EPA-560/6-77-025
      ENVIRONMENTAL MONITORING
         NEAR INDUSTRIAL SITES
          METHYLCHLOROFORM
               AUGUST 1977
         ENVIRONMENTAL PROTECTION AGENCY
            OFFICE OF TOXIC SUBSTANCES
             WASHINGTON, D.C. 20460

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EPA-560/6-77-025
              ENVIRONMENTAL MONITORING NEAR INDUSTRIAL SITES
                             METHYLCHLOROFORM
                               August  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, B.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 trade names 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.  SAMPLING RATIONALE	   2-1

3.  SAMPLING PROTOCOL	   3-1

         Air	   3-1
         Water	   3-2
         Sediment	   3-2
         Soil	   3-2
         Vegetation	   3-3
         Tissue	   3-3
         Number of Samples	   3-3

4.  ANALYTICAL METHODS	   4-1

         Determination of Methylchloroform in Ambient Air	   4-1
         Determination of Methylchloroform in Water	   4-4
         Determination of Methylchloroform in Soil and Sediment .   .   4-19

5.  MONITORING DATA	   5-1

         Production Sites Monitored 	   5-1
         User Site Monitored	   5-1
         Background Site Monitored	   5-1
         Discussion of Results  	   5-1


                                  FIGURES

Number                                                                Page

 4.1     Schematic of EC/GC ambient air analysis system 	   4-2

 4.2     Calibration curves for chlorinated hydrocarbons—Varian
           1200/EC detector 	   4-5

 4.3     Calibration curves for chlorinated hydrocarbons—ATC
           140A/EC detector	   4-6
                  •                       •*
 4.4     Schematic of a  liquid-sample concentrator	   4-8


                                    iii

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                           FIGURES  (Continued)

Number                                                                Page

 4.5     Chromatogram of chlorinated solvents	   4-9

 4.6     Chromatogram showing 500 ppb each of methylchloroform,
           trichloroethylene, and perchloroethylene using FID
           detector	   4-11

 4.7     Chromatogram showing 50 ppb each of methylchloroform,
           trichloroethylene, and perchloroethylene using FID
           detector	   4-12

 4.8     Calibration curves  for the determination of methylchloro-
           form and  trichloroethylene using FID detector	   4-14

 4.9     Calibration curves  for the determination of methylchloro-
           form and  trichloroethylene using electron-capture
           detector	   4-16

 4.10    Chromatogram of several chlorinated hydrocarbons using
           electron-capture  detector after completion of
           development work	   4-17

 4.11    Schematic of soil and sediment analysis apparatus	   4-21

 4.12    Sample Chromatogram for sediment	   4-23

 5.1     Sampling locations  at Dow  Plant A, Freeport, Texas—
           methylchloroform  production site 	   5—5

 5.2     Sampling locations  at Vulcan Materials Company, Geismar,
           Louisiana—methylchloroform production site	   5-14

 5.3     Sampling locations  at Ethyl Corporation, Baton Rouge,
           Louisiana—methylchloroform production site	   5-21

 5.4     Sampling locations  at PPG  Industries, Lake Charles,
           Louisiana—methylchloroform production site	   5-27

 5.5     Sampling locations  at Boeing Company, Auburn, Washington—
           methylchloroform  user site	   5-33

 5.6     Sampling locations  at St.  Francis National Forest,
           Helena, Arkansas—background site	   5-39
                                     iv

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                                 TABLES

Number                                                               Page

 2.1    Sites Monitored for Methylchloroform	   2-1

 4.1    Operating Conditions and Performance Characteristics of
          the EC/GC Systems Used for Ambient Air Measurements of
          Chlorinated Hydrocarbons 	   4-3

 4.2    Volatile Impurities in Waters	   4-13

 5.1    Ambient Air Measurements at Dow Chemical Plant A
          (Methylchloroform Producer)	   5-6

 5.2    Analysis of Water,  Soil, and Sediment Samples from Dow
          Chemical Plant A (Methylchloroform Producer) 	   5-10

 5.3    Descriptions of Sampling Locations at Dow Chemical
          Plant A, Freeport, Texas (November 9-12, 1976)  	   5-11

 5.4    Ambient Air Measurements at Vulcan Materials Plant
          (Methylchloroform Producer)	   5-15

 5.5    Analysis of Water,  Soil, and Sediment Samples from
          Vulcan Materials  Plant (Methylchloroform Producer)  .  .  .   5-18

 5.6    Descriptions of Sampling Locations at Vulcan Materials,
          Geismar, Louisiana (December 2,  1976)	   5-19

 5.7    Ambient Air Measurements at Ethyl  Corporation (Methyl-
          chloroform Producer)	   5-22

 5.8    Analysis of Water,  Soil, and Sediment Samples from Ethyl
          Corporation (Methylchloroform Producer)   	   5-24

 5.9    Descriptions of Sampling Locations at Ethyl Corporation,
          Baton Rouge,  Louisiana (November 18-19,  1976)	   5-25

 5.10   Ambient Air Measurements at PPG Industries (Methylchloro-
          form Producer)	   5-28

 5.11   Analysis of Water,  Soil, and Sediment Samples from PPG
          Industries (Methylchloroform Producer	   5-30

 5.12   Descriptions of Sampling Locations at PPG Industries,
          Lake Charles, Louisiana (December 6, 1976)  	   5-31

 5.13   Ambient Air Measurements at Boeing/Auburn Plant
          (Methylchloroform User)	   5-34

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                             TABLES (Continued)

Number                                                               Page

 5.14   Analysis of Water, Soil, and Sediment Samples from
          Boeing/Auburn Plant (Methylchloroform User)	   5-36

 5.15   Descriptions of Sampling Locations at Boeing Company,
          Auburn, Washington (January 10-12, 1977) 	   5-37

 5.16   Ambient Air Measurements'at St. Francis National Forest
          (Rural Background)	   5-40

 5.17   Analysis of Water, Soil, and Sediment Samples from the
          St. Francis National Forest (Background Site)  	   5-41

 5.18   Descriptions of Sampling Locations at Storm Creek Lake,
          St. Francis National Forest, Helena, Arkansas
          (November 30, 1976)	   5-42
                                   vi

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                           EXECUTIVE SUMMARY
        The levels of methylchloroform in various environmental media were
determined at four production sites, one user site, and a background site.
The following sites were monitored:

             Dow Chemical Co., U.S.A	Freeport, Texas
             PPG Industries, Inc	 Lake Charles, Louisiana
             Ethyl Corporation	Baton Rouge, Louisiana
             Vulcan Materials Company .... Geismor, Louisiana
             Boeing Company (User Site) . . . Seattle, Washington
             St. Francis National Forest. . . Helena, Arkansas
                (Background Site)

        Approximately 2 days were devoted to monitoring ambient air levels
for methylchloroform and collecting water, soil, and sediment samples at
each site.  The samples were returned to Battelle-Columbus Laboratories
for analyses.  The ambient air level of methylchloroform was determined
on-site by direct injection of the ambient air into a gas chromatograph
followed by detection and quantification with an electron capture detector.

        For the analyses of water samples, the methylchloroform was
sparged from the water and collected on a trap material using a commercial
liquid sample concentrator.  The trapped organic material was then back-
flushed onto a gas chromatograph column which was connected to an electron
capture detector used to quantify the methylchloroform in the original
sample.  A similar technique was used for the quantification of methyl-
chloroform in soil and sediment but the, apparatus was not of commercial
design.                                '

        For each site, a map is presented with sampling points indicated.
The results from the analyses of the samples and detailed descriptions of
the sampling locations are given and are keyed to the site map.

        Considerable variation was observed in the maximum downwind levels
of methylchloroform 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 frac-
tions of a ppb to. over 16 ppm.   Concentrations in soil and sediment ranged
from the limits  of detection to  6.1 ppb.
                                   VII

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                              1.   INTRODUCTION
        Methylchloroform (MC) is a chlorinated hydrocarbon which is produced
in major quantities in the U.S. and is used in a variety of solvent cleaning
operations.  This compound has a relatively low boiling point; therefore,
its emission into the atmosphere probably represents one of the more signi-
ficant pathways to human exposure,  To date, however, very little air
monitoring data have been generated to assess potential exposure hazards.
In particular, existing data are devoid of measurements in the environment
around manufacturing and user facilities where the highest concentrations
(and thus the highest exposures) might be expected.

        This report describes the sampling rationale, the collection of
samples, that is, the sampling protocol, and the analytical methods used
to determine the environmental concentrations of methylchloroform at several
sites.  The results are presented using maps in conjunction with tabulated
data and descriptions of the samples.   A separate set of data is presented
for each site monitored, and these sets are grouped together under
production sites, user sites, and background site.
                                    1-1

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                            2.   SAMPLING  RATIONALE
         The  objective  of  this  sampling program was  to  determine  levels  of
 methylchloroform in  the environment.  To  do  this, several  important  factors
 were  considered.  Among these  were  the type  of site (production,  user,  or
 background);  the source of  the substance  (discharge practices—how the
 substance  is  released  to  the environment); the ecological  compartments  to
 be  sampled (air,  water, soil,  sediment, biota);  the conditions at the
 time  of  sampling (meteorological conditions, plant  operation, geography,
 interfering  elements); and  statistical requirements.   These factors  are
 discussed  further under specific environmental compartments in the following
 section  on the  sampling protocol.

         Sites were selected based on the  fact  that  methylchloroform  is  a
 volatile organic  compound and  is most likely to  reach  the  environment
 where it is produced and used.  Table 2.1 lists  the four major producers
 of  methylchloroform, a major user site, and a  background site.
              TABLE 2.1.  SITES MONITORED FOR METHYLCHLOROFORM
                              Production Sites

          Dow Chemical Company, U.S.A.   .  .  Freeport, Texas
          PPG Industries, Inc	Lake Charles, Louisiana
          Ethyl Corporation  	  Baton Rouge, Louisiana
          Vulcan Materials Company   ....  Geismor, Louisiana

                                 User Site

          Boeing Company  	  Seattle, Washington

                              Background Site

          St. Francis National Forest .  .  .  Helena, Arkansas
        The air sampling effort at each facility was conducted to obtain the
following information:  (1) the concentration profile around the plant,  (2)
•maximum concentration levels, (3) temporal variations in concentration, and
                                     2-1

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(4) the variation in concentration as a function of distance downwind from
the plant.

        Measurements were made in four quadrants surrounding the plant
location.  The highest concentrations prevailed downwind from the plant
location.  Therefore, the majority of the sampling and analysis effort was
then concentrated in the downwind direction to determine maximum concentra-
tions and temporal and spatial concentration variations.

        The air monitoring equipment, a field electron-capture gas chromato-
graph, used for the methylchloroform analyses also permitted measurement of
trichloroethylene, carbon tetrachloride, and perchloroethylene.  Therefore,
concentrations of these chlorinated hydrocarbons in ambient air were also
determined.                                                                f

        In order to -detect concentration levels associated with process water
discharge, water samples were taken in the receiving stream at the plant out-
fall and upstream and downstream of the outfall.  Samples of aquatic animal
tissue, usually fish, were also collected at locations upstream and downstream
of plant outfalls.  In order to measure the amount present in a normal day's
discharge, which may not be accurately represented in grab samples, a 24-hour
composite of the effluent was obtained from plant personnel.  Water samples
were also taken from the naturally occurring surface waters in the immediate
area.

        In order to determine possible associated levels of methylchloroform
in sediments, samples were taken in close proximity to water sampling sites.

        Soil, vegetation, and mammal tissue samples were also taken in the
four quadrants surrounding the plant location designated for air sampling.
Samples were taken as close to the exact site of the air sampling as possible.
The proximity of these samples should yield data suitable for associating
levels of methylchloroform in air with those found in soils.
                                   2-2

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                            3.  SAMPLING PROTOCOL
Air
        Approximately 2 days were devoted to monitoring ambient air levels
of methylchloroform in the vicinity of each producer and user plant.  On
the first day, measurements were made at several sites (usually 6 to 12)
surrounding the plant to obtain a profile of the ambient chlorinated hydro-
carbon concentrations and to identify any other emission sources in the
vicinity.  At least two grab sample measurements were made at each site over
approximately a 1-hour period.

        For subsequent monitoring, the sampling and analysis van was located
at downwind sites and measurements were made over a 20 to 24-hour period to
determine temporal and spatial variations and maximum concentration levels.
When necessary, the van was moved to attempt to remain centered in the plant
plume as well as possible.  During this sampling period, grab samples of the
ambient air were analyzed at approximately 15 to 30-minute intervals, the
sampling rate being limited by the perchloroethylene retention time.  Teflon-
bag grab samples integrated over a 15-minute collection period were taken at
upwind and crosswind sites during the period in which the van was used for
downwind measurements.  During the 2-day monitoring period at each location,
approximately 50 ambient air measurements were performed.

        At each site, two ambient air samples were collected on Tenax traps
for GC/MS confirmation of the field EC/GC measurement data.  The samples
were collected over a 1 to 2-hour period coincident with the field measure-
ments .

        Meteorological data were collected at each of the sites during the
sampling.  If a U.S. Weather Bureau Station was located nearby, data were
obtained from their records.  If not, a MRI Model 1071 portable weather
station was set up near the site to make meteorological measurements.  The
parameters recorded on an hourly basis were wind speed and direction,
temperature, barometric pressure, relative humidity, precipitation, and
general weather conditions.

