DETERMINATION AND EVALUATION OF
ENVIRONMENTAL LEVELS OF TRICHLOROETHYLENE
                     to
       ENVIRONMENTAL PROTECTION AGENCY
         OFFICE OF COXIC SUBSTANCES
               July 29, 1977
         Contract No. 68-01-1983
                  BATTELLE
           Columbus Laboratories
              505 King Avenue
           Columbus, Ohio  43201

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                   NOTICE
This document is a preliminary draft.  It has
not been formally released by EPA and should
not at Lbis stage be construed to represent
Ayency policy.  It is being circulated for
comment on its technical accuracy and policy
implications.
                        ii

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                             TABLE OF CONTENTS

                                                                        Page

EXECUTIVE SUMMARY 	    vii

1.  INTRODUCTION	   1-1

2.  OCCURRENCE OF TRCCHLOROETHYLENE IN THE ENVIRONMENT	   2-1

    Sources of Trichloroethylene in the Environment 	   2-1
         TrLchloroethyJene Production	   2-1
         Uses of TrichloroeLhylene	   2-4
         Pathways for Entry of Trichloroethylpne into the
           Environment	   2-7
    Trichloroethylene Levels in the Environment 	   2-10
         Oata from the f.iturature	   2-10
         Data from the Jiadtelle Monitoring Program	   2-18
         Discussion of the Data	   2-19

3.  BEHAVIOR OF TRICHLOROETHYLENE IN THE ENVIRONMENT	   3-1

    Physical/Chemical Characteristics of Trichloroethylene in
      the KnvLronment	   3-1
    Trans formation of Trichloroethylene in the Environment	   3-3
    Toxicology of Trichloroethylene and its Possible Degradation
      Produces	   3-8

4.  OCCURRKNCIS OF TRIC11LOROETHYLENE IN FOOD AND OTHER PRODUCTS
    THAT COME IN CONTACT WITH MAN	   4-1

    Food	   4-1
    Drinking Water	   4-1
    Other Substances	   4-12

5.  EXPOSURE AND BIOLOGICAL ACCUMULATION OF TRICHLOROETHYLENE IN MAN.   5-1

    Exposure	   5-1
    Biological Accumulation 	   5-5

6.  ENVIRONMENTAL TRENDS	   6-1

7.  BIBLIOGRAPHY	   7-1
                                     iii

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                          LIST OF FIGURES

Figure 2.1   Trichloroethylene (TCE) in the Environment. .  .   2-2

Figure 2.2   Trichloroethylene Production Processes	   2-5

Figure 2.3   Pathways for Entry of TCE into the Environment.   2-9

Figure 2.4   Industrialized Area Where Surface Water Was
               Sampled	   2-16

Figure 3.1   Reactants and Products of Trichloroethylene and
               NO- irradiation	   3-5

Figure 3.2   Transformation of Trichloroethylene 	   3-6

Figure 3.3   Uptake in Relation to Alveol.ir Concentration
               After 30 Minutes of Exposure at Rest and
               During Exercise 	   3-9



                            LIST OF TABLES


Table 2.1   Manufacture of Trichloroethylene	'     2-2

Table 2.2   Trichl oroeLhy Lcue Consumption	     2-6

Table 2.3   Physical Properties of Trichloroethylene ....     2-8

Table 2.4   Occurrence of TCE in the Environment	     2-]i

Table 2.5   Maximum and Minimum Levels of TCE at Various
              Locations in the United States  	     2-13

Table 2.6   Typical Levels of TCE	     2-14

Table 2.7   Miscellaneous Monitoring Data for TCE in the
              Atmor.phere	     2-15

Table 2.8   Trichloroethylene Concentration in Surface Water
              .Samples Taken by the Institute  for
              Environmental Studies   	     2-17
                                  IV

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Table 2.9


Table 2.10
                        TABLE OF CONTENTS
                           (Continued)
Concentration Ranges for Trichloroethylene in
  the Atmosphere Around Producer and User Sites.

Concentration of Trichloroethylene in Water,
  Soil, and Sediment in the Vicinity of
                                                               Pace
2-20
Table 3.1
Table 3.2
Table 3.3
Table 3.4
Table 3.5
Table 4 L
Table 4.2
Table 4.3
Table 4.4
Table 4.5
Table 4.6
Table 4.7
Table 4.8
Physical/Chemical Properties of Trichloroethylene
Transformation of TCE in the Environment ....
Comparative Toxicity of Trichloroethylene and
Summary of Data on the Carcinogen Lcity of
Toxicity of Trichlorocthy]ene and Its Trans-

Proper ti.es and TCE Concentration of Finished
Water in Five Cities 	
Some of the Organic Compounds Identified in
Miami, FlorLda- — Finished and Raw Water Samples.
TCE Concentration in Water Sources for Des
Moines, Iowa, Drinking Water and in Controls .
TCE Concentration in Infiltration Gallery and
in Associated Waters .............
TCE Concentrations in North End of Infiltration
Summary of TCE Data for Des Moines Finished
Representative Commercial Products Containing
3-2
3-4
3-11
3-] l\
3-] 5
4-2
4-4
4-5
4-7
4-8
4-10
4-11

              Trichloroethylene.
                                                   4-13

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                     LIST OF TABLES (Continued)


Table 5.1    Occupational Exposure	     5-2

Table 5.2    Occurrence of Trichloroethylene in Human
               Tissue	      5-6

Table 5.3    Trichloroethylene Recovered from Tissue .  .  .      5-7

Table 5.4    Chlorinated Hydrocarbons in Marine Organisms.      5-8
                                VI

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                              EXECUTIVE SUMMARY






      This report is a determination and evaluation of environmental levels




of trLchloroef.1iy.lene (TCE), based on a review of the literature and other




information sources and on monitoring data obtained to fill gaps in the




published data.




      Tr Ichiloroethylene is of environmental concern because of its toxicity




and its widespread use.  The major users by far are metal degrcasing and




dry r-leaning, and, chough TCE is incurring disfavor ir these applications,




it may soon find wide application in nonaqucous textile processing and




finishing.  The major production of TCE in the U.S. is on the Gulf Coast of




Louisiana and Texns, acid the annual production is about 435 million pounds




(197A figures).  It ir. estimated that approximately 60 percent of this is




released into the envirnment each year.




      The concentrations of TCE in the atmosphere of the U.S. ranges from




about 1 ppt in remote areas to over .100 ppb in areas near where the substance




is manufactured or used.  The concentration drops off rapidly as one moves




away from a source facility.




      Surface water concentrations, of TCE range from less than 1 ppb (the




limit of detection) to several hundred ppu in the vicinity of TCE manufacturers.




One measurement as high as; 5 ppm was made in a canal of stagnant water near




a producer site.




           TCE concentrations in sediments range from less than 0.04 ppb




to over 100 ppb.  Again the high values were found near manufacturers, but
                                    vil

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some of the lowest values were as well.



           Soil concentrations of TCE appear to be no higher near




manufacturers than in rural areas, though the data are very limited.  The




concentrations are only a few ppb or less.




           The behavior of TCE in the environment is controlled by its




structure.  TCE is an unsaturated chlorinated hydrocarbon which is not




susceptible to hydrolysis and thus is relatively stable in water and in




the soil.   However, the double bond in the compound is susceptible to




attack by free rad Lais and electrophilic reagents and thus is easily




degraded in a photochemical environment such as ambient air.  The ultimate




degradation product;.; are simple species commonly found in the environment,




but there arc some intermediates for which little toxicity data exist.




           There are very little data on the presence of TCE in food raised




and sold in the U.S.  However, data froth the United Kingdom suggest that




TCE Ls found on the ordc-r of parts per billion iti almost all common




foodstuffs.  Measurrd concentrations of TCE in U.S. drinking water are less




tlu'iu ] ppb except :in unusual circumstances such as in Des Moines, Iowa.




An unknown source oc TCE contamination has caused levels of TCE as high as




80 ppb to be found in Dee Molnes water.




           There is little evidence Lo judge if TCE is accumulating in




living systems.  Ljiiiited data on TCE levels in human tissue and in marine




organisms show levels on the order of a few parrs per billion.




           The data ace also insufficient to enable trends in the TCE




levels in the environment to be determined.
                                   viii

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                            1.  INTRODUCTION




      Trichloroethylene  (TCIi) is an important chemical whose health and




ecological effects, environmental behavior, and technologic and economic




aspects arc important to the U.S. Environmental Protection Agency.  In a




recent report prepared for the EPA by the Office of Toxic Substances, the




reasons for concern regarding TCE are discussed (U.S. Environmental Pro-




tection Agency, 1976).  These include its wide use in the production of




fabricated metals and cleaning fluids which results in extensive worker




exposure; the detection of this compound in ambient air and water, in




food, and in human tissues; and finally its identification by the National




Cancer Inrtitute (NCI) as a carcinogen in laboratory animals.




      The purpose of this program has been to determine and evaluate envi-




ronmental levels of trii:hloroethylcne.  The approach taken involved four




distinct phases:




      1.  Review and evaluation of literature and other sources




          of previously collected monitoring data




      2.  Development of an environmental monitoring program for




          fill ing selected data gaps




      3.  Environmental sample collection and analysis




      4.  Presentation of the above material as an integrated




          information data package.




Previously collected monitoring data from the literature and levels of




triclilorocthylene in the environment as determined under this program




will be summarized and evaluated.
                                   1-1

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      Levels of a substance in the environment can be reported in various




ways.  The level of trichlorocthylene in air will be reported in two ways --




as ppb (volume/volume) and in  ug/mr.  Either both values will be given or




a conversion factor will be indicated.  For all other media -- water, soil,




and sediment -- the data will be given as ppb (weight/weight).  Various




conversion factors can be found in Table 2.3.




      There are several important reviews on the subject of trichloro-




ethylene:  Specifically, a preliminary study of selected potential environ-




mental contaminants including trichloroethylcne (U.S. Environmental Protec-




tion Agency, 1975), a preliminary economic impact assessment of possible




vegulatory action to control atmospheric emissions of selected halocarbons




(Shamel et al., 1975),  an .impact  overview and an abstracted literature collection




on trichloroethylene (Waters el al., 1976), an air pollution assessment of tri-




chloroethylene (FulJer, 1976), a criteria foe a recommended standard for




occupational exposure to t.i Ichloroethylcnrie (National Institute for Occu-




pational Safety and Health, 1973), a proposed occupational exposure




standard for trichloroethylcne (Department of Labor, 1975), a toxicology




study called "Methylchloroform and Trichloroethylene in the Environment"




(Aviado et al., 1976).  These references have been consulted  (in addition to




many original journal articles and various reports) in preparing this




document.
                                   1-2

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           2 .   OCCURRENCE OF TRICI1LOROETIIYLENE TN THE ENVIRONMENT




SOURCES OF TRrCllLOROETIlYLENE IN THE ENVIRONMENT



      In Figure 2.J, the presence of trich]oroethylene in the environment and


the flow from production to use to human exposure is diagrammed.  Some of the


information to he presented Ls summarized in this figure.  Trichloroethylene


is a synthetic material created by man in huge amounts.  The ultimate sources


are the production facilities, and the amount produced largely determines how


much tricnloroethylene might eventually find its way into the environment.



TrichloroetliyJene Product Ion



      The evidence is that all trichloroethylene that appears in the environ-


ment is produced by man.  The estimated world production capacity for tri-

                            •3
chloroethylene is 3,010 x JO"  tons/year (1973) (McConnell et al., 1975).


U.S. production of trJchloroethylene was 435,000 x 10  pounds in 1974


(Chemical and Engineering News, May 19, 1975).  Of the total, world produc-

                                                 3
tion, it is estimated that approximately 600 x 10  tons of trichloroethylene


arc released to the atmosphere and 10,000 tons to the ocean each year.


