     Law and Goerlitz (1974), in a GC-MS study of chlorinated hydro-
carbons in bottom material from streams tributary to San Francisco Bay,
          /kg of chlorinated naphthalenes present in a Guadalupe River
sample.  The authors point out that the sample came from an area of no
apparent industrial activity.
     Several instances of a disease called bovine hyperkeratosis (Olson,
1969) in the early 1950' s were traced to chlorinated naphthalenes as a
contaminant in pelletized cattle feed.  This contamination was due to
the use of a lubricant containing chlorinated naphthalenes in machines
for pelletizing cattle feed.  (See Biological Effects - Toxicity below).
     Chlorinated naphthalenes have also been detected as a contaminant
in foreign commercial PCB formulations (Phenoclor, Clophen and Kanechlor)
along with chlorinated dibenzofurans.  Early investigators did not
detect chlorinated naphthalenes in domestic PCB formulations (Aroclors)
(Vos e_t al., 1970; Roach and Pomerantz, 1974).  Chlorinated naphthalenes
are present in domestic PCBs but at lower levels than in foreign formulations,
Bowes e_t aj_. (1975), using a more sensitive analytical technique, identified
by MS three peaks of a chromatogram of Aroclor 1254 as chlorinated
naphthalenes.
     Environmental decomposition of chlorinated naphthalenes has received
limited study.  Only the monochlorinated naphthalenes have been studied
under biological conditions similar to those found in the environment.
Walker and Wittshire (1955) examined the decomposition of both 1-chloro-
and 1-bromonaphthalene by soil bacteria and found that two species of
bacteria, obtained from soil, would grow in a mineral salts medium with
1-chloronaphthalene as the sole carbon source.  The isolation of
                         -14-  .

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8-chloro-l,2-dihydro-1,2-dihydroxynaphthalene and 3-chlorosalicylic acid
suggests the metabolic  route shown in Figure 2.   Similar results were
reported for 2-chloronaphthalene by Canonica and coworkers (1957).
     Okey and Bogan (1965) examined the rate of  metabolism of 1-chloro-
and 2-chloronaphthalene by sewage sludge bacteria that were first grown
on unsubstituted naphthalene.  The initial  concentration of chlorinated
substrates was 1 mg/1 and the substrate was the  only source of carbon.
The following relative  rates of metabolism were  observed:
     naphthalene >» 2-chloronaphthalene» 1-chloronaphthalene.

     The microbial degradation of the highly chlorinated naphthalenes
has not been studied.  Gibson (1972) has suggested that the initial
reactions in mammalian  and microbial systems are quite different as is
depicted in Figure 3. There is little certainty about the environmental
fate of chlorinated naphthalenes.  No literature references are available
on the environmental stability and transport of chlorinated naphthalenes
within the biosphere, including bioaccumulation and behavior in ecological
food chains, although at least a potential for bioaccumulation appears
to have been demonstrated since traces have been detected in one species
of fish-eating birds (Koeman et al_., 1973) and in stream sediments
(Crump-Wiesner et al_.,  1973; Law and Goerlitz, 1974).  Further, an
evaluation of the physical and chemical data on these compounds together
with the available data on mammalian and microbial metabolism and an
intuitive correlation based on the  similarities in chemical structure
and physical properties (low water  solubility, low volatility) between
PCBs and chlorinated naphthalenes,  indicate that the higher chloro-
naphthalenes are relatively stable and are likely to persist when
released  to the environment  (Howard and Durkin, 1973).
     Recent photolysis studies have shown a potential for photodegradation
of polychlorinated naphthalenes in  the environment.  Experiments
                       -15-

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              FIGURE 2
 Suggested Route of Decomposition of
1-Chloronaphthalene by Soil  Bacteria.
                -16-

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                  FIGURE 3
Proposed mechanism of naphthalene dihydrodiol
formation in mammalian and microbial  systems.
             (From :Gibson, 1972)
            Pseudomonas
            microsomes
                                     2e-
                                     2H+
                                       epoxide
                                       hydrase
                                                         H  OH
                    -17-

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various polychlorinated naphthalenes in methanol  solution irradiated
at a peak energy output of 300 nm resulted in dechlorination and di-
merization.  Sunlight irradiations were carried out on solid films
in quartz vessels and resulted in insoluble polymeric material  (Ruzo
et al_., 1975).