        During the 2 days at each plant location, water,  sediment,  soil, and
biota samples were taken while personnel in the air sampling van monitored
the air for chlorinated hydrocarbons.  In addition, a 24-hour composite
effluent sample was obtained from plant personnel and samples were prepared
for shipment to Battelle's Columbus Laboratories for analyses.  Sampling of
each medium is described below.  The analyses of these samples are described

                                   3-1

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in subsequent sections, except for biota samples which were not analyzed
during the course of this program.
Water
        Samples taken by hand were collected approximately 2 to 5 cm below
the surface of the water.  Care was taken to avoid bubbling as the water
entered the bottle.  Samples taken with the Teflon-lined vertical sampler
were usually taken as close to the surface as possible.  In cases where the
discharge was expected to stratify in the receiving stream, different depths
in the water column were sampled at one location.

        All water samples in the receiving stream were taken on the same day
in as short a time frame as possible.  The request made to the plant personnel
for the 24-hour composite effluent sample was made for the day on which the
sampling was conducted.

        Sample bottles and the sampler were rinsed thoroughly in the water
to be collected before the samples were taken.  Samples were taken in clear
glass bottles sealed with septa and crimped metal caps.  At the sites sampled
during the initial trip, 12 samples were taken at each sampling location.
During the remainder of the program the sample size was reduced to 6 per
location; 3 samples were held on wet ice and 3 at ambient temperature.  At
all locations, 2 additional water samples were taken in 1-ounce amber bottles
and frozen on dry ice.  Samples of the 24-hour composite and a tap-water
sample were similarly prepared.
Sediment
        Whenever possible, sediment samples were taken in the same locations
at the same time as the water samples.  Sediments were collected either by
a dredge or by hand.  Upon collection, the sediment surface was placed in
the bottom of the sample jar.  The volume collected approximated a 2-inch
soil core.  Two samples were collected in glass jars at each site.  Sample
jars were immediately wrapped in foil and placed in wet ice,.then frozen as
soon as possible, usually within 8 hours.
Soil
        Six 2- inch soil cores were taken in each of the four quadrants around
the plant.  The corer was washed and rinsed with distilled water and acetone
between each location and between each soil type at one location.

        To dislodge the sample from the corer, the sampler was inverted over
a glass jar.  (Soil surface was on the bottom of the jar.)  Samples were
                                    3-2

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 immediately wrapped in foil, held on wet ice, and then frozen as soon as
 possible.

        After the initial sampling trip, the sample number was reduced to  two
 per location.
Vegetation
        Six 1-ounce-volume vegetation samples were taken at each soil and
air sampling site.  The vegetation sampled was directly associated with
(growing out of) the soil core taken.  Samples were coded with subscripts to
preserve this correlation.  The samples comprised live, whole plants except
in cases of large plants, where parts of several were clipped to provide a
more representative sample.  Samples were collected in amber bottles, placed
on wet ice, then frozen as soon as possible.  The sample size for any future
collections will be reduced to two per location.
Tissue
        In the case of both fishes and mammals, specimens were held on wet
ice until dissection and/or sample preparation was completed.  A minimum of
10 g of muscle tissue comprised each sample.  Whenever possible, the tissue
was provided by three specimens.  For fish, flank muscles were taken; for
mammals, muscle was stripped from each of the two hind legs.  For both fish
and mammals, whole livers were removed.  Liver and muscle tissues from the
same organisms were coded to preserve possible correlations.  In the case of
small organisms whose dissection would not provide sufficient sample size,
whole bodies were taken.

        Dissected tissues were placed in amber bottles; whole bodies were
placed in clear glass jars and wrapped in foil.  All tissue samples were
frozen.

        Sample size was dependent upon the availability of the organisms.
Six specimens of each species was considered maximum.
Number of Samples
        A breakdown of the numbers of samples collected from eight locations
monitored November, 1976, through January, 1977, is given below:
                                   3-3

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               Sample Type        Producer    User    Background

            Air determinations      354        45         23
            Water—clear glass      254        42         12
            Water—amber glass       58        14          4
            Sediment                 38         4          2
            Soil                    112         8          2
            Vegetation              112         8          2
            Tissue                   79         9         12
        Methods were developed for the analyses of air, water, soil, and
sediment samples; and these are described in the following section.  However,
no satisfactory method for the analyses of vegetation and tissue samples
could be developed with-in the time limits of this program.  The vegetation
and tissue samples are stored in a frozen state for possible future analyses.
                                    3-4

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                           4.  ANALYTICAL METHODS
Determination of Methylchloroform in Ambient Air
        A method for measurement of methylchloroform in air has been
developed and evaluated.  The method involves direct injection of the
ambient air into a gas chromatograph (GC) followed by detection of the
emerging compounds with an electron-capture detecter (EC).

        Equipment and Procedures—A schematic diagram of  the system used
for on-site field measurements of methylchloroform is shown in Figure 4.1.
Ambient air is continuously drawn through a stainless steel line extending
about 4.2 m above the ground and passed through a 5 cc loop attached to a
Carle 6-port sampling valve.  During sample injection, the carrier flow is
diverted through the sampling loop for 15 seconds and the 5 cc air sample
is swept onto the GC column.  An electronic timer is used to control the
injection period and automatically start the integrator at the end of
sample injection.  The integrator was used primarily to record retention
times.  The chromatograms obtained from the stripchart recorder were used
to quantify the chlorinated hydrocarbon concentrations based on peak height.

        Two EC/GC systems were used in the ambient air analysis program.
Measurements at Dow, Ethyl Corporation, Vulcan Materials, PPG, and
St. Francis National Forest (rural background) were performed with a
Varian 1200 EC/GC system.  A system using the more sensitive Analog
Technology Corporation, Model 140A, EC detector was used for measurements
at the Boeing Company plant.  The operating conditions and performance
characteristics of the two systems are given in Table 4.1.

        Primary calibration of the EC/GC systems is discussed in the following
section.  Secondary calibrations in the field were performed with a standard
TCE/nitrogen gas mixture.  The sampling system was checked regularly for
contamination by injection of the same gas (zero oxygen nitrogen)  which was
used as the carrier.  Very slight, uniform residual background levels equi-
valent to about 0.1 ppbv of methylchloroform and perchloroethylene were
obtained with the more sensitive ATC system.  Ambient air measurements made
with the system were corrected for these background considerations.   Residual
backgrounds from trichloroethylene and carbon tetrachloride were not detected.

        The gas chromatograph system was operated in Battelle's Columbus
Laboratories mobile sampling laboratory.  The laboratory is equipped with a
7.6 kw gas-powered generator to provide power for sampling and analysis in
any location accessible via a roadway.


                                    4-1

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    3.18 mm stainless steel
    sampling line ^4.2 m
    above ground level
   Carrier
  Gas Inlet
    QOQQQO
                              HP 3370A
                              Integrator
            H
Recorder
                       Gas Chromatograph
                              Sampling Valve  Operation
                            Inject                 Analyze
                           Position                Position
  Sampling
   Valve
Carle No.  2018
                   Ballast
                    Tank
Diaphragm
Sampling
  Pump
1.  5 ml sample loop
2.  Air sample inlet
3.  Sampling pump
4.  5 ml sample loop
5.  Carrier inlet
6.  Carrier to GC  column
         Figure 4.1.   Schematic of EC/GC ambient air analysis system.

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       TABLE 4.1.  OPERATING CONDITIONS AND PERFORMANCE CHARACTERISTICS
                   OF THE EC/GC SYSTEMS USED FOR AMBIENT AIR MEASUREMENTS
                   OF CHLORINATED HYDROCARBONS
                                 Varian 1200
                                    ATC-140A
Column size/material


Column material



Column temperature

Carrier gas

Carrier flow

Detector

Detector temperature

Baseline adjustment
Read-out


Air sample volume

Injection time
Typical Retention
Times, sec
  Chloroform
  Methylchloroform
  Carbon tetrachloride
  Trichloroethylene
  Perchloroethylene

Relative Detector Response
at 50 ppb, TCE =1.0
  Methylchloroform
  Carbon tetrachloride
  Trichloroethylene
  Perchloroethylene
Estimated Minimum
Detection Levels, ppbv
  Methylchloroform
  Carbon tetrachloride
  Trichloroethylene
  Perchloroethylene
3.18 mm x 305 cm, stain-
less steel

20% SP-2100/0.1% Carbo-
wax-1500 on 100-120 mesh
Supelcoport

50 C, isothermal
Matheson nitrogen,
oxygen free

^35 cc/min

EC, tritiated titanium

150 C

NA

Honeywell 193 recorder,
1.27 cm/min

5 cc

15 sec
326
424
498
633
1632
 3.9
28.5
 1.0
 4.8
 0.3
 0.05
 1.0
 0.3
 3.18 mm x 305 cm, stain-
 less steel

 20% SP-2100/0.1% Carbo-
 wax-1500 on 100-120 mesh
 Supelcoport
 55 C, isothermal

 Matheson nitrogen,
 oxygen free

 37.5 cc/min

 EC, tritiated scandium

 240 C

 275
 Honeywell 193 recorder,
 1.27 cm/min

 5 cc

 15 sec
 240
 308
 365
 462
 1124
 1.9
 8.6
 1.0
 2.0
 0.02
<0.01
 0.03
 0.02
                                        4-3

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        In addition to direct injection of ambient air, grab samples were
also collected in Teflon bags for GC analysis.  A stainless steel diaphragm
pump powered by a portable gas-powered generator was used for sample
collection.  Analysis was performed with the Varian or ATC EC/GC systems
by attaching the Teflon bag to the inlet of the sampling loop on the Carle
valve.

        Gas Chromatograph Calibration—The Varian 1200 EC/GC system was
calibrated for measurement of methylchloroform, trichloroethylene, carbon
tetrachloride, and perchloroethylene over the concentration range of 1 to
1000 ppbv.  The ATC 140A system was calibrated for the four compounds over
the concentration range of about 0.1 to 100 ppbv.  The calibrations were
performed by concurrently injecting the four compounds into the Battelle
smog chamber to produce initial concentrations of either 100 or 1000 ppbv.
Successive dilutions of' the chamber air were made to produce a series lower,
known concentrations to complete the calibration curve.  The dilution factor
for each dilution step was determined independently by following the decrease
in concentration of methane injected into the chamber with the chlorinated
hydrocarbons.  A Beckman Model 109 hydrocarbon analyzer was used for the
methane measurements.

        In calibrating the Varian GC system, a Matheson 1200 ppbv TCE
standard was compared with the chamber concentration of TCE to verify that
an initial concentration of 1000 ppbv was obtained.

        The calibration curves showing detector response for the Varian and
ATC systems are shown in Figures 4.2 and 4.3, respectively.  Each point on
the calibration curves is the average of two determinations.  Agreement
between all duplicate determinations was within 5 percent.  Both systems
exhibit excellent linearity over the concentration range encountered in the
field monitoring program.

        Field calibrations were performed to verify detector response and
retention times using a Matheson gas mixture of 1200 ppbv TCE in nitrogen.
Calibrations were performed before, after, and at 6 to 8-hour intervals
during the sampling  program at each plant.


Determination of Methylchloroform in Water
        The analytical method  selected for development is based on sparging
the methylchloroform from  the  water with an inert gas.  These compounds are
collected on a trap material and  then desorbed onto a gas chromatography
column for analysis.

        If an inert gas is bubbled through water containing organic compounds
which exhibit a low solubility in water, the compounds will be quantitatively
partitioned into the gas phase.   The enriched gas phase is then passed
through a trap that retains the organics but allows the purge gas and most
of the water to pass through.  A  large concentration factor of the volatile


                                    4-4

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 100,000
  10,000
c
o
•H
J-l
cd
c
a)
4J
4J
CO
a
o
•H
CO
•H
S
P
4-1
CO
6
   i,ooo
         Concentration vs. Peak Height
         Peak Height in Chart Divisions
         Chart Paper - 193-8"
         Chart Speed - 2 min/inch
                                        — 1— Carbon
                                          Tetrachloride
                                      Perchloroethylene
                                      Methylchloroform
                                      Trichloroethylene
     100
                             10         100
                         Concentration, ppbv
                                                   1,000
10,000
           Figure 4.2.
                        Calibration curves for chlorinated
                        hydrocarbons—Varian 1200/EC Detector
                        (Reference: Matheson 1.2 ppm TCE - 36.4
                        .divisions - Attenuation-100) .
                                  4-5

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 100,000
  10,000
   1,000
c
o
c

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 organics out of the aqueous phase is accomplished.  The trapped organics are
 then back-flushed onto a gas chromatography column or into a mass spectro-
 meter  for analysis.

        Instrumentation—A Tekmar Liquid Sample Concentrator, Model LSC-1,
 was purchased and integrated with a Packard 1700 Series gas chromatography
 instrument, as shown in Figure 4.4, which shows the purge gas entering the
 flow meter, the purge-gas-rate control valve, and passing through the water
 sample sparging tube.  The partitioned organics enter the gas phase and are
 deposited on the collection trap after passing through one path of the 6-way
 gas control valve.  During the water purging cycle, the gas-chromatography
 carrier gas enters the 6-way control valve at the desorb gas "in" location
 and passes out of the valve onto the gas chromatography column.

        The desorb mode is shown in the lower portion of Figure 4.4, with
 the 6-way control valve switched so the gas chromatography carrier gas back-
 flushes the organics onto the gas chromatography column at the same time the
 trap is heated.  The water sample purge gas valve is off during this period
 and another water sample can be sparged during the analysis of the first
 sample.