      The production sites, annual capacity, and raw material for the manu-


facture of trirhloroethylcne arc given in Table 2.1.  As is obvious from the


table, the bulk of trichloroethylene is produced on the Gulf coast of


Louisiana and Texas.
                                     2-1

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to
 I
                                                                                                                      •2 26 x  10  Ib - i-orld
                                                                                                                      • 0 135 x .09 - U s  1973
                                                                                                                                                                            .1' 5 !>pb
                                                                                                                                                                           0 37 p,!1! (lousier, Toxrs)
                                                                                                                                                                           Sc.i aco- 0  1  te  1  9 pub
                                                                                              rBa. .,  i Pl,b
                                                                                             BoJv Fa:  1  to  10 pih
   B  1  to  100 ??b
 "j-nal-,  1  to 10 D,-l
1 Lo 10 ,ipb

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                   TABLE 2.1  MANUFACTURE OF TRICHLOROETHYLENE
    Company and Location
                          Annual Capacity as
                          of September 1972,
                          millJons of pounds
Raw Material
Dow Chemical. U.S.A.a
  Freeport, Texas

Diamond Shamrock Chemical Co.
  Electric Chemicals DLv.
  Deer Park, Texas

Ethyl Corporation
  Industrial Chemicals Div.
  Baton Rouge, Louisiana

Hooker Chemical Corporation0-
  Industridi Chemicals Div.
  Tacoma, Washington
  Taft, Louisiana

PPG Industries, Inc.d
  Industrial Chemicals Div.
  Lake Charles, Louisiana

Total
                                  150
                                   60
                                   50
                                   30
                                   40

                                  200
                                  530
Source:
a
U.S. Environmental Protection Agency, 1975.
Ethylene


Ethylene



Ethylene
Acetylene
Acetylene

Ethylene
 An additionaJ 50 million pounds per year unit was closed in late 1971.
 An 18--iuorith modernization beginning Jn 1977 is planned.  New project
 will result:  in improved technology to reduce hy-products and increase
 efficiency in use of raw material chlorine.  Expected capacity of
 refurbished unit will be 120 million pounds per year.
"Believed to be producing only small quantities (production was not
 reported to the U.S. Tariff Commission in 1971 or in the first 6 months
 of 1972).  Capacity of the plant will be expanded by April, 1973.

cA 60-million-pounds-per-year acetylene-based TCE plant at Niagara Falls,
 New York, was closed in early 1972.
^Expanding to 280 million pounds per year by the end of 1973.
                                     2-3

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      Based on the reactions involved in the production of trichloroethylenc




(Figure 2.2), several other chlorinated hydrocarbons  might also be expected




to reach the environment.  Thus, at the trichloroethylene plants,  Ln addition




to trichloroethylene, tetrachloroethane, hexachlorobutadicno,  and  dichloro-




ethane might be detected.  At all sites, chlorine and hydrogen chloride arc




important inorganics that are generated and consumed  in these  processes.







Uses of Trichloroethylone







      Table 2.2 gives some indication of the major uses to which trichloro-




cthylene was put in 1971.  By far, the major use of this solvent was in metal




degreasing and dry cleaning.  Trichloroethylene has,  in the past,  been the




solvent of choice in vapor degreasing; but because of its lower toxicity and




less severe pollution problem, methylchloroform is replacing trichloroethylenc




in many places.  While trichloroethylonc has incurred disfavor in  these




applications, it may soon find wide application in nonaqueous  textile proc-




essing and finishing.




      Trichloroethylene has also been used as an anesthetic and many hospital




personnel arc routinely exposed to tricliloroethylene  (Lloyd et al, 1975).




      Some of the other industries that are using tricliloroethylene on a




large scale are the following:  food products, textile mill products, paper




produces, printing trades, chemical manufacturing, rubber and  plastics manu-




facturing, stone and clay products, primary steel manufacturing, metal




fabrication, machinery manufacturing, electrical equipment, transportation




equipment, communication, wholesale trade, business services,  auto repair,




and mechanical, services.  Each of these industries is estimated to have over




1,000 people exposed to Lrichloroethylene (Lloyd et al., 1975).
                                     2-4

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From Kthylene Through Ethylene Dichloride  (90%  of  Total Product-ion)
                                      C1CH2CH2C1
                    8C1CU2CH2C.L
                                       + 4
]?ron Acetylene (10% of Total Production)
                    1IC H CH + 2C1  -v Cl CHCUC1
                    C10CHCHC1.,  — -rT-r--r~>  C1CH  =  cclo + HCL
                      2      2 or Catalyst              2
        Fjgure 2.2  Trichloroethylene Production  Processes
                                    2-5

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  TABLE 2.2  TRICHLOROETHYLENE CONSUMPTION,  197]
Mi 11 Jons of Pounds Percent
Met. i.l cleaning
Exports
Miscc] Inneous
Total
'i!>5
52
32
539
84
]0
6
]00
Source: U.S. Environmental Protection Agency, 1975
                      2-G

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Pathways for Entry of TrLchlorocthylenc into the Environment






      The pathways for entry of trichloroethylene into the environment are




determined primarily by the physical properties and to a lesser degree by the




chemical properties of the compound.




      Trichloroethylene (TCE) is a colorless,  nonflammable, volatile Id quid,




which boLLs at 87 C at atmospheric pressure.  Tt has appreciable vapor




pressure—58 mm Hg at 20 C—and limited, though not insignificant, solubility




in water—0.11 g trichloroethylene in 100 g H20 at 25 C.  This 'compound is




thermally stable, is sensitive to oxidation, but is resistant to hydrolysis.




These and other properties are summarized in Table 2.3.




      TrichLoroethylene Lb manufactured on a large scale—about 435 million




pounds in 1974 in Lhc U.S.  Trichloroethylene is used primarily as a cleaning




solvent: either in vapor decreasing or in cold cleaning.  It is estimated




that approximately 60 percent of the trichloroethylene produced is released




into the environment each year.




      These facts lead Io the conclusion Lhat trichloroethylene is released




into the air  In relatively large amounts.  There is some evidence that




trichloroethylene is rapidly degraded and has a relatively short half-life




in the atmosphere.  However, the fate of trichloroethylene in air is not




clearly understood, and its fate in water is even less well understood.




      All of these related facts arc combined into a picture depicting the




pathways for entry of trichloroethylene into the environment in Figure 2.3.




The heavier the line, the more important is the pathway.  Thus, Eor




trichloroethylcue, the most important pathway for entry into the environment




is release of this substance by users into the air, followed by release into
                                     2-7

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               TABLE 2.3  PHYSICAL PROPERTIES OF TR1C11LOROETHYLENE
Structural formula:
                     CIN
     H
oc
                    C HC1 o
           C, 18.128 percent;
                     cr      CL
Molecular formula:
Analysis:
Molecular weight:  131.29
Appearance:  Colorless liquid
Boiling point:  86.7 C
Melting point:  -87.1 C
Decomposition temperature:  700 C
Flash point:  None
Autoignition temperature:  410 C
Specific gravity (20 C/4 C):   1.465
Vapor density at 25 C:  4.53 g/£
Surface tension at 20 C:  29 dyne/cm
Odor threshold:  Aproximately 20 ppm
Viscosity at 20 C:  0.58 centipoise
Refractive index at
Dielectric constant
Vapor pressure:  _^C
                  0
                 20
                 40
Solubility in water
     H, 0.77 percent; Cl,  80.95 percent
20 C: 1
(liquic1)




°C
25
60
.4773
at 16
inm Hg
20.1
57.8
146.8



                                       3.42
Solubility of water in TCK:
                              .
                            25
                            60
Distribution coefficient of solubility:
                           Water/air
                           Blood/air
                           Plasma/air
                           Fat/water
Conversion factors:  Air (25 C):
          /IQOg water
             0.] 1
             0.125
         g/lOOg TCE
             0.033"
               080
                20
                                      0.
                                            C
37 C
                   Water (20 C)
                   Other media:
                3         .1.6
               18-22      8-10
               16-20
               34.4
         1 ppb (vol/vol)  = 5.27 ug/m
         1 ug/1 = 186.2 ppb (vol/vol)
         1 ppb (vol/vol) = 1.465 ppb (vol/vol)
         1 ppb (wt/wt)  = 1 yg/]
         1 ppb (wt/wt)  = 1 ytg/kg
                                    2-8

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                         TERRESTRIAL   ECOSYSTEMS
mmrnmiDisTn LBUTIO
                                             BY-PRODUCTS
                                             VASCULAR !

                                                                 INVERTEBRATES
                                            SEDIMENTS
                                AQUATIC   ECOSYSTEMS
             Figure  2.3  Pathways for entry of trichloroethylene into the environment.

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the air by manufacturers, followed by release into water by manufacturers and




users, followed by absorption in soil, collection in sediment, and then all




of the other Interactions shown in the figure.  The environmental media would




thus be ranked as follows in order of decreasing trichloroethylene concen-




tration:  air, water, soil, sediment, and biota.







TRICHLOROF/L'llYUiNE LEVELS IN THE ENVIRONMENT







Data From the Literature







      No extensive monitoring programs designed specifically for




trichloroethylene have been identified.  The concentration of trichloro-




ethylene in various parrs of the environment has been estimated, Table 2.^.




In addition, trichloroethylene has been quantified in air and surface, water




at various sites and these data cire presented in the following sections.




      However, there arc serious gaps in these data.  There are no data




available in the literature on production 5iil.es or on sites or cities? where




there is known to be extensive use of trichloroethylene.  New information on




such sites is reported in the section on "Dnta From the Battelle Monitoring




Program".  In addition, time studies could be very informative.  For example,




how does the trichloroethylene concentration vary from hour to hour, from




day to day, and from season to season?  Is washout important?  Is the amount




of sunshine critical to the degradation of trichioroethylene or is degradation




relatively constant?  These and similar questions might be answered if a




single site were sampled over an extended period of time.  No such study has




yet been undertaken.
                                     2-10

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   TABLE 2.4  OCCURRENCE OF TRTCHLOROETHYLENE
              IN THE ENVIRONMENT
Typical Concentrations


Air
Radn v/ater
Surface wafer

Potable water
Sea v-/ater
Marine sediments
Marine invertebrates
Fish
Watcrbirds
Marine maunio-7
>io-B
io"8
io-9
—9
10
	 n
10
Source:  McConnel]  et al., 1975.
                        2-11

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TTich]oroethy]enK in the Atmosphere






      TrLchloroethylcne has been determined along with other halocarboris at




various locations throughout the U.S. and around the world.  The most ex-




tensive data are reproduced in Tables 2.5 and 2.6.  These data are taken from




a study done at Cook College, Rutgers University (Lillian et al., 1975).




Other data nre summarized Ln Table 2.7.






Trichloroethy.1c.ne in Surface Waters






      In 3975, a program entitled "Monitoring to Detect Previously




Unrecognized Pollutants" began at the University of Illinois at Urbana-




Champaign.  This program is administered within the Institute for Environ-




mental Studies under a contract with the U.S. Environmental Protection Agency.




The coprincipal investigators are Professor E.S.K. Chian, Department of Civil




Engineering, and Professor B. S. Ewing, Director of the Institute for




Environmental Studies.




      The objective oJ: the program is to direct previously unrecognized




pollutants in surface waters.  Approximately 200 x^ater samples are being




collected from 14 heavily industrialized river basins.  These areas and




the approximate number oE samples to be taken at each location are indicated




in Figure 2.4 (Chian and Ewing, 1976.  Progress Report No. 4).  The results




are summarized in Table 2.8.  For some of the samples, values for




trLchloroethyleiie were not reported.  When the presence of a substance was




not reported, ii: is not clear whether the substance was not present, was




not quantified, or wos not detected for some reason such as interference




by  another compound.  However, trirhloroethy.lene was detected in 142 of
                                    2-12

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   TABLE 2.5  MAXIMUM AND MINIMUM LEVELS OF TRICHLOROETHYLENE
              IN THE ATMOSPHEKF, AT VARIOUS LOCATIONS  F.N THE
              UNLTEU STATES
  Monitoring Period
     and Location
LevcJ s
Concentration,
    ppb
June 18-L9, J974
Seagirt, N.J.
(National Guard Base)

June 27-28. 1974
New York, N.Y.
(45th & Lexington)

July 2-5, .1974
Sandy Hook, N.J.
(Fort Hancock)

July 8-.10, 1974
Delaware City, Delaware
(Road 448 f> Route  72
intersection)

JuJy L1-.I2, J974
Baltimore, MD.
(170J Poncabircl Pass,
Ford Ho "Labi rd area)

July 16-26, 1974
Wilmington, OH
(Clinton County Air
Force Base)
 Max.
 Min.
 Mean

 Max.
 Min.
 Mean

 Max.
 Min.
 Mean

 Max.
 Min.
 Mean
 Max.
 Min.
 Mean
 Max.
 Min.
 Mean
    2.8
   <0.05
    0.26

    1.1
    0.1]
    0.71

    0.80
   <0.05
    0.34

    0.56
   <0.05
    0.35
   <0.05
   <0.05
    0.63
   <0.05
    0.19
September 16-19, .1974
Wlri.tr Face Mountains
(New York State)
March-December, 1973
Bayonne, N.J.