     Another aspect about which there is little certainty but considerable
concern is the potential epoxidation of the chlorinated naphthalenes to
produce a relatively small stable agent capable of covalent linkage imp!icited
in carcinogenicity of epoxides like dieldrin (Figure 3).
                                   -18-

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III.   BIOLOGICAL EFFECTS

Metabolic Effects

     The primary observed metabolic effect of the chlorinated naphtha-
lenes is to interfere with the metabolism of carotene and its trans-
formation to Vitamin A and is reflected in decreased plasma Vitamin A
(Olson, 1969).  The Vitamin A effect is highly variable and subject to
species-specific variation (Hansel  and McEntee, 1955).  Goats, sheep,
swine, mice, chickens, and rats are much less susceptible than cattle
fOlson, 1969).
     In the surveyed literatures male rabbits were the only subjects
used to study the metabolism of chlorinated naphthalenes (Cornish arid
Block, 1958).  The compounds studied were 1-chloronaphthalene, di-,
tetra-, penta-, hepta-, and octachloronaphthalene.  Naphthalene metabo-
lites and the presence of unchanged compound were tested for in urine
after administration by stomach tube of 1 gram of each test compound.
1-Chloronaphthalene, dichloronaphthalene, and tetrachloronaphthalene
showed patterns of excretion similar to naphthalene.  The excretion
products of naphthalene are largely glucuronides with small amounts
converted to mercapturic acid derivatives, sulfates, and phenolic compounds,
The higher chlorinated naphthalenes did not yield an increase in these
urinary metabolites.  Less than 20% of the administered dose of penta-
and heptachloronaphthalenes were found to be excreted in urine and
feces.
     This study suggested that the toxic symptoms produced in the rabbit
by highly chlorinated naphthalenes can be related to the inability of
the animal to metabolize and excrete these compounds.  However, these
compounds may be metabolized by pathways which yield excretory products
not included  in this  study, or they may be deposited  in the tissue,
particularly  fat depots, and metabolized or excreted unchanged over  long
periods of time  (Cornish and Block, 1958).
                        -19-

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Toxicity
     Evaluation of the available toxicity information on the chlorinated
naphthalenes indicates that the degree of toxicity,  in general,  increases
with the degree of chlorination.  Under acute conditions of human dermal
exposure"to mono, di, tri, and tetra compounds, slight or no observable
reactions were reported. The higher chlorinated members of this  class,
on the other hand, especially the penta and hexa compounds, have been
associated with dermal toxicity (chloracne) and liver damage of  some
severity under occupational exposure conditions prior to and during
World War II years.  A few fatalities from chloronaphthalene-induced
liver necrosis from occupational exposure have been  reported, the last
in 1944.  Recent study of occupational chloracne problems associated
with chlorinated naphthalene exposure has shown limited systemic toxicity
and no evidence of liver involvement (Kleinfeld, 1972).
     Three natural routes are available for the human intake of  chlorinated
naphthalenes:  ingestion, inhalation, and cutaneous  absorption.   Of
these, Crow (1970) concluded, after a critical review of substances
associated with chloracne pathology, that the more important route in
occupational exposure is inhalation. The absence of  chloracne in workers
handling cold chloronapthalene solids (Collier, 1943; Crow, 1970) led to
the recognition that the vapors from molten chlorinated naphthalenes are
a critical factor in the toxic responses observed.  However, the dermal
absorption route should not be disregarded.  Past occupational studies
often failed to characterize adequately the exposure conditions  so that
the mode of entry in most situations is best considered as a probable
combination of vapor inhalation and cutaneous absorption.  In domestic
animals, ingestion is by far the most common route of exposure and
results in the most severe pathology (Huber and Link, 1962; Olson,
1969).
                         -20-

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     Because chlorinated naphthalenes have never enjoyed widespread
household use, occupational  rather than accidental  or environmental
exposure predominates in the relevant literature on human toxic effects.
Two clinically distinct but often concurrent and possibly physiologically
related syndromes have been described:  liver necrosis and chloracne.
(Chloracne is a general term and describes the skin irritation that can
be produced not only by chlorinated naphthalenes but also by other
chlorinated compounds including commercial grade biphenyls, a few specific
benzenes, phenols, and dibenzofurans.  Chloracne accompanied by itching,
however, may be specific to the chlorinated naphthalenes.)
     Any attempt to label these syndromes as acute or chronic is potentially
misleading.  Exposures of three to four months are often noted in the
clinical literature (e.g., Schwartz and Peck, 1943; Collier, 1943:,
Greenburg 
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The symptomatic course of the disease is not unlike that of other forms
of liver damage resulting in hepatitis with consequent jaundice,  and may
be accompanied by nausea, vomiting, loss of appetite, fatigue, fever,
and/or acute abdominal pain (Kleinfeld e_t al_.,  1972;  Collier,  1943).
Autopsies of fatally exposed workers revealed severe  yellow atrophy of
the liver.  Most researchers seem to agree that the liver is the  primary
internal organ directly damaged by chlorinated  naphthalenes (Collier,
1943; Straus, 1944; Kleinfeld et al_., 1972).  Detailed descriptions of
the pathology are available in the literature  (See especially Greenburg,
1939).  Understandably, very few detailed descriptions of liver damage
are available for non-fatal exposures (Strauss, 1944).
     Three fatal cases investigated by Greenburg (1939) revealed  that
all were exposed to chlorinated naphthalenes directly or indirectly in
the workroom.  A 17-year old girl worked at a plant that manufactured
electrical condensers for use in radios. The condensers were impregnated
with tri- and tetrachloronaphthalene.  At the same time she was exposed
to vapors of the higher chlorinated naphthalenes from the sealing operations
conducted near the soldering tables where she was stationed.  After
seven months of soldering and labelling condensers which involved her in
direct exposure, she became intensely jaundiced and was admitted  to a
hospital.  She died two days later.  Death was  attributed to acute
yellow atrophy of the liver.