        Initial evaluation of this system was not satisfactory because of
broadening of the chromatographic peaks.  The LSC-1 was modified to replace
 the resistance heater wrapped around the trap column with direct resistance
heating of the stainless steel trap column.  A step-down transformer, coupled
with a Variac set at 50, heated the trap to 150 C in 8 seconds compared with
 the 3 minutes required for the original heater.  Other modifications included
 replacing some Teflon lines with stainless steel and heating the transfer
 line from the LSC-1 to the gas-chromatography instrument.

        Column Selection for the Gas Chromatograph—Several column materials
were evaluated for the separation of chlorinated organic compounds.  The
material selected was 20 percent SP-2100 with 0.1 percent Carbowax-1500 on
100 to 120 mesh Supelcoport.  Figure 4.5 shows a chromatogram from the vendor
literature for 11 chlorinated solvents.  The most likely interference with
methylchloroform (1,1,1-trichloroethane), peak 5, is 1,2-dichloroethane,
peak 4.

        The SP-2100 is methyl silicone.  The support material is diatomaceous
earth which has been acid washed and silane treated.  The addition of the 0.1
percent Carbowax is essential for high-quality chromatograms.  A standard
mixture containing methylchloroform, chloroform, carbon tetrachloride,
trichloroethylene, and 1,2-dichloroethane showed the latter compound to be
extremely insensitive to the electron-capture detector.

        Quantitative Analysis Using the Flame lonization Detector—The initial
quantitative evaluation of this system was done in the 50 to 500-ppb range
using a flame ionization'detector.   A 3-component standard containing methyl-
chloroform,  trichloroethylene, and perchloroethylene was prepared in water
tha.t had been demineralized and double distilled.  A 500 ppb volume per
Volume in water at ambient temperature and a 50 ppb standard were prepared.
                                   4-7

-------
           Deaorb Gas
             Out
Desorb Gas
   In
                                                                HOPfe
                                                       Trap Column 25 C
                                                           Purge Gas
                                                              Irt
      Decorb Gas + Sample•
             Out
Deaorb Gas
    Zn
                                                         BEStiRB. MODE

                                                      trap Cdlumri 125°C
                                     Sampler
Flow-
iheter
                                                           Purge Gas
                                                              in
  Figure 4*4.   Schematic of  a liquid sample concentrator.
                                  4-8

-------
                    1. Methylene chloride
                    2. 1,1-dichloroethane
                    3. Chloroform
                    4. 1,2-dichloroethane
                    5. 1,1,1-trichloroethane
                    6. Carbon tetrachloride
                    7 - Trichloroethylene
                    8. 1,1,2-trichloroethane
                    9. Perchloroethylene
                   10. 1,1,1,2-tetrachloroethane
                   11. 1,1,2,2-tetrachloroethane
                           10
Figure 4.5.  Chromatogram of chlorinated solvents,
                     4-9

-------
        Instrumental conditions used for analysis of this standard were as
follows:

             Liquid Sample Concentrator

                  Sample size - 5 cc standard water solution
                  Purge gas rate - nitrogen at 40 cc/min for 10 min
                  Degas temperature - 150 C reached in 10 sec
                  Trap material - Tenax plus silica gel

             Gas Chromatography Conditions

                  Column - 10 ft x 1/8-in stainless steel packed
                           with 20 percent SP 2100/0.1% Carbowax
                           1500 on 100 to 120-mesh Supelcoport
                  Temperatures - Column - 55 C
                                 Detector - 150 C
                                 Injection - 140 C
                  Gas flows - Nitrogen carrier - 30 ml/min
                              Hydrogen - 30 ml/min
                              Air - 300 ml/min
                  Electrometer - 1 x 10"10 amp, 500 volts.

The recording system was a HP 3380A integrator which prints retention time
directly above each peak, and then records the total counts for each peak,
based on the total area under the peak.  The area percentage for each peak
recorded in the right-hand column is not significant in this work because
it is based on percentage of total area and we do not know the sensitivity
factor or the identification of other peaks appearing in the chromatograms.

        A reproduction of t"he actual chromatograms is shown in Figures 4.6
and 4.7.  Both chromatograms show some impurities which are caused by the
dilution water and/or impurities in the compounds added to the water.  The
methylchloroform has a retention time of 3.44 to 3.36 minutes and the tri-
chloroethylene 4.99 and 5.01 minutes for Figures 4.6 and 4.7, respectively.
The integrator counts representing the area under these peaks were as follows;

                    Compound          500 ppb      50 ppb

               Methylchloroform        624,861      62,092
               Trichloroethylene     1,121,598     122,636

The linearity from 50 to 500 ppb using the flame ionization detector is
excellent for these two compounds.  The degas temperature for the 50 ppb
chromatogram did not reach 150 C and this probably explains why the per-
chloroethylene was not linear.  The x values directly above the retention-
time values are the attenuation factors used to keep the peaks on scale.
Since both compounds were attenuated times 8 and a 5 ml sample was used, it
would appear that a sensitivity of about 500 ppt could be reached with a
20-ml sample using the FID detector, provided purer water is used for the
standards.  The 50 ppb methylchloroform and trichloroethylene represents
                                    4-10

-------
                                                                  X64
                                                12. 27
                                               XI6
                                                PCE
   'STOP
    RT
  2. 63
  3. 44
  '4. 99'
  8. 52
 12. 27
                           flREfl 5i
TYPE
 T
 TM
   RRER
  137973
_ 624861.
 ii21598
          82634
         893973
  4. 824
 21. 85__
'39. 21 _
  2. "867
 31. 25
HP 3330R
DLV   1.
MV/M  1. 08
        STOP 38
        RTTN     16
                   REJECT  OFF
        Figure 4.6.
           Chromatogram showing 500 ppb  each  of
           methylchloroform  (3.44 minutes),
           trichloroethylene  (4.99 minutes),  and
           perchloroethylene  (12.27 minutes)  using
           FID detector.
                             4-11

-------
         INJ
                             3. 26  X8  MC

                                     5. 01
                                                                     X2
                                                               ft  fifi
                                 12. 41
                           X2   PCE
    •STOP
                           RRER  '/.

1.
1.
2.
3.
5.
8
12.
RT
35
65
65
36
01
66
41
TYPE

M

M



fiRER
181478
139296
146339
62092
122636
966^5
14751

23.
18.
1-9
8.
16.
12 .
1.

77
26
18
134
©"g "••-••" '
66
932
HP 3380R
DLV   1.
MV/M  3. 0Q
STOP  30
RTTN
REJECT OFF
         Figure  4.7.
     Chromatogram showing 50 ppb each of
     methylchloroform (3.36 minutes),
     trichloroethylene (5.01) minutes), and
     perchlo-roethylene (12.41 minutes) using
     FID detector.
                               4-12

-------
 50  x  10~9 ml/ml of water or  68 and  73 ng/ml of water, respectively.   Figure
 4.8 shows the FID calibration curve.

        Quantitative Analysis Using the Electron Capture Detector—The
 instrumental settings  for  the liquid-sample concentrator and  the gas
 chromatography were the same as described above except  for  the  detector
 power source and the air and hydrogen required for  the  operation of the
 flame.  The electron-capture-detector electrometer  settings were 1 x  10~10 i
 and 25 V.

        Preparation of standards required special treatment of  the dilution
 water.  All distilled  and  demineralized water supplies  checked  contained
 methylchloroform and trichloroethylene, including a.demineralized and
 double-distilled supply.   Untreated well water was  lowest in  these com-
 pounds but had a high  iron content; therefore, the  well water was not used
 for dilutions.  The integrator counts representing  total impurities in the
 various waters checked are shown in Table 4.2.  The Ohio State  University
 demineralized and double-distilled  water was sparged with nitrogen while
 being boiled for 3 hours,  which reduced the methylchloroform  and trichloro-
 ethylene to undetectable amounts; therefore, this water was used to prepare
 standards.
                 TABLE 4.2.  VOLATILE IMPURITIES IN WATERS
                 Source of Water                          Impurity Counts

     City Products Corp., storeroom supply                   10,160,000
     Tap water, City of Columbus, Ohio                        8,910,000
     Biology Department, glass still                          5,792,000
     Deionized water, analytical section                        810,000
     Ohio State University, double distilled                    317,000
     Ohio State University, sparged with nitrogen               217,000
     Olentangy River, 5th Ave. and King Ave. north of dam       211,000
     Ohio State University, boiled and sparged with N£           15,825
     Well water, untreated, Fairfield County                      3,203a
     a
      All values were determined by concentrating 5 ml of water except
      this well water; 20 ml was concentrated with a total impurity count
      of 12,812; therefore, one-fourth this amount was reported above.
        Standards containing methylchloroform and trichloroethylene at a
concentration of 500, 100, and 50 ppt were prepared in the special dilution
water using the electron-cap.ture detector.  The calibration curves for these

                                   4-13

-------
       100     200     300     400
               Concentration, ppb
500
Figure 4.8.  Calibration curves for the determina-
             tion of trichloroethylene and methyl-
             chloroform using the FID detector.
                  4-14

-------
 runs are shown in Figure 4.9.  The sensitivity for methylchloroform is much
 greater than that for trichloroethylene, which is reversed with the flame
 ionization detector.  The 500 and 100 ppt standards were analyzed by sparg-
 ing 5 ml of the standard, and the 50 ppt standard was analyzed using 20 ml.
 The 50 ppt concentration is equivalent to 67.5 pg/ml of water for methyl-
 chloroform and 73.3 pg/ml for trichloroethylene.

        These calibration curves were not used in the analysis of samples
 since the HP 3380A integrator is a dedicated computer which retains data
 input on a standard sample and the amount of a compound per area can be
 listed for each standard peak in the chromatogram.  If the amount per area
 shows a sudden change under the same operating conditions, this would
 indicate operation beyond the linearity range of the detector, a poor
 standard or that some other instrument trouble exists.  A sample run is
 automatically computed from the standardization data retained by the computer.
 A multiplication factor to adjust for sample size or amount of dilution can
 be added to the stored data at the time each sample is injected.  The
 electron-capture detector was used for all sample analyses with a maximum
 standard concentration of 50 ppb.  If the first run on a sample indicated
 that the concentration was much higher than 50 ppb, the sample was diluted
 to bring it into range or minor adjustment was made by reducing the quantity
 of sample.  A 5-ppb standard was generally used for low concentrations and
 up to 20 ml of sample.

        The initial objective was to obtain chlorinated hydrocarbons through
 perchloroethylene without use of our program temperature facilities; however,
 as shown in Figure 4.6, the resolution would not be adequate to elute per-
 chloroethylene in 13 minutes with methylchloroform, carbon tetrachloride, and
 other possible impurities in industrial waters.  The flow and temperature
were reduced slightly to provide a retention time of about 13 minutes for
 trichloroethylene as shown in Figure 4.10.  The relative concentrations of
 carbon tetrachloride in the samples were not as high as shown in Figure 4.10;
 therefore, many samples were analyzed with the trichloroethylene retention
 time set at 10 minutes.

        Preparation of Standards—Standards are prepared from the specially
 prepared water described earlier.  A 1-liter volumetric flask is filled with
 the special water and a hypodermic syringe is used to inject a known quantity
 of the compounds.  The flasks are placed on a shaker for 16 hours (overnight)
 and this forms the base standards which are diluted to lower concentrations.
 Base standards containing 5 Vg/H of water (5 ppm) and 2 yg/£ of water have
been rediluted and analyzed on the electron-capture detector.   Good agreement
was obtained that would indicate that the measurements of these small
 quantities were reproducible and also that these quantities were completely
 soluble in 1 liter of water.  The base standards and diluted standards were
protected from light at all times.   The base standards were used for 2 to 3
weeks before any concentration deterioration was noted, but the diluted
standards were made fresh daily.

        Precision and Accuracy—The precision of the method was tested using
10 determinations of a standard containing 50 ppb by volume of both
                                   4-15

-------
   24
   20
   16
o
o
o
-*-1'  i o
cd  12
)-i
oc
cu
     0
100
200     300     400
Concentration,  ppt
500
       Figure 4.9,
        Calibration curves for the determi-
        nation of trichloroethylene and
        methyicnloroform using the electron
        capture detector.
                      4-16

-------
        INJ
                                                2. 21
                                              9  52
                   Retention Time,
                      minutes

                        6.02
                        7.97
                        9.52
                       13.21
                         Compounds

                         Chloroform
                         Methylchloroform
                         Carbon tetrachloride
                         Trichloroethylene
Figure 4.10.
Chromatogram of several chlorinated hydrocarbons
using the electron-capture detector after
completion of development work.
                              4-17

-------
methylchloroform and trichloroethylene.  The following precision data were
obtained:

                              Methylchloroform   Trichloroethylene

             Average                49.75              50.29
             Sigma  (a)               1.65               1.68
             Coefficient of          3.3                3.4
               variation

Five of the above analyses were made on different  standards and the  other
five on the same standard.  Two different  operators were involved.

        Since no primary standards  exist for this  type work or no cross-
laboratory analyses among several laboratories have been performed to our
knowledge, the absolute accuracy is not known.

