EPA-905/4-80-009
vEPA
a
         Region V
   Protection   Toxic Suostances Office
         230 South Dearborn Street
         Chicago, Illinois 50604
                                   September 1980
uanon
             iuspected Environmental
            Contamination Of The
            Hemlock, Michigan
            Area
           *
          HEMLOCK

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        EVALUATION OF SUSPECTED
    ENVIRONMENTAL CONTAMINATION OF
      THE HEMLOCK, MICHIGAN AREA
U. S. ENVIRONMENTAL PROTECTION AGENCY
               REGION V
        TOXIC SUBSTANCES OFFICE
       230 SOUTH DEARBORN STREET
       CHICAGO, ILLINOIS  60604
            SEPTEMBER 1980

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                                 TABLE OK CUNTENTS

  LIST OF FIGuRES	 ii

  LiST uF TAdLES	 ii

  I.   EXECuTIvE SviMrtARY	  1

 II.   I'NTRuOUC>'IuN	  5

III.   PREVIOUS IiWESTIGATIONS CONDUCTED BY hICHIGAd STATE
      AUD LOCAL AGENCIES	  7

 IV.   EPA INVESTIGATION	 12

      A.   Introduction	 12

      6.   Environmental Samples From Residential Sites	 14

          1.   Water	 14
          2.   Water  distillation residue	 22
          3.   Soil	 24
          4.   Dust	 34
          5.   Sediment and sludge	 38
          5.   Tests  for dioxin	 4U

      C.   Environmental Samples From Hemlock's Municipal
          Water and  Sewage Treatment Systems	 41

          1.   Water	 
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                                    LIST OF  FIGURES
    Figure 1  -  Map of Hemlock Area and  Sampling
               Sites	 15
                                    LIST OF  TABLES


    Table 1  - Samples  Collected From Residential  Sites	 16

    Table 2  - Results  of Analyses  of Water Samples  From
              Res i dent i a 1  Si t es	 17

    Table 3  - Residue From Water Distillation  Units  Used  at
              Residential  Sites	 23


    Table 4  - Downspout Soil  Samples From Residential  Sites	 25

    Table 5  - Garden,  Uncultivated,  and  Sump Soil Samples  From
              Residential  Sites	 26

    Table 6  - Soil,  Dust,  Sediment,  and  Sludge Samples From
              Residential  Sites (Chemical Compounds  Tentatively
              Identified by a  Gas  Chromatography-Mass  Spectrometry
              Scan)	 27,28

    Table 7  - Uust  Samples From Residential  Sites	 35

    Table 8  - Sediment and Sludge  Samples From Residential Sites	 39

    Table 9  - Water and Sludge Samples From  Hemlock's  Municipal
              Systems	 42

   Table 10  - Plant  and Animal Tissue Samples	 45,46

Table 11(a)  - Fish  Tissue Samples  From 30 Day  Bioconcentration
              Study Using Water From Residential  Site  #4	 51

Table ll(b)  - Fish  Tissue Samples  From 30 Day  Bioconcentration
              Study Using Mater From Hemlock Municipal Water  System....!..... 52

   Table 12  - Description of Samples Collected From the Dow Brine
              System and Areas Located Near  It	 54

   Table 13  - Samples  Collected From Dow's Brine  System and Areas
              Located  Near It	 55,56

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                              Executive  Summary

Background
Numerous complaints of human and domestic  animal  health  problems  in the Hemlock,
Michigan area have been reported to various  governmental  agencies  since 1977.
Some area residents have attributed these  health  problems  to chemical contamina-
tion of drinking water supplies.  One concern of  the residents was that ground-
water used for drinking might be contaminated due to the  presence  of brine wells
and a reinjection system operated by Dow Chemical Company in the  vicinity of Hemlock.

PREVIOUS INVESTIGATIONS
From 1977 to 1979, the following investigations were conducted by  Saginaw
County and Michigan State agencies:
     *  Michigan Department of Agriculture and Michigan  State University
        analyzed environmental and animal  tissue  samples  for the  presence
        of nine contaminants.  No evidence of environmental contamination
        was found.

     *  Michigan Department of Public Health and  Saginaw  County Health Department
        analyzed well  water samples for  significant  levels  of 27  parameters
        and several pesticides, and examined the  construction of  four private
        wells for compliance with state  regulations.  No  contaminants were present
        at levels which could be associated  with  the alleged health1 effects.  The
        well construction was determined to  be adequate  and in compliance with
        state regulations for private wells.

     *  Michigan Department of Natural Resources  conducted  a comprehensive ground-
        water quality  investigation in Hemlock, which included laboratory testing
        of water samples for additional  parameters,  static  bioassay tests and field

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        surveys.   These analyses  did  not  indicate  any chemical contamination



        of the water other than the presence  of sodium chloride  (salt)  in  high



        enough concentrations  to  affect the taste  of the water.