     Greenburg (1939) also described the fatal  cases  of two young men
who, after working in a factory at coating wire with  "wax", became
jaundiced after 4 to 5 months of exposure.  The wax used in the coating
process contained higher chlorinated naphthalenes.  The process involved
a molten bath of the "wax" through which the wire to  be coated was
passed.  The process was only partially enclosed with exhaust ventilation
in use.  Both died from acute yellow atrophy of the liver.  All three
cases reviewed by Greenburg (1939) revealed no predisposing causes for
the conditions except exposure  to chloronaphathalenes.   No medical  history
 suggesting  a hepatic disorder  prior to  exposure  was  given.
                        -22-

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     Strauss (1944) reviewed 6 fatal  cases related to exposure to Halowax.
All deaths were attributed to acute yellow atrophy of the liver resultinn
from exposure to Halowax fumes in a "war plant".   One case revealed a
minute amount of arsenic (no quantitation) in the liver which, it was
concluded, could have increased the susceptibility of the liver to
Halowax exposure.  Information given by Strauss on conditions of exposure
was incomplete.  Also, no information was given on which specific Halowax
or chloronaphthalenes were involved.

     Kleinfeld ejt a]_. (1972) could find no evidence of liver damage in a
recent outbreak of chloracne associated with occupational exposure to
wax containing a mixture of tetra-/pentachloronaphthalene.  The melted
wax used to insulate electrical components was applied by immersion. No
exposure estimates were given, but Kleinfeld attributed the toxic effects
observed to exposures to chlorinated naphthalenes through direct dermal
contact and inhalation of vapors as a result of poor industrial hygiene
practices, including an inadequate and poorly maintained exhaust ventilation
system.
     In contrast to the low incidence of liver damage, chloracne resulting
from exposure to chlorinated naphthalenes is a common and persistent
problem in manufacturing and use.  Chlorinated naphthalene dermatitis
was reported as early as 1918  (Jones, 1941) and remains a problem in
spite of advances  in industrial hygiene (Kleinfeld, 1972). The chloracne
skin lesion is morphologically similar in all cases and has been referred
to as the chloracne cyst--a sore 1 mm to 1 cm in diameter with an ill-
defined central opening.  These cysts are formed from necrotic material
retained in the hair follicle or sebaceous gland and are covered by a
horny layer of skin causing a dark crusty appearance (Crow, 1970).  Hair
follicles swell into acne-type sores and sebaceous glands degenerate.
In severe cases, lesions may cover extensive areas of the body.
                         -23-

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     The lower chlorinated naphthalenes seem to be innocuous with
respect to man.  Mixtures of mono-/dichloronaphthalene (Halowax 1000)   •
and tri-/tetrachloronaphthalene (Halowax 1001)  at 500 mg/g in a mineral
oil suspension applied to the human ear caused  no response over a 30-day
period.  A mixture of penta-/hexachloronaphthalene (Halowax 1014) under
the same conditions did cause acne, but heptachloronaphthalene (Halowax
1052) and octachloronaphthalene (Halowax 1051)  did not (Shelly and
Kligman, 1957).  Even at concentrations as small  as 30 mg/g acetone,
typical chloracne developed in six weeks as penta-/hexachloronaph-
thalene was applied to the backs of human volunteers (Hambrick, 1957).

     Chlorinated naphthalene toxicity in birds  and non-human mammals  has
been studied in attempts to understand not only occupational hazards  to
man but also highly chlorinated naphthalene poisoning of cattle.  In
order to supplement available human clinical data, investigations have
been conducted primarily with controlled exposures of known concentrations
to rats.  Investigations of cattle toxicity have concentrated primarily
on a complete description of the syndrome and on attempts to induce a
toxic response in other farm animals under closely monitored conditions.
Cattle poisoning as described below usually involves a relatively high
dose with rapid physical deterioration.  Thus,  it may be characterized
as acute.  By contrast, studies relating to occupational exposure usually
involve attempts to elicit a gradual response to a minimum dosage and
effects may thus be characterized as chronic.