        Water Sample Data to be Presented—In addition to the concentration
of trichloroethylene and methylchloroform  in each  sample, the following
information is given:

                 (1)  Date sampled

                 (2)  Data analyzed

                 (3)  Amount of sediment in the sample

                 (4)  Sparging characteristics

                 (5)  Rough quantitative values fbr chloroform
                     and carbon tetrachloride

                 (6)  Comments which indicate which samples
                     are composites, tap waters, or required
                     unusually high sample dilutions, and
                     other miscellaneous remarks.

         The sediment in  the samples was classified as C=clear, IXLight,
M=medium,  and H=heavy.   The sediment concentrations were judged before
shaking  the samples prior to analysis.  If no particles had settled  on
the bottom, they were  classified as clear; any observable particles  on
the bottom were  noted  as light; if  the bottom was  nearly covered, it was
classified as medium;  and if the bottom was entirely covered, this was
considered heavy.   The samples classified  as heavy contained only a  very
thin coating on  the bottom.  Some of these sediments appeared to be  a
gelatin-like substance.

         The column  headed "sparging foam"  indicates the degree of foam
generated while  sparging the compounds from the water samples.  These are
designated as ND=none  detected, L=light, M=medium, and H=heavy.  Blank
areas  indicate that we made no observation.  None  of the samples produced


                                    4-18

-------
sufficient foam to cause trouble with carry-over to the collection trap;
however, many of the samples were diluted before analysis, which would
reduce foaming.

        The results reported for chloroform and carbon tetrachloride were
obtained by analyzing a standard mixture containing these two compounds
plus the methylchloroform and trichloroethylene.  Sensitivity ratios were
calculated based on trichloroethylene as 1 and this permitted a rough
quantitative estimation of these compounds.
Determination of Methylchloroform in Soil and Sediment
        Methylchloroform is expected to be present in soil and sediment
samples at levels of the order of 10" * to 103 ppb by weight.  The analysis
technique must, therefore, be capable of detecting 10"1 to 10~2 ng of each
substance in reasonably sized samples of 0.1 to 1.0 g.  Furthermore, a high
level of specificity is required to avoid interferences from the many other
organic substances commonly present in soil and sediment samples.

        Electron-capture gas chromatography (EC/GC) is ideally suited to
detection of these volatile chlorinated hydrocarbons because of its very
specific response to electrophilic substances at the required concentration
levels.  However, before EC/GC can be applied to such samples, the tri-
chloroethylene and methylchloroform must be extracted to a phase suitable
for injection into the chromatograph.  Either gaseous or liquid samples can
be handled by the chromatograph.  The three methods used for these types of
samples therefore involve a preliminary conversion of the methylchloroform
sorbates to either gaseous or solution forms.

        Extraction Methods—Basically three different methods for methyl-
chloroform extraction have been considered:

        (1)  Thermal desorption—A sample of soil is heated while
             being purged by a stream of nitrogen.  The eluted
             methylchloroform is trapped on Tenax or other suit-
             able sorbents and then injected into the chromato-
             graph by flash heating of the trap.

        (2)  Liquid extraction—The methylchloroform is solvent
             extracted using acetone and/or hexane.  The resulting
             solution can then be injected directly into the
             chromatograph.

        (3)  Aqueous sparging—Inasmuch as methylchloroform has
             low solubility in water, this substance can be used
             to disperse soil and sediment samples to render them
             susceptible to purging by nitrogen.  The effluent
             methylchloroform is then handled much the same as
             with the thermal desorption method.
                                    4-19

-------
        Method (1) has been shown to be useful for analysis of trichloro-
ethylene and certain other chlorinated hydrocarbons in dry or only slightly
wet samples.  However, the excessive amounts of water likely to be present
with sediment samples render this approach difficult at best.  Furthermore,
it has been shown that certain chlorinated hydrocarbons, such as chloroform
and methylchloroform, are not recovered efficiently by this method.  Indeed,
results with some model soils suggest that methylchloroform is chemisorbed
and can be recovered only as vinylidene chloride by this method.

        Method (2) is efficient and satisfactory providing care is taken to
minimize sample losses during the extraction and subsequent concentration
steps of the procedure.   (If aliquots of solution are analyzed, the
sensitivity of the method is reduced.)

        Method (3) also suffers from poor recovery of methylchloroform that
is chemisorbed in the soil surface.  However,  this procedure more closely
imitates the probable mechanism for mobilization of methylchloroform and
trichloroethylene in the  environment.  Furthermore, Method (3) is an "on-
line" procedure with little or no chance for either losses or gains of
methylchloroform and trichloroethylene due to  exposure of the sample to
laboratory air.  The method is equally applicable to wet and dry samples.
The results of its application reflect the availability of methylchloroform
and trichloroethylene to  the environment rather than total methylchloroform
and trichloroethylene exposure.

        Apparatus—A schematic representation  of the apparatus used for
sparging of soil samples  is shown in Figure 4.11.  In use, presparged water
(3 to 4 cc) is loaded into the fritted glass vessel, the soil sample injectdr
is mounted, and the sparger is attached to the sample trap valve.  The sample
side of the system is then flushed with zero nitrogen until a suitable blank
reading for methylchloroform and trichloroethylene is obtained.  Usually,
this is possible within about 10 minutes or less; but flushing is continued
for approximately the 30  minutes required for  the blank analysis.  The soil
sample is then injected into the water and the effluent trichloroethylene
and methylchloroform are  trapped on Tenax maintained at room temperature.
During sparging of the soil-water mixture, the sample is agitated by
immersion in an ultrasonic bath.  This serves  to rapidly disperse the soil
and facilitate sparging.  Sparging periods of  10 minutes at 30 to 40 cc/min
are sufficient.  Following the sparging period, the by-pass around the
sparger is opened to permit flushing of the water vapor from the Tenax trap.
A flushing period of 5 to 6 minutes is sufficient to remove the water vapor
without removing trichloroethylene or methylchloroform from the Tenax.  The
trap valve is then switched to permit flushing by the zero-nitrogen GC
carrier gas and the trap  is heated rapidly (at ^500 C/min) to 190 C to
inject the methylchloroform and trichloroethylene into the chromatograph.

        The soil or sediment injector is constructed as a syringe-like
device with its open end  capped by a tight-fitting Teflon plug.  The injector
is weighed and then used  to core the analysis  sample directly from the bulk
as-received sample.  Reweighing and capping of the injector are done rapidly
to minimize contact with  the laboratory air.   The injector is then kept closed


                                    4-20

-------
.p-
fo
I-1
                             By-Pass
Heated Section
                   Zero
              Fritted Sparger
              with Soil Injector
                                                                           EC/GC
Tenax Trap
                            Ultrasonic Bath
                                                                                       Standard
                                                                                          THE
                                        i
                                                                                       Zero N2
                                                                                       Carrier
                       Figure 4.11.  Schematic of soil and sediment analysis apparatus,

-------
until injection of the soil into the sparger, at which time both the soil
and Teflon plug are manually ejected.

        The chromatograph is a Varian 1200 equipped with a Ti(H3) detector.
The column is a 1/8-inch by 10-foot stainless steel column packed with
SP-2100 (GP 20 percent SP-2100/1 percent Carbowax-1500 on 100-120 mesh
Supelcoport).  Output signals are quantified using an Infotronics Model CRS
204 integrator coupled to a TTY output.

        Standardization is accomplished using a precalibrated gas standard
of TCE in nitrogen.  Approximately 4-ng samples of trichloroethylene are
usually used for standardization.  Such samples yield peak areas on the
order of lO4 uv/sec, and peaks on the order of 102 to 103 yv/sec can be
separated from the inherent background noise.  Comparative calibrations with
methylchlorofonn and trichloroethylene indicate a relative response of 3.36
for MC/TCE at equal concentrations.  The response curve of the detector is
not perfectly linear but rather varies with c1'05 in the concentration range
of interest.  A sample chroiflatogram showing response obtained with one
sediment sample is shown in Figure 4.12.

        Quality of Results—There are several points thajt must be recognized
in discussion of the significance of the results of trichloroethylene and
methylchloroform analyses on soil and sediment samples.  Ideally, standardi-
zation should be performed using well-characterized standards of trichloro-
ethylene and methylchloroform on substrates that closely simulate those of
subject samples, and these standards should be traceable to primary standards
established by independently certified means.  Such standards are not
available for methylchloroform and trichloroethylene in soils and sediments,
nor is it possible to reliably prepare such standards because of the inherent
instability of this type of specimen.  Because of the general stability of
trichloroethylene in a nonoxidizing atmosphere, we have chosen to use
trichloroethylene in nitrogen as the reference standard for the current work.
Analysis of the standard was made by the manufacturer and has been cross-
checked with samples of the same concentration prepared by injection of liquid
samples into the Battelle smog chamber.  The standard being used appears to
be accurate to within a few percent.

        A second infringement on the quality of the results is related to the
basic heterogeneity of the samples.  Any soil sample is likely to be a
composite of various organic and inorganic structures, e.g., sand particles,
clays, organic residues, plant fragments, etc.  Such local heterogeneity is
likely to be reflected in appreciable local gradients in the distribution of
methylchloroform and trichloroethylene.  These local-gradient tendencies are
likely to be superimposed on the natural vertical and horizontal gradients
that are caused by temporal and spatial variation in the flux of methyl-
chloroform or trichloroethylene to a given sample area.  Because of the
limited size of the analytical sample, the results must therefore be consi-' •-
dered as point analyses rather than as representative analyses.  This situa-
tion is magnified further with the sediment samples.  With sediments, the
fraction of the sample that is present as a liquid phase is much larger than-
with the soil samples.  Results can vary considerably thereby reflecting the
partitioning of methylchloroform and trichloroethylene between the solid and
liquid phases.
                                   4-22

-------
                                          Materials Belong To:
                                          GJ'i'T Library
                                          401 M Strrei, S\V (TS-7S3)
                                          Washiiijton, DC  -JO460
                                        Sample
                                        (atten. = 50)
                                 Blank  (atten.  = 10)
Figure 4.12.   Sample chromatogram for sediment.
                        4-23

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                             5.  MONITORING DATA

        The sampling rationale, sampling protocol, and analytical methods
have been described.  The results are presented as a series of maps and
tables which describe the locations, the nature of the samples, and the
concentrations of methylchloroform in the samples.  A separate set of data
is presented for each site.
Production Sites Monitored
        For each methylchloroform production site a map is presented with
sampling points indicated (Figures 5.1 to 5.4).  The results from the
analysis of the samples and detailed descriptions of the sampling locations
are presented (Tables 5.1 to 5.12).
User Site Monitored
        The data obtained at a methylchloroform user site are presented
in Figure 5.5 and Tables 5.13 to 5.15.
Background Site Monitored
        The data obtained at St. Francis National Forest near Helena,
Arkansas, are presented in Tables 5.16 to 5.18.  This site represents a
rural background site "and is removed from known sources of methylchloroform
and major industrial activity (see Figure 5.6).
Discussion of Results
        The ambient air concentration profiles around all facilities
monitored are characterized by increased concentrations of methylchloroform
in the downwind direction from the source.  Upwind measurements, which
showed significantly lower methylchloroform concentrations, do not give any
evidence of other methylchloroform sources which would contribute to the
observed downwind levels.
                                   5-1

-------
        Considerable variation was observed  in  the maximum  downwind  levels
of methylchloroform at the various production plants.  Maximum concentra-
tions ranged from 12 to 155 ppbv at  the methylchloroform production
facilities.  The variations in the observed  maximum  concentrations among
plants may be due to differences in  (1) production processes,  (2) ejnission
control equipment, (3) meteorological  conditions, and  (4) distance from
plant.  Higher production capacity apparently does not necessarily imply
higher emissions since the maximum concentrations observed  at  the larger
plants were lower than those  observed  at the smaller operations.

        Very large temporal variations were  generally  observed at a  given
site downwind from the methylchloroform production facilities.  Changes in
meteorological conditions  (wind speed  and  direction) and/or variations in
the process emissions may account for  this phenomenon.   Less temporal
variation was noted in the ambient air concentrations  downwind from  the
methylchloroform solvent cleaning facility.  Due to  the  nature of solvent
cleaning operations, more uniform emission rates might be expected.  In
addition, meterological conditions  (essentially no wind) during much of
the sampling period reduced dispersion of  the plume.

        Duplicate analyses on some of  the  soil  samples suggest that  sample
heterogeneity may contribute  30 to 50  percent deviation  in  the reported
values for individual analyses.  It  is interesting to .note  that both soil
and sediment samples from  the background site display  methylchloroform
content equal to or greater than many  of the plant-site  samples.  However,
if it is assumed that a true  average background level ,can be obtained  'by
averaging all results equal to or less than  the background-site levels,
there still remains a number  of samples containing significantly more
methylchloroform than the background.

        The highest levels of methylchloroform  are generally associated
with sediment samples.  Chromatograms  of these  high-roo:ncentration-.ley,el
samples also show the presence of appreciable quantities 
-------
        However, the trichloroethylene content of the water was nearly an
order of magnitude smaller in the water than in the bulk sample.  While
these experiments are not conclusive, they suggest that the trichloroethylene
was truly associated with the solid phase and that the observed methylchloro-
form was primarily associated with the liquid phase.  In other words, if
there is any methylchloroform absorbed on the solid phase of these samples,
it is present in a form that is not readily mobilized.
                                 5-3

-------
 MONITORING DATA




PRODUCTION SITE 1
         5-4

-------
Oi

Ul
   	  Residential
«r 0  Emission Source
       Highway
       Railroad
       Plant Proper
       Industrial
       Marsh
       Air Site
  •    Soil Site
  A    Water Site
  *    Sediment Site

  Mile
                                                                      0     .51
                                                                         Kilometer
                   Figure 5.1.   Sampling locations at Dow Chemical  Plant A,  Freeport,
                                 Texas—methylchloroform production  site.