Max.
Min.
Mean
Max.
Min.
Mean
0.35
<0.05
0.10
8.8
<0.05
0.92
Source:  Li.IJ.ian et al., 1975.
                               2-13

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         TABLE 2.6  TYPTCAL LEVELS OF TRICHLOROETHYLENE
                    IN THE ATMOSPHERE
   Date and TUTK-:
        Location
Concentration, ppb
June 27, 1974
      2300
New York, N.Y.
        0.11
September 17, 1974
      ]200

July 2, L974
      1400
July 19, 1974
      1300

JuLy 17, ]974
      1228
July 17, 1974
      1203
White Face Mountains             <0.02
N.Y. State (noiiurban)

Over Ocean                        0.18
Sandy Hook, N.J.
4.8 km (3 m:i.) offshore

Seagirt, N.J.                     <0.02
(National Guard Base)

Above tin; Inversion              <0.02
elevation 1500 m (5000 ft.)
Wilmington, Ohio

InversJon Layer                   0.075
elevation 450 m (1500 ft.)
Wilmington, Ohio
Source:  Lillian el al., 1975.
                                2-14

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                      TABLE 2.7.  MISCELLANEOUS MONITORING  DATA FOR TRICHLOROETHYLENE  IN THE ATMOSPHERE
Ni
I
             Location
                     Date of. Data
                      Collection
                 Concentration
                             Method
                                                                                  3
                           Reference
New Brunswick NJ
ii ii
Kansas City-NASN
Station
Houston TX and
vicinity
Los Angeles Basin
Worldwide
Pullman WA
1973
Unreported
1974

Nov. 1974

April 1975
1974
Dec. 1974 to
Detected
0.75 ppb
Detected

ii

"
5 ppb
<5 ppt
Coulometric GC
ii ii
GC/MS

GC/MS computer

ii ii
Estimate
GC/MS
Lillian and Singh, 1974
ii ii
Bunn et al. , 1975

Pellizzari et al., 1976

1! II
Goldberg, 1975
Grimsrud and Rasmus sen,








1975
Western Ireland
North Atlantic
Northern Hemisphere
Southern Hemisphere
Liverpool, England
Rural areas of
  Britain
Over the northeast
  Atlantic
Britain, perimeter
  of a manufactur-
  ing plant
Heath, near the
  above plant
Suburban area, re-
  moved from plant
Tokyo
  Feb. 1975
June/July 1974
Oct. 1973
1974
1974
March 1972
1972

Aug. 1972

1972-1974
                             May  1974-
                               April  1975
15 ppt
<5 ppt
15 ppt
1.5 ppt
850 ng/m3 (^160 ppt)
11 ng/n3 (average)

6 ng/m3

40-64 ppb (mass)


12-42 ppb (mass)

1-20 ppb (mass)

1.2 ppb (annual
  average_
                                                                      Coulometric  GC
                                                                            ii      M
EC/GC
                                                                        n
                                                                        ii
Lovelock, 1974

Cox et al., 1976
     11     M
Murray and Riley, 1973




Pearson and McConnell, 1975

-------
h-1
              Encircled numbers indicate quantity of
              samples  to be collected in each area.
                                         Figure  2.4.  Industrialized area where  surface water
                                                       was sampled (Source: Chian and Swing, 1976),

-------
     TABLE 2.8.  TRIC11LOROETHYLENE CONCENTRATION IN SURFACE WATER SAMPLES
                 TAKEN BY THE INSTITUTE FOR ENVIRONMENTAL STUDIES
        Area
Type of Water Analyzed
Chicago, Illinois




Illinois

Pennsylvania


New York City area

Hudson River area

Upper and Mi.dd.le
Mississippi RLver

Lower Mississippi
River

Houston area


Alabama


Ohio River Basin

Great Lakes



Tennessee River Basin
u
Lake Michigan, sewage         9
treatment plant effluent,
filtration plant, chan-
nels

II]inois River               11

Delaware, Schuylkill,        25
and Lehigh Rivprs

Hudson River and bays        16

Hudson River                 12

Mississippi River            19


Mississippi River             9
Calveston Bay and             8
channels

Black Warrier, Tornbigee,      7
Alabama, and Mobile Rivers

Ohio River and tributaries   10

Lake Superior, Michigan,     13
Huron, Ontario, Erie, and
vicinity

Tennessee River and           1
tributaries
                                       Concentration.
                          Number of   Range (Average),
                           Samples         ppb


                              9         0.5 to 10(5)
                                       <1 to 7  (<2)

                                       <1 to 18 (-2)


                                       <1 to 7  (<3)

                                       <1 to 4  (
-------
the over 200 samples analyzed and the concentrations range: Erom <1 ppb to




188 ppb in the surface waters sampled.  This information has all been taken




from the first five progress reports from the Institute for Environmental




Studies on KPA Contract 68-01-3232 (Chian and Ewing, 1976).




      Many other organics have been identified and quantified and elemental




inorganic analyses were done during this program.  From this information and




details of the methodology used, the reader is referred to the original




reports.




      Pearson and McConnel] (1975) report concentrations of 0.15 ppb




trichlorocthylcne in rainwater collected in Runcorn, England.  The highest




concentrations that these researchers measured in upland river waters was




6 ppb.  These same authors also reported that they have rever detected




organochloiines in well waters.  With a normal detection limit of 0.01 ppb,




Pearson and McConnell (1975), between April, 1973 and August, 1973, determined




that: the average concentration of trichloroethylene in Liverpool Bay sea




water was 0.3 ppb with the maximum concentration of 3.6 ppb found.  Tn




Liverpool Bay sediments a maximum trichloroethy]ene concentration of 9.9 ppb




was found.




      There have been several studies on the presence of trichloroethylene




and other liaHocarbons in drinking water and raw water samples.  This




information is presented in the section on "Drinking Water".






Data From the Battelle Monitoring Program






      A program to determine environmental levels of trichloroethyiene was




initiated :in 1976 at the Tlattelle Columbus Laboratories.  Rased on a review




of the literature, it was decided that determinations of trichloroethylene
                                     2-18

-------
levels in the vi.cin.Lty of producer rind user plants were lacking.  A sampling




rationale and protocol were established.  During late 1976 and early 1977,




samples were collected from various production sites, a user site, and A




background site.  The samples were analyzed and Uie results are summarized




in Table 2.9 and 2.10.  Details of the results and methodology can he found




in a  companion  report  (Battelie Columbus Laboratories, 1977).







Discussion of the Data







      The concentration of trichloroethylene in the atmosphere ranges from




about 1 ppt in remote areas to over 100 ppb in areas where the substance is




manufactured or used.  1'earson and McConncJl (1975) point out that as one




moves away from a manufacturing facility, the conceiti at.Lon of trichloro-




ethylene in air drops off rapidly.  These results are summarized in Table 2.7.




Ohta and coworkers (1.976) make a similar observation.  They state that the




distribution peak for trichloroethylene coincides with locations of machine




or met.'il product plants which use the solvent.




      The BatLelle Columbus Laboratories (1977) study in the United States




confirms these observations.  In Table 2.9, the highest concentrations of




trichloroethylene are observed downwind from a producer or user site and




the concentration seems to be dependent on the dibtance from the discharge




point.  Most of the higher concentrations are observed at distances of less




than 1 kni.  Considerable variation, however, was observed in the maximum




downwind levels of trichloroethylene at various production sites.  The




variations in the observed maximum concentrations between plants may be




due to differences in (1) production processes, (2) emission control




equipment, (3) meteorological conditions, and (A) distance from the plant.
                                     2-19

-------
TABLE 2.9.  CONCENTRATION RANGES FOR TRICHLOROETHYLENK TN THE
            ATMOSPHERE AROUND PRODUCER AND USER SITES
Date of
Location Collection
Dow Chemical Co. Nov. 1976
Freeport TX







Hooker Chemical Nov. 1976
Hahnvillc LA







Ethyl Corporation Nov. 1976
Baton Rouge LA






PPG Industries Dec. 1976
Lake Charles LA






Boeing Company Jan. 1977
Seattle WA
(user)

St. Francis Na- Nov. 1976
tional Forest AK
(background)
Concentration, Distance
Site ppba from Plant
1
2
3
4
5
6
7
8
9
1
2
3
4
5
6
7
8
9
1
2
3
4
5
6
7
8
1
2
3
4
5
6
7
8
1
2
3
4
_



-------
       TABLE 2.10.  CONCENTRATION OF TRICHLOROETIIYLENE IN WATER, SOCL,
                    AND SEDIMENT IN THE VICINITY OF PRODUCER SITES
    Location
 Date of
Collection
  Description of Medici
Concentration,
     ppb
Dow Chemical Co.,      Nov. 1976
Plant B, Freeport TX
Hooker Chemical Co.
Hahnville LA
Nov. 1976
                                                                      13
                                                                     0.9
                                                                 <0.06 to 0.45
                                                                     0.15
                                                                  None detected
                                                                     0.04
Surface water, mouth of          172
plant effluent canal

Water, as above except 4 m       197
deep

Surface water, 400 m down-         5
stream from plant outfall

Water, as above except 5—
6 in deep

Surface water, 800 m
upstream of plant outfall

Soil, approximately 2 km
from plant:

Sediment, mouth of plant
effluent canal

Sediment, 400 in downstream
of plant ouLfall

Sediment:, 800 111 upstream
of plant out Fall

Surface water, Mississippi         1
River, 150 m upstream of
plant outfall

Surface water, at plant          535
outfall

Surface water, 1 km down-         22
stream of plant outfall

Surface water, open stag-      5,227
nant canal about 2.7 km
from plant

Soil, close to the plant out  0.23 to 5.6
to about 2.7 km

Sediment, 150 m upstream         0.18
of plant outfall

Sediment, 100 m downstream       0.63
of plant outfall

Sediment, 200 m downstream       0.03
of plant outfall	
                                     2-21

-------
                           TABLE 2JO (Continued)
Location
Ethyl Corpor.it ion
Baton Rouge LA





PPG lndusLri.es
Lake Charles LA




Date oE
Collection DescrLption of Media
Nov. 1976 Surface water immediately
above settling pond
Surface water, 200 m
upstream of plant outfall
Surface water, 300 m down-
stream of plant outfall
Soil , various locations in
vicinity of plant
Sediment, 200 m upstream
of plant outfall
Sediment, 300 m downstream
of plant outEall
Dec. 1976 Surface water, 50 m
upstream of plant outfall
Surface water , at plant
outfall No. 1
Surface water, at plant
outfall No. 2
Surface water, 50 in doxm-
stream of outfall No . 2
Surface water, lake — down-
Concentration ,
ppb
128
0.4
37
None detected
None detected
116
353
447
179
403
29
St. Francis National
Forest AK
(backgrotmd)
Nov. 1976
stream of plant outfalls

Soil, quadrants surrounding
plant
Sediment, 50 m upstream
oE plant outfall

Sediment, at plant outEall
No. 2
Surface water, from lake

Soil
Sediment
None detected
to 0.11

     146


      15


    <0.05

     0.63
     2.2
                                        2-22

-------
Higher production capacity apparently does not necessarily imply higher




emissions since the maximun concentrations observrd at the larger: plants




were no higher than those observed at the smaller operations and sometimes




lower.  Large temporal variations are observed when measurLng these




chlorinated hydrocarbons downwjnd from a production facility.  Changes in




meteorological conditions, particularly wind speed and direction, and/or




variations in the emissions may account for this phenomenon.




      The range of concentrations in surfoce waters is more difficult to




judge.  The analytical techniques presently used do not allow routine




determinations at the ppt level.  So the actual backgroundjhas to be taken




as somewhat less than 1 ppb.   However, surface waters in urban areas can




have concentrations on the order of 100 ppb.




      The study by the Institute for Environmental Studies (Chian and Ewing,




1976) indicates the concentration of trichlnroethylene in surface waters




may be as high as 188 ppb (in the vicinity of Lake Erie), but for the most




part surface waters contain less than .1 ppb (Table 2.8.)-




      In the Battellc study carried out in the vicinity of manufracturing




plants, the concentration of trichloroethylene was higher (Table 2.10).  One




sample went as high as 5 ppm.  Again, the distance from the source was




important as the concentration dropped off with distance.  Also, samples




upstream from plant discharge channels usually had lover concentrations than




samples taken downstream.