     *  Michigan  Department of Public  Health  and Saginaw County  Health  Depart-



        ment conducted an epidemiological  study to compare the frequency of health



        complaints in Hemlock  with  that of a  neighboring locality.  Although this



        study showed a greater frequency  of reported health complaints  in  the



        Hemlock area than in the control  area, the investigation was  unable



        to establish a link between the complaints and private well water  supplies.





EPA INVESTIGATION



In July 1979, the United States Environmental Protection Agency  (EPA) was  asked to



conduct additional investigations into the possibility of environmental contamina-



tion in the Hemlock, Michigan  area.  This  report describes the results  of  that



investigation.  A concurrent investigation of the  alleged Hemlock  health problems,



conducted by the  Center for Disease Control,  is described in  a separate report.





EPA initiated its investigation with  a field  reconnaisance and the collection



of environmental  and animal tissue  samples which included:



     *  15 water samples from  12 residential  sites



     *  17 soil samples from 9 residential sites



     *  Dust samples from 7 vacuum cleaners  and 2  furnace filters



     *  2 wel 1 sediment and 1  septic  tank sludge sample



     x  Samples from the municipal  water  supply



     x  Samples from the municipal  sewage treatment  facility



     x  Fish samples from 3 Hemlock area  creeks  and  the  Tittabawasee  River



     x  Algae samples from one well



     x  8 domestic and wild animal  tissue samples

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The environmental samples were analyzed for numerous  parameters  including:



arsenic, cadmium, lead, calcium,  sodium, bromide,  chloride,  fluoride,  iodide,



pesticides, PCBs, PPBs, dioxin, and various other  organic chemicals.   A gas



chromatograph/mass spectrometer scan,  which has  the capability of  identifying



virtually an unlimited number of organic compounds, was  run  on the samples to



detect the presence of organic compounds that  could not  be detected by any specific



test.  Approximately 150U analyses  were conducted  on  these samples.  All analyses



were conducted with current state-of-the-art techniques, using the best technology



available at the time of the study.





Evidence of chemical contamination  of  the environment was not found other than



elevated levels of sodium chloride  (the principal  component  of table salt),



which can affect the taste of the water.  It is  believed that ingestion of high



levels of sodium may be correlated  with high blood pressure  in some individuals



susceptible to hypertension and may be a risk  to persons with heart or kidney



disease.  Hemlock area residents  who had been  drinking water with  elevated



sodium concentrations and who might be on sodium restricted  diets  have been



encouraged to contact their physicians about the sodium  level in their water.





The concentrations of heavy metals  and other contaminants for which health-based



standards exist, were below U.S.  EPA's maximum contaminant levels  for  drinking



water.





Methylene chloride, a solvent commonly used in laboratories, was found in several
                                                                  i


water samples including the control sample. The quality control data  indicate



that the presence of methylene chloride was due  to sample contamination after the



sample was collected, rather than contamination  of the water supplies.  Subsequent



sampling indicated the absence of methylene chloride  in the  water.

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The soil, sediment, sludge,  and dust  samples  were  found to contain several
naturally occurring organic  compounds.   In  addition,  traces of several phthalates,
a common component of plastic  was  found  in  several samples.  The presence of
phthalates was not considered  to be indicative  of  an  environmental contamination
problem because of the widespread  use of this chemical in paints, varnishes,
rust preventati ves, adhesives, cleaning  agents,  floor-waxes, and plastics.

Traces of other compounds,  which have been  widely  used in consumer products
were found in some of the household dust samples.

Numerous samples were analyzed for dioxin to  determine if the area might be
contaminated with that extremely toxic compound.   Dioxin was not found in any
samples taken from the Hemlock area.  The presence of dioxin could only be
confirmed in a caged fish taken from the Tittabawassee River downstream from
the Dow Chemical Company, a  waterway  known  to be contaminated with dioxin.

Thirty-day fish bioconcentration studies were conducted in two water supplies
to test for the presence of chemicals that  could bioaccumulate.  The results
of these studies do not indicate that the water supplies were contaminated
with chemicals.

Data on Dow Chemical Company's brine system were evaluated to determine if its
brine reinjection system could contaminate  aquifers  used for drinking water.
This study did not find evidence that these wells  could be responsible for
cross-contamination between geological  formations.