-------
           TABLE 5.1  AMBIENT AIR MEASUREMENTS AT DOW CHEMICAL PLANT A (METHYLCHLOROFORM PRODUCER)
Ul
Distance
from
Site Plant,
No. km
1A 2.6

2A 1.9



3A 3.2

4A 2.1

5A 0.8



6A 1.9

7A 2.6



'
8A 2.6





10A 3*2



Direction
from
Plant,
degrees3
300

285



265

225

120



010

080




260





350



Meteorological Observations0
Date
1976. Time
11/8 0940
1020
11/8 1055
1110
11/9 1536
11/10 1346
11/8 1140
1155
11/8 1330
1345
11/8 1420
1433
11/9 1614
11/10 1420
11/8 1610
1625
11/8 1523
1535
11/9 1450
1746
11/10 1309
11/8 1712
1738
1745
1758
1812
1825
11/9 0924
0940
1015
1030
Concentration in
Ambient Air, ppbv^
MG
2.3
£0.3
£0.3
1.1
0.7
0.5
1.2
£0.3
£(K 3
£0.3
£0.3
£0.3
0.6
0.7
£0.3
£0.3
£0.3
£0.3
1.1
0.8
0.7
£0.3
0.8
£0.3
2.2
0.8
0.4
£0.3
£0.3
£0.3
^0.3
CClfy
0.30
0.25
1.4
2.1
0.15
0.15
0.60
1.1
0.15
0.15
0.15
0.15
0.15
0.14
0.14
0.15
0.15
0.16
0.14
0.14
0.13
0.19
0.24
0.18
0.58
0.38
0.22
0.22
0.17
0.14
0.54
TGE
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
PCE
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Wind
Speed,
m/s
5-10
5-10
5-9
5-9
4-7
6-7
5-9
5-9
4-7
4-7
4-7
4-7
4-7
6-7
3-7
3-7
4-7
4-7
5-8
2-4
5
3-9
3-9
3-9
4-5
4-5
4-5
2-4
2-4
2-4
2-4
Wind
Direction,
degreesa
080
080
080
080
180
155
080
080
080
080
080
080
-180
155
065
065
080
080
185
165
155
075
075
075
070
070
070
150
150
150
150
Temper-
ature, RH, Barometer,
C % mm Hg
17
17
18
18
24
24
19
19
21
21
21
21
24
24
21
21
21
21
24
23
23
20
20
20
19
19
19
21
21
21
21
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
772
772
772
772
764
761
771
771
770
770
769
769
764
761
769
769
769
769
764
763
761
769
769
769
769
769 *
769
767
767
767
767

-------
TABLE 5.1. (Continued)
Distance Direction
from from
Site Plant, Plant, Date
No. km degrees3 1976 Time
10A 3.2 350 11/9 1900
(Cont) 1915
2200
11/10 1430
1445
1500
12A 2.6 005 11/9 1155
1210
1220
1235
1250
1305
1320
1335
1350
1405
1420
1450
1505
1630
1645
1755
2300
2315
2330
2345
2400
11/10 0020
0035
0050
0105
Meteorological Observations0
Concentration in
Ambient Air, ppbv^
MC
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
7.6
6.2
5.8
4.2
9.4
0.9
4.2
1.5
—
1.4
2.2
2.4
£0.3
£0.3
0.7
£0.3
7.2
6.5
9.8
3.0
9.8
2.2
11.5
6.5
7.6
CC14
0.25
0.22
0.22
—
0.15
0.15
0.27
0.48
0.27
0.21
0.58
0.16
0.50
0.18
0.48
0.23
0.28
0.31
0.26
0.16
0.27
0.15
0.94
2.4
3.3
1.2
3.8
0.48
1.8
1.3
3.4
TCE
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
*1
PCE
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Wind
Speed,
m/s
3-5
3-5
3-4
6
6
6
4-6
4-6
4-6
3-6
3-6
3-6
3-6
4-7
4-7
4-7
4-7
5-8
5-8
3-5
3-5
2-4
2-3
2-3
2-3
2-3
2-3
2-3
1-2
1-2
1-2
Wind
Direction,
degrees3
165
165
170
150
150
160
180
180
180
185
185
185
185
180
180
180
180
185
185
175
175
165
170
170
170
185
185
185
170
170
170
Temper-
ature, RH, Barometer,
C % mm Hg
22
22
21
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
24
24
24
23
21
21
21
21
21
21
21
21
21
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
763
763
763
761
761
761
765
765
765
764
764
764
764
764
764
764
764
764
764
763
763
763
763
763
763
763
763
763
763
763
763

-------
                                            TABLE 5.1.  (Continued)
00
Distance
from
Site Plant,
No. km
12A 2.6

























13A 5.1

14A 7.8

Direction
from
Plant, Date
degrees3 1976 Time
005 11/10 0120
0135
0150
0210
0225
0245
0315
0345
0415
0445
0515
0545
0615
0645
0715
0745
0815
0845
0915
0945
1015
1045
1115
1145
1215
1245
34.5 11/10 1630
1645
355 11/10 1700
1715
Meteorological Observations0
Concentration in
Ambient Air, ppbv^
MC
1.1
£0.3
£0.3
£0.3
£0.3
1.4
£0.3
2.2
2.6
1.1
1.8
0.7
£0.3






£0 . 3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
0.5
£0.3
£0.3
CC14
1.2
0.33
0.58
0.84
0.18
0.84
0.14
0.14
0.14
0.10
0.14
0.14
0.10






0.14
0.14
0.18
0.14
0.14
0.14
0.14
0.11
0.10
0.13
0.15
TCE
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1






£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
PCE
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND






ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Wind
Speed,
m/s
1-2
2
2
2
2
2
2
2
2
2-3
2-3
2
2
2-3
2-3
2-3
2-3
4-5
4-5
2-5
2-5
4-6
4-6
4
4
4
2-5
2-5
2-5
2-5
Wind
Direction,
degrees3
170
160
160
160
160
155
155
• 170
170
155
155
140
140
120
120
110
110
155
155
155
155
165
165
165
165
165
155
155
155
155
Temper-
ature, RH,
C %
21
21
21
21
21
21
21
21
21
21
21
21
21






22
22
23
23
23
23
23
22
22
22
22
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND






ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Barometer,
mm Hg
763
763
763
763
763
763
763 '
762
762
762
762
762
762






763
763
763
763
763
762
762
761
761
761
761

-------
    FOOTNOTES FOR TABLE 5.1
Ui

VO
                - 360°.
         •L                  q
          To convert to )ig/m  at 25 C multiply ppbv by
               MC      5.46
               CC14 — 6.29
               TCE  — 5.37.
         Q
          General weather conditions:
               11/18/76 Clear, sunny, no precipitation
               11/9/76 Clear, sunny, no precipitation
               11/10/76 Slightly cloudy in morning, clearing in
                 afternoon, no precipitation.

          ND = not determined.

-------
                       TABLE 5.2.   ANALYSIS OF WATER,  SOIL,  AND SEDIMENT SAMPLES FROM

                                   DOW CHEMICAL PLANT A (METHYLCHLOROFORM PRODUCER)3
K
o
Sample
No.
Date
Sampled
Date
Analyzed
Sediment Sparging Concentration, ppb by
in Sample Foam
MC
TCE CHC13
weight
CC14
Comments
Water
A-l
A-2
A-5
A-6
A-7
A-8
A- 9
1


Sample
No.
A-2
A-4
A-7
A-12
11/9/76
11/9/76
11/9/76
11/9/76
11/9/76
11/10/76
11/13/76
11/12/76

Sample
Weight,
g
0.166
0.141
0.155
0.628
11/23/76
11/28/76
11/23/76
11/23/76
11/17/76
11/19/76
11/30/76
12/1/76
Soil
Water
Content ,
%
11.4
7.8
21.3
20.5
Clear
Light
Heavy
Heavy
Heavy
Medium
Clear
Light

Light
Light
Light
Light
ND
Medium
ND
Medium

117
119
0
1
0
12
17
35

Concentration,
ppbb
MC
0.20
NDC
ND
0.68

TCE
ND
NDC
0.22
0.045
Sample
No.
A-l-S
A-5-S
A-7-S

126
122
.8 5
13
.1 0
2
19
76

Sample
Weight ,
g
0.616
0.240
0.244

82
25
1
3
.9 1
' 2
<0.1
12
Sediment
Water
Content ,
%
71.3
46.8
49.0

116
32
5
7
0.3
0.3
<0.1
24

Surface
Bottom
Surface
Bottom
Surface
Surface
Tap water
Composite

Concentration ,
ppt
MC
6.1
0.34
0.31

>b
TCE
0.21
ND
0.036

      Notes:  ND = none detected.

        for description of terms.



      Dry basis, ppb by weight.
See "Determination of Methylchloroform in Water"
     "Practical detection limits:   MC = 6 pg;  TCE = 10 pg.

-------
          TABLE 5.3.  DESCRIPTIONS OF SAMPLING LOCATIONS AT DOW CHEMICAL PLANT A,
                      FREEPORT, TEXAS (NOVEMBER 9-12, 1976)
                                        WATER

(Water sample sites Al, A2, A5, A6, and A7 are not shown on the map,  Figure 2.32.   These sites are
  upstream, west of the boundaries of this map, and are upstream and  downstream of the location
  where the canal from Dow Chemical Plant A discharges into the Brazos River.)

Al - Surface sample, effluent canal from Plant A taken approximately  10 meters  upstream in canal
     from confluence with Brazos River—moderate current, turbid.

A2 - Bottom sample (approximately 2-1/2 meters deep)—same location as Al.

A5 - Surface sample, 400 meters downstream of plant outfalls in Brazos River—taken in center of
     channel—30 meters wide, 5-6 meters deep—swift current, turbid.

A6 - Bottom sample, same location as A5--taken 4 meters deep.

A7 - Surface sample, 800 meters upstream from plant outfalls in Brazos River—30 meters wide, 5-6
     meters deep—steep banks bounded by recreational areas—swift current, turbid.

A8 - Shoreline surface sample in East Union Bayou—corresponds to air sampling site 12A—bayou bound-
     ed by dredge spoils—40 meters wide—moderate current, clean.

A9 - Tap water from Lake Jackson, Holiday Inn, Freeport, Texas.

1    One 24-hour composite effluent sample collected November 11-12,  1976.

                                      SEDIMENT

A1S - Effluent canal from Plant A, 10 meters upstream in canal from confluence with Brazos River—
      light tan, compacted sheet-like clay.

-------
                               TABLE 5.3.  (Continued)
                                      SEDIMENT

ASS - 400 meters downstream of plant outfalls in Brazos River—fine textured,  dark loam.

A7S - 800 meters upstream plant Outfalls in Brazos River—brown,  fine textured silt/clay.

                                        SOIL

A2 - Northeast of Freeport, south of turning basin on flood control levee—corresponds to air samp-
     ling site 2A—light industrial and commercial area—dredge spoil/gumbo—hard sand/silt over
     hard, compact clay.

A4 - 400 meters east of Phillips petroleum plant—corresponds to air sampling site 4A—sand/shell
     spoil and root-bound sandy silt.

A7 - Overgrown vacant lot 200 meters south of Shrimp Hut in Surfside—residential area on Gulf—
     fine sand, some roots.

A12 —250 meters south off Route 332 near East Union Bayou—corresponds to air sampling site 12A—
     open dredge spoil area—fine sand eroded from spoil piles and roadway, some roots.

