EPA 560/6-77-030
   MULTIMEDIA  LEVELS
       METHYLCHLOROFORM
            SEPTEMBER 1977
      (J.S.ENVRONMENTAL PROTECTION AGENCY
         OFFICE OF TOXIC SUBSTANCES
           WASHINGTON, D.C. 20460

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EPA 560/6-77-030
                            MULTIMEDIA LEVELS
                            METHYLCHLOROFORM
                             September 1977
                                 BATTELLE
                           Columbus Laboratories
                              505 King Avenue
                           Columbus, Ohio  43201
                            Vincent J.  DeCarlo
                              Project  Officer
                           Contract  No.  68-01-1983
                    ENVIRONMENTAL PROTECTION AGENCY
                       OFFICE OF  TOXIC  SUBSTANCES
                       WASHINGTON, D.C.   20460

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                       NOTICE
     This report has been reviewed by the Office of
Toxic Substances, Environmental Protection Agency, and
approved for publication.  Approval does not signify
that the contents necessarily reflect the views and
policies of the Environmental Protection Agency.
Mention of tradenames or commercial products is for
purposes of clarity only and does not constitute
endorsement or recommendation for use.
                         ii

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                              TABLE OF CONTENTS

                                                                      Page

1.  INTRODUCTION	   1-1

2.  OCCURRENCE OF METHYLCHLOROFORM IN THE ENVIRONMENT	   2-1

         Methylchloroform in the Atmosphere 	   2-1
         Methylchloroform in Soil and Sediment	   2-6
         Methylchloroform in Surface Waters 	   2-6
         Methylchloroform in Drinking Water 	   2-9
         Methylchloroform Near Industrial Sites—
           Multimedia Levels	   2-9

3.  TRANSFORMATIONS OF METHYLCHLOROFORM IN THE ENVIRONMENT	   3-1

4.  OCCURRENCE OF METHYLCHLOROFORM IN FOOD	   4-1

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

         Exposure	   5-1
         Biological Accumulation	   5-2

6.  BIBLIOGRAPHY	   6-1


                                 FIGURES

Number                                                                Page

  2.1    Industrialized areas where surface water was sampled. .  .  .   2-7

  2.2    Sampling locations at Dow Chemical Plant A, Freeport,
          Texas—methylchloroform production site  	   2-11

  2.3    Sampling locations at Vulcan Materials Company, Geismar,
          Louisiana—methylchloroform production site 	   2-13

  2.4    Sampling locations at Ethyl Corporation, Baton Rouge,
          Louisiana—methylchloroform production site 	   2-15
                                    iii

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                              FIGURES (Continued)

Number                                                                Page

 2.5    Sampling locations at PPG Industries, Lake Charles,
          Louisiana—methylchloroform production site 	   2-17

 2.6    Sampling locations at Boeing Company, Auburn, Washington—
          methylchloroform user site	   2-19

 2.7    Sampling locations at St. Francis National Forest,
          Helena, Arkansas—background site 	   2-21

 3.1    Transformations of methylchloroform 	   3-3

 3.2    Simulated sea level irradiation of methylchloroform ....   3-4

 3.3    High altitude photoreaction of methylchloroform 	   3-5
                                   TABLES

 2.1    Maximum and Minimum Levels of Methylchloroform in the
          Atmosphere at Various Locations in the United States. .  .    2-2

 2.2    Typical Levels of Methylchloroform in the Atmosphere. . .  .    2-3

 2.3    Miscellaneous Monitoring Data for Methylchloroform in the
          Atmosphere	    2-4

 2.4    Methylchloroform Concentration in Surface Water Samples
          Taken by the Institute for Environmental Studies	    2-8

 2.5    Concentration of Methylchloroform in Air, Water, Soil, and
          Sediment at Dow Chemical Plant A (Methylchloroform
          Producer	    2-10

 2.6    Concentration of Methylchloroform in Air, Water, Soil, and
          Sediment at Vulcan Materials Company (Methylchloroform
          Producer)	    2-12

 2.7    Concentration of Methylchloroform in Air, Water, Soil, and
          Sediment at Ethyl Corporation (Methylchloroform Producer)    2-14

 2.8    Concentration of Methylchloroform in Air, Water, Soil, and
          Sediment at PPG Industries (Methylchloroform Produder).  .    2-16

 2.9    Concentration of Methylchloroform in Air, Water, Soil, and
          Sediment at Boeing Company (Methylchloroform User)....    2-18

                                   iv

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                               TABLES (Continued)

Number                                                                Page

 2.10   Concentration of Methylchloroform in Air,  Water, Soil, and
          Sediment at St. Francis National Forest  (Background). .  .    2-20

 3.1    Transformations of Methylchloroform in the Environment. .  .    3-2

 3.2    Evaporation of Methylchloroform under Various Conditions.  .    3-6

 4.1    Methylchloroform in Foodstuffs	    4-1

 5.1    Chlorinated Hydrocarbons in Marine Organisms	    5-3
                               v and vi

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                             EXECUTIVE SUMMARY
     This report discusses environmental levels of methylchloroform, based
on a review of the literature and other information sources.

     The concentrations of methylchloroform in the atmosphere of the U.S.
range from about 0.1 yg/m3 (20 ppt) in remote areas to over 500 yg/m3
(100 ppb) in some 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 methylchloroform range from somewhat
less than 1 ppb to several hundred ppb in the vicinity of methylchloroform
manufacturers.  The highest measurement reported (3 ppm) was made"in a
roadside ditch near a producer site.

     Methylchloroform has been detected but not quantified in U.S.  drinking
water except in one case when approximately 10 ppb was reported.

     Soil and sediment concentrations of methylchloroform appear to be no
higher near manufacturers and users than in rural areas, though the data
are very limited.  The levels are on the order of fractions of a ppb.

     Methylchloroform is a saturated chlorinated hydrocarbon which is
relatively stable in the atmosphere.  However, the molecule is susceptible
to hydrolysis or dehydrohalogenation and reacts with water relatively rapidly
and is thus degraded in soil and water.

     There are very few data on the presence of methylchloroform in food
raised and sold in the U.S.  However, data from the United Kingdom suggest
that methylchloroform is found on the order of parts per billion in some
common foodstuffs.

     There is little evidence to judge whether methylchloroform accumulates
in living organisms.  Limited data on levels in marine organisms show levels
on the order of a few parts per billion.
                                     vii

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                               1.  INTRODUCTION


     Methylchloroform  (MC) is one of the chemicals whose health and
ecological effects, environmental behavior, and technologic and economic
aspects are important  to the U.S. Environmental Protection Agency.  The
literature has been searched in an effort to determine the environmental
levels of methylchloroform, the behavior of methylchloroform in the
environment, and the ways in which methylchloroform may come in contact
with man.

     The literature has been examined using the following search strategy.
An initial computer search of the following data bases was conducted:

           •  National Technical Information Service (NTIS)

           •  Smithsonian Science Information Exchange (SCD-SSIE)

           •, Engineering Index

           •  Pollution Abstracts

           •  TOXLINE

           •  MEDLARS  (National Library .of Medicine's National
                Interactive Retrieval Service)

           •  Air Pollution Technical Information Center (APTIC)

           •  USGS Water Quality Monitoring Data.

All searches were carried out in June, 1976.  Original journal articles
with relevant titles or abstracts were then examined and data extracted.
In addition, various journals were screened manually through December,
1976.  These journals included: Analytical Chemistry, Atmospheric Environ-
ment, Bulletin of Environmental Contamination and Toxicology, CRC Critical
Reviews in Environmental Control, Environment, Environmental Pollution,
Environmental Research, Environmental Science and Technology, International
Journal of Environmental Analytical Chemistry, Journal of Environmental
Science and Health, Journal Water Pollution Control Federation, and Water
Research.  Other journals were also screened but are not listed because
they did not cover the indicated period, or were of more limited interest
to those seeking information on environmental levels of methylchloroform.