      The literature provides no information on the presence of trichloro-




ethylene in soil.  In the Battelle study, it was found that the concen-




tration of trichloroethylene in soil in the vicinity of manufacturing plants
                                      2-23

-------
was on the order of a few ppb or less (Table 2.10); but unexpectedly, the




same concentration was found at a background site in Arkansas.  Sediment




samples analyzed in this same study showed more variable results.  Concen-




trations ranged from less than 0.04 ppb to as high as 146 ppb (Table 2.10);




but again the rural background site showed a level of 2.2 ppb which was higher




than anticipated.




      It is clear that the source of trLchloroethylene is anthropogenic,  tt




is at highest concentration where it is made and used.  The background level




in the atmosphere is Cairily low, on the order of 5 ppt, indicating that




trichloroethylene is degraded in the atmosphere.  However, in close proximity




to manufacturing or user plants the concentration may be considerably higher




and at tlines m.iy approach !1 ppm.
                                 2-24

-------
             3.  BEHAVIOR OF TRICHLOROETHYLENE IN THE ENVIRONMENT







PHYSICAL/CHEMICAL CHARACTERISTICS OF TRICHLOROETHYLENE IN THE ENVIRONMENT






      This sectLon might also be considered the degradability section since




the data contained herein deals with how long trichloroethylene holds up in




the environment and in the human body.  Table 3.1 brings together some of.




this information.




      The structure of the compound dictates its behavior in the environment.




Trichlorocdiylene is an uns&turated chlorinated hydrocarbon.  The double




bond is  susceptible to attack by free radLcals and electrophilic reagents.




Thus, it is not suprising that it is easily degraded in a photochemical




environment such as ambient aLr.  On the other hand, since the vinyl bond




between carbon and chlorine is very strong, this molecule is not susceptible




to hydrolysis and is relatively stable in water and in the soil.




      Some researchers have concluded that "... not only are the simple




chloroa.Lipliat.Lc compounds not particularly persistent, but their degradation




products are simpJe species commonly found in the environment" (McConnell




et a.l . , 1975).   This statement needs to be accepted with some reservations




for there is still the question of how quickly the "simple species commonly




found in the environment" form and of what the intermediates in these processes




might be.  The next section attempts to answer these questions.
                                     3-1

-------
             TABLE 3.1.  PHYSICAL/CHEMICAL CHARACTERISTICS OF
                         TRICHLOROETHYLENE IN THE ENVIRONMENT
     Media
   Half-Life/Changc
       Reference
Human blood; after
human exposure at
100 ppm, 6 h/10 days

Ditto
Human, anaesthesia
Human
SJimi.lal.ed atmospheric
condition0-

One ppm  In waLcr
contninJng naturaJ
and added contami-
nants

Troposphere, 3.1
parts/thousand
13.3 hr/trichloroethanol   Mueller et al., 1974
disappearance
99 hr/trichloroacetJc
acid disappearance
    min/chloral hydrate
from blood
    hr/urinary meta-
bolites excreted

Estimate 5-.12 hr under
bti.glit sunlight

19 irrln/evaporat Lon
6 weeks (±50%)
Cole et al., 1975
Ikeda and Imamura, 1973
Dilling et al., 1976
Pearson and McConnell, 1975
                                         3-2

-------
TRANSFORMATIONS OF TRICIILOkOKTHYLENF, IN THE ENVIRONMENT






      This section indicates what new substances are produced when




trichloroethylene enters the environment.  This information is summarized




in Table 3.2.  Figure 3.1 shows the transformations of trichloroethylene




schematically.  Figure 3.2 shows the degradation of trichloroethylene in a




photochemical chamber in the presence of nitrogen/dioxide in air (Gay et al.,




1976).  The chamber was irradiated with ultraviolet light as the reactants




and products were continuously monitored using longpath infrared spectroscopy.




This study was undertaken in order to obtain more information on the atmo-




spheric degradation of halogenated compounds particularly with regard to the




rates of photooxidation and the identity of photooxidation intermediates




and final products.




      What is seriously needed in this area .is the same kind of study on




a more comprehensive environmental scale.  What is the rate, fate, and




transport mechanism for the dispersion and degradation of trichloroethylene




in the environment?  Perhaps this can best be determined in studies of




model ecosystems using labeled compounds as tracers and sophisticated




analytical procedures for the analysis of the substances and their degra-




dation products.  Radiolabeled trichloroethylene (trichloroethylene




[1,2-^Cj) is available from various suppliers on special order.




      In looking at the various transformations of trichloroethylene, the




question of the toxiciLy of the intermediates arises.  Some of the compounds




that are produced are simple molecules that have been previously studied.




These are carbon dioxide, carbon monoxide, hydrogen chloride, chlorine,




acetic acid, and ozone; but others such as dichloroacetic chloride, phosgene,
                                    3-3

-------
                TABLE 3.2.  TRANSFORMATIONS OF TRICHLOROETHYLENE
                            IN THE ENVIRONMENT
       Media
  What is Produced
       Reference
Photochemical Chamber,
TCE (3.45 ppm) with
toO^ (^-&6 ppm)

Atmosphere near
welding
Smog chamber

Human (LOO ppm,
6 h/10 clays)
Atmosphere, xenon arc
exposure
Dichloroacetyl chloride,
HC1, CO, phosgene
(TCE haLE-liEe: ^2 hr)

I1C1, C1.2, and phosgene
(severe decomposition,
dangerous levels)

Ozone

Trichloroethanol and
tr.Lchloroac.efLc acid in
blood

Dlchloroacet.ic acid,
C02, HC1
Gay et al., 1976
Rinzema and Silverstein,
1972
Farber, 1973

McNutt et al., 1975



McConnell et al., 1975
                                3-4

-------
         Trichloroethylcne
                                         Dicliloroacetyl
                                            Chloride
     20    40   60
        80   100   120   140  160
            TIME IN (min.)
180  200
Figure 3.1.  Reactants and products of trich]oroethylene
             and NO,
             1976).'
and NO  irradiation (Source: Gay ot al .,
               3-5

-------
                                           C12C = CHC1
OJ
            Human Metabolism
            Biological t-l/2a 41 hr'
            (Ikeda & Imaraura, 1973)
                  [C13CCH(OH)2]
                (Chloral Hydrate)
    t-1/2  5-12 hr (bright sunlight) (Billing et al . , 1976)
       t-l/2a 6-12 weeks (McConnell et al., 1975)
NO,
             C13CC02H
                                                   Water,
                                                    Soil
    Persists 2-18 months
    (Abrams et al.,  1975)

             or

          2.5 years
(Pearson &-McConnell,  1975)
                ClgCHCOCl, HC1, 03, C1COC1, CO, HCOgH, HNOg
                    4              (phosgene) ((.ay efc ^ ig?6)

                C12CHC02H
                                                                                            C02,"  HC1
                      Microorganisms
                       in Sea Water
                     V
                 Unknown
          Degradation Products
        (McConnell et al., 1975)
             t-1/2 =  Time  required  for  one-half  of  the  chlorinated
             hydrocarbon to  disappear by  the  indicated  process.
                                     Figure  3.2.   Transformations  of  trichloroethylene.

-------
and dichloroacctic acid arc not commonly found in the environment and may




be of some concern.  The toxicity of. these materials is addressed in the next




section.  The evidence ns that phosgene, although extremely toxic, is not




produced in very large amounts except under special circumstances such as




when high concentrations of trichlorocthylene are present in the atmosphere




where welding Ls taking place.  According to Pearson and McConnell (1975)




any phosgene produced in the atmosphere would he quickly hydrolyzed to carbon




dioxide £ind hydrogen chloride.




      There are other special circumstances that could produce toxic




substances.  Trichloroethylene in the presence of a strong base or at high




temperatures is converted to dichloroacetylcnc which is extremely toxic but




is quickl} converted by moisture to phosgene.  Thes3 toxic products of




trichloroethylcne would not be expected to exist in significant concen-




trations for any length of time under normal circumstances in Lhe environment.




      The only degradation products that may exist i.n the environment in




appreciable quantities for ciny period of time arc dichloroacetyl chloride




produced by the photodcgrndatLon of trichlorocLhylene in the atmosphere and




dichloroacctic acid produced by the hydrolysis of dichloroacetyl chloride.




Limited animal, experimentation suggests low toxicity for dichloroacetyl




chloride although it may be irritating to eyes and mucous membranes.   There




is also little information available on dichloroacetic acid (see next section)




There is some evidence that the ultimate fate of the dichloroacetyl chloride




and dichLoroacetic acid is degradation by microorganisms (McConnell et al.,




1975).  Although the degradation products have not been determined, they are




probably carbon dioxide cind chloride ions which are already present in the
                                      3-7

-------
environment.  The effect of dichloroacetyl chloride on the environment and




its ultimate fate should, however, be determined since such large quantities




of trichloroetliylene are being released into the atmosphere and degraded




each year.






TOXICOLOGY OF TRIC1ILOROET1IYLENE AND [TS POSSIBLE DEGRADATION PRODUCTS






      In the introduction to this section on trichloroethylene, some of the




reasons for the concern over this substance were enumerated; but boiled down,




this concern amounts to the fact that a large amount of this material is




produced and used by people who are exposed to it and who may be directly




or indirectly harmed by such exposure.  This section attempts to answer the




question:  In what way does, or might trichloroethylene harm people?




      There are several reviews on the toxicity and toxicology of




trichloroethyJ.ene.  A recant and comprehensive reviex* by Avaiado et al.,




1976, is available arid the toxicity oE thJs substance is discussed at




length in the review by the U.S. Environmental Protection Agency (1975).




Biological studies and toxicology of trichloroethylene are discussed in




other reviews as wo LI (National Institute for Occupational Safety and Health,




1973; Waters, et al., 1976; World Health Organization, 1976).  Of somewhat




older vintage is the text by Browning  (1965)| dealing with industrial solvents




in general and specifically with trichloroethylene.  Some of this information




will be summarized here.




      Regardless of the exposure of a substance, there :is no harm possible




unless there is some interaction with the organism.  Figure 3.3 shows the




uptake of trichloroethylcne and other solvents in relation to the
                                     3-8

-------
       %
       uptake
 80
 60
 40
  20
            20
40
60
80
                                            O  Methylene chloride
                                                                   \
                       $•  TrichloroethyJLene

                       D  Aliphatic white ^spirit

                       H  Aromatic white spirit

                       A  Styrene
alveolar concentration x 100
  i-nspiratory concentration
Figure  3.3   Uptake  (percentage of amount supplied) in relation to alveolar
            concentration  (percentage of concentration in inspiratory air)
            after 30 minutes of exposure at rest and during exercise.
            (Each symbol gives the mean value  of two subjects for styrene
            and the aliphatic and aromatic  components of white spirit, the
            mean value of  four or five subjects for raethylene chloride,
            and the mean value of five subjects for trichloroethylene.
            {Regression line:  y = -0,72x = 74.91)  (Source:  Astrand,
            1975).
                                  3-9

-------
concentration in inspiratory air.  This figure was taken from a review by




Astrand (1975) on the uptake of solvents in the blood and tissues of man.




Once inside the body the inhalation (as above) or through skin absorption




(Fukabori et al., 1976) or by ingestion (U.S. Environmental Protection




Agency, 1975), this substance is rapidly metabolized and the major products




are excreted.  The metabolites are trichloroethanol, trichloroethanol




glucuronide, and trichloroacetic acid.  Monochloroacetic acid is also a




detectable trichloroethylene metabolite.  Chloral hydrate is a demonstrated




intermediate in the metabolism of trichloroethylene to trichloroethanol




and trichloroacetic acid (Cole et al., 1975).




      It is obvious then that trichloroethylene is taken into the body and




interacts (is metabolized) with it.  The question now becomes, what effect




does this interaction have on the tissues of the organism?  Table 3.3




summarizes the toxicity of trichloroethylene and compares it with related




compounds (Waters et al., 1976).  The U.S. Environmental Protection Agency




(1976) summarized trichloroethylene health effects.  Trichloroethylene has




been responsible for the death of humans.  One study reports on trichloro-




ethylene poisoning in 284 cases, including 26 fatalities, in European plants




where trichloroethylene vapors were inhaled.  Toxic action involves the




central nervous system.  Short-term studies indicate that exposure to a




concentration of 100 ppm in air may interfere with psychophysiological




efficiency.  Six students exposed to 110 ppm from two 4-hour periods




separated by 1-1/2 hours showed significantly lower levels of performance




in perception, memory, and manual dexterity tests.