-------
 MONITORING DATA




PRODUCTION SITE 2
     5-13

-------
                                                       Enrission Sourc
                                                         Highway
                                                         Plant Proper
                                                         Residential
                                                         Air Site
                                                         Soil Site
                                                         Water Site
                                                         Sediment  Site
Figure 5.2.
Sampling locations at Vulcan Materials Company,
Geismar, Louisiana—methylchloroform production
site.
                                5-14

-------
             TABLE 5.4.   AMBIENT AIR MEASUREMENTS AT VULCAN MATERIALS (METHYLCHLOROFORM PRODUCER)
Ui

M
Ui
Distance Direction
from from
Site Plant, Plant, Date
No. kma degrees** 1976 Time
1 0.4 090 12/2 0950
1015
1040
1135
1150
2025
2055
12/3 0005
0032
0101
Ol29
0156
0225
0252
0320
0348
0415
0443
0511
0539
0606
0634
0702
0734
0802
1035
2 0.3 010 12/2 1215
1230
2115
2145
12/3 1030
Meteorological
Concentration in
Ambient Air, ppbvc
MC
£0.3
£0.3
£0.3
£0.3
£0.3
2.0
0.8
1.2
2.5
0.8
1.6
18
3.8
8.8
5.0
17
16
8.8
7.0
6.7
3.5
2.7
2.4
2.2
1.6
0.6
£0.3
£0.3
2.7
7.0
140
CC14
0.
0.
0.
0.
0.
5.
3.
23
18
8.
8.
20
11
14
8.
15
15
8.
7.
6.
4.
4.
5.
4.
3.
6.
0.
0.
24
42
30
22
17
73
7
7


0
0



0


2
6
8
6
8
3
3
5
3
20
17

TCE
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
20 ^1
22

sl
Wind
Speed,
PCE
£0
£0
£0
<0
£0
0
£0
1
1
0
0
7
1
3
1
2
2
3
1
1
0
0
0
0
£0
0
£0
£0
1
2
2
.3
.3
.3
.3
.3
.8
.3
.1
.1
.5
.8
.2
.1
.0
.4
.3
.3
.6
.9
.0
.8
.8
.5
.5
.3
.5
.3
.3
.5
.3
.3
m/s
5
5
5
4
4
0
0
0
0
0
0
1
1
0
0
0
0
1
1
0
0
1
1
2
2
1
4
4
0
0
1
Observations^
Wind Temper-
Direction, ature, RH, Barometer,
degrees3 C % mm Hg
320
320
340
360
360
—
—
—
—
—
—
010
010
—
—
—
—
070
070
—
—
060
060
060
060
060
260
260
—
—
060
12
12
12
13
13
4
4
1
1
1
-
0
0
0
0
-1
-1
1
1
1
1
2
2
2
2
14
13
13
3
3
14
51
51
52
50
50
71
71
84
84
84
84
84
84
86
86
88
88
88
88
89
89
90
90
90
90
63
50
50 '
76
76
63
765
765
765
765
765
764
764
764
764
764
764
764
764
764
764
764
764
764
764
764
764
764
764
764
764
764
765
765
764
764
764

-------
                                            TABLE 5.4.  (Continued)
Ul
i
Distance Direction
from from
Site Plant, Plant, Date
No. kma degrees13 1976 Time
2 0.3 010 12/3 1057
1150
1220
1330
1357
1425
1453
1520
1545
3 0.3 230 12/2 1252
1303
12/3 0928
1000
4 0,4 150 12/2 1330
1355
1425
1451
1520
5 0.6 3.40 12/2 1555
1625
6 0.6 120 12/2 1645
1720
1745
1815
1845
1910
7 0,4 045 12/2 2215
2240
2310
2335
Meteorological Observations^
Concentration in
Ambient Air, ppbvc
MC
77
31
9.2
5.6
£0.3
27
1.2
92
140
£0.3
£0.3
^0.3
£0.3
£0.3
75
8.6
41
8,8
155
5.5
11
14
4.2
3.8
1.4
1.2
4.0
1,4
2,7
1,4
CC14
8,8
6.4
3.4
1.7
0.18
4.5
4.1
10
12
0.20
0,20
4.2
0.88
0,73
10
2.2
68
1
10
0.28
11
10
3.6
7,0
10
6.3
10
5.9
52
50
TCE
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
*l
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
PCE
3.6
<0.3
—
1.1
*0.3
1.1
0.6
2.3
4.2
0.3
0.3
0.3
0.3
0.3
23
7.5
2.0
19
7
0,3
4.3
6.2
0.8
0.5
0.3*
0.3
2.3
3.6
6.7
3.6
Wind
Speed,
m/s
1
4
4
2
2
2
3
3
3
4
4
4
4
3
3
4
4
4
4
4
3
3
0
0
0
0
0
0
0
0
Wind
Direction,
degrees3
060
140
140
290
180
180
170
170
190
260
260
100
100
290
290
360
360
360
280
280
.280
280
__
—
—
—
—
00
. —
—
Temper-
ature, KH, Barometer,
C % mm Hg
14
15
15
14
13
13
18
18
18
13
13
13
13
14
14
14
14
14
15
15
14
14
9
9
6
6
3
3
1
1
63
63
63
62
62
62
38e
38e
46e
51
51
60
60
52
52
53
53
53
54
54
54
54
58
58
64
64
78
78
80
80
764
764
764
763
762
762
762
762
762
764
764
764
764
764
764
764
764
764
764
764
766
766
764
764
764
764
764
764
764
764

-------
                                         TABLE 5.4. (Continued)
Distance
from
Site Plant,
No. km a
8 0.3

9 3

Direction
from
Plant , Date
degreesb 1976 Time
190 12/3 0835
0902
1252
030 12/3 1615
1645
Meteorological Observations d
Concentration in
Ambient Air, ppbv°
MC
0.8
£0.3
£0.3
0.5
£0.3
cci4
6.7
1.4
0.23
1.2
0.7
TCE
£1
£1
£1
£1
£1
PCE
1.0
£0.3
£0.3
£0.3
£0.3
Wind
Speed.
m/s
3
3
2
3
3
Wind
Direction,
degrees3
110
110
290
150
150
Temper-
ature, RH,
C %
10
10
17
18
18
82
82
58
46
46
Barometer,
mm Hg
764
764
763
762
762
Ul
I
 Distance and direction estimated scaled map unavailable.

bNorth - 360°.
c                  3
 To convert to pg/m  at 25 C multiply ppbv by  MC   — 5.46
                                               CC14 — 6.29
                                               TCE  — 5.37
                                               PCE  — 6.78.
d
 General weather conditions:  12/2/76 Partly cloudy in morning becoming clear about
                                        1600 hours, no precipitation
                              12/3/76 Clear, sunny, no precipitation.
Q
 Possible malfunction of RH instrument.

-------
                   TABLE 5.5.  ANALYSIS OF WATER, SOIL, AND SEDIMENT SAMPLES  FROM
                               VULCAN MATERIALS PLANT  (METHYLCHLOROFORM PRODUCER)3

Sample Date
No . Sampled
Date
Analyzed
Sediment Spargj
in Sample Foai
Lng Concentration^ ppb by
a MC
IT*/"ITO OTJf^l **
ICrli L.nL.J.3
weight

CC14 Comments
Water





V
K-"
gp




E-l 12/2/76
E-2 12/2/76
E-3 12/2/76
E-4 12/2/76
E-5 12/2/76


Sample
Sample Weight,
No. g
E-6 0.298
E-7 0.304
12/30/76
12/28/76
12/27/76
12/29/76
12/29/76
Soil

Water
Content ,
%
26.3
20.4
Light
Light
Light ,.
Medium
Clear


ND

Heavy
ND


2
344
169
3,314
16,500


Concentration ,
ppbb
MC
0.45
0 . 94

TCE
0.62
0.18
Sample
No.
E-l-S
E-3-S



4,


Sample
Weight
8
0.209
0.255
5 6
74 394
24 ' 226
360 152
300 31,675
Sediment

Water
, Content,
%
54.3
27.7
2
193
92


629 Diluted 1-KLOO
9,060 Composite


Concentration,
ppbb
MC TCE
0.13 0.25
2.6 3.2
1+500







Tifotes:  ND = none detected.  See "-Determination of Methylchleroform in Water1'
   for description of terms.

 Dry basis, ppb by weight.

-------
                 TABLE 5.6.  DESCRIPTIONS OF SAMPLING LOCATIONS AT VULCAN MATERIALS,
                             GEISMAR, LOUISIANA (DECEMBER 2, 1976)
                                       WATER
El- Surface sample taken from bank of Mississippi River 30 meters  upstream from plant outfall—
      area used for barge mooring—moderate current, turbid.

E 2 - Surface sample taken at end of submerged outfall pipe in Mississippi River—effluent dis-
      charged subsurface—moderate current, turbid.

E 3 - Surface sample from bank of Mississippi River 75 meters downstream from plant outfall—barge
      moored within 20 meters of sampling point—moderate current,  turbid.

E 4 - Roadside ditch 60 meters north of Vulcan office (1 meter wide, 1-3 centimeters deep)—ditch
      received runoff from heavily trafficked road.

E 5 - Twenty-four-hour composite effluent sample from inside plant.

                                     SEDIMENT
E1S - Shoreline sample in Mississippi River 30 meters upstream from plant outfall—gray-black silt/
      sand, oil texture.

ESS - Shoreline sample in Mississippi River 75 meters downstream from plant outfall—gray-black silt/
      sand, oily texture.

                                       SOIL
E 6 - 100 meters east of Vulcan office—road cut in front of plant—sandy soil.

E 7 - 200 meters south of plant—strip between service road and railroad--sandy silt,  little humus
      or roots.

-------
 MONITORING DATA




PRODUCTION SITE 3
          5-20

-------
Ul
NJ
t-1
Emission Source
Highway
Railroad
Plant Proper
Industrial
Residential
Air Site
Soil Site
Water Site
Sediment Site
    Mile
     1/2
                                                                            Kilometer
                 Figure 5.3.   Sampling locations at Ethyl Corporation, Baton  Rouge,
                               Louisiana—methylchloroform production site.

-------
                TABLE 5.7.   AMBIENT AIR MEASUREMENTS AT ETHYL CORPORATION (METHYLCHLOROFORM PRODUCER)
Ui
I
to
Ni
Distance Direction
from from
Site Plant, Plant, Date
No. km degreesa 1976 Time
1 0.4 240 11/18 0815
0845
2 0.2 195 11/18 0915
0945
11/19 0300
1014
1100
1200
3 2.4 150 11/18 1015
1730
1800
1930
2000
2030
2100
2130
2200
2230
2300
2330
2400
11/19 0030
0100
0130
0200
0545
0615
0700
0730
0800
0830
Meteorological Observations0
Concentration in
Ambient Air, ppbv^
MC
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
0.6
1.1
1.0
1.5
1.0
—
2.2
3.9
0.6
1.5
0.9
0.9
1.6
£0.3
£0.3
£0.3
£0.3
£0.3
0.5
cci4
7.3
1.9
0.80
4.8
1.1
2.4
47
0.90
0.15
0.16
0.12
0.12
0.13
0.15
0.15
0.21
0.33
0.26
—
0.52
0.50
2.7
1.9
1.3
0.9
0.33
0.37
0.32
0.26
0.26
0.22
TCE
5.6
1.9
£1
£1
£1
5.4
7.2
2.4
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
PCE
5.2
1.6
0.7
3.2
£0.3
5.1
37
8.5
£0.3
£0.3
£0.3
0.5
0.6
0.6
0.6
1.0
1.0
0.8
0.6
0.4
0.4
0.5
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
Wind
Speed,
m/s
4
4
4
4
3
4
4
4
4
0
0
2
2
0
0
0
0
0
0
0
1
0
0
0
1
2
2
4
4
3
3
Wind
Direction,
degrees3
020
020
060
060
120
030
060
030
060
'360
360
360
360
360
360
360
360
360
360
360
140
360
360
360
120
090
090
060
070
060
060
Temper- RH, %
ature , (Free . , Barometer ,
C cm) mm Hg
14
14
16
16
12
11
11
11
18
17
17
17
17
16
16
16
16
16
16
16
14
14
14
12
12
12
12
10
10
11
11
NDd
ND
ND
ND
(trace)
(trace)
(0.1)
(0.4)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(0.02)
ND
(0.02)
(0.02)
ND
.(0.02)
ND
(trace)
ND
761
761
761
761
758
758
758
758
761
759
759
759
759
759
759
759
759
759
759
759
759
759
759
759
758
759
759
758
758
758
758

-------
                                             TABLE 5.7  (Continued)
w
Distance Direction
from from
•Site Plant, Plant,
No . km degrees3
3 2.4 150


4 2.6 180

5 2.2 095

6 0.7 010





7 2.2 330
8 3.2 240



Meteorological
Date
1976
11/19


11/18

11/18

11/18

11/19



11/18
11/18

11/19

Concentration in
Ambient Air, ppbv^
Time
0900
0930
1000
1055
1125
1155
1225
1255
1355
0345
0415
0445
0515
1445
1545
1615
1300
1330
MC
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
SQ.3
SQ. 3
SQ.3
SQ. 3
SQ. 3
£0.3
£0.3
£0.3
SQ.3
cci4
0.21
0.19
0.18
0.12
0.12
0.11
0.17
0.85
0.36
0.38
1.3
0.18
0.43
0.16
0.14
0.13
0.67
0.17
TCE
^
^1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
PCE
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
0.5
0.4
£0.3
0.6
£0.3
£0.3
SQ. 3
£0.3
£0.3
£0.3
SQ.3
Wind
Speed ?
m/s
4
4
4
2
2
1
1
1
2
2
2
1
1
0
2
2
4
4
Wind
Direction,
degrees3
060
060
030
020
020
070
070
240
340
350
350
340
340
360
080
080
040
040
Observations0
Temper- ^ %
ature, (Free., Barometer,
C cm) mm Hg
11
11
11
18
18
18
18
19
19
12
12
12
12
18
18
18
11
11
(trace)
ND
(trace)
ND
ND
ND
ND
ND
ND
(trace)
ND
(0.07)
ND
ND
ND
ND
(0.7)
ND
758
758
758
761
761
761
761
761
761
758
758
758
758
761
761
761
757
757
            -  360°.
     b                   3
     To  convert  to  yg/m at  25 C multiply ppbv by MC
     "General weather  conditions:
                                             — 5.46
                                        CC14 — 6.29
                                        TCE  — 5.37
                                        PCE  -- 6.78.
                        11/18/76 Clear in morning becoming cloudy about 1400 hours with light
                                   intermittent rain beginning about 2200 hours
                        11/19/76 Cloudy all day, intermittent rain throughout the day.
      ND
not determined.

-------
                        TABLE 5.8.   ANALYSIS  OF WATER,  SOIL,  AND SEDIMENT SAMPLES FROM

                                    ETHYL CORPORATION (METHYLCHLOROFORM PRODUCER)3
I
NJ
Sample
No.