     Several important reviews on the subject of methylchloroform were
also consulted.  Specifically, a preliminary study of selected potential


                                    1-1

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environmental contaminants including methylchloroform (U.S. Environmental
Protection Agency, 1975a), a preliminary economic impact assessment of
possible regulatory action to control atmospheric emissions and selected
halocarbons (Shamel, 1975), a criteria for a recommended standard for
occupational exposure to 1,1,1-trichloroethane (methylchloroform) (U.S.
National Institute for Occupational Safety and Health, 1976), and a
toxicology study called "Methylchloroform and Trichloroethylene in the
Environment" (Aviado et al., 1976) were consulted.
                                    1-2

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          2.  OCCURRENCE OF METHYLCHLOROFORM IN THE ENVIRONMENT
METHYLCHLOROFORM IN THE
ATMOSPHERE

     No extensive monitoring program designed specifically for methylchloro-
form has been identified.  However, methylchloroform has been detected along
with other halocarbons at various locations throughout the U.S. and around
the world.  The most extensive data are reproduced in Tables 2.1 and 2.2.
These data are taken from a study done at Cook College, Rutgers University
(Lillian et al., 1975).  Other data are summarized in Table 2.3.  In
addition, various industrial sites were monitored for methylchloroform in a
study carried out by the Battelle Columbus Laboratories in late 1976 and
early 1977 (see the last section of this chapter, "Methylchloroform Near
Industrial Sites—Multimedia Levels").

     The concentration of methylchloroform in the atmosphere ranges from
about 0.1 yg/m3 (20 ppt) in remote areas to over 500 vig/m3 (100 ppb) in
areas where the substance is manufactured or used.  Pearson and McConnell
(1975) point out that as one moves away from a manufacturing facility, the
concentration of methylchloroform in air drops off rapidly (Table 2.3).
Battelle data support this conclusion and Ohta et al. (1976) make a similar
observation.  They state that the distribution peak for methylchloroform
coincides with locations of machine or metal products plants which use the
solvent.

     It was found in the Battelle study that the highest concentrations of
methylchloroform are generally observed downwind from a producer or user
site and the concentration seems to be dependent on the distance from the
discharge point.  Most of the higher concentrations are observed at
distances of less than 1 .km.  Considerable variation, however, was observed
in the maximum downwind levels of methylchloroform at various production
sites.  The variations in the observed maximum concentration among plants
may be due to differences in (1) production processes, (2) emission control
equipment, (3) meteorological conditions, and (4) distance from the plant.
Higher production capacity apparently does not necessarily imply higher
emissions since the maximum concentrations observed at the larger plants
were no higher than those observed at the smaller operations, and were
sometimes lower.  Large temporal variations are observed when measuring
these chlorinated hydrocarbons downwind from a production facility.
                                    2-1

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TABLE  2.1.  MAXIMUM AND MINIMUM LEVELS OF METHYLCHLOROFORM
            IN THE ATMOSPHERE AT VARIOUS LOCATIONS  IN THE
            UNITED STATES
  Monitoring Period
    and Location
           Concentration,
Levels          ppb
June 18-19, 1974            Maximum
Seagrit, New Jersey         Minimum
(National Guard Base)       Mean

June 27-28, 1974            Maximum
New York, New York          Minimum
(45th and Lexington)        Mean

July 2-5, 1974              Maximum
Sandy Hook, New Jersey      Minimum
(Fort Hancock)              Mean

July 8-10, 1974             Maximum
Delaware City, Delaware     Minimum
(Road 448 and Route 72      Mean
  intersection)

July 11-12, 1974            Maximum
Baltimore, Maryland         Minimum
(1701 Poncabird Pass,       Mean
Ford Holabird area)

July 16-26, 1974            Maximum
Wilmington, Ohio            Minimum
(Clinton County Air         Mean
  Force Base)

September 16-19, 1974       Maximum
White Face Mountains        Minimum
(New York State)            Mean

March-December, 1973        Maximum
Bayonne, New Jersey         Minimum
                            Mean
               0.20
               0.044
               0.10

               1.6
               0.10
               0.61

               0.33
               0.030
               0.15

               0.30
               0.03
               0.10
               0.21
               0.044
               0.12
               0.35
               0.030
               0.097
               0.13
               0.032
               0.067

              14.4
               0.075
               1.59
Source: Lillian et al., 1975.
                         2-2

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TABLE 2.2.  TYPICAL LEVELS OF METHYLCHLOROFORM IN THE ATMOSPHERE
   Date and Time
        Location
Methylchloroform
 Concentration,
      ppb
June 27, 1974
    2300

September 17, 1974
    1200

July 2, 1974
    1400
July 19, 1974
    1300

July 17, 1974
July 17, 1974
    1203
New York, New York            0.28
Urban

White Face Mountains          0.083
New York State (nonurban)

Over Ocean                    0.18
Sandy Hook, New Jersey
4.8 km (3 mi) offshore)

Seagirt, New Jersey           0.072
(National Guard Base)

Above the Inversion           0.025
elevated 1500 m (5000 ft)
Wilmington, Ohio

Inversion Layer               0.065
elevation 450 m (1500 ft)
Wilmington, Ohio
Source: Lillian et al., 1975.
                            2-3

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               TABLE 2.3.   MISCELLANEOUS MONITORING DATA FOR METHYLCHLOROFORM IN THE ATMOSPHERE
Location
Los Angeles Basin
San Bernadino Mts.
New Brunswick NJ
ii
Kansas City-NASN
Station
Worldwide
Houston TX and
vicinity
Los Angeles Basin
Pullman WA
Date of Data
Collection
Fall 1972
Fall 1972
1973
Unreported
1974

1974
Nov. 1974

April 1975
Dec. 1974 to
Concentration
0.37 ppb (avg.)
0.05 ppb (avg.)
0.27 ppb
0.83 ppb
Detected

5xlO-9 ml/ml of air
Detected

it
100115 ppt
Method3
GC/EC
n
Coulometric GC
n
GC/MS

Estimate
GC/MS computer

n
GC/MS
Reference
Simmonds et al., 1974
it ii
Lillian and Singh, 1974
n n
Bunn et al. , 1975

Goldberg, 1975
Pellizzari et al., 1976

n n
Grimsrud and Rasmussen, 197
Western Ireland
North Atlantic
Britain, perimeter
  of a manufacturing
  plant
  Heath, near the
  above plant
  Suburban area, re-
  moved from plant
Tokyo

Southern Hemisphere
Northern Hemisphere
Stanford Hills CA

Point Reyes CA
  Feb. 1975
June/July 1974
Oct. 1973
1972-74
1972-74

1972-74

May 1974-April
     1975
1974
1974
Nov. 1975

Dec. 1975
64.8 ppt
75.1 ppt
16 ppb (mass)
6.2 to 11 ppb (mass)

<0.1 to 6 ppb (mass)

0.8 ppb (annual avg.)

24.4 ppt
64.8 ppt
77.6 ppt (avg.
  75 measurements)

90.3 ppt (avg. 300
  measurements)
Coulometric GC
     ii
GC/EC
Lovelock, 1974
     ii
Pearson and McConnell, 1975
                 Ohta et  al.,  1976

                 Cox et al., 1976
                     n       n

                 Singh et al., 1977
 GC/EC = Gas chromatography with electron capture detector; GC/MS = Gas chromatography,  mass  spectroscopy

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Changes  in meteorological conditions, particularly wind speed and direction,
and/or variations in the emissions may account for this phenomenon.