In summary, the EPA has performed a comprehensive  study to determine if chemical
contamination  had occurred in the Hemlock,  Michigan  area.  A wide  variety of
environmental  samples were analyzed for the presence of an extensive number of
possible contaminants.  No evidence of  a chemical  contamination  problem  in
Hemlock, Michigan was found.
                                      4

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II.  INTRODUCTION
Beginning in the fall  of 1977, public  agencies  were receiving  reports  of  human
and animal health problems in the Hemlock,  Michigan area.   Some  residents  of
Hemlock believed their health problems were caused  by  drinking groundwater
contaminated with chemicals. Some claimed,  specifically, that  chemical contamination
had resulted from Dow Chemical Company's  operation  of  brine wells  and  reinjection
lines located throughout the area.

For over twenty years, Dow has pumped  naturally occurring  brine,  located  approxi-
mately 3,000 feet below ground level,  up  to the surface.   The  brine  is then carried
through a network of buried pipes to the  Dow plant  site in Midland,  fourteen miles
north of Hemlock.  Dow reports that after salts and minerals are  removed  from the
brine, it is returned to the underground  formations by injection  wells.   Residents'
claims of contamination were based upon the theory  that chemical  wastes could have
contaminated the brine during processing  and that operation of the injection
wells or occasional leaks occurring in the buried  lines may have  caused chemical
contamination of upper-lying aquifers  used for  drinking water  supplies.

Between 1977 and 1979, a series of investigations were conducted  by  the Saginaw
County Health Department and several Michigan State agencies.  These  agencies
were unable to either identify contaminants in  the  water supplies  or correlate
the use of private well water with health complaints in the Hemlock  area.

In 1979 the U.S. Environmental Protection Agency (EPA) was requested to further
investigate the possibility of water contamination  and to  determine'the possibility
of other chemical contamination in the Hemlock  area.   To accomplish  this,  samples
were collected from selected residential  sites  in the  area. Water,  residues from
water stills, household dusts, well sediments,  garden  soils, and  uncultivated
soils were among the samples collected.   Tissue samples from domestic  and  wild

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animals in the Hemlock area were also  taken.   To  identify chemical contaminants
which may have been present in the spent  brine, various samples were collected
from the brine wells and lines,  and from  soil  which may have been previously
subject to brine spills.
Extensive field studies, laboratory analyses,  including tests for dioxin, and
bioconcentration studies were conducted.   The  Dow brine wells and reinjection
system were evaluated for possible cross-contamination between geological form-
ations.  The results of these studies  are presented in the following pages.
In conjunction with EPA's study, the Center  for Disease Control (CDC) conducted
an investigation of human health problems in the  area.  Representatives from CDC
evaluated the extent of the human health  problems  reported in the area to deter-
mine if the occurrence of health problems was  higher  than expected.  Results
from the CDC investigation will  be presented in a separate report.

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III.  PREVIOUS INVESTIGATIONS CONDUCTED BY MICHIGAN STATE AND LUCAL AGENCIES


The initial investigation of the Hemlock situation began in October 1977  after

a resident of the Hemlock area reported a high incidence of health  problems

in her livestock.  At this time a variety of samples  and whole specimens  of

livestock were submitted to the Michigan Department of Agriculture  (MDA)  for

analysis and examination. The Michigan Department of Agriculture  Laboratory

Division, with assistance from the Animal/Health Diagnostic Laboratory  of Michigan

State University (MSU), conducted autopsies and field investigations  to determine

the cause of the livestock's problems.  Between November 1977 and April 1978,

these laboratories also analyzed samples of well water, raw milk, animal  feed,

and various animal tissues and organs.



The samples were analyzed for the following parameters:

     1.   arsenic              4.  copper               7.  PCBs
     2.   lead                 5.  nitrates             8.  PBBs
     3.   mercury              6.  fluoride             9.  pesticides


This initial investigation concluded that the animal  health effects were  not  due

to exposure to excessive levels of these nine parameters.  Rather,  the  health

problems were attributed to chronic mastitis of the herd.  Evidence was not

found that indicated environmental contamination.


A second investigation was initiated in mid-1978, when residents  of the Hemlock

area expressed the additional concern that adverse human health effects might

be associated with environmental contaminants in this area.  The  residents were

especially concerned about the Dow Chemical Company's operation of  brine  rein-

jection  wells in the Hemlock area.  Some residents of that area believed  that

toxic chemicals were entering this system from the Dow plant and  contaminating

the groundwater used for drinking water supplies.  To investigate these reports,

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the Saginaw County Health Department and the Michigan  Department  of  Public
Health, Division of Water Supply,  collected water samples  from the Hemlock  area
and examined the construction of four private wells  which  were suspected  of
being contaminated.  The construction of these wells was  determined  to  be adequate
and in compliance with the Michigan State regulations.  Tests  were performed  for
twenty-seven parameters in the water samples.  All  parameters  were at levels  which
could not be associated with the alleged health effects.   The  parameters  were:
     1.  hardness (CaCU )      10.   bicarbonate        19.   zinc
     2.  fluoride              11.   carbonate          20.   cadmium
     3.  chloride              12.   sulfate            21.   lead
     4.  nitrate               13.   total solids        22.   silver
     5.  sodium                14.   pH                 23.   arsenic
     6.  potassium             15.   conductance        24.   barium
     7.  calcium               16.   iron               25.   selenium
     8.  magnesium             17.   manganese          26.   mercury
     9.  zinc                  18.   copper             27.   chromium