C-l
C-2
C-3
C-8
C-9


Sample
No.
C-4
C-5
C-6
C-7
Date
Sampled

11/18/76
11/18/76
11/18/76
11/18/76
11/19/76

Sample
Weight ,
g
0.246
0.261
0.274
0.192
Date
Analyzed

12/22/76
12/22/76
12/21/76
12/22/76
12/22/76
Soil
Water
Content ,
%
26.3
20.5
27.5
17.3
Sediment Sparging Concentration, ppb by
in Sample Foam MC
Water
Light ND 74
Heavy Heavy 0 .
Heavy Heavy 20
Clear Light 10
Clear ND 0 .
* t
Concentration,
ppb^ Sample
MC TCE No.
0.20 NDC C-2-S
0.25 ND C-3-S
0 . 13 ND
0.28 ND
TCE CHC13

128 105
4 0.4 6
37 37
10 32
05 0.4 2
Sediment
Sample Water
Weight, Content,
g %
1.07 27.2
0.330 77.5


weight
CC14

67
0.1
23
12
0.2

Comments


Surface
Surface
Composite
Tap water

Concentration ,
ppb
MC
0.81
ND


b
TCE
ND
116


     "Notes:   ND =  none  detected.

        for description  of  terms.


     b
     Dry basis,  ppb  by  weight.
See "Determination of Methylchloroform in Water"
     "Practical detection limits:  MC  =  6  pg;  TCE  =  10 pg.

-------
                    TABLE 5.9.   DESCRIPTIONS  OF SAMPLING LOCATIONS  AT ETHYL CORPORATION,
                                  BATON ROUGE,  LOUISIANA (NOVEMBER 18-19,  1976)
                                                    WATER
               Cl  - Effluent sample taken immediately above the settling pond weir to receiving bayou—strong aro-
                   matic odors—light blue-green color, very slippery feel.

               C2  - Surface sample taken in receiving bayou 200 meters upstream from plant outfall  (7 meters wide,
                   0.5-1.5 meters deep)—moderate current; anaerobic odor; black murky color with oil slick and
                   tar globules on surface (bayou flows through heavily industrialized area  and under railroad
                   tracks).

               C3  - Surface sample taken in receiving bayou 300 meters downstream from plant  outfall (7 meters
                   wide, 1-2 meters deep)—moderate flow; water quality appearance same as at C2 with additional
                   slippery feel.

 I              C8  - 24-hour composite effluent sample—6:00 a.m. November 18 to 6:00 a.m. November  19, 1976.
KJ                             »

-------
 MONITORING DATA




PRODUCTION SITE 4
         5-26

-------
Ul
10
                                                             Emission Source
                                                             Highway
                                                             Railroad
                                                             Industrial
                                                             Plant Proper
                                                             Residential
                                                             Marsh
                                                             Tailings Pond
                                                             Air Site
                                                             Soil Site
                                                             Water  Site
                                                             Sediment Site
Figure 5.4.   Sampling locations at PPG Industries, Lake Charles,
              Louisiana—methylchloroform production site.

-------
            TABLE 5.10.   AMBIENT AIR MEASUREMENTS AT PPG INDUSTRIES (METHYLCHLOROFORM PRODUCER)
Cn

NJ
00
Distance Direction
from from
Site Plant, Plant, Date
No. km degrees3 1976 Time
1 1.3 215 12/6 1014
1043
2 4.2 140 12/6 1123
1152
3 3.5 1 85 12/6 1302
1330
12/7 0900
4 2.7 40 12/7 1512
1540
5 1.4 195 12/6 2100
2129
2157
2226
2254
6 4.0 150 12/6 2331
2400
12/7 0028
0056
0125
0153
0222
0249
0317
0345
0413
0441
0509
0537
0605
0633
0701
Meteorological Observations0
Concentration in Wind
Ambient Air, ppbv^ Speed,
MC
1.
0.
£0.
£0.
£0.
SO.
0.
0.
SO.
SO.
SO.
SO.
SO.
SO.
SO.
sO.
SO.
0.
1.
SO.
SO.
1.
5.
8.
0.
so.
6.
SO.
1.
1.
1.
3
8
3
3
3
3
7
5
3
3
3
3
3
3
3
3
3
4
7
3
3
5
0
5
7
3
5
3
4
2
4
cci4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.24
.17
.13
.19
.13
.20
.24
.21
.17
.18
.15
.15
.17
.20
.17
.31
.28
.20
.88
.19
.20
.64
.21
.31
.19
.20
.92
.15
.17
.26
.17
TCE
2.7
2.2
si
Si
si
si
si
si
si
si
si
si
si
si
si
si
si
si
15
si
si
6.6
si
2.2
si
si
12
si
si
si
si
PCE
0.4
0.3
SO. 3
SO. 3
SO. 3
SO. 3
0.4
SO. 3
SO. 3
SO. 3
so. 3
SO. 3
so. 3
SO. 3
SO. 3
SO. 3
SO. 3
SO. 3
3.8
0.4
£0.3
2.5
SO. 3
0.7
^0.3
£0.3
5.0
£0.3
^0.3
£0.3
£0.3
m/s
8
8
7
7
9
9
7
7
7
10
10
10
9
9
7
7
6
6
6
7
7
6
6
7
7
7
7
6
6
7
7
Wind
Direction,
degrees3
150
150
160
160
160
160
340
330
330
360
•360
350
350
350
350
350
360
360
360
360
360
340
340
340
340
340
340
350
350
350
350
Temper-
ature, RH, Barometer,
C % mm Hg
15
15
17
17
17
17
6
8
8
14
14
12
12
12
12
12
12
12
12
11
11
9
9
8
8
7
7
6
6
6
6
87
87
90
90
87
87
76
60
60
80
80
80
77
77
76
76
74
74
74
80
80
80
80
80
80
79
79
79
79
79
79
755
755
754
754
753
753
759
760
760
756 -
756
756
756
756
756
756
756
756
756
757
757
757
757
757
757
758
758
758
758
758
758

-------
                                           TABLE 5.10.  (Continued)
Ul
i
N>
IO
Distance
from
Site Plant,
No. km
6 4.0













7 0.6
8 1.3
Direction
from
Plant, Date
degreesa 1976 Time
150 12/7 0727
0755
0823
0855
0958
1015
1030
1045
1100
1205
1232
1259
1328
1358
360 12/7 1030
265 12/7 1052
Meteorological Observations0
Concentration in Wind
Ambient Air, ppbv^ Speed,

2
5
5
£0
£0
£0
£0
£0
£0
2
£0
5
2
£0
£0
0
MC
.6
.0
.3
.3
.3
.3
.3
.3
.3
.4
.3
.0
.1
.3
.3
.4
cci4
0.65
0.96
0.73
0.20
0.15
0.15
0.13
0.15
0.23
0.40
0.20
0.64
0.26
0.20
0.21
0.75
TCE
5.8
8.0
5.8
£l
£l
£l
£l
£l
£l
4.6
£l
7.0
4.6
£l
£l
£l
PCE
2.9
3.2
3.2
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
1.8
£0.3
£0.3
£0.3
£0.3
£0.3
0.4
m/s
7
6
6
7
8
8
7
7
7
6
7
7
6
6
7
7
Wind
Direction,
'degrees a
350
350
350
340
320
320
320
320
320
320
340
340
340
340
320
320
Temper-
ature,
C
6
6
6
6
5
5
5
5
5
6
6
6
7
7
6.7
6.7
RH, Barometer,
% mm Hg
79
76
76
76
76
76
73
73
73
73
70
70
68
68
73
73
758
758
758
759
759
759
760
760
760
760
760
760
760
760
760
760
    aNorth - 360°.
    |_                  O
     To convert to  g/m  at 25 C multiply ppbv by  MC   — 5.46
                                                   CC14 — 6.29
                                                   TCE  — 5.37
                                                   PCE  — 6.78.

    °General weather conditions:  12/6/76 Cloudy, rainfall recorded  from  1000  to  2100 hours,
                                            very heavy at times
                                  12/7/76 Cloudy with very slight  clearing  in  late  afternoon,
                                            no precipitation.

-------
                  TABLE 5.11.   ANALYSIS OF WATER,  SOIL, AND SEDIMENT SAMPLES FROM
                               PPG INDUSTRIES (METHYLCHLOROFORM PRODUCER)3

Sample
No.
Date
Sampled
Date
Analyzed
Sediment Sparj
in Sample Fo<
?ing Concentration, ppb by
im MC
TCE CHC13
weight
CC14 Comments
Water







Ul
i
UJ
o





F-l'
F-2
F-3
F-4
F-5
F-10



Sample
No.
F-6
F-7
F-8
F-9
12/7/76
12/7/76
12/7/76
12/7/76
12/7/76
12/7/76


Sample
Weight,
g
0.337
0.286
0.232
0.782
1/5/77
vim
vim
1/6/77
1/4/77
12/13/76
Soil

Water
Content ,
%
12.2
22.5
19.6
28.3
Heavy
Heavy
Heavy
Heavy
Heavy
Clear
* «

Concentration,
ppbb
MC TCE
0.14 0.11
1.0 NDC
0.61 0.077
0.22 ND
132
181
58
161
5
0



Sample
No.
F-l-S
F-2-S
F-3-S
F-4-S
353
447
179
403
29
.3 0.


Sample
Weight,
g
0.263
— d
0.265
..d
11
85
30
34
12
1 <0.1
Sediment

Water
Content ,
%
72.6

71.0

29
40
12
38
<0.1
<0.1 Tap water


Concentr at ion ,
ppbb
MC TCE
2.2 146

1.1 15

 Notes:  ND - none detected.   See "Determination of Methylchloroform in Water"
   for description of terms.

 Dry basis, ppb by weight.

Practical detection limits:   MC - 6 pg;  TCE = 10 pg.

 Samples damaged in shipping  (including duplicates).

-------
                    TABLE 5.12.  DESCRIPTIONS OF SAMPLING LOCATIONS AT PPG INDUSTRIES,
                                 LAKE CHARLES, LOUISIANA (DECEMBER 7, 1976)
                                            WATER

    Fl - Surface sample 50 meters upstream from plant outfall in Bayqu d'lnde (10 meters wide, 2.5 -3
         meters deep)—slow current; high conductivity (>8000 microohms/cm);  dark colored, turbid.

    F2 - Surface sample—confluence of northernmost PPG effluent canal in Bayou d'lnde--5 meters wide,
         1 meter deep.

    F3 - Surface sample—confluence of southernmost PPG effluent canal in Bayou d'lnde—200 meters below
         confluence of first canal (F2); 5 meters wide, 1 meter deep.

    F4 - Surface sample—50 meters downstream of southernmost PPG effluent canal (F3) in Bayou d'lnde—
         10 meters wide, 2-3 meters deep.

Y1   F5 - Surface sample taken at mouth of Calcasieu River in Prien Lake, downstream of PPG outfall.
CO
H
    F10 - Top water taken from the Sheraton Motel, Lake Charles, Louisiana.

                                          SEDIMENT

    FlS - 50 meters upstream from plant outfall in Bayou d'lnde—black ooze.

    F2S - Confluence of northernmost PPG effluent canal in Bayou d'lnde—black, oily ooze.

    F3S - Confluence of southernmost PPG effluent canal in Bayou d'lnde—black, oily ooze.

    F4S - 50 meters downstream of southernmost PPG effluent canal (F3) in Bayou d'lnde—black, oily ooze.

                                            SOIL

    F6 - Lake  Shore Drive near Port of Lake Charles—residential area—sand/clay roadfill.

    F7 - 1210  drainage ditch 400 meters north of bridge over Prien Lake—ditch composed of both  concrete
         and sandy clay.