      Recently as a part of a continuing NCI bioassay program to screen




chemicals for cancer-causing activity, trichloroethylene was tested and
                                     3-10

-------
               TABLE 3.3.   COMPARATIVE  TOXICITY OF TRICHLOROETHYLENE AND RELATED COMPOUNDS
Compound and
parent alkane
Chloroform



(Methane
Enhalation, LC50,
Oral LD50 rag/kg
Rat: 800
Rat: 2,180



ppm
Mouse: 5,
Mouse:
Rabbit:
Dog:


687/7 hr
28
59
100

Lowest published toxic
concentration, ppm
Human : 10/yr
Systemic effects



Structural
forms
Cl
1
Cl-C — H
1
Cl
  derivative)

Carbon tetra-
  chloride
(Methane
  derivative)

1,1,1-Trichloro-
  ethane
Mouse: 12,800
Rat:    1,770
Rat:    7,460
Rabbit: 6,380
Guinea
  Pig:  9,470
Rabbit: 5,660
(Ethane
  derivative)

1,1,2-Trichloro-
  ethylene
Rat:
Rat:
Dog:
5,200
4,920
5,900
                                  Mouse:  9,526/8 hr
                                  Mouse:  9,528/7 hr
                                  Rat:   23,900/30 min
                                  Rat:   14,000/7 hr
                                  Rat:   18,000/3 hr
                                        Human:
                                        CNS:
                                        20
                                        toxic effects
                                        Human:  350
                                        Psychotrophic effects

                                        Human:  920/70 min
                                        CNS:    toxic effects
                                 Cl
                                 I
                             Cl- C -
                                 I
                                 Cl
                                                                                                Cl


Cl —


Cl
1
C —
1
Cl
H
1
C
1
H


•— • H


Human:  160/83 min
CNS:    toxic effects

Human:  11C/8 hr
                                                                                      Cl
                                                                              Cl
                                                                                          C = C
                                                                                        /     \
                                                                                      Cl
                                                                              H

-------
                                             TABLE  3.3.  (Continued)
    Compound and                      Inhalation, LC50,       Lowest published toxic      Structural
    parent alkane   Oral LD50 mg/kg         ppm                 concentration, ppm           forms

    (Ethylene
      derivative)
i-j
NJ
    1,1,2,2-Tetra-
      chloroethylene  Mouse:  8,850
                      Mouse: 10,900
    (Ethylene
      derivative)
    Source:  Waters et al., 1976.
Human:  230
Systemic effects

Human:  280/2 hr
Eye:    toxic effects

Human:  600/10 min
CNS:    toxic effects
                                                                                          Cl
                                                                                            \
                                                                                          Cl
Cl
Cl

-------
found to be active in mice (Anonymous, 1976).   Much of the data is described




in that HEW News release.  The report goes on to day that investigations of




compounds that can be substituted for trichloroethylene (such as methyl-




chloroform) are underway, but NCI states concern regarding substitution for




trichloroethylene before the alternative compounds can be adequately




evaluated.




      The carcinogenicity of trichloroethylene has also been reviewed




recently by the International Agency for Research on Cancer (World Health




Organization, 1976).




      Table 3.4 presents a summary of carcinogenic data for trichloroethylene




(Waters et al., 1976).  The question remains whether any relationship exists




between tiichloroethylene and liver cancer in man.  Until that is resolved,




trichloroethylene must be regarded as a useful but potentially hazardous




substance.




      In the section on "Transformations of Trichloroethylene in the




Environment", some of the known transformations of trichloroethylene in the




environment were indicated.  In considering the possible harm of a substance




to people or to animals, it is not sufficient to know the toxicity of the




parent compound; the toxicity of the degradation or transformation products




must also be considered and evaluated in terms of the quantities of these




by-products produced.  Table 3.5 provides a summary of the toxicity of




trichloroethylene and its various transformation products.  Unfortunately,




little is known about the quantities of these substances that are produced




when trichloroethylene is degraded.
                                    3-13

-------
             TABLE 3.4  SUMMARY OF DATA ON THE CARCINOGENICITY
                        OF TRICHLOROETHYLENE
 Species
Number
Exposure
Results
Dogs           16
Rats           12
Guinea pigs    11
Monkeys         2
Rabbits         4
Cats
Mice           28
Rats
                   Inhalation
         150-750 ppm in air 20-48 hr/wk
           for 7-16 wk

                   Inhalation
         3,000 ppm, 27 exposures
         100 ppm, 132 exposures
         200 ppm, 148 exposures
         200 ppm, 178 exposures

                   Inhalation
         200 ppm 75 min/day for 6 rao

                  Intragastric
         0.1 ml in 40% oil solution 2/wk
         2,339 mg/kg (M) 5 wk for 78 wk
         1,739 mg/kg (F) 5 wk for 78 wk
         1,169 mg/kg (M) 5 wk for 78 wk
           869 mg/kg (F) 5 wk for 78 wk

                  Intragastric
         1,097 mg/kg (M&F) 5/wk for 78 wk
           549 mg/kg (M&F) 5 wk for 78 wk
                        No tumors, no deaths
                        3 rats died, no tumors
                        No tumors, no deaths
                        No tumors, no deaths
                        Hepatocellular carci-
                        noma; Metastases,
                        mainly lung
                        No hepatocellular
                        carcinoma, many deaths
                        from toxic doses
                        during experiment
Source:  Waters et al., 1976.
                                      3-14

-------
                TABLE 3.5.  TOXICITY OF TRICHLOROETHYLENE AND  ITS TRANSFORMATION PRODUCTS
      Compound
                Toxicity
                            Threshold Limit Value
Trichloroethylcne
Chloral hydrate
orl-hmn LDLo
ihl-hmn TCLo
ihl-man TCLo
orl-rat LCLo
orl-mus TDLo
   TFX:CAR
ihl-mus LCLo
ivn-mus LD50
orl-dog LDLo
ipr-dog LD50
ivn-dog LDLo
ihl-rbt LCLo
scu-rbt LDLo

orl-rat LD50
ipr-rat LDLo
scu-rat LD50
orl-mus LD50
skn-mus TDLo
  TFX:NEO
ipr-mus LDLo
scu-mus LDLo
orl-dog LDLo
orl-cat LDLo
orl-rbt LDLo
scu-rbt LDLo
ivn-rbt LDLo
rec-rbt LDLo
orl-frg LDLo
par-mus LDLo
:857 mg/kg
:160 ppm/83M TFX:CNS
:110 ppm/8H
:8000 ppm/4H
:351 gm/kg/78WI

:3000 ppm/2H
:34 mg/kg
:5860 mg/kg
:1900 mg/kg
:150 mg/kg
:11000 ppm
:1800 mg/kg

:285 mg/kg
:500 mg/kg
:620 mg/kg
:1100 mg/kg
:960 mg/kg/W

: 650 mg/kg
:800 mg/kg
:1000 mg/kg
:400 mg/kg
:1200 mg/kg
:1000 mg/kg
:400 mg/kg
:1000 mg/kg
:938 mg/kg
:900 mg/kg
100 ppm *>535 mg/m
U.S. OCCUPATIONAL STANDARD USDS
air TWA:100 ppm;  C:200 ppm;
PK:300 ppm/5M/2H
GRIT DOC: RECOM.  STANDARD air
TWA:100 ppm:C 150 ppm

-------
                                             TABLE 3.5  (Continued)
       Compound
             Toxicity
Threshold Limit Value
Trlchloroethanol
Triehloroacetic acid
Dichloroacetic acid
Formic acid
Hydrochloric acid
Hydrogen chloride
orl-rat LD50:600 mg/kg
ipr-rat LDLo:300 mg/kg
ivn-tnus LD50:201 mg/kg
ivn-rbt LDLo:50 mg/kg

orl-rat LD50:3320 mg/kg
irp-mus LDLo:500 mg/kg

orl-rat LD50: 2820 mg/kg
skn-rtb LDSO:510 mg/kg

orl-rat LD50:1210 mg/kg
orl-mus LD50:1100 mg/kg
ipr-mus LD50:940 mg/kg
irn-mus LU50:145 mg/kg
orl-dog LD50:4000 mg/kg
ivn-rbt LDLo:239 mg/kg

ihl-hmn LCLo:1300 ppm/30M
ihl-rat LC50:3124 ppm/lH
ihl-mus LC50:2142 ppm/30M
ipr-mus LD50:40 mg/kg
orl-rbt LD50:900 mg/kg

ihl-rat LC50:470L ppm/30M
ihl-mus LC50:2644 ppm/30M
ihl-rbt LCLo:4416 ppm/30M
ihl-gpg LCLo:4416 ppm/30M
ihl-mam LCLorlOOO mg/m3/2H
5 ppm ^9 mg/m
 5  ppm ^7 mg/m~

-------
                                               TABLE 3.5 (Continued)
          Compound
                                              Toxicity
                                         Threshold Limit Value
Ozone
Phosgene
Chioroacetyl chloride

Dichloroacetyl chloride



Carbon monoxide
ihl-man TCLo:1860 ppb/75M
    TFXrCNS
ihl-hmn TCLo:100 ppb TFXrIRR
ihl-hmn TCLorl ppm TFX:PUL
ihl-rat LC50:4.8 ppm/4H
ihl-mus LC50:3.8 ppm/4H
ihl-mus LCLo:4.5 ppm/50HI TFX:NEO
ihl-ham LC50:10.5 ppm/4H

ihl-hmn TDLo:25 ppm/30M TFX:IRR
ihl-rat LC50:75 ppm/30M
ihl-mus LC50:110 ppm/30M
ihl-dog LCLo:79 ppm/30M
ihl-mky LC50:1087 ppm/lM
ihl-cat LC50:1482 ppm/lM
ihl-rbt LC50:3211 ppm/lM
ihl-gpg LC50:141 ppm/30M
ihl-gpg LDLo:31 mg/m3/20M

ihl-rat LCLo:1000 ppm/4H

orl-rat LD50: 2460 mg/kg
ihl-rat LCLo:2000 ppm/4H
skn-rbt LD50:650 mg/kg

ihl-man LCLo:4000 ppm/30M	
ihl-man TCLo":650 ppm/45M TFX:"CNS "
ihl-rat LC50:1807 ppm/4H
ihl-mus LC50:5718 ppm/4H
ihl-dog LCLo:3841 ppm/46M
ihl-cat LCLo:8730 ppm/35H
ihl-gpg LC50:2444 ppm/4H
                                                                          01 ppm ^02 mg/m
                                                                      	50 ppm ^55 mg/m"
Nitric "acid'
                                                                           	  	-_ O	
                                                                           2 ppm 'v/S' mg/m-3

-------
                                           TABLE 3.5 (Continued)
                                            Key to Abbreviations
i-1
00
AZTX - aquatic toxicity

CNS - central nervous system
gpg - guinea pig
H   - hour
hum - human
ihl - inhalation
ipr - intraperitoneal
ivn - intravenous

LC50 - lethal concentration 50% kill
LCLo - lowest published lethal
         concentration
LD50 - lethal dose 50% kill
LDLo - lowest published lethal dose

M   - minute
mam — mammal
mus - mouse

pph - parts per hundred (V/V)(percent)
Pfy - psychotropic
Pk  - peak concentration
rbt - rabbit
rec - rectal
scu - subcutaneous
skn - skin

TCLo - lowest published toxic concentration
TDLo - lowest published toxic dose
TFX  - toxic effects
TLV  - threshold limit value
TWA  - time weighted average
TXDS - qualifying toxic dose

USOS - U.S. Occupational Health Standard
  Source:  Christensen and Luginbyhl,  1975.

-------
          4.  OCCURRENCE OF TRICHLOROETHYLENE IN FOOD AND
              OTHER PRODUCTS THAT COME IN CONTACT WITH MAN
FOOD

     There are, unfortunately, very little data on the presence of TCE

in food raised and sold in the United States.  There is some informa-

tion on the presence of TCE in foodstuffs found in the United Kingdom.

This information is summarized in Table 4.1.  TCE is found on the order

of parts per billion in almost all common foodstuffs.