     Highly chlorinated naphthalene poisoning,  also referred to as
bovine hyperkeratosis or X-disease, was of major economic concern in  the
United States during the 1940's and 1950's.  The disease was caused in
most cases by accidental ingestion of chlorinated naphthalenes from
lubricants in machines used to make pelletized feed (Crow, 1970). X-
disease was also associated with the chemical's use in wood preservatives
(Crow, 1970) and its use in wax for binding twine (Bentz and Herdmann,
1955).  The relation of chlorination to toxicity in accidental cattle
                            -24-

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poisoning seems to agree well  with human toxicity experiences in that
the penta-/hexachloronaphthalene are usually the toxic agents.   However,
octachloronaphthalene has been reported as having greater oral  toxicity
than hexachloronaphthalene in cattle (AIHA, 1966).  As with reports on
human exposure, detailed dosage data are often lacking in animal studies
due not only to use of uncertain concentrations but also to ad  libitum
exposure.
     The pathological course of bovine hyperkeratosis has been  described
in considerable detail and needs only a cursory examination in  this
report (Olson, 1969).  A primary effect of chloronaphthalene poisoning
is to interfere with the biotransformation of carotene to vitamin A.
Chronologically, this is one of the first effects of exposure and many
of the subsequent symptoms - especially of the skin and horns - may be
due to vitamin A deficiency in the blood plasma.  Vitamin A depression
is quickly followed by inflammation of the oral mucosa, lacrimation,
excessive salivation, and irregular food consumption. As the disease
progresses, grossphysical effects may include a general thickening of
the skin caused by over-development of the skin's horny layer with loss
of hair  (hyperkeratosis).  The horns may show signs of degeneration or
irregular growth.  With continued exposure, the disease progresses
through  anemia, dehydration, loss of weight, fever, and death.   Liver
damage may be  severe.   (The resemblance of this syndrome to severe
chloronaphthalene  intoxication in man should be noted but no unequivocal
comparisons can be made.)  A combination of penta/hexachloronaphthalene
at a  total dosage  of  5.5 mg/kg body weight given  orally over a  five
'day period will cause a sharp drop  in plasma vitamin A by the end  of
the third day  and  depressed plasma  vitamin A for  over thirty days.
A single oral  dose of hexachloronaphthalene at  11 mg/kg body weight
has caused mortality  within two weeks  (Olson,  1969).

      A  recent  incident  of hyperkeratosis  in dairy cows was  reported  by
Vos e_t  aj_.  (1971).   The cause was determined to  be  contamination by  PCBs
and chlorinated naphthalenes of rubber mats used  on  the floor of the
dairy barn.   Skin  lesions were  localized  in those areas where the  cows
                          -25-

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came in contact with the floor.   GC-MS analysis of extracts  of the mats
revealed the presence of PCBs (60 % Cl) and predominantly hexachlo-
ronaphthalenes in a ratio of about 3:1.

     Other domestic animals prove much less susceptible to chloro-
naphthalene poisoning than do cattle.  Swine show no toxic effect to
hexachloronaphthalene at ten times the above mentioned lethal dosage for
cattle.  Marked vitamin A depression is noted in swine only at dosages
of 154 mg/kg body weight and death does not occur until 198 mg/kg body
weight doses are given.  Pentachloronaphthalene applied to the skin at
60 mg/liter, 3 liters per day, six times a week for six weeks - 180
mg/day for a total dose of  6.3 g - causes only mild hyperkeratosis
(Link et^ a_l_., 1958).  Similar doses administered orally (176-200 mg/kg
body weight over a 8-9 day period) cause only slight systemic effects
and ataxia (Huber and Link, 1962).  Although hyperkeratosis did not
result from oral administration, lethal oral doses did result in moderate
to severe liver damage ranging from yellow discoloration to swelling and
hemorrhage. Following non-fatal oral doses, depression of plasma vitamin
A was reversible upon oral administration of vitamin A (Link et a!.,
1958).
     Experimental studies to produce toxic effects in sheep suggested
that a ten-fold increase in dose over  that required to produce toxicity
in cattle is necessary.  Sheep apparently have a greater tolerance for
these compounds and do not show cutaneous hyperkeratosis or as excessive
a drop in the plasma vitamin A level as that observed in cattle.  Observed
effects included nasal discharge, weakness, loss of weight, loss of
appetite, ascites, necrosis and cirrhosis of the liver, and cardiovascular
injury (Brock et aj_., 1957).
     Ingestion studies with chloronaphthalenes have been conducted using
broad breasted bronze poults (turkeys) and New Hampshire chickens.
Feeding in both studies was ad libitum and, given the erratic effect of
chloronaphthalene on the appetite, exact dosages cannot be meaningfully
                         -26-