-------
MONITORING DATA




  USER SITE
           5-32

-------
                                                  Emission Source
                                                  Highway
                                                  Railroad
                                                  Industrial
                                                 Plant Proper

                                                 Residential
                                                 Air Site
                                                 Soil Site
                                                 Water Site
                                                 Sediment Site
  0     .5      1
    Kilometer
Figure 5.5  Sampling locations at Boeing Company,  Auburn,
            Washington-~methylchloroform user  site.
                          5-33

-------
          TABLE  5.13.  AMBIENT AIR MEASUREMENTS AT  BOEING COMPANY,  AUBURN PLANT (METHYLCHLOROFORM USER)
Ul
I
U3
Distance Direction
from from
Site Plant, Plant, Date
No. km degrees3 1977
1 0.7 335 1/10



1/11



2 0.6 125 1/10

3 0.9 165 1/10

1/11
1



4 1.1 280 1/10

1/11


5 0.9 005 1/10
6 0.4 050 ;L/1L

7 1.2 215 1/11





Meteorological Observations0
Concentration in Wind Wind
Ambient Air, ppbv*5 Speed, Direction,
Time
1330
1350
1410
1925
0750
0810
0900
1630
1455
1515
1542
1602
1006
1027
1655
1715
1735
1630
1655
1550
1610
1825
1945
0.9Z3.
0943
1120
1140
1200
1220
1240
1325
MC
10.
4.
6.
0.
3.
5.
2.
1.
0.
0.
0.
0.
2.
3.
4.
4.
5.
0.
0.
6.
5.
5.
0.
0
6
8
8
8
0
0
6
4
5
4
,4
3
0
5
9
0
6
6
2
2
2
9
0-6
2.
6.
7.
7.
7.
6.
7.
3
9
3
3
4
9
3
CC14
0.11
0.10
0.11
0.11
0.09
0.06
0.09
0.10
0.11
0.13
0.13
0.13
0.10
0.07
0.10
0.11
0.11
0.14
0.13
0.11
0.11
0.14
0.15
0..09.
0.13
0.09
0.09
0.08
0.10
0.10
0.10
TCE
0.38
0.15.
0.15
0.14
0.64
0.64
0.26
0.26
0.34
0.14
0.14
0.14
1.8
0.92
0.83
0.80
0.90
0.14
0.14
0.90
0.76
0.92
0.18
GUIS
0.30
0.80
0.84
0.76
1.0
1.0
1.0
PCE
0.29
0.18
0.29
0.29
0.20
0.25
0.69
0.69
0.08
0.11
0.06
0.06
0.98
1.4
0.60
0.66
0.66
0.08
0.11
0.94
0.94
0.69
0.42
0.65
0.76
0.90
0.73
0.69
0.73
0.78
0.82
m/s
0.8
0.8
1.4
	 d
d
d
"d
0.6
1.4

1.2
1.2
0.6
0.6
0.6
0.6
0.5
0.7
0.7
0.5
0.5
__ d
— d
— d
— d
	 d
	 	 n
0
0.5
0.5
— d
degrees3
180
180
180
— d
— d
— d
— d
150
180

180
180
50
50
150
150
150
150
150
210
210
— d
— d
	 d
Q
Q^
— d
Q_
360
360
— d
Temper-
ature, RH, Barometer,
C % mm Hg
-1
-1
0
-1
-1
0
0
3
0

-2
-2
1
1
3
3
2
2
2
3
3
2
1
-1
-1
1
1
1
2
2
2
86
86
86
88
92
92
92
93
86

87
87
92
92
93
93
93
87

94
94
94
88
92
92
92
92
92 f
93
93
93
761
761
761
761
758
758
758
754
760

761

757
757
753
753
753
761

754
754
753
761
758
758
757
757
757
757
757
757

-------
                                           TABLE  5.13.  (Continued)
i
uj
Ul
Site
No.
7
8
9
>
10

Distance Direction
from from
Plant, Plant,
km degrees3
1.2
2.0
2.9

1.1

215
210
200

255

Meteorological Observations0
Date
1977
1/11
1/11
1/11

1/11

Concentration in Wind
Ambient Air, ppbv^ Speed,
Time
1805
1345
1405
1430
1450
1510
1530
MC
4.8
7.8
8.4
4.4
4.0
7.0
8.1
CC14
0.10
0.10
0.09
0.11
0.11
0.10
0.10
TCE
0.80
1.0
1.1
0.82
0.78
1.2
1.1
PCE
0.66
0.90
1.0
0.69
0.65
0.97
1.0
m/s
__d
__d
0.6
0.6
0.5
0.5
. Wind
Direction,
degrees3
__d
	 d
180
180
210
210
Temper-
ature, RH,
\J 10
2
2
2
3
3
3
3
93
93
93
93
93
93
93
Barometer,
mm Hg
753
756
756
756
756
756
756
       - 360°.
•L.               O
 To convert ug/m  to ppbv multiply by MC   — 5.46
                                      CC14 — 6.29
                                      TCE  — 5.37
                                      PCE  — 6.78.

°General weather conditions:  1/10/77 Heavy overcast of fog; no precipitation
                              1/11/77 Heavy overcast of clouds, fog; light rain from 0600 to 1500 hours.

 vfind speed below starting threshold of 0.75 mph for MRI 1071 weather station.

-------
                  TABLE 5.14.  ANALYSIS OF WATER, SOIL, AND SEDIMENT SAMPLES FROM

                               BOEING COMPANY, AUBURN PLANT (METHYLCHLOROFORM USER)3
Sample
No.

J-2
J-3
J-4
J-5
J-6
J-10



Sample
No.
J-l
J-7
J-8
J-9
Date
Sampled

1/11/77
1/11/77
1/11/77
1/11/77
1/11/77
1/12/77


Sample
Weight ,
g
0.258
0.238
-T-C
	 c
Date
Analyzed

2/8/77
2/8/77
2/8/77
2/8/77
2/8/77
2/8/77
Soil

Water
Content ,
%
33.3
32.6


Sediment Sparging Concentration, ppb by
in Sample Form MC TCE CHC13

Light
Light
Light
Light
Light
Light



ND
ND
ND
ND
ND
ND

•*•»
Concentration ,
PP
MC
0.40
0.65


bb
TCE
0.33
0.43


Water
18 30 4
12 17 7
6 82
6 5 0.4
18 26 8
26 44 24
Sediment

Sample Water
Sample Weight, Content,
No, g %
J-4-S 0.694 28.2
J-5-S 0.805 28.8


weight
CC14

<0.1
0.6
0.2
0.2
0,4
1.0


Comments






5-hr composite


Concentration ,
PI
MC
0.039
NDd


)b0
TCE
0.42
ND


 Notes:  ND = none detected.   See "Determination of Methylehloroform in Water"

   for description of terms.


b
 Dry basis, ppb by weight,

c
 Sample primarily roots and peat moss—-could not be run as soil sample.



 Practical detection limits:   MC = 6 pg;  TCE = 10 pg.

-------
        TABLE  5.15.   DESCRIPTIONS OF  SAMPLING LOCATIONS  AT  BOEING  COMPANY,
                         AUBURN,  WASHINGTON  (JANUARY 10-12,  1977)
	^	

                                       WATER

J2  -Surface sample—Boeing outfall from settling pond—taken as effluent spilled from concrete cul-
     vert—water clear, warm, smelled of chlorine, slippery to  touch.

J3  -Surface sample 1 meter upstream in outfall canal to Stuck  River 3 kilometers downstream of plant
     outfall (1 meter wide, 0.5 meter deep)—clear, moderate current.

J4  -Surface sample 100 meters downstream from plant outfall in Stuck River  (50 meters wide, 0.5-1
     meter deep)—swift current, turbid, very cold, ice cover near  shore; receives runoff from land-
     moving operation near banks.

J5  -Surface sample 30 meters upstream from plant outfall in Stuck  River (40 meters wide, 0.5-1
     meter deep)—turbid, very cold, ice cover near bank, swift current.

J6  -Surface sample—Boeing outfall canal 1.5 kilometers downstream from plant outfall—residential
     area; 3-4 meters wide; 0.5 meter deep; taken below bridge; clear, moderate current.

J10 - 5-hour composite effluent sample—undiluted—first 5 hours of  8-hour discharge.

                                     SEDIMENT

J4S  - 100 meters downstream from plant outfall in Stuck River—compact, fine sand.

J5S  - 30 meters upstream from plant outfall in Stuck River—compact,  fine  sand.

                                        SOIL

Jl  - dead end road northwest  of plant—corresponds  to air sampling  site 4;  overgrown vacant lot at
     side of road—20 meters  north of intersection, light to moderate traffic—root-bound sandy clay.

J7  - 0.5 kilometers southwest of southern plant guard gate—corresponds generally to air sampling
     site 3—taken 10 meters  east  off moderately  trafficked blacktop road—wet,  sandy clay.

 J8   -Ditch paralleling railroad tracks  on  northwest corner  of  plant property,  50 meters from plant
      fence—corresponds  to air sampling site  1—loam.

 J9   -Ditch between C  Street and railroad tracks  east  of plant, 30-40 meters from plant fence—peri-
      odically  heavy  train and auto traffic—corresponds to  air sampling site 6—loose textured,  root-
      bound  loam.

-------
MONITORING DATA




BACKGROUND SITE
       5-38

-------
Figure 5.6.
Sampling locations at St. Francis National Forest,
Helena, Arkansas—background site.
                               5-39

-------
          TABLE 5.16.  AMBIENT AIR MEASUREMENTS AT ST. FRANCIS NATIONAL FOREST (RURAL BACKGROUND)
Ul
I
Concentration in
Ambient Air, ppbva Wind Speed,
Date Time
11/30/76 1030
1055
1125
1146
1216
1243
1308
1334
1400
1426
1452
1517
1545
1611
1636
1700
1730
1800
1825
1850
1917
1955
2022
MC
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
£0.3
CC14
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
15
15
13
14
15
12
11
14
14
13
15
14
15
14
14
15
15
14
15
14
14
15
15
TCE
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
£1
PCE
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
£0.
3
3
3
3
3
3
3
3
3
3
3
3 .
3
3
3
3
3
3
3
3
3
3
3
m/s
1
1
1
2
2
3
3
3
3
3
4
.„ 4
3
3
2
2
2
2
2
2
2
4
4
Meteorological Observations0
Wind Direction,
degreesb
170
170
170
210
210
230
230
225
225
225
220
220
160
160
165
165
165
165
165
160
160
170
170
Temperature, RH,
C %
3
3
3
5
5
4
4
5
5
4
4
' 4
4
4
2
2
1
1
1
1
1
2
2
41
41
41
38
38
39
39
42
42
44
44
44
49
49
58
58
66
66
66
70
70
73
73
Barometer,
mm Hg
761
761
761
760
760
760
760
759
759
759
759
759
759
759
759
759
759
759
759
759
759
758
758
      a                  3
       To convert to pg/m  at 25 C multiply ppbv by MC -- 5.46;  CC14 — 6.29;  TCE — 5.37;  PCE — 6.78.

      bNorth - 360°.

      c
       General weather conditions: Clear, sunny, no precipitation.

-------
                     TABLE 5.17.  ANALYSIS OF WATER, SOIL, AND SEDIMENT SAMPLES FROM

                                  THE BACKGROUND SITEa
Ul
I
Sample
No.
D-l
D-3
Sample
No.
D-2
D-2
Date
Sampled
11/30/76
11/30/76
Sample
Weight ,
g
0.200
0.641
Date
Analyzed
12/20/76
12/14/76
Soil
Water
Content,
25.8
24.3
Sediment Sparging Concentration, ppb by weight
in Sample Foam MC
Water
Clear ND 0 .
Clear ND 0.
Concentration,
ppbb Sample
MC TCE No .
0.54 0.63 D-l-S
0.29 <0.42C D-l-S
TCE CHC13
4 <0.
4 22
Sample
Weight,
g
0.198
0.115
05 2
3
Sediment
Water
Content ,
45.0
54.0
CC1A
Comments
0.2
<0.1 Tap water
Concentration,
ppbb
MC
0.67
0.23
TCE
2.2
NDd
     Notes:   ND = none detected.  See "Determination of Methylchloroform in Water"

       for description of terms.


     Dry basis, ppb by weight.

    c
     Possible interference present.


     Practical detection limits:   MC =  6 pg;  TCE = 10 pg.

-------
TABLE 5.18.  DESCRIPTIONS OF SAMPLING LOCATIONS AT STORM CREEK LAKE,
             ST.  FRANCIS NATIONAL FOREST,  HELENA, ARKANSAS (NOVEMBER
             30,  1976)
                                WATER
 Dl - Surface sample taken from concrete boat dock on Storm Creek Lake
      100 meters south of parking lot—little wave action; clear.

 D3 - Top water taken from the Holiday Inn, Helena, Arkansas.

                              SEDIMENT
 DlS - Taken from boat dock on Storm Creek Lake 100 meters south of
       parking lot—mud and sand with cover of light leaf litter; snail
       and mussel shells abundant.

                                SOIL
 D2 - west-facing slope north of boat ramp 75 meters west-southwest of
      parking lot—sandy humus with decomposing leaf litter and many
      roots—dense undergrowth of honeysuckle vines.
                                 5-42

-------
                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-56075-77-02 S
                              2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
  ENVIRONMENTAL MONITORING NEAR INDUSTRIAL SITES
  METHYLCHLOROFORM
5. REPORT DATE
  August 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

  Battelle Columbus Laboratories
8. PERFORMING ORGANIZATION REPORT \Z
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Battelle Columbus Laboratories
  505 King Avenue
  Columbus, Ohio  43201
                                                            10. PROGRAM ELEMENT NO.
11. CONTRACT/0WWPWNO.
   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
  The levels of methylchloroform (MC)  in various environmental media were determined
  at four production sites, one  user site,  and a background site.   The  ambient air
  level was determined on-site by direct injection of the ambient air into a gas
  chromatograph followed by detection and quantification with an electron capture
  detector.  Water, soil, and sediment samples were returned to Battelle  for analyses.
  For the analyses of water samples, MC was sparged from the water  collected on a trap
  material using a commercial liquid sample concentrator.  The trapped  organic
  material was then backflushed  onto a gas  chromatograph column which was connected
  to an electron capture detector used to quantify the MC in the original sample.  A
  similar technique was used for the quantification of MC in soil and sediment.  The
  results from the analyses and  detailed descriptions of the sampling locations are
  given and keyed to site maps.   Considerable variation was observed in the maximum
  downwind levels of MC at various production plants.  Concentrations in  ambient air
  ranged from less than 0.3 ppb  to 155 ppb.  Concentrations in surface  water in
  vicinity of production and user plants was even more variable ranging from fractions
  of a ppb to over 16 ppm.  Concentrations  in soil and sediment range from the limits
  of detection to over 6.1 ppm.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Me thy 1 chlo ro f o rm
18. DISTRIBUTION STATEMENT
Distribution! unlimited
b.lDENTIFIERS/OPEN ENDED TERMS
Environmental monitoring
19. SECURITY CLASS (This Report}
Unclassified
20. SECURITY CLASS (This page)
Unclassified
c. COSATI F-'icld,'Group :

21. NO. OF PAGES
74
22. PRICE
EPA Form 2220-1 (Revi 4-77)   PREVIOUS EDITION is OBSOLETE

-------