     Trichloroethylene has also been used to extract spice oleoresins

and to decaffeinate coffee.  The FDA regulations of the concentration

of TCE in these materials are listed in the section on "Exposure and

Biological Accumulation of Trichloroethylene in Man".  In 1974,

approximately 90 percent of the decaffeinated coffee was produced

using trichloroethylene (Valle-Riestra, 1974); but since July, 1975,

TCE has not been used by U.S. makers of decaffeinated coffee.  It has

largely been replaced by methylene chloride,  according to FDA, even

though the safety of methylene chloride has not been established.  In

a recent publication, TCE was not detected in any of the oleoresins

analyzed for that substance (Page and Kennedy, 1975).

DRINKING WATER

     Shortly after the identification of trichloroethylene and other

halogenated hydrocarbons in New Orleans drinking water, the results

were published (Dowty et al., 1975a and 1975b) and several other

significant events occurred.   The Safe Drinking Water Act was signed

into law in December, 1974, and a National Organics Reconnaissance

Survey (NORS) was undertaken.
                                4-1

-------
            Table 4.1  TRICHLOROETHYLENE IN FOODSTUFFS
  Foodstuff                        Concentration, pg/kg


Dairy produce
  Fresh milk                               0.3
  Cheshire cheese                          3
  English butter                          10
  Hens eggs                                0.6

Meat
  English beef (steak)                    16
  English beef (fat)                      12
  Pig's liver                             22

Oils and fats
  Margarine                                6
  Olive oil (Spanish)                      9
  Cod liver oil                           19
  Vegetable cooking oil                    7.
  Castor oil                              ND

Beverages
  Canned fruit drink                       5
  Light ale                                0.7
  Canned orange juice                     ND
  Instant coffee                           l\
  Tea (packet)                            60
  Wine (Yugoslav)                          0.02

Fruit and vegetables
  Potatoes (S. Wales)                     ND
  Potatoes (N.W. England)                  3
  Apples                                   5
  Pears                                    4
  Tomatoes                                 1.7
  Black grapes (imported)                  2.9
  Fresh bread                              7


a  Tomato plants were grown on a reclaimed lagoon at Runcorn
   Works of ICI.
b  ND = not detected.
Source:  McConnell et al., 1975.
                                 4-2

-------
     As part of the NORS, drinking water supplies at five selected




sites were analyzed.  These supplies were chosen to represent the




major types of raw water sources in the United States at that time.




The results for ICE are summarized in Table 4.2.  The NORS was extended




to cover a total of 10 cities in the United States.  In the extended




survey, trichloroethylene was also detected but not quantified in the




drinking water of Lawrence, Massachusetts (U.S. Environmental Protection




Agency, 1975b).  A follow-up study on finished and raw water samples




from Miami, Florida, was carried out.  The results of this study are




summarized in Table 4.3.




     Several U.S. Environmental Protection Agency regional offices




have analyzed various waters for TCE.  The Surveillance and Analysis




Division of Region IV under the direction of James H. Finger has




detected TCE at the following locations at the estimated concentrations




shown:




          Dalton, Georgia, Wastewater Treatment Plant - < 5 ppb




          Rome, Georgia, Treatment Plant              - < 0.5 ppb




          Rome, Georgia, Wastewater Treatment Plant   - < 5 ppb.




Region IV personnel also analyzed discharge from the Stauffer Chemical




Co. plant at Louisville and determined the TCE concentration to be 500 ppb.




It is believed that Stauffer produces TCE at this plant.  Region IV




personnel may have conducted an organics study of the Ohio River, but




this information is not yet available.




     As a result of a National Organic Monitoring Survey conducted




between March 1 and April 3, 1976, which indicated that trichloroethylene




was present in the finished drinking water at Des Moines, Iowa, to the
                               4-3

-------
                Table 4,2  PROPERTIES AND TCE CONCENTRATION OF FINISHED WATER IN FIVE CITIES
Type
of
City supply
Cincinnati, Surface
Ohio
Miami, Ground
Florida
Ottumwa, Surface
Iowa
*• Philadelphia, Surface
*• Pennsylvania
Seattle, Surface
Washington
Type Nonvolatile
of raw total organic
water carbon, mg/1
Industrial 1.3
waste
Natural 6.5
waste
Agricultural 2.3
waste
Municipal 1.9
waste
Natural 1.0
waste
TCE
Conductivity, Chlorine, concentration,
MMHOS/CM mg/1 pH ppb
295 2.7 8.6 0.1
350 2.3 8.7 0.3
500 1.4 9.2 <0.1
260 2.0 8.3 0.5
50 0 6.6 ND
ND = not detected.




Source:  Keith, 1976.

-------
      Table 4.3  SOME OF THE ORGANIC COMPOUNDS  IDENTIFIED IN
                 MIAMI,  FLORIDA-FINISHED AND  RAW WATER SAMPLES


Organic
compound
identified
Trichloroethylene
Methylchloroform
Carbon Tetrachloride
Chloroform
Finished
water,
1/29/75,
ppb
Pa
P
P
311
Finished
water,
7/7/75,
ppb
P
P
P
220
Raw
water ,
7/7/75,
ppb
P
P
ND
0.7
Test
wall,
7/7/75,
ppb
NDb
ND
ND
ND
Source:  Keith, 1976.

a  P = Present but not quantified.
b  ND = Not detected.
                                      4-5

-------
extent of 32 ppb, the Surveillance and Analysis Division of Region VII




under the direction of Donald A. Townley became involved in a rather




extensive sampling and analysis effort.  This effort was lead by




Dr. Robert D. Kleopfer, Organic Chemistry Working Unit Leader,




Laboratory Branch, Region VII.  Following is a summary of the results




obtained in this study.




     Samples taken at Des Moines, Iowa, on August 4, 1976, were




analyzed using a Tekman liquid sample concentrator with computerized




gas chromatography/mass spectrometry.  Raw water was determined to




have no detectable TCE while the finished water contained TCE at a




concentration of 53 ppb.  Then on August 12, 1976, a more extensive




series of samples were taken.| The results are reproduced in Table 4.4.




It was concluded that the TCE originates in the gallery infiltration




system and is not being produced in the water treatment process.




     The next step was to attempt to determine the ultimate source of




TCE by sampling the infiltration gallery at various points along the




system.  The gallery system is approximately 3 miles in length and




access by manholes is available at 2,000-foot intervals.  Assuming




a flow of 25 million gallons per day through the gallery\and a TCE




concentration of 61 ppb, the source would have to provide 5,772 g




(12.7 Ibs.) or 3.95 liters (1.04 gallons) of TCE per day to the




infiltration gallery water.  On September 2, 1976, samples were taken




at various points along the gallery.  The samples were analyzed and the




results are summarized in Table 4.5.  It was concluded that contamination




of the gallery infiltration system was responsible for the presence




of TCE in Des Moines drinking water and that the contamination occurs
                              4-6

-------
Table 4.4  TCE CONCENTRATION IN WATER SOURCES FOR DBS MOINES, IOWA,
           DRINKING WATER AND IN CONTROLS
Sample description
Concentration, ppb
Raccoon River at Rock Dam
  recharge pumping station
Raccoon River water treated
  with hypochlorite
Gallery infiltration water
Gallery infiltration water
  treated with hypochlorite
Raccoon River water from
  sedimentation basin
Mixed water prior to softening
Mixed water after softening
Finished water at Des Moines Airport
Finished water at water treatment
  plant laboratory
Kansas City, Kansas, water trans-
  ferred at water treatment plant lab
Meredith Canal
Meredith Canal just prior to recharge
  basin
        NDe

        ND
        61

        33

        ND
        39
        41
        24

        31

        ND
        11
a  ND = none detected; the detection limit was 1 ppb.
                              4-7

-------
Table 4.5  TCE CONCENTRATION IN INFILTRATION GALLERY AND
           IN ASSOCIATED WATERS
Sample description                     Concentration, ppb
Meredith composite at west
  end of creek                                 1
Meridith composite of process
  water at north end of building               8
Meredith composite of process
  water at east end of creek                  12
Meredith grab of process water
  at east end of creek                        14
Meredith canal grab just prior
  to recharge basin                            2
Grab at Cabin Creek bridge                    NDa
South bank at middle of west
  part of recharge basin #14                   1
Gallery at manhold #12                        ND
Gallery at valve chamber #11                  ND
Gallery at valve chamber #10                  ND
Gallery at valve chamber  #8                  ND
Gallery at valve chamber  #5                  ND
Gallery at water plant                        45
Raccoon River at intake                       ND
Finished water at lab                         22
a  ND = not detected; the detection limit was 1 ppb.
                                4-8

-------
somewhere downstream from Valve Chamber Number 5.  On September 22




and 23, 1976, samples were taken downstream from Valve Chamber Number 5




and at other sites.  The analytical results are presented in Table 4.6.




These results show that the north end of the gallery is heavily con-




taminated by TCE.  The exact source of this substance has not been




reported at this writing.  Table 4.7 summarizes the data for Des Moines




finished water.




     It is interesting to note that the levels of TCE reported in




Des Moines, Iowa, drinking water may result from the dumping of 1




gallon per day of this substance into the water system.




     In an earlier, unrelated study (1974), raw wastewater processed




in the Oro, Iowa, Sanitary District of the San Francisco Bay was esti-




mated to contain 1.2 mg per liter in the 49,205 cubic meters per day




average discharge (Camisa, 1975).




     In an investigation of the chlorination of water for purifica-




tion and the potential for the formation of potentially harmful chlori-




nated compounds by this process, T.A. Bellar, et al (1974) at the




National Environmental Research Center of EPA at Cincinnati, Ohio,




reported the following concentrations of trichloroethylene in water




from a sewage-treatment plant:  Influent before treatment, 40.4 p,g/j&;




effluent before chlorination, 8.6 p,g/A; and effluent after chlorination,




9.8 ng/jt.   These workers concluded that the number of organohalides formed




during the chlorination process does not constitute any immediate threat




to the public health.




     The prevalence of TCE and other halogenated hydrocarbons in the




environment cannot be denied.  However, the source of these substances
                               4-9

-------
Table 4.6  TCE CONCENTRATIONS IN NORTH END OF INFILTRATION
           GALLERY AND IN ASSOCIATED WATERS
Sample description                 Concentration, ppb
                                            ,a
                                            j
Gallery pump discharge                     37*
Laboratory tap (9/23/76)                   16C
                                            ,a
River intake                               ND
Valve chamber #1                          391a
Manhole #1                                457a
Manhole #2                                229a
Birds Run sewer overflow                   ND
Raccoon River below dam                    ND
Raccoon River near steel sheeting          ND
Drainage culvert                           ND
                                             ft
Sewer manhole west                        151
a  These samples all contained lesser amounts of dichloro-
   ethylene.
b  ND = not detected; the detection limit was 1 ppb.
c  This sample contained significant amounts of TCE, methyl-
   chloroform and dimethyldisulfide with smaller amounts of
   dichloroethane and dichloroethylene.
                                4-10

-------
   Table 4.7  SUMMARY OF TCE DATA FOR DES MOINES FINISHED WATER
Date of sample
December 10 or 11, 1974
March 20, 1975
March-April, 1976
Spring, 1976
August 4, 1976
August 12, 1976
August 12, 1976
September 2, 1976
Location
At Plant
Ditto
it
ii
it
ii
At Airport
At Plant
Concentration, ppb
Pa
80a
32b
53b
53
31
24
22
a  Two analyses were done by the Iowa State Hygienic Laboratory;
   the earlier sample indicated a "third peak" which was tenta-
   tively identified as trichloroethylene.
b  These samples were taken as part of a national survey.
                               4-11

-------
in such media as drinking water has not been determined.  Much more




information about the presence of these substances in the environment




is needed as well as information on the mechanism of transport from




one medium to another.




OTHER SUBSTANCES




     Trichloroethylene occurs in many commercial products, but infor-




mation on these products is not readily obtained from the manufacturers.




There are several reasons for this which include the proprietary nature




of many manufacturer's formulations, the constantly changing types and




composition of products manufactured, the alertness of manufacturers to




new information on the hazards of chemicals contained in their formula-




tions, and regulations imposed by various agencies.