     There is some question about the source of methylchloroform in the
atmosphere.  Lovelock  (1974) suggested that some methylchloroform may
occur naturally while  discussing evidence for the natural origin of carbon
tetrachloride.  He suggests that carbon tetrachloride may result from a
biological source such as algae or more probably from an atmospheric
process.  He cites the following reasons for postulating a natural origin
of carbon tetrachloride: (1) the abundance of carbon tetrachloride does
not differ appreciably between the northern and southern hemispheres, which
is not consistent with a northern industrial source, (2) air arriving at
Western  Ireland shows  a strong correlation between the concentration of
fluorocarbons and continental European origin.  No such correlation is
observed for carbon tetrachloride, (3) reaction in air between methane and
chlorine at a concentration of 10"^ results in the production of small but
significant amounts of carbon tetrachloride in the laboratory.  After this
discussion, Lovelock concludes that "there is some indication from their
spatial distribution that chloroform and methylchloroform may also in
part at least have a similar natural origin to carbon tetrachloride".

     More recently, Cox et al. (1976), in considering oxidation of methyl-
chloroform and other halocarbons by OH radicals, came to the conclusion
that the industrial output of methylene chloride, chloroform, and methyl-
chloroform is probably insufficient to balance the sink due to OH attack,
pointing to a natural  source.  These workers point out, however, that the
observed hemispheric concentration differences are consistent with an
anthropogenic source (see Table 2.3).

     The natural source theory for carbon tetrachloride has recently come
under attack.  Galbalby (1976) concludes that a large fraction, perhaps all
of the carbon tetrachloride observed in the atmosphere, could be man-made,
and carbon tetrachloride is a global atmospheric pollutant.  He attributes
the ubiquitous nature  of carbon tetrachloride and the similar concentra-
tions found in background air in both hemispheres to the fact that carbon
tetrachloride has a long lifetime in the atmosphere, and that a near
equilibrium state of man-made emissions and destruction of the compound in
the atmosphere exists.  If this is true, it seems unlikely that a more
complicated G£ molecule such as methylchloroform could be generated in the
atmosphere in any quantity.

     From chemical kinetic computations, Graedel and Allara (1976) conclude
that the possibility is remote that any of the observed atmospheric halo-
carbons including methylchloroform and carbon tetrachloride are produced
from natural or anthropogenic precursors by atmospheric chemical processes.

     Based on their measured background concentration for methylchloroform
of 84 ppt in the northern hemisphere (Table 2.3)' and on a calculated
cumulative worldwide emissions output of 3.3 million tons of methylchloro-
form up to December, 1975,  which they calculate would correspond to a
background atmospheric concentration of 146 ppt, Singh et al. (1977) .


                                    2-5

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 conclude  that no natural  sources  for methylchloroform can be  inferred.
 However,  they suggest  that methylchloroform residence time  in the tropo-
 sphere must be much  longer than the 1.1 years  suggested by  others (Table
 3.1)  or else secondary anthropogenic or natural  sources must  exist.

      The  resolution  of this  question depends on  the  gathering of  more
 data  and  a better understanding of the atmospheric chemistry  of halocarbons,
METHYLCHLOROFORM IN SOIL AND SEDIMENT

     The only information available on methylchloroform levels in  soil and
sediment was obtained from the Battelle study  (Battelle's Columbus Labora-
tories, 1977).  This information is presented  in the section on Methyl-
chloroform Near Industrial Sites.

     In general, the concentrations in soil range from less than 0.1 ppb
to about 1 ppb.  There does not seem to be any correlation with the distance
from production or user sources, and a concentration of 0.42 ppb was found
in a background sample taken many miles from any known source of methyl-
chloroform.                                           .

     Methylchloroform levels in sediment samples were somewhat higher on
the average than the levels in soil.  Levels in sediment ranged from less
than 0.1 ppb to about 6 ppb.  The background level was 0.45 ppb at a site
far removed from known sources of methylchloroform.
METHYLCHLOROFORM IN SURFACE WATERS

     Approximately 200 water samples have been collected and analyzed for
various organic substances (Chian and Ewing, 1976).  These samples were
collected from 14 heavily industrialized river basins.  These areas and
the approximate number of samples taken at each location are indicated in
Figure 2.1 (Chian and Ewing, 1976, Progress Report No. 4).  The results are
summarized in Table 2.4.   Methylchloroform was detected in 63 of the
approximately 200 samples analysed and the concentrations ranged from
less than 1 ppb to 8 ppb in these surface waters.

     In the vicinity of production plants, the concentration of methylchloro-
form in surface waters is much higher.  Levels up to 200 ppb are common
and at one site a level of 3.3 ppm was found.   The data appear in the last
section of this chapter.

     Pearson and McConnell (1975) report methylchloroform concentrations of
0.09 ppb in rainwater collected in Runcorn, England.  The highest concen-
trations that these researchers measured in upland river waters was 0.3 ppb.
These same authors also reported that they have never detected organo-
chlorines in well waters.  With a normal detection limit of 0.2 ppb,
Pearson and McConnell (1975), between April and August, 1973, determined
that the maximum concentration of methylchloroform in Liverpool Bay
                                       2-6

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ho
I
             Encircled numbers Indicate quantity of
             samples  to be collected In each area.
                                        Figure  2.1.  Industrialized areas where surface water
                                                      was sampled (Source: Chian and Ewing, 1976),

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      TABLE 2.4. METHYLCHLOROFORM CONCENTRATION IN SURFACE WATER SAMPLES
                 TAKEN BY THE INSTITUTE FOR ENVIRONMENTAL STUDIES
Area
 Type of Water Analyzed
                                                               Concentration
                                                  Number of   Range  (Average) ,
                                                   Samples          ppb
Chicago Lake Michigan, sewage 7
treatment plant effluent,
filtration plant, chan-
nels
Illinois Illinois River 11
Pennsylvania Delaware, Schuylkill, 12
0.5 to 8(3)
<1 to 3 (<1)
<1 to 3 (<1)
New York City area

Hudson River area

Upper and Middle
Mississippi River

Lower Mississippi
River

Houston area


Ohio River Basin


Great Lakes



Tennessee River Basin
and Lehigh Rivers

Hudson River and bays        14

Hudson River                  1

Mississippi River             3


Mississippi River             1
                Galveston Bay and             3
                channels

                Ohio River and tribu-         3
                taries

                Lake Superior, Michigan,      6
                Huron, Ontario, Erie,
                and vicinity

                Tennessee River and           2
                tributaries
                                                            to 2 (<1)
                                         1 to 2 (1)
                                            and 4 (<2)
                                   2-8

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seawater was 3.3 ppb.  In Liverpool Bay sediments, a maximum combined
concentration of methylchloroform and carbon tetrachloride was 9.9 ppb.
METHYLCHLOROFORM IN DRINKING WATER

     The National Organics Reconnaissance Survey  (NORS) was initiated by
the U.S. Environmental Protection Agency in November, 1974.  NORS had
three major objectives:  (1) Determine the extent  of the presence of four
trihalomethanes in finished water;  (2) Determine  what effects the source
and treatment of water had on the formation of these compounds; (3)
Characterize as completely as possible the organic content of 10 drinking
waters from sites representing five major categories of raw water souces.

     During the survey of 10 cities, at least 129 compounds were identi-
fied in drinking water.  Some were quantified and others were detected
without quantification.  Methylchloroform was one of the latter.  Its
presence was detected in the drinking water in Ottumwa, Iowa; Philadelphia,
Pennsylvania; and Cincinnati, Ohio  (U.S. Environmental Protection Agency,
1975b).  Methylchloroform was also detected in the drinking water from the
Belmont water treatment plant in Philadelphia, Pennsylvania, on August 8,
1975, using continuous liquid-liquid extraction of the water followed by
identification by gas chromatography/mas spectrometry (Keith, 1976).
Methylchloroform was also detected in tap water at the National Institute
of Environmental Health Sciences, Research Triangle Park, North Carolina,
on May 7, 1975, using gas chromatography/mass spectrometry (Keith, 1976).