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approximated.  With the broad breasted bronze poults, a mixture of
penta-/hexachloronaphthalene (Halowax 1014), at concentrations of 5, 10,
50, and 100 ppm (mg/kg feed) for 40 days, gives an LC5Q of 20 ppm with
an average decrease in weight of the turkeys of 51 percent.  Even at 5
ppm, weight gain was reduced by 33 percent with a 6.5 percent mortality
and the prognosis was that prolonged feeding would result in death by
marketing age.  At 100 ppm, all of the broad breasted bronze poults died
within 33 days.  Gross histologic examination revealed enlarged and
darkened livers as the only histopathologic manifestation, reinforcing
the specificity of action found in human exposures. Similar to human
topical application, octachloronaphthalenes at 125 ppm in feed caused no
significant effect.  The investigators speculated, but without elaboration,
that this might reflect the high melting point and low solubility of
octachloronaphthalene (Pudelkiewicz e_t al_., 1958).

     The New Hampshire chicken was studied in a subsequent experiment!
and found to be appreciably more resistant to penta-/hexachloronaphthalene
(Halowax 1014) poisoning.  A dose of 100 ppm only prevented egg production
in the New Hampshire.  With levels of 4, 20, 100, 500 and 2500 ppm in
feed over 35 days, 100 percent fatality was achieved only with the
highest level after a two week exposure period.  A fourfold increase in
dietary vitamin A markedly decreased effects.  Again, enlarged fibrous
livers were the most common pathological finding.  Other pathological
findings included lack of feather pigmentation and pericardial and
peritoneal edema  (Pudelkiewicz e^ al_., 1959).
     The clinical history  of occupational  poisoning  due  to  chloro-
naphthalenes  has  stimulated much  of  the work done  on "subacute"  and
"chronic" exposure  of  non-human mammals.   A selective  but represen-
tative sample of  the available data  is  included  in the  following  discussion.
Because the  toxic properties of the  chlorinated  naphthalenes  vary considerably
with  the degree of  chlorine  substitution,  the  discussion is presented  in
ascending  levels  of chlorination.
                         -27-

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     Mono and Mono/Pi Combinations

     These compounds are commonly considered to have low toxicity.
No effects to the skin were observed with daily topical  application
of mono-/dichlorinated naphthalenes to the human ear at 500 mg/g in
mineral oil suspension for 30 days (Shelly and Kligman,  1957).
However, when applied to the much more sensitive rabbit ear for 5-7
days, 1-chloronaphthalene produces mild reddening at 90 mg/g acetone
and severe reddening - but without decrease of sebaceous glands - at
590 mg/g acetone (Hambrick, 1957). Inhalation and ingestion experi-
ments were not encountered in the literature surveyed.

     Dichloronaphthalenes

     When applied topically to the rabbit ear at concentrations of
45 mg/g acetone and 290 mg/g acetone, dichloronaphthalene produced
effects similar to those observed with 1-chloronaphthalene (Ham-
brick, 1957).  When ingested in ad libitum feeding by the rat at 5
g/kg of feed for 15 days, liver weight was increased, growth impaired,
and coat texture roughened (Wagstaff, 1971). No inhalation experi-
ments were encountered.

     Tri- and Tri/Tetra- Combinations

     Topical application of trichloronaphthalenes to mice and rats
at an unspecified concentration for 2 hr/day for 40-60 days produced
no effects (Shakovskaya, 1953).  This is in agreement with a study
showing no effects from a mixture of tri-/tetrachloronaphthalenes
applied to the human ear at 500 mg/g solvent for 30 days (Shelly and
Kligman, 1957).
     Experiments feeding trichloronaphthalene to mice at 2.5 mg/mouse/day
for 20 days produced no effect (Shakhnovskaya, 1953).  However, at
300 mg/rat/day for 9-136 days (total dose of 2.7 g - 41  g), a slight but
                                -  28 -