     Table 4.8 lists representative commercial products containing




trichloroethylene.  This list appeared in 1975 and is probably out of




date in many respects.  It is meant to show types of products that




might come in contact with man and is not meant to reflect negatively




on any manufacturer.
                               4-12

-------
                 Table 4.8  REPRESENTATIVE COMMERCIAL PRODUCTS CONTAINING TRICHLOROETHYLENE
     Product
                                              Composition
        Substance
Percent
     Manufacturer
 I
M
U)
Brush Top Spot Remover2
regular Expersol 2530 (xylene)
        Trichloroethylene
        Perchloroethylene
        Methylene Chloride
Brush Top Spot Remover , super
Carbona Cleaning Fluid


Carbona #10 Special Spot
  Remover

Carbona Spray Spot Remover
Crater 2X and 5X Fluid


DuPont Dry Clean
Dux Water Repellant
        Chlorinated solvents
        Triethane
          (1,1,1-trichloroethane)
        Trichloroethylene
        Perchloroethylene
        Methylene Chloride

        Trichloroethylene
        Petroleum hydrocarbons
        1,1,1-Trichloroethane
        Trichloroethylene
        Petroleum hydrocarbons

        Trichloroethylene
        1,1,1-Trichloroethane
        Cab-0-Sil
        Freon 12

        Petroleum lubricating oil
        Trichloroethylene
        Pine tar

        Trichloroethylene

        Piccotex 120 Solution
          (synthetic resin)
        Wax (paraffin)
        Trichloroethylene
   87
   10
    1.5
    1.5
  100

   50
   25
   10
    5
   44
   56

   10
   40
   50
   25
Product Sales Company
        Ditto
Carbona Products Co.


        Ditto
Texaco, Inc.


duPont
Detrex Corp.

-------
                                                Table 4.8   (Continued)
           Product
                                                 Composition
Substance
Percent
      Manufacturer
 I
M
JN
      Glamorene  Dry  Cleaner  for Rugs
        (Formerly  Galmorene  Wool Rug
        Cleaner)

      Glamorene  Rug  Cleaner
      Helmac  Spot  Pic-Up
        Aerosol  spot  remover

      HH Tree Wound Healer
        Protective seal for pruned
        and damaged trees and  shrubs
      Instant  Chimney  Sweep
       Aerosol  spray  application

      Joy  Solvent3
      Kwik Kleen Drug  Shampoo3
       Dry  shampoo
      Lash Bath
       Cleanser for false eyelashes
Chlorinated hydrocarbon
  (trichloroethylene)
Petroleum distillate
Wool flour
Trichloroethylene
Ethylene dichloride
Heavy naphtha

Perchloroethylene
Methylene chloride
Trichloroethylene

Asphaltum
Petroleum oils
Phenylmercury oleate
Allantoin
Inert ingredients:
  Dichlorodifluoromethane
  Trichloroethylene
  Methylene chloride

Trichloroethylene
Active chemicals
Propellant (Freon)

Trichloroethylene
Trichloroethylene


Naphtha
Trichloroethylene
  34
  41
  25
                 Glamorene Products Corp..
                          Ditto
                 Helmac Products Corp.
                 Hubbard-Hall Chem. Co.
Miracle Adhesives


Joy Chemical Inc.
Royal Bond, Inc.

Revlon

-------
                                           Table 4.8  (Continued)
   Product
                                                 Composition
Substance
Percent
Manufacturer
0'Cedar Sea Spray'
Perm-A-Clor NA

Sears Air Freshener

Sears Odor Neutralizer
Spot Chief0
Surfisan Spray
  Surface disinfection, preser-
  vation and deodorizing

Triad Metal Cleaner

Triad Metal Polish

Trichlor - Solvent
Methylene chloride
Trichloroethylene
Cellosolve acetate
Wax
Freon propellant

Trichloroethylene
Essential oils                    55.2
Perfume                           10.4
Trichloroethylene                 34.5
Trichloroethylene
Perchloroethylene
Solvent 310 (petroleums)
Solvent 310 (petroleum solvent)
Paradichlorobenzene
Lanolin
1,1,1-Trichloroethane
Freon 12

Chloroform
Kerosene
Camphor
Trichloroethylene
Trichloroethylene

Trichloroethylene

Trichloroethylene                 100
               0'Cedar
               Detrex Corp.
               Sears, Roebuck & Co.
               White Frost, Inc.
               Royal Bond, Inc.
               PPG Industries,
                Chemical Division

-------
                                                Table 4.8   (Continued)
        Product
                                           Composition
Substance
Percent
Manufacturer
      Tri-Clene Dry Clean
Trichloroethylene
                     PPG Industries, Chemical
                       Division
      Source:  Lloyd et al., 1975.  The above product descriptions are not to be construed as current or
              accurate since changes in product composition are being made continually by manufacturers,

      a  No  longer marketed, but some may still be in use.
      b  No  longer contains TCE but listed since some products may still be in use.
•e-
o^

-------
    5.  EXPOSURE AND BIOLOGICAL ACCUMULATION OF TRICHLOROETHYLENE IN MAN






EXPOSURE






      Following is a table with an estimation of the number of workers




exposed to trichloroethylene by industry.  Table 5.1 not only gives an




indication of the number of workers exposed but also indicated the diverse




industries using this solvent.  It is also estimated that approximately




5,000 medical, dental, and hospital personnel are routinely exposed to




trichloroethylene as an anesthetic (Lloyd et al., 1975).




      A 2-year series of studies involving cleaning operations throughout




the United States was carried out by Dow Chemical (Skory, 1974).  The purpose




was to determine the extent of worker exposure during solvent vapor degreaslng




and to compare the three most commonly used chlorinated solvents: trichloro-




ethylene, methylchloroform, and perchloroethylene.  Dow estimates that there




are over 25,000 chlorinated solvent vapor degreasers throughout the United




States.  The studies were conducted in the worker breathing zones which were




adjacent to some 275 industrial vapor degreasing operations.  The results of




this study show that trichloroethylene and perchloroethylene vapor concen-




trations measured around vapor degreasers frequently exceeded the allowable




standards for health arid safety.  Peak concentrations were high enough to




present a definite health and safety hazard from anesthetic affects such as




dizziness, lack of coordination, and impaired judgment.  Although the




national primary and secondary photochemical oxidant standards for chlorinated
                                     5-1

-------
        TABLE 5.1.  OCCUPATIONAL EXPOSURE
                                   Estimated Number
        Industry                       Exposed

Agricultural Services                      124
Oil and Gas Extraction                     267
Ordnance                                   57
Food Products                           2,502
Textile Mill Products                   1,014
Apparel/Textile Products                   858
Lumber Products                            72
Furniture Mfg.                             162
Paper Products Mfg.                     2,240
Printing Trades                         2,876
Chemical Mfg.                           9,552
Petroleum Products                         713
Rubber/Plastics Mfg.                    4,985
Leather Products                           725
Stone/Clay Products                     2,685
Primary Steel Mfg.                      11,672
Metal Fabrication                       11,709
Machinery Mfg.                          7,481
Electrical Equipment                    66,727
Transportation Equipment                54,174
Instrument Mfg.                         4,815
Miscellaneous Mfg.                      1,516
Trucking/Warehousing                       642
Air Transportation                         23
Communication                           5,560
Wholesale Trade                         3,327
Automotive Dealer                          223
Furniture Stores                           597
Banking                                 2,391
Personal Services                          583
Misc. Business Services                 27,759
Auto Repair                             5,246
Misc. Repair                            17,198
Amusement Services                      7,987
Mechanical Services                     20,053
Misc. Unclassified                      4,138

ESTIMATED TOTAL                        282,653
 Source:  Lloyd et al.,  1975.
                5-2

-------
solvents are < 3 Ib/hr or 15 Ib/day maximum for each piece of equipment, it


is not uncommon for an idling open top (measuring 24 x 58 inches) vapor


degreaser to lose 47 Ib/day of trichloroethylene or 33 Ib/day of


methylchloroform (Archer, 1973).   Judging from production figures, this


material is being lost to the atmosphere and is then replaced.


      It is estimated that 2 x 10  tons of chlorinated hydrocarbons are

                                                                          4
lost to the environment each year (Murray and Riley, 1973) and that 1 x 10


tons of trichloroethylene are discharged annually (Abrams et al., 1975).


      It is estimated that 500 tons/day of industrial effluents are released


into the air over Los Angeles County.  Of this amount, 25 tons are dry


cleaning fluids and 95 tons are degreasing solvents, that is, chlorinated


riydrocarbcns (Simmonds et al., 1974).  Because trichloroethylene has been


implicated as an oxidant-producing contaminant, its use in Los Angeles County


has been restricted since 1967 (Farmber, 1973).  This restriction, the famous


Rule 66, may provide a control in monitoring trichloroethylene.  Since the


amount of trichloroethylene over Los Angeles County should be reduced in


relationship to other chlorinated hydrocarbons that have replaced it, the


determination of the relative amounts there and over other cities where


there no restrictions should be very informative.


      Trichloroethylene is subject to certain county, state, and federal


regulations.  The regulation of trichloroethylene in Los Angeles County has


already been mentioned.  Also, NIOSH has recommended that the current 8-hour


time-weighted average (TWA) exposure limit for trichloroethylene of 100 ppm


be kept; but the ceiling limit of 200 ppm be reduced to 150 ppm measured


over a 15-minute period, and the current 300 ppm peak concentration be


eliminated (Anonymous, 1976).
                                     5-3

-------
      In addition, the Food and Drug Administration (FDA) has set the




following limits:   10 ppm trichloroethylene in instant decaffeinated coffee,




25 ppm trichloroethylene in decaffeinated ground coffee and 30 ppm trichloro-




ethylene in spice oleoresins (Valle-Riestra, 1974).




      The basis for these regulations is various toxicological data.  The




stricter regulations for trichloroethylene are based on more recent information




including studies on the carcinogenicity of trichloroethylene.  The toxicology




of trichloroethylene was considered in an earlier section.




      Concentrations of chlorinated hydrocarbons around a vapor degreaser




should be controlled but their presence comes as no surprise.  What of




solvents in the home or living area?  In a study of the air near a solvent




recovery plant in Maryland, levels of carbon tetrachloride were measured and




compared with levels of indoor air.  At times, concentrations of 10 to 45 ppm




of carbon tetrachloride were measured inside a house near the plant when




levels outside were 1 ppm.  The highest indoor concentration record was 90 ppm




(Bridbord et al.,  1975).




      What about trichloroethylene in the vicinity of manufacturing plants




or industrial areas using large quantities of these solvents?  There are




no good answers at this time.  There are no published reports of environmental




levels experienced in the manufacture of trichloroethylene (National Institute




for Occupational Safety and Health, 1973).  The data that are available are




summarized in the section on "Occurrence of Trichloroethylene in the




Environment".
                                     5-4

-------
BIOLOGICAL ACCUMULATION






      There is little evidence to judge if trichloroethylene is accumulating




in living systems, and the opinions of scientists conflict with each other.




      There is some limited data on the occurrence of trichloroethylene in




human tissue (Table 5.2).  Also, dogs were exposed to relatively high




concentrations (7,000 to 20,000 ppm) of trichloroethylene and then, after




sacrificing the animals, tissure was analyzed for trichloroethylene (Table




5.3).  The limited human data and the lack of exposure and medical histories




makes this data of little value in judging if trichloroethylene is accumu-




lating in man.  In the care of dogs, such massive doses were given by




inhalation that judgements about accumulation in living tissue are impossible.




      Doruty et al., (1975a) in a paper on hologenated hydrocarbons in




drinking water concludes that "in view of the lipophilic nature of hologenated




hydrocarbons and their occurrence in drinking water,  it is not surprising




that they might be found accumulating in blood or other body tissues".  There




authors present no data or references to support their contentions.  They




not only lack quantitative information about levels of hologenated




hydrocarbons in blood and body tissues, but fail to produce quantification




of these substances in drinking water.  Even in their full paper (Doruty




et al., 1975b) they are still talking about relative concentrations.