     Methylchloroform was identified as a component of New Orleans drinking
water but it was not quantified (Dowty et al., 1975a).  The only quantita-
tive information available was that reported by Bellar et al. (1974).  In
an investigation of the chlorination of water for purification and the
potential for the formation of potentially harmful chlorinated compounds
by the process, scientists at the National Environmental Research Center
at the Environmental .Protection Agency in Cincinnati, Ohio, reported the
following concentrations of methylchloroform in water from a sewage-
treatment plant: influent before treatment, 16.5  yg/S,; effluent before
chlorination, 9.0 yg/£; and effluent after chlorination, 8.5
METHYLCHLOROFORM NEAR INDUSTRIAL
SITES—MULTIMEDIA LEVELS

     A program to determine environmental levels of methylchloroform was
initiated in 1976 at Battelle's Columbus Laboratories.  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 the results
are summarized in Tables 2.5 through 2.10 and in the corresponding maps of
the plant locations on which the sampling sites are indicated Figures 2.2
through 2.7).  Details of the results and methodology are given in a com-
panion report, EPA-560/6-77-025 (Battelle's Columbus Laboratories, 1977).
                                    2-9

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        TABLE 2.5.  CONCENTRATION OF METHYLCHLOROFORM IN AIR,
                    WATER, SOIL, AND SEDIMENT AT DOW CHEMICAL
                    PLANT A  (METHYLCHLOROFORM PRODUCER)

Air

Distance Upwind (U) ,
Concentration, From Plant, Downwind (D) ,
Site ppbva km or Variable (V)














Site
Al

A2
A5

A6
A7

A8
A2,A4,
A7,A12
A1S
ASS
A7S
1A <0. 3 to 2.3 2.6
2A <0.3 to 1.1 1.9
3A <0. 3 to 1.2 3.2
4A <0.3 2.1
5A <0.3 to 0.7 0.8
6A <0.3 /1.9
7A <0. 3 to 1.1 2.6
8A <0. 3 to 2.2 2.6
10A <0.3 3.2
12A <0.3 to 11.5 2.6
13A <0.3 to 0.5 5.1
14A <0.3 7.8
Water, Soil, and Sediment

Description of Media
Surface water, 10 m upstream of effluent
canal
Water, as above, except 2.5 m deep
Surface water, 400 m downstream of plant
outfall
Water, as above except 4 m deep
Surface water, 800 m upstream of plant
outfall
Surface water, bayou 2.6 km from plant
Soil, quadrants around plant at 2 km

Sediment, from effluent canal
D
V
D
D
U
U
V
D
D
D
D
D

Concentration,
ppb
117

119
0.8

1.0
0.1

12
0.06 to 0.68

6.1
Sediment, 400 m downstream of plant outfall 0.34
Sediment , 800 m upstream of plant outfall
. 0.31
Limits of detection: 0.3 ppbv.  To convert to yg/m3 at 25 C,
multiply ppbv by 5.46.
                               2-10

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                                                                  Residential
                                                               O Emission Source
                                                               	-Highway
                                                                  Railroad
                                                                  Plant Proper
                                                                  Industrial
                                                             Q  Marsh
                                                             •   Air  Site
                                                             •   Soil  Site
                                                            *   Water Site
                                                            ~   Sediment Site
Figure 2.2.


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       TABLE 2.6.  CONCENTRATION OF METHYLCHLOROFORM IN AIR,
                   WATER, SOIL, AND SEDIMENT AT VULCAN MATERIALS
                   COMPANY  (METHYLCHLOROFORM PRODUCER)


Air
Distance

Upwind (U),
Concentration, From Plant, Downwind (D) ,












Site
El

E2
E3

E4

E6,E7
E1S

E3S

Site ppbva km or
1 <0.3 to 18 0.4
2 <0.3 to 140 0.3
3 <0.3 0.3
4 <0.3 to 75 0.4
5 5.5 to 155 0.6
6 1.2 to 14 0.6
7 1.4 to 4.0 0.4
8 <0.3 to 0.8 0.3
9 <0.3 to 0.5 3.0
Water, Soil, and Sediment

Description of Media
Surface water, 30 m upstream from plant
outfall
Surface water, at end of outfall pipe
Surface water, 75 m upstream of plant
outfall
Surface water, roadside ditch 60 m from
plant
Variable (V)
V .
V
V
D
D
D
-
V
D

Concentration,
ppb
2

344
169

3,314

Soil, within 200 m of plant on each side 0.45 and 0.94
Sediment, shoreline 30 m upstream of
plant outfall
Sediment, shoreline 75 m downstream of
plant outfall
0.13

2.6

Limits of detection 0.3 ppbv.  To convert to yg/m3 at 25 C,
multiply ppbv by 5.46.
                             2-12

-------
                                                 Emission Source
                                                    Highway
                                                    Plant Proper
                                                    Residential
                                                     Air Site
                                                     Soil Site
                                                     Water Site
                                                     Sediment  Site
Figure 2.3.
              site.
                               2-13

-------
         TABLE 2.7.  CONCENTRATION OF METHYLCHLOROFORM IN AIR,
                     WATER, SOIL, AND SEDIMENT AT ETHYL
                     CORPORATION (METHYLCHLOROFORM PRODUCER)



Air
Distance
Concentration, From Plant,

Upwind (U) ,
Downwind (D) ,
Site ppbva km or Variable (V)










Site
Cl

C2

C3

C4,C7

C2S

C3S

1 <0.3 0.4
2 <0.3 0.2
3 <0.3 to 3.9 2.4
4 <0.3 2.6
5 <0.3 2.2
6 <0.3 0.7
7 <0.3 2.2
8 <0.3 3.2
Water, Soil, and Sediment

Description of Media
Surface water, immediately above
settling pond
Surface water, 200 m upstream of plant
outfall
D
D
D
D
-
U
-
D

Concentration,
ppb
74

9,4

Surface water, 300 m downstream of plant 20
outfall
Soil, various locations in vicinity
of plant
Sediment, 200 m upstream of plant
outfall
Sediment, 300 m downstream of plant
outfall

0.13 to 0.28

0.81

None detected

Q                                                  O
 Limits of detection:  0.3 ppbv.   To convert to yg/md at 25 C,
 multiply ppbv by 5.46.
                               2-14

-------
                                                      O  Emission Source
                                                          Highway
                                                          Railroad
                                                          Plant Proper
                                                          Industrial
                                                          Residential
                                                          Air  Site
                                                          Soil Site
                                                          Water Site
                                                          Sediment Site
                                                              Mile
                                                              1/2
                                                       I -•
                                                       0
                                               •5      1
                                            Kilometer
Figure 2.4.
Sampling  locations at Ethyl  Corporation, Baton  Rouge,
Louisiana—methylchloroform  production site.