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progressive increase in fatty accumulation in liver cells was evident
(Bennett el^ a_K , 1938).  Tri/tetrachloronaphthalene at 15 mg/kg body
weight/day for 60 days (total dose of .9 q/kq body weight) had no observed
effect in rabbits (Greenburg e_t al_., 1939).
     Inhalation experiments yield similar results with rats.  At 0.05-
0.2 mg/1 for 2 hrs/day for 20 days and 1.31 mg/m3 for 16 hrs/day for 134
days, no toxic signs developed (Shakhnovskaya, 1953, Bennett et a!.,
1.938).  But at 10.98 mg/m3 for 16 hrs/day for 102 days, a slight liver
discoloration appeared, and 5 percent of the rats showed increased fatty
degeneration (Bennett, 1938).
     Tetra/Penta- Combinations

     With the introduction of the five chlorine atom compound, the first
cases of severe poisoning develop.  Rats fed 50 mg/rat/day for 63 days
(total dose of 2.12 g/rat) became fatally intoxicated, showing jaundice
and fatty degeneration of the liver (Bennett ejt al_., 1938).  Rabbits
seem even more sensitive, with fatal intoxication at 15 mg/kg body
weight/day subcutaneously injecte'd for 12-26 days for a total dose of
180-390 mg/kg body weight (Greenburg et. iL > 1939). No inhalation or
topical experiments were encountered.
     Penta and Penta/Hexa Combinations

     Pentachloronaphthalene alone has received relatively little attention.
Applied to swine's skin at 60 mg/liter x 3  liters for 6 day/wk for 4
weeks  (180 mg/day, total exposure 43.2 gm)., slight hyperkeratosis was
produced (Link et^ al_., 1958).
     Combinations of  penta-/hexachloronaphthalenes  are among the most
often  cited in human  toxicity studies and  have also been  studied  in  some
detail  in non-human mammals. Orally administered penta-/hexachloro-
                         -29-

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naphthalenes mixtures have been found to be highly toxic to rabbits and
rats.  In rats, oral doses of 300 mg/rat/day (maximum dose of .99 g/rat)
were fatal in 33 days or less.  The livers were markedly yellow and
showed signs of extreme fatty degeneration.  A dosage of 100 mg/rat/day
(.55 g/rat total dose) had the same effect over a 55 day period.  Slower
and less severe liver damage was noted with a dose of 62.5 mg/rat/day,
but further details are not given (Bennett e_t al_., 1938).  In rabbits,
the lethal dose is 15 mg/kg body weight/day for 12-26 days (total dose
of 180-390 mg/kg body weight) with similar organ damage.   (Greenburg  e_t
al_., 1939)
     Inhalation studies with  rats show a  similar dosage/effect  relation-
ship.  Exposure to  1.16 mg/m  for 16 hrs/day for 52 days yields  jaundice,
enlarged yellow liver, and 69 percent fatality  (Bennett  et al_.,  1938).
     Applied to the  skin of the rabbit ear, 30  mg/g acetone/day  for 5
days caused only mild dermatitis with follicular attenuation  (Hambrick,
1957).   In guinea pigs, a 2.5 mg/kg daily oral  dose of technical grade
pentachloronaphthalene in peanut oil was  fatal  after 48  days.  Severe
weight loss and fatty degeneration of the liver were noted at  necropsy
(Bentz and Herdmann,  1955).
     Hexachloronaphthalene
     Like pentachloronaphthalenes, hexachloronaphthalenes  have  received
little attention.   In ad libitum feeding  to rats,  20 mg/kg and  63  mg/kg
in  the diet caused  weight loss over an 84-day period and 200 mg/kg in
the  diet caused an  unspecified number of  fatalities  (Weil  and  Goldberg,
1962). Exposure to  the rabbit ear at 30 mg/g acetone for five  days
caused a decrease in  sebaceous gland tissue (Hambrick, 1957).
     Heptachloronaphthalene
     No  "chronic" studies on  heptachloronaphthalene were encountered.
                         -30-

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Octachloronaphthalene

     The toxicity of Octachloronaphthalene is somewhat problematical.
Most current investigators consider it innocuous (Crow, 1970; Olson,
1969).  No significant toxic effects have been observed after testing  in
man or chicken (Shelly and Kligman, 1957; Pudelkiewicz ejt aJL, 1958).
However, ad 1ibitum feeding of rats at dietary concentrations of .5 g, 2
g, or 5 g/kg for 22 days has shown a decrease in liver but not plasma
vitamin A (Deadrick et^ al_., 1955).  Further, a single oral dose of 1
g/rabbit caused death in seven days (Cornish and Block, 1958).
                         -31-

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IV.  HANDLING PRACTICES, STANDARDS, AND REGULATIONS

     The high thermal  stability and resistance to chemical  attack of the
chlorinated naphthalenes reduces any instability problems which might
otherwise be encountered during packing and transport.   Liquid chlorinated
naphthalenes (Halowax 1031 and 1000) are usually shipped and stored in
55-gallon steel drums and are occasionally transported  in tank cars.
The higher chlorinated solids are usually shipped in small  quantities
(50 Ibs.) in fiber pack containers.
     The manufacturer recommends that equipment using the Halowaxes be
enclosed, and fumes and vapors be exhausted; individuals having a history
of skin disease, liver disorders, or alcoholism should  not be employed;
work clothing should be completely supplied (including  close-weave
coveralls, socks, caps, underwear, gloves, and aprons), and the clothing
should be changed twice a week; and face and hands should be washed
before eating and a shower taken upon quitting work (Koppers, b).