      A Study Panel on Assessing Potential Ocean Pollutants (1975) reports




that the bioaccumulation of low-molecular weight chlorinated hydrocarbons




is quite low compared to accumulation of chlorinated pesticides in




vertebrates.  This same group reports on another study in which it was




determined that bioaccumulation factor is determined by the partition
                                      5-5

-------
TABLE 5.2.  OCCURRENCE OF TRICHLOROETHYLENE IN HUMAN TISSUE
Age of
Subject
76
76
82
48
65
75
66
74
Sex Tissue
F Body fat
Kidney
Liver
Brain
F Body fat
Kidney
Liver
Brain
F Body fat
Liver
M Body fat
Liver
M Body fat
Liver
M Body fat
M Body fat
F Body fat
Concentration, p-g/kg
(wet tissue)
Trichloroethylene
32
<1
5
1
2
3
2
<1
1.4
3.2
6.4
3.5
3.4
5.2
14.1
5.8
4.6
4.9
   Source:  McConnell et al.-, 19751
                             5-6

-------
                     TABLE 5.3.   TRICHLOROETHYLENE RECOVERED FROM TISSUE
Animal
Number

12
15
16
17
20
25
14
21
19
22
24



12
15
16
17
20
25
14
21
19
22
24
Mode of
Exposure

Acute
Acute
Acute
Acute
Acute
Acute X3
Chronic-Acute
Chronic-Acute
Chronic
Chronic
Chronic



Acute
Acute
Acute
Acute
Acute
Acute X3
Chronic-Acute
Chronic-Acute
Chronic
Chronic
Chronic
Concentrations, mg %, wet weight
Adrenal
22.4
6.24
	
	
22.5
13.8
60.6
23.1
	
0.94
1.06


Lung
2.8
2.2
0.92
0.92
0.40
10.4
2.0
1.3
0.53
0.26
0.13
Blood
72.5
46.0
52.7
22.3
28.4
50.0
46.1
50.6
9.6
0.13
0.25


Muscle
2.7
	
0.15
3.3
5.1
9.3
	
3.8
4.1
0.45
0.30
Brain
17.0
15.1
19.7
	
8.2
20.9
— —
23.6
2.7
0.22
0.22 	


Pancreas
	
3.2
9.8
6.4
14.1
43.8
8.1
16.0
2.5
<0.05
0.28
Fat
17.9
14.7
	
4.8
70.4
70.5
— —
22.1
""30.7
14.4
6.5

Spinal
Cord
8.8
	
— —
	
	
28.3
.

'
0.13
0.13
Heart
8.6
5.0
5.4
4.2
18.9
13.9
7.5
12.9
1.2
0.11
0.11
Cerebro
Spinal
Fluid
_
3.8
1.5
0.61
1.7
	
0.15
1.8
0.15
0.15
0.15
Kidney
1.6
8.2
5.8
3.6
3.2
17.5
21.1
5.3
1.0
0.13
0.25


Spleen
0.71
3,9
1.2
5.4
1.3
5.1
••
8.5
0.71
<0.05
0.12
Liver
27.0
9.6
38.8
10.8
9.2
49.4
20.6
9.7
3.2
0.12
0.25


Thyroid
—
2.0
6.6
•
3.9
14.1
5.8
7.4
1.1
<0.05
0.63
Source:  U.S. Environmental Protection Agency, 1975.

-------
                            TABLE 5.4.  CHLORINATED HYDROCARBONS IN MARINE ORGANISMS'
oo
Species
plankton
plankton
Nereis diversicolor
(ragworm)
Myjtilus edulis
(mussel)
Cerastcderma edule
(cockle)
Ostrea edulis
(oyster)
Buccinum undatum
(whelk)
Crepidula fornicata
(slipper limpot)
Cancer pagurus
(crab)
Carcinus maenas
(shore crab)
Eupagurus bernhardus
(hermit crab)
(Concentrations
Source
Liverpool Bay
Torbay
Mersey Estuary
Liverpool Bay
Firth of Forth
Thames Estuary
Liverpool Bay
Thames Estuary
Thames Estuary
Thames Estuary
Tees Bay
Liverpool Bay
Firth of Forth
Firth of Forth
Firth of Forth
Thames Estuary
expressed as
CC12CHC1
Invertebrates
0.05-0.4
0.0
ND
4-11.9
9
R
6-11
2
ND
9
2.6
10-12
15
12
15
5
g
parts per 10 by mass on wet tissue)
0 (*-*••- CiC/-i-A C^rirt t*w J. M i Uv* J. »
0.05-0.5 0.03-10.7 0.04-0.9
2.3 2.2
2.9 0.6
1.3-6.4 2.4-5.4
9 10 2
1 5 0.7
2-3 0-2 0.4-1
0.5 0.9 0.1
1 6 0.9
2 4 0.3
2.3 8.4
8-9 5-34 3-5
71 2
6 14 3
15 0.7 1
2 2 0,2

-------
TABLE 5.4.  (Continued)
Species
.Crangon crangon
(shrimp)
Asterias rub ens
(starfish)
Solaster sp.
(sunstar)
Echinus esculentus
(sea urchin)
Enteromorpha
compressa
Ulva lactuca
Fucus vesiculosus
Fucus serratus
Fucus spiralis
Rajj clavata
(ray) flesh
liver
Pleuronectes
platessa flesh
(plaice) liver
Q
(Concentrations expressed as parts per 10 by mass on wet tissue)
Source CCljCHCl CC12CC12 CH2CC12+CC1A
Firth of Forth
Thames Estuary
Thames Estuary
Thames Estuary
Mersey Estuary
Mersey Estuary
Mersey Estuary
Mersey Estuary
Mersey Estuary
Liverpool Bay
Liverpool Bay
Liverpool Bay
Liverpool Bay
16
5
2
1
Marine algae
19-20
23
17-18
22
16
Fish
0.8-5
5-56
0.8-8
16-20
326
1 5 0.8
2 3 0.2
1 3 0.1
14-14.5 24-27
22 12
13-20 9,4-10.5
15 35
13 17
0.3-8 2-13
14-41 1,5-18
4-8 0.7-7
11-28 2-47

-------
                                        TABLE 5.4.  (Continued)
Species
Platycthys
£lesus_
(flounder)
Limanda
limanda
(dab)
Scomber
scombrus
(mackerel)
Limanda
limanda
Pleuronectes.
platessa
Y1 Solea solea
g (sole)
AspJLtrigla
cuculus


flesh
liver

flesh
liver

flesh
liver
flesh
flesh

flesh
flesh
guts
flesh
guts
Source

Liverpool Bay
Liverpool Bay

Liverpool Bay
Liverpool Bay

Liverpool Bay
Liverpool Bay
Red ear, Yorks
Thames Estuary

Thames Estuary
Thames Estuary
Thames Estuary
Thames Estuary
Thames Estuary
(Concentrations expressed
CCL2CHC1

3
2

3-5
12-21

5
8
4.6
2

3
2
11
11
6
as parts per
cci2cci2

2
1

1.5-11
15-30

1
ND
5.1
3

3
4
1
1
2
9
10 by mass

4
3




5
3

4

3
2
26
4
10
on wet tissue)
CH2CC12+CC1,

2
0.3

1.3-8
2-14

2
ND
9.9
0.3

0.9
6
1
0.6
0.3
  (red gurnard)

Trachurus
  trachurus  flesh
  (scad)
Trisopterus
  luscus
  (pout)

Squalus
  acanthias
  (spurdog)
             flesh
             flesh
Thames Estuary


Thames Estuary



Thames Estuary
0.3
                                                                                  ND

-------
TABLE 5.4.  (Continued)
Species
Scomber
scombrus flesh
(mackerel)
Clupea
sprattus flesh
Gadus
morrhus flesh
(cod) air bladder
Sula bassana liver
(gannot) eggs
Phalacrocerax
aristotelis eggs
(shag)
Ale a torda
(razorbill) eggs
Rissa tridactyla
(kittiwake) eggs
Cvenus olor liver
(swan) kidney
Gallinula liver
chloropus muscle
(moorhen) eggs
Anas
platyrhvncos
(mallard) eggs
(Concentrations
Source

Torbay, Devon
Torbay , Devon
Torbay, Devon
Torbay, Devon
Sea and
Irish Sea
Irish Sea

Irish Sea

Irish Sea
North Sea
Fro d sham Marsh
(Merseyside)
(Merseyside)
(Merseyside)
(Merseyside)
(Merseyside)
expressed
CC12CHC1

2.1
3.4
0.8
freshwater
4.5-6
9-17

2.4

23-26
33
2.1
14
6
2.5
6.2-7.8
9.8-16
as parts per

ND
1.0
3^6
birds
1.5-3.2
4.5-26

1.4

19-29
25
1.9
6.4
3.1
0.7
1.3-2.5
1.9-4.5
9
10 by mass on wet tissue)

2.4
5.6
3.3
NA
1.2-1.9
17-20

39.4-41

35-43
40
4.7
2.4
1,6
1.1
14.5-21.8
4.2-24

-------
                                         Table 5,1  (Continued)
Spefcies
Halichoerus
grypus
(grey seal)
Sorex
araneus
(common
shrew)
Source
blubber Fame Is.
liver Fame Is,
Frodsham
9
(Concentrations expressed as parts per 10 by mass
CC12CHC1 CC12CC12
Mammals
2.5-7.2 0,6-19
3-6.2 0-3.2
Marsh 2.6-7.8 1
on wet tissue)
CH2CC12+CC14
16-30
0.3-4.6
2.3-7
Notes:  NA, no analysis; ND, not detectable.
a  Source:  Barson and McConnell, 1975.

-------
of the compound between the water and the tissues of the organism,




and further that the log of bioaccumulation is linearly related to the




log of the partition coefficient between octanol and water for some




compounds.  This relationship offers a method of estimating bioaccumula-




tion.  A compound such as trichloroethylene would act similarly to carbon




tetrachloride in organisms, exhibiting rapid uptake to steady state con-




centration and rapid clearance.




     By far the most definitive study on bioaccumulation was carried out




by Pearson and McConnell (1975).  Based on the results of an extensive




analysis of a large number of species, reproduced in Table 5.4, these




authors made some estimates of bioaccumulation in nature.  They estimated




that the maximum overall increase in concentration, between sea water




and the tissues of animals at the top of food chains such as fish liver,




bird eggs, and seal blubber is less than 100-fold for a solvent like




trichloroethylene; while a higher molecular weight chlorinated compound




such as hexachlorobutadiene would have a maximum factor of 1000.  They




further concluded that the pattern of extensive bioaccumulation of




marine food chains, which is postulated for chlorinated insecticides,




does not appear.   In laboratory tests where organisms are maintained




for up to 3 months in apparatus similar to that used for toxicity




determinations, Pearson and McConnell (1975) have shown that bioaccumula-




tion can*occur.  These results indicate the following:   (1)  the concen-




tration of chlorinated hydrocarbons accumulated in a tissue tends to




an asymptotic level, (2) concentrations in fatty tissues such as liver
                                5-1J

-------
are higher than in muscle (concentration is proportional to fat content),




and (3) when the test organism is returned to clean sea water, the




concentration of the chlorinated hydrocarbon in the tissue falls.




These researchers conclude that there is no evidence for the bio-




accumulation of C1/C2 compounds in food chains and the maximum concen-




trations found in the higher trophic levels are still only parts per




10° by mass.




     Despite this strong statement, it is based on a limited set of




data, and caution should be exercised.  More information is needed




before final judgment is made about the accumulation of volatile




chlorinated hydrocarbons in the tissues of animals and man.
                               5-14

-------
                      6.  ENVIRONMENTAL TRENDS






     To describe environmental trends, it would be necessary to have




accurate data on TCE determined over a period of time for various




media.  Such data are not available for trichloroethylene.  Any




environmental trends would have to be inferred from actions taken




with regard to the manufacture, use, or regulation of trichloroethylene.




     There is evidence that trichloroethylene is widespread in the




environment, that it interacts with living systems, and that it appears




in air, water, food, and animal tissue.  Whether it is accumulating




in the environment, in living systems, or in food cannot be judged




from the evidence available at this time.




     The highest environmental concentrations of Trichloroethylene




are in close proximity to manufacturers and users.  Near these sources,




levels on the order of hundreds of parts per billion are found in the




aLr and surface waters.  In remote areas the levels are less than 1 ppb.




     Because of the efforts of manufacturers and users to reduce the




quantity of TCE being released to the atmosphere, because of its




recognized toxicity, and because of regulations, it is likely that the




amount in that media will decline in the future.  However, an offsetting




factor is the increased use of the solvent in other ways such as a




textile solvent.  This will perhaps lead to the appearance of more TCE




in water and probably in the air.  The net effect cannot be determined




without more extensive monitoring data.




     Perhaps such efforts as the National Organics Reconnaissance Survey




will ultimately provide sufficient information to establish a trend for




environmental levels of trichloroethylene.





                                6-1

-------
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                                    7-1

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Chian, E.S.K. and B. B. Ewing.  1976.  Monitoring to Detect Previously
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