-------
        TABLE 2.8.  CONCENTRATION OF METHYLCHLOROFORM IN AIR,
                    WATER, SOIL, AND SEDIMENT AT PPG INDUSTRIES
                    (METHYLCHLOROFORM PRODUCER)

Air

Distance Upwind (U)
Concentration, From Plant, Downwind (D) ,
Site ppbva km or Variable (V)


Site
Fl
F2
F3
F4
F5
F6-F9
F1S
F3S
1 0.8 to 1.3 1.3
2 <0.3 4.2
3 <0.3 to 0.7 3.5
4 <0.3 2.7
5 <0.3 1.4
6 <0.3 to 8.5 4.0
7 <0.3 0.6
8 0.4 1.3
Water, Soil, and Sediment
Description of Media
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 m downstream of
outfall No. 2
Surface water, lake downstream of plant
outfall
Soil, quadrants surrounding plant
Sediment , 50 m upstream of plant
outfall
Sediment, at plant outfall No. 2
U
U
V
U
D
D
U
U

Concentration,
ppb
132
181
58
161
5
0.14 to 1.0
2.2
1.1
Limits of detection: 0.3 ppbv.  To convert to yg/m3 at 25 C,
multiply ppbv by 5.46.
                                 2-16

-------
M
~J
                                                             Emission Source
                                                             Highway
                                                             Railroad
                                                             Industrial
                                                             Plant Proper
                                                             Residential
                                                             Marsh
                                                             Tailings Pond
                                                             Air Site
                                                             Soil Site
                                                             Water Site
                                                             Sediment Site
                                                    .5     1
                                                 Kilometer
                                        • 2
Figure 2.5.   Sampling locations  at PPG Industries,  Lake Charles,
              Louisiana—methylchloroform production site.

-------
         TABLE 2.9.  CONCENTRATION OF METHYLCHLOROFORM IN AIR,
                     WATER, SOIL, AND SEDIMENT AT BOEING COMPANY
                     (METHYLCHLOROFORM USER)



Concentration ,
Site ppbva












Site
J2

J6

J3

J4
1
2
3
4
5
6
7
8
9
10


Surface
pond
Surface
from
Surface
plant
Surface
0.8 to 10.0
0.4 to 0.5
0.4 to 5.0
0.6 to 6.2
0.9
1.6 to 2.3
4.8 to 7.4
7.8 to 8.4
4.0 to 4.4
7.0 to 8.1
Water, Soil

Description
water, outfall

water, outfall
plant
water, outfall

Air
Distance Upwind (U)
From Plant , Downwind (D) ,
km or Variable (V)
0.7 D
0.6 U
0.9 U
1.1
0.9
0.4
1.2 D
2.0
2.9 U
1.1
, and Sediment
Concentration ,
of Media ppb
from settling 18

canal, 1.5 km 18

canal, 3 km from 12

water, 100 m downstream of plant 6
 J5

 Jl
 J7
 J4S


 J5S
  outfall

Surface water, 30 m upstream of plant
  outfall

Soil, about 1 km from plant
Soil, about 0.5 km from plant
Sediment, 100 m downstream of plant
  outfall  .                     ,
0.40
0.65
0.039
Sediment, 30 m upstream of plant outfall   None detected
aLimits of detection: 0.3 ppbv.  To convert to yg/m3 at 25 C,
 multiply ppbv by 5.46.
                              2-18

-------
                                                      Emission Source
                                                      Highway
                                                      Railroad
                                                      Industrial

                                                      Plant Proper
                                                     Residential

                                                     Air Site

                                                     Soil Site

                                                     Water Site

                                                     Sediment Site
      0     .5     1
         Kilometer
Figure 2.6.   Sampling locations at Boeing  Company, Auburn,
              Washington—methylchloroform  user site.
                                 2-19

-------
TABLE 2.10.  CONCENTRATION OF METHYLCHLOROFORM IN AIR,
             WATER, SOIL, AND SEDIMENT AT ST. FRANCIS
             NATIONAL FOREST (BACKGROUND)
                    Media                Concentration

             Air                      <0.3 ppbv
             Surface water, from lake  0.4 ppb (average)
             Soil                      0.42 ppb  (average)
             Sediment                  0.45 ppb  (average
                           2-20

-------
       Dam
  I|  Parking Lot
       Air  Site

       Soil Site

       Water Site

       Sediment Site



         Meters
Figure 2.7.  Sampling locations at St. Francis National Forest,
             Helena, Arkansas—background site.
                            2-21

-------
     In general, concentrations of methylchloroform downwind from the various
industrial sites were higher than in the upwind direction, but considerable
variation was observed in the maximum downwind levels at various production
plants.  Concentrations of methylchloroform in ambient air ranged from less
than 0.3 ppb (limit of detection) to 155 ppb.

     Concentrations of methylchloroform in surface water in the vicinity of
the production and user plants was even more variable ranging from fractions
of a ppb to over 16 ppm.  Concentrations in soil and sediment ranged from
the limits of detection to 6.1 ppb.
                                   2-22

-------
          3.  TRANSFORMATIONS OF METHYLCHLOROFORM IN THE ENVIRONMENT
     This section indicates the changes that methylchloroform can undergo
in various real and simulated environmental media.  The information on the
subject is summarized in Table 3.1 and represented schematically in
Figure 3.1.

     Methylchloroform is oxidized photochemically in the troposphere.
The photochemical removal rate is estimated to be 0.9 million tons per year
(Cox et al., 1976), which is in excess of world production resulting in
release estimated by the same authors to be 0.28 millions tons per year.
The implications of these results are discussed in Chapter 2.  The residence
of methylchloroform in the troposphere is longer than that for a compound
containing unsaturation such as trichloroethylene, but much shorter than
the residence time for completely halogenated compounds such as carbon
tetrachloride or the freons with lifetimes of over 300 years.

     There is evidence that methylchloroform is relatively stable under
simulated sea-level conditions as shown in Figure 3.2  Sunlight in these
experiments was initiated using sunlamps with an intensity of one to two
times that of noontime sea-level sunlight at wavelengths greater than
295 nm.  Figure 3.3 shows the rapid oxidation of methylchloroform at
simulated high-altitude conditions.  These conditions, however, are some
10 to 100 times as intense as would be observed from 40 km upward, and
so the rate is probably exaggerated.  These results indicate that methyl-
chloroform is fairly nonreactive in sea-level atmospheres but as it mixes
upward its photochemical decomposition increases.

     Methylchloroform has a half-life of 30 weeks in sea water of pH 8 at
10 C.  The primary degradation product is vinylidene chloride (Pearson and
McConnell, 1975).  However, at higher temperatures (approximately 70 C),
methylchloroform hydrolyses to acetic acid.  Evaporation from water into
the atmosphere is probably the principal mode of removal.  Billing et al.
(1975) estimate that a half-life of 17 minutes for evaporation.  In good
agreement is the data from Dow Chemical, Table 3.2.  Here evaporation from
a variety of substances is reported.

     Pearson and McConnell (1975) were unable to identify any biological
oxygen demand (BOD) for the chlorinated hydrocarbons.
                                    3-1

-------
                  TABLE  3.1.  TRANSFORMATIONS OF METHYLCHLOROFORM
                             IN THE ENVIRONMENT
     Media
 Change or Products Observed
                                   Reference
 Simulated atmospheric
   conditions

 Simulated atmospheric
   conditions
Simulated atmospheric
  conditions

One ppm  in water con-
  taining natural and
  added  contaminants

Water, 25C

Sea Water (pH 8, 10 C)

Atmosphere

Troposphere

Troposphere, 4.4
  parts/thousand
Smog chamber
Atmosphere near
 welding
<5% decomposed in 23.5 hr
  with  (NO)

<5% decomposed in 8 hr
(50 ppm methylchloroform
10 ppm  N0~)

Est. half-life »1700 hr
17 min half-life for
  evaporation
                                 Billing, et al., 1976
                                 Billing, et al., 1976
                                 Billing, et al., 1976
                                 Billing, et al., 1975
6.9 mo half-life for hydrolysis  Dilling, et al.,  1975

                                 McConnell, etal,,  1975

                                 McConnell, et al.,  1975

1.1 years (lifetime)

26 weeks half life
9 mo half-life, vinylidene
  chloride and acetic acid
10-33 weeks half life
                                 Cox, et al., 1976
Ozone

HC1, Cl£ (in low concentra-
  tions)
                                 Pearson and McConnell,
                                 1975
                                 Farber, 1973
                                 Rinzema and Silverstein,
                                   1972
                                    3-2

-------
OJ

U3
                                     Air,
                                      Light
                  t-1/2   » 1700 hr
                (Billing et al., 1976)
                  CO,  C02, H20, HC1,  C12
                 (McConnell et al.,  1975)
                                                 C13CCH3
 Lt-l/2a 39
     Water, 70 C

[CH'QCOC1]
    CH2 = CC12
Vinylidene Chloride
(Pearson and McConnell, 1976)
        CH3C(TCOCH3
     Acetic Anhydride
                  t-1/2 = time required for one-half of the chlorinated hydrocarbon
                  to disappear by the indicated process.
                                   Figure 3.1.   Transformations of methylchloroform.