     The primary hepatotoxic agents for man seem to be  penta- and hexa-
chloronaphthalene (AIHA, 1966).  Current industrial hygiene standards
                  3                                 2
(TLV's) are 5 mg/m  for trichloronaphthalene, 2 mg/m  for tetrachloro-
                     3                                         3
naphthalene, 0.5 mg/m  for pentachloronaphthalene, and  0.2 mg/m  for
hexachloronaphthalene (AC6IH, 1975).  These levels are  recommended to
prevent liver damage and to minimize the incidence of chloracne.  Where
mixtures are used, the limit recommended for the most toxic compound
must be taken into consideration when evaluating the exposure (ACGIH,
1971).  These ACGIH standards are identical to those adopted by  the
Occupational Safety and Health Administration in 1971 as occupational
exposure limits.
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                              REFERENCES

American Confernece of Governmental  Industrial  Hygienists (1971),
     Documentation for the Threshold Limit Values for Substances
     in Work room Air,.

American Conference of Governmental  Industrial  Hygienists (1975),
     TLVs, Threshold Limit Values for Chemical  Substances in
     Work Room Air Adopted by ACGIH for 1975.

American Industrial Hygiene Association, (1966) "Chloronaphtha-
     lenes", Hygienic Guide Series,  Jan-Feb.

Armour, J. A., and J. A. Burke (1971), "Behavior of Chlorinated
     Naphthalenes in Analytical Methods of Organochlorine Pesti-
     cides and Polychlorinated Biphenyls", J. Ass. Offic. Anal.
     Chem., 54_, 175-177.

Bennett, G. A., C. K. Drinker and M. F. Warren (1939), "Morpho-
     logical Changes in the Liver of Rats Resulting form Exposure
     to Certain Chlorinated Hydrocarbons", J. Ind. Hyg. Toxicol.,
     20, 97-123.

Bentz, H. and I. Herdman (1955), "The Suitability of the Guinea
     Pig as a Test Animal for the Determination of Poisoning by
     Chlorinated Naphthalenes" (Transl. form German), Archiv fur
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Bowes, G. W., B.R.T. Simoneit, A.C. BurTingame, and R. W. Risebroug
     (1975), "Identification of Chlorinated Dibenzofurans in
     American Polychlorinated Biphenyls," Nature, 256, 305-307.

Brock, W. E., E. W. Jones, R. MacVicar anf L. S. Pope  (1957),
     "Chlorinated Naphthalene Intoxication in Sheep", Am. J. Vet.
     Res. 18, 625-630.

Canonica, L., A. Fiecchi and V. Treccani  (1957), "Products of
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Collier, E. (1943),  "Poisoning by Chlorinated Naphthalenes",
     Lancet, 1_, 72-74.

Cornish, H. H. and W.  D. Block (1958),  "Metabolism of  Chlorinated
     Naphthalenes",  J.  Biol. Chem., 231.  583-588.

Crow,  K. D. (1970),  "Chloracne", Trans. St. John Hosp. Dermato1,
     Soc.,  56, 79-99.
                         -33-

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Crump-Wiesner, H. R. Feltz, and M.  L.  Yates (1973), "A Study of
     the Distribution of Polychlorinated Biphenyls in the Aquatic
     Environment", U.S.  Geol.  Surv.  J.  of Res.  ]_, 603-607.

Deadrick, R. E., J. G. Bieri and R.  R.  Cardenas (1955), "Effects
     of Octachloronaphthalene on Vitamin A Metabolism in the
     Rat", J. Nutrition, 57., 286-295.

Food and Drug Administration (1975)  Private Communication from
     C.F. Jelinek, Director, Divison of Chemical Technology,
     Bureau of Foods.

Gibson, D. T. (1972), "Degradation of Aromatic  Hydrocarbons -
     Initial Reactions"  in Degradation of Synthetic Organic
     Molecules in the Biosphere, National Academy of Sciences,
     Washington, DC, p.  116.

Goerlitz, D. F., and L.  M. Law (1972), "Chlorinated Naphthalenes
     in Pesticide Analysis", Bull.  Environ. Contam. Toxicol., 7.,
     243-251.