In addition, the private wells which were potentially  subject  to  agricultural
runoff were tested for some common pesticides (p,p'DDT; p.p'DDE;  okp'DDT).
The results of this investigation,  completed in the  early  part of 1978, did not
indicate environmental contamination of the water which could  be  linked to  the
reported human and animal health effects.
Because some of the area residents  desired more extensive  testing and research,
they obtained the services of two independent laboratories  to  analyze further
for contaminants.  These residents  and their representatives presented  results
of a water sample analysis at a meeting in October 1978,  in Lansing, Michigan,
with representatives of the Michigan Department of Natural  Resources (MDNR),
Water Duality Division, and representatives from other Michigan State agencies.
The analysis indicated the presence of four organic  compounds  in  the sample:
diethyl ether, 1,1,2-trichlorotrifluoroethane, toluene, and trichloroethylene.
The presence of these chemicals was based on a gas chromatograph/mass spectrometer
(GC/MS) analysis for purgeable hydrocarbons in the sample.
                                      8

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A review of this data indicates that there v/as  no quality  assurance  program

associated with these analyses.  That is, there were no quality control  samples

shipped or analyzed to insure that contaminants were not present in  the  sampling

bottles themselves, or that contamination did not occur during shipment  and

analysis of the samples.  Because of the lack of quality assurance data  and

due to the fact that the contaminants detected are commonly used solvents  in

the analytical laboratory, it is impossible to conclude that these results

demonstrate chemical contamination of the sampled groundwater.


To determine if, in fact, the groundwater was contaminated, the MDUR conducted a

water quality investigation in the Hemlock area (Investigation of Groundwater

Quality in the Hemlock Area of Saginaw County,  MDNR, April, 1979).   This investi-

gation involved water sampling and analysis, surveys to identify potential  sources

of groundwater contamination, determination of hydrogeological  factors which

might influence groundwater quality, and a static bioassay study for general

toxicity.  MDNR tested for the following parameters in the water samples:

     "1.  Uiethyl ether, toluene, freon, and trichloroethylene, the  substances
          identified. .  . as being in one sample from" a private well.
     "2.  Thirty-nine chemicals listed on the Critical Materials Register,  (the
          1978 list or a previous register).  Thirty-four  of these thirty-nine
          chemicals are reported to be used or produced at the Dow Chemical facil-
          ity in Midland.
      3.  The presence of organic chemicals using gas chromatography with  as
          many as three different GC scans per sample.
      4.  Several inorganic chemicals including heavy metals and salts.
      5.  General water quality parameters.
      6.  Total and fecal coliform." (j_d.at, p. 9)


The results from the analyses did not indicate chemical contamination of the water.

However, some groundwater sources contained high salt (sodium chloride)  concen-

trations.  The concentrations were sufficiently high to affect the taste of the

water.


In addition, the MDNR used a static hioassay study to determine the  general

toxicity of the water.  The bioassay involved exposing Daphnia magna, an aquatic

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invertebrate, to water from the  test  locations under specific conditions and

monitoring the Daphnia for toxicological  effects.  The bioassay results were

inconclusive since the results  neither  supported or eliminated the possibility

of water contamination.


The MDNR study also included a search for localities where groundwater contamina-

tion could potentially occur.   Neither  map and file inspections nor site visits

by MUNR staff indicated any potential contamination sites.  The study indicated

that factors such as past coal  and  oil  exploration practices or some natural

hydrogeological  conditions may  affect groundwater quality; however, it appeared

unlikely that any contamination  had resulted  from natural or artificial sources

located in the deep formations  from which brine was extracted.  Hydrogeologic

factors which were believed to  influence  the  Hemlock area aquifiers included

naturally occurring salts located in  the  upper bedrock formations.


The Michigan Department of Public Health  (MUPH) and the Saginaw County Health

Department conducted an epidemiological study (MDPH, 1979) to determine the

significance of the alleged human health  problems in the Hemlock area.  This

study was based on information  obtained through interviewing sample populations

in the northern half of Fremont  Township  and  the southern half of Richland Township.

A total of 88 households representing 3U3 residents responded.  A comparison popu-

lation was selected from the Blumfield  Township, located in the northeast section

of Saginaw County.  Seventy-four households,  representing 2b