-------
80
70
60
50
40
30
(
—
-
• 1 •
• 1 * t
. I • o I
* • • 9
i BOppmCHjCCIj
— lOppmNO-
30% RH
27 °C
1
II 1 1 1 1 1 1 1 1
) 2 4 6 8 10 12 14 16 18 20 22 24 26 28
TIME (days)
80
70
60
I 50
40
30

—
-
-
l ? 1 9 I • •
1 • • ° • •
50ppmCH,CCI-
__ « w
35% RH
— ', 25-26 °C
1 1 1 I 1 1 1 1 1
3 2 4 6 8 10 12 14 16 18
                       TIME (days)
Figure 3.2.  Simulated sea level irradiation  of
             methylchloroform (Source: Dow Chemical
             Company data as reported by Study Panel
             on Assessing Potential Ocean Pollutants,
             1975).
                        3-4

-------
                         SOppmCHjCCIj
                         OppmNO.,
                         35% RH
                         25-3 3 °C
6
a
                              15

                          TIME (minutes)
                                      20
30
 Figure 3.3.  High altitude photoreaction of
              methylchloroform (Source:  Dow
              Chemical  Company data as reported
              by Study  Panel on Assessing
              Potential Ocean Pollutants, 1975).
                  3-5

-------
TABLE 3.2.  EVAPORATION OF METHYLCHLOROFORM
            UNDER VARIOUS CONDITIONS3
                              Time (min) fo'r 50%
       Condition                Disappearance


Tap water @ 25°                       22
Tap water @ 1-2°                      33
3% Salt solution                      25
^500 ppm peat moss                    20
^500 ppm wet bentonite clay           20
2.2 mph wind                          17
Conditions:  250 ml beaker with 20 ml water with
 1 ppm solute initially at 25°.  Stirred at 200 rpm.-

Source:  Dow Chemical Company data as reported by
Study Panel on Assessing Potential Ocean Pollutants,
1975.
                      3-6

-------
                  4.  OCCURRENCE OF METHYLCHLOROFORM IN FOOD
     There are very few data on the presence of methylchloroform in food
raised and sold in the United States, but there is some information on the
presence of methylchloroform in foodstuffs found in the United Kingdom.
This information is summarized in Table 4.1.  Methylchloroform concentra-
tions on the order of parts per billion are found in several common
foodstuffs.
                  TABLE 4.1.  METHYLCHLOROFORM IN FOODSTUFFS
                                              Concentration,
                                                  yg/kg
                  Meat
                    English beef, steak              3
                    English beef, fat                6
                    Pig's liver                      4

                  Oils and fats
                    Olive oil (Spanish)             10
                    Cod liver oil                    5
                    Castor oil                       6

                  Fruits and vegetables
                    Potatoes (S.  Wales)              4
                    Potatoes (N.W.  England)          1
                    Apples                           3
                    Pears                            2

                  Tea (packet)                       7
                  Fresh bread                        2
                  Source:   McConnell et al., 1975.
                                    4-1

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

     NIOSH estimates that 100,000 workers are exposed to methylchloroform
(U.S. National Institute for Occupational Safety and Health, 1976).  Methyl-
chloroform is the principal solvent in wet cleaning applications and its use
as a vapor degreaser is expected to increase by 10 percent per year as tri-
chloroethylene undergoes further restrictions (U.S. Environmental Protection
Agency, 1975a).

     A two-year series of studies involving cleaning operations throughout
the United States was carried out by Dow Chemical  (Skory et al., 1974).
The purpose was to determine the extent of worker exposure during solvent
vapor degreasing and to compare the three most commonly used chlorinated
solvents: methylchloroform, trichloroethylene, 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 concentrations measured around vapor degreasers
frequently exceeded the allowable standards for health and safety.  Peak
concentrations were high enough to present a definite health and safety
hazard from anesthetic effects such as dizziness, lack of coordination,
and impaired judgment.  These authors further concluded that methyl-
chloroform emissions during vapor degreasing can be controlled easily at
levels below standards established by OSHA.

     Although the national primary and secondary photochemical oxidant
standards for chlorinated solvents are less than 3 Ib/hour or 15 Ib/day
maximum for each equipment, it is not uncommon for an idling open-top
vapor degreaser measuring 24 x 58 inches to lose 47 Ib/day trichloroethylene
or 33 Ib/day 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 105 tons of chlorinated hydrocarbons are lost
to the environment each year (Murray and Riley, 1973) and that 3 x 105 tons
of methylchloroform are discharged annually (Shamel et al., 1975).  In
Los Angeles County alone, it is estimated that 500 tons/day of industrial
effluents are released into the air, and of this amount, 25 tons are dry
cleaning fluids and 95 tons are degreasing solvents, that is, chlorinated
hydrocarbons (Simmonds et al., 1974).
                                    5-1

-------
 BIOLOGICAL ACCUMULATION

     Dowty et  al,  (1975b)  in  a paper  on halogenated  hydrocarbons  in  drinking
 water  concludes  that  "in view of  the  lipophilic nature  of  halogenated hydro-
 carbons  and  their  occurrence  in drinking water, it is not  surprising that
 they might be  found accumulating  in blood  or  other tissues".   These  authors,
 however,  present no data or references to  support their contentions.

     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 verte-
 brates.   This  same group reports  on another study in which  it  was  determined
 that the  bioaccumulation factor is determined by the partition 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 bioaccumulation.  Bioaccumulation
 for methylchloroform  was estimated to be 13.  This compound would  be
 expected  to  act similarly to  carbon tetrachloride in organisms, exhibiting
 rapid  uptake to steady state  concentration, and rapid clearance.

     By far  the most  definitive study on bioaccumulation was carried out
 by Pearson and McConnell (1975.   Some of the results that they report are
 complicated  by the fact that  methylchloroform and carbon tetrachloride were
 not distinguished  in  the early analytical  work that was done.  Nevertheless,
 these  authors determined the  amount of methylchloroform present in a large
 number of species  and their results are tabulated in Table  5.1.  They
 estimated that the maximum overall increase in concentration,  between
 sea water and the  tissues of  animals  at the top of the  food chains such as
 fish liver,  bird eggs, and seal blubber is less than 100-fold  for  solvents
 similar to methylchloroform; 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 bioaccumulation can occur.
 Their  results indicate the following: (1)  the concentration of chlorinated
 hydrocarbons accumulated in a tissue  tends to an asymptotic level, (2) con-
 centrations  in fatty  tissues such as  liver 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 hydro-
 carbon in the tissue  falls.  These researchers conclude that there is no
 evidence for the bioaccumulation  of C-±/C2 compounds in  food chains and the
maximum concentrations found in the higher trophic levels are  still only
 parts per 108 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.
                                     5-2

-------
                                TABLE 5.1.  CHLORINATED  HYDROCARBONS  IN MARINE  ORGANISMS

                            (concentrations expressed as parts  per  109 by mass  on wet  tissue)
Ul
I
Species
Plankton
Plankton
Nereis diversicolor
(ragworm)
Mvtilus edulis
(mussel)
Cerastoderma edule
(cockle)
Ostrea edulis
(oyster)
B_uccinum undatum
(whelk)
Crepidula fornicata
(slipper limpot)
Cancer pagurus
(crab)
Carcinus maenas
(shore crab)
Eupagurus bernhardus
(hermit crab)
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
CC12CHC1
Invertebrates
0.05-0.4
0.0
ND
4-11.9
9
ft
6-11
2
ND
9
2.6
10-12
15
12
15
5
CC12CC!2 CHjCCl,^
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 5.1.  (Continued)
Ui
I
Species
Crangon crangon
(shrimp)
Asterias rubens
(starfish)
Sqlaster sp.
(sunstar)
Echinus esculentus
(sea urchin)
Enteromorpha
compressa
Ulva lactuca
Fucus vesiculosus
Fucus serratus
Fucus spiralis
Raja clavata
(ray) flesh
liver
Pleurone c t e s
p_latessa flesh
(plaice) liver
Source
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
CC1 CHC1
16
5
2
1
Marine algae
19-20
23
17-18
22
16
Fish

0.8-5
5-56
0.8-8
16-20
CC12CC12 CH3CC13+CC14
3 26
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 5.1. (Continued)
Species
Platycthys
flesus
(flounder)
Limanda
limanda
(dab)
Scomber
scombrus
(mackerel)
Limanda
limanda
Pleuronectes
platessa
§olea solea
(sole)
Aspitrigla
cucuius


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
Redear , Yorks
Thames Estuary

Thames Estuary
Thames Estuary
Thames Estuary
Thames Estuary
Thames Estuary
CCL2CHC1

3
2

3-5
12-21

5
8
4.6
2

3
2
11
11
6
cci2cci2

2
1

1.5-11
15-30

1
ND
5.1
3

3
4
1
1
2


4
3




5
3

4

3
2
26
4
10
CH3CC13+CC1A

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
  (scad)
flesh   Thames Estuary
Trisopterus
  luscus     flesh
  (pout)

ScLualus
  acanthias  flesh
  (spurdog)
        Thames Estuary
        Thames Estuary
ND
                0.3

-------
                                              TABLE 5.1.  (Continued)
Ul
Species
Scomber
scombrus flesh
(mackerel)
CjLu£ea
sprattus flesh
Gadus
morrhus flesh
(cod) air bladder

Sula bassana liver
(gannot) eggs
Phalacrocerax
aristotelis eggs
(shag)
Alca torda
(razorbill) eggs
Rissa tridactyla
(kittiwake) eggs
Cyj»nus olor liver
(swan) kidney
Gallinula liver
chloropus muscle
(moorhen) eggs
Ana_s
platyrhyncos
(mallard) eggs
Source

Torbay , Devon


Torbay , Devon

Torbay, Devon
Torbay, Devon

Irish Sea
Irish Sea

Irish Sea


Irish Sea

North Sea
Frodsham Marsh
(Merseyside)
(Merseyside)
(Merseyside)
(Merseyside)


(Merseyside)
CC12CHC1

2.1


3.4

0.8
<0. 1
Sea and freshwater
4.5-6
9-17

2.4


23-26

33
2.1
14
6
2.5
6.2-7.8


9.8-16
cci2cci2

ND


1.0

<0.1
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
CH3CC13+CC1

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

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                                         TABLE 5.1.  (Continued)
Species Source

Halichoer_us
grypus blubber Fame Is.
(grey seal) liver Fame Is,
Sorex
araneus Frodsham Marsh
(common
shrew)
(~*r* 1 fu/"1"! r*r* i /T*I fxj /"i/"ii 1001
OO J- « V./n.O J- VjVjX,-iVJ^iJL-i Ull n\J V> -L rtTV>*-^ J- »
2 22 334
Mammals

2.5-7.2 0.6-19 16-30
3-6.2 0-3.2 0.3-4.6

2.6-7.8 1 2.3-7


Source: Pearson and McConnell, 1975.




Note:  NA = no analysis; ND = not detectable.

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                               6.  BIBLIOGRAPHY
Archer, W. L.  1973.  Selection of a Proper Vapor Degreasing Solvent.  In:
Cleaning Stainless Steels, Special Technical Publication No. 538.  American
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Aviado, D. M., S. Zakhari, J. A. Simaan, and A. G. Ulsamer.  1976.  Methyl-
chloroform and Trichloroethylene in the Environment.  CRC Press, Inc.,
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Battelle's Columbus Laboratories.  1977.  Environmental Monitoring Near
Industrial Sites—Methylchloroform.  EPA-56-/6-77-025.  U.S. Environmental
Protection Agency, Office of Toxic Substances, Washington, D.C.

Bellar, T. A., J. J. Lichtenberg, and R. C. Kroner.  1974.  The Occurrence
of Organohalides in Chlorinated Drinking Waters.  Journal of the American
Water Works Association.  66;703-706.

Bunn, W. W., E. R. Deane, D. W. Kelin, and R. D. Kleopfer.  1975.  Sampling
and Characterization of Air for Organic Compounds.  Water, Air and Soil
Pollution.  4_: 367-380.

Chian, E.S.K. and B. B. Ewing.  1976.  Monitoring Data to Detect Previously
Unrecognized Pollutants.  Progress Reports 1 to 5.  U.S. Environmental
Protection Agency.  Contract No. 68-01-3234.  Institute for Environmental
Studies, University of Illinois at Urbana-Champaign.

Cox, R. A., R. G. Derwent, A.E.J". Eggleton, and J. E. Lovelock.  1976.
Photochemical Oxidation of Halocarbons in the Troposphere.  Atmospheric
Environment.  10;305-308.

Dilling, W. L., C. J. Bredeweg, and N. B. Tefertiller.  1976.  Organic
Photochemistry—Simulated Atmospheric Photodecomposition Rates of Methylene
Chloride, 1,1,1-Trichloroethane, Trichloroethylene, Tetrachloroethylene, and
Other Compounds.  Environmental Science and Technology.  10(4);351-356.

Dilling, W. L., N. B. Terfertiller, and G. J. Kallos.  1975.  Evaporation
Rates and Reactivities of Methylene Chloride, Chloroform, 1,1,1-Trichloro-
ethane, Trichloroethylene, Tetrachloroethylene, and Other Chlorinated
Compounds in Dilute Aqueous Solutions.  Environmental Science and
Technology.  9/9):833-838.

Dowty, B., D. Carlisle, J. L. Laseter, and J. Storer.  1975a.  New Orleans
Drinking Water Sources Tested by Gas Chromatography-Mass Spectrometry.
Environmental Science and Technology.  j?:762-765.

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Dowty, B., D. Carlisle, J. L. Laseter, and J. Storer.  1975b.  Halogenated
Hydrocarbons in New Orleans Drinking Water and Blood Plasma.  Science.
187:75-77.

Farber, H. A.  1973.  Chlorinated Solvents and the Environment.  In: Textile
Solvent Technology-Update  '73.  Sponsored by the Solvent Processing Techno-
logy Committee of the American Association of Textile Chemists and
Colorists.  January 10-11, 1973.  pp 6-12.

Galbally, I. E.  1976.  Man-Made Carbon Tetrachloride in the Atmosphere.
Science.  193:573-576.

Goldberg, E. D. (chmn.)  1975.  A:Entry, Distribution, and Fate of Heavy
Metals and Organohalogens  in the Physical Environment.  In: Ecological
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Proceedings of a NATO Science Committee Conference held at Mont Gabriel,
Quebec, May 6-10, 1974.  Plenum Press, New York,  pp 233-256.

Graedel, T. E. and D. L. Allara.  1976.  Tropospheric Halocarbons: Estimates
of Atmospheric Chemical Production.  Atmospheric Environment.  10:385-388.

Grimsrud, E. P. and R. A. Rasmussen.  1975.  Survey and Analyses of Halo-
carbons in the Atmosphere by Gas Chromatography-Mass Spectrometry.
Atmospheric Environment.  j)1014-1017.

Keith, L. H. (ed.).  1976.  Identification and Analysis of Organic Pollu-
tants in Water.  Ann Arbor Science Publishers, Inc.  766 p.

Lillian, D. and H. B. Singh.  1974.  Absolute Determination of Atmospheric
Halocarbons by Gas Phase Coulometry.  Analytical Chemistry.  46(8);1060-1063.

Lillian, D., H. B. Singh, A. Appleby, L. Lobban, R. Arnts, R. Gumpert, R.
Hague, J. Toomey, J. Kazazis, M. Antell, D. Hansen, and B. Scott.  1975-
Atmospheric Fates of Halogenated Compounds.  Environmental Science and
Technology.  9^(12): 1042-1048.

Lovelock, J. E.  1974.  Atmospheric Halocarbons and Stratospheric Ozone.
Nature.  252:272-274.

McConnell, G., D. M. Ferguson, and C. R. Pearson.  1975.  Chlorinated
Hydrocarbons and the Environment.   Endeavour.  34(121);13-18.

Murray, A. J.  and J. P.  Riley.  1973.  Occurrence of Some Chlorinated
Aliphatic Hydrocarbons in the Environment.  Nature.  242(5392):37-38.

Ohta, T., M. Masatoshi,  and I. Mizoguchi.   1976.  Local Distribution of
Chlorinated Hydrocarbons in the Ambient Air in Tokyo.  Atmospheric
Environment.  10:557-560.

Pearson, C. R. and G. McConnell.  1975.  Chlorinated GI and C2 Hydrocarbons
in the Marine Environment.  Proceedings of the Royal Society of London.  B.
189:305-332.

                                   6-2

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Pellizzari, E. C., J. E. Bunch, R. E. Berkley, and J. McRae.  1976.
Determination of _race Hazardous Organic Vapor Pollutants in Ambient
Atmospheres by Gas Chromatography/Mass Spectrometry/Computer.  Analytical
Chemistry.  48(6);803-807.

Rinzema, L. C. and L. G. Silverstein.  1972.  Hazards from Chlorinated
Hydrocarbon Decomposition During Welding.  American Industrial Hygiene
Association Journal  33(1);35-40.

Shamel, R. E., R. Williams, J. K. O'Neill, R. Eller, R. Green, K. D. Hallock,
and R. P. Tschirch.  1975.  Preliminary Economic Impact Assessment of Possi-
ble Regulatory Action to Control Atmospheric Emissions of Selected Halo-
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Office of Air Quality Planning and Standards, Research Triangle Park, North
Carolina.

Simmonds, P. G., S. L. Kerrin, J. E. Lovelock, and F. H. Shair.  1974.
Distribution of Atmospheric Halocarbons in the Air Over the Los Angeles
Basin.  Atmospheric Environment.  8>(3) :209-216.

Singh, H. B., L. J. Salas, and L. A. Cavanagh.  1977.  Distribution, Sources,
and Sinks of Atmospheric Halogenated Compounds.  Journal of the Air Pollution
Control Association.  27(4) :332-336.

Skory, L., J. Fulkerson, and D. Ritzema.  1974.  Vapor Degreasing Solvents:
When Safe?  Products Finishing.  38_(5) :64-71.

Study Panel on Assessing Potential Ocean Pollutants.  1975.  Report to the
Ocean Affairs Board, Commission on Natural Resources, National Research
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Washington, D.C.

U.S. Environmental Protection Agency.  1975a.  Preliminary Study of Selected
Potential Environmental Contaminants-Optical Brighteners, Methylchloroform,
Trichloroethylene, Tetrachloroethylene, Ion Exchange Resins.  Final Report.
July 1975.  EPA-560/2-72-002.  U.S. Environmental Protection Agency, Office
of Toxic Substances.  Washington, D.C. 286 p.

U.S. Environemntal Protection Agency.  1975b.  Preliminary Assessment of
Suspected Carcinogens in Drinking Water.  Report to Congress.  U.S. Environ-
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U.S. National Institute for Occupational Safety and Health.  1976.  Criteria
for a Recommended Standard-Occupational Exposure to 1,1,1-Trichloroctane
(Methylchloroform).  HEW Publication No. (NIOSH) 76-184.  U.S. Department
of Health, Education, and Welfare, National Institute for Occupational
Safety and Health, Cincinnati, Ohio.  179 p.
                                   6-3

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                                   TECHNICAL REPORT DATA
                            (Pirate rcad /nslnirtitinx on Ilic reverse before completing)
 1. HLPQRT NO.
  EPA-560/6-77-030
                              2.
4. TITLE AND SUBTITLE

  MULTIMEDIA LEVELS—METHYLCHLOROFORM
                                 5. REPORT DATE
                                    September 1977
                                                            6. PERFOFtMING ORGANIZATION CODE
                                                            3. RCCIPILNT'S ACCESSION NO.
7. AUTHOR(S)
  Battelle Columbus Laboratories
                                                            8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Battelle  Columbus Laboratories
  505 King  Avenue
  Columbus,  Oh'io  43201
                                                            10. PROGRAM ELEMENT NO.
                                  11. CONTRACT/GRANT NO.

                                    68-01-1983
12. SPONSORING AGENCY NAME AND ADDRESS

  Environmental Protection Agency
  Office  of Toxic Substances
  Washington,  D.C.   20460
                                  13. TYPE OF REPORT AND PERIOD COVERED
                                  14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
 This report discusses environmental levels  of  methylchloroform  (MC) based  on a review of
 the literature  and  other information sources.   The concentrations of MC  in the U.S.
 atmosphere ranges from about 0.1 ug/m3  (20  ppt)  in remote areas to over  500 pg/m3 (100
 ppb) in some areas  near where the substance is manufactured or used.  The  concentration
 drops off rapidly as  one moves away from a  source  facility.  Surface water contamination
 of MC range from somewhat less than 1 ppb to several hundred ppb in the  vicinity of MC
 manufacturers.  The highest measurement reported (3 ppm) was made in a roadside ditch
 near a producer site.   MC has been detected but  not quantified in U.S. drinking water
 except in one case  when approximately 10 ppb was reported.  Soil and sediment concentra-
 tions of MC appear  to be no higher near manufacturers and users than in  rural areas,
 though the data are very limited.  The levels  are  on the order of fractions of a ppb.
 MC is a saturated chlorinated hydrocarbon which  is relatively stable in  the atmosphere.
 However, the molecule is susceptible to hydrolysis or dehydrohalogenation  and reacts
 with water relatively rapidly and is thus degraded in soil and water.  There are very
 few data on presence  of MC in food raised and  sold in the U.S.  However, data from the
 United Kingdom suggest that MC is found on  the order of parts per billion  in some common
 foodstuffs.  There  is little evidence to judge whether MC accumulates in living
 organisms.  Limited data on levels in marine organisms show levels on the  order of a
 few parts per billion.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
 Methylchloroform
 Water
 Sediment
 Soil
 Air
 Human
Food
Behavior
                    b.IDENTIFIERS/OPEN ENDED TERMS  C. COSATI l-'iclil/Group
 8. DISTRIBUTION STATEMENT

 Distribution unlimited
                    19. SECURITY CLASS (This Keport)

                       Unclassified	
                                                                          21. NO. OF CAGES
                                              20. SECURITY CLASS (This page)
                                                 Unclassified
                                                                          22. PRICE
EPA form 2220-1 (Rov. 4-77)   PREVIOUS COITION is OOSOLETIC

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