Greenburg, L., M. R. Mayers and A.  R.  Smith (1939), "The Systemic
     Effects Resulting from Exposure to Certain Chlorinated
     Hydrocarbons", J. Ind. Hyg. Toxicol., 21_,  29-38.

Hambrick, G. W. (1957),  "The Effect of Substituted Naphthalenes
     on the Pilosebaceous Apparatus of Rabbit and Man", J. Invest.
     Dermat 28_, 89-103.

Hansel, W. and K. McEntee (1955), "Bovine Hyperkeratosis (X-
     Disease): A Review", J. Dairy Sci., 38, 875-882.

Hardie, D. W. F. (1964), "Chlorocarbons and Chlorohydrocarbons:
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     Techno!., 2nd Edit., John Wiley and Sons,  N.Y., Vol. 5, 297-
     303.

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     Hazard Assessment of Chlorinated Naphthalenes, Silicones,
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     EPA-560/2-74-001 (NTIS PB-238 074/AS).

Hoy, K. (Febuary, 1975), oral communication (Marketing manager, Koppers
     Company, Inc.).

Huber, W. G. and R. P. Link (1962), "Toxic Effects of Hexachloro-
     naphthalene on Swine", Toxicol. Appl. Pharmacol., £, 257-
     262.
                         -34-

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Hunt, R. H. and M. J. O'Neal (1967), "Petroleum Composition", in
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     to Acne of Occupational Exposure",  J. Ind. Hyg. Toxicol.,
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     Effects Of Chlorinated Naphthalene Exposure", J. Occup.
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     (1973), Effects of PCB and DDE in Cormorants and Evaluation
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     Pert., Suppl. 19, 353-364.

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     naphthalene  Compounds".

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     Durkin  (1973).

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     Hydrocarbons in Bottom Material from Streams Tributary to
     San Francisco Bay",  Pesticides Monitoring Journal, 8_(1),
     33-36.

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                          -35-

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Pudelkiewicz, W.  J., R.  V.  Boucher, E.  W.  Callenbach, and R.  C.
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     Act. Pharmacol. et Toxicol., 19, 129-138.
                        -36-

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             UATA
SHEET
i. Kepott No.
 EPA- 560/8-75-001
                                                                      3. Recipient's Accession No.
4. Title and Subtitle
           ENVIRONMENTAL  HAZARD ASSESSMENT REPORT
           Chlorinated Naphthalenes
                                                 5. Report Date
                                                  December
                                                 6.
7. AUthor(S)   Frank D. Kover
            Office of Toxic  Substances  U.S. FPA
                                                 8. Performing Organization Kept.
                                                   No.
?. Performing Or(|niiixn(ion Numr nnil
      Office  of Toxic  Substances
      U.S.  Environmental  Protection Agency
      401 "M"  Street,  S.W.
      Washington, D.C,  20460    	
                                                 10. Pmjroi/Tn,sk/W,.rk llnii N...
                                                 11. Contract/Grn nt Ni>.
12. Sponsoring Organization Name and Address
                                                 13. Type of Report & Period
                                                    Covered

                                                       Final
                                                                      14.
 15. Supplementary Notes
           This  is the first in a series of reports  to be released by OTS/EPA which
           evaluate chemical  compounds  fnr environmental hazard potential.	
 16. Abstracts
           The  report is  an  analysis  of available  information  on chlorinated naphthalenes
           pertinent to an assessment of the potential  environmental hazard  posed by  thes
           compounds.  Aspects discussed are environmental exposure factors, biological
           effects, general  information on uses, production and  chemical  properties as
           well  as associated handling practices,  and applicable standards and regulation
           Conclusions as to current  hazard potential  are presented and recommendations
           for  further study made.
 17. Key Words and Document Analysis. 17a, Descriptors

      naphthalene compounds
      production  capacity
      marketing
      utilization
      toxicity
      chemical properties
      toxicology
      occupational  diseases
      pollution
 I'/b. Identifiers/Open-Ended Terms

      chlorinated naphthalenes
      environmental  exposure
      environmental  effects
 17e. COSATl Field/Group   06/A ,C , F , J ,M,0 ,T  07/C,D
 18. Availability Statement
                                      19..Security Class (This
                                         Report)
                                      	UNCLASSIFIED
                                                           20. Security Class (This
                                                              Page
                                                           	UNCLASSIFIED
21. 'No. of Pages
                                                            22. Price
 FORM NTis-35 (REV. 10-73)  ENDORSED BY ANSI AND UNESCO.
                                  IS FORM MAY BE REPRODUCED
                                 > •  k.
                                                                                  USCOMM.OC B288-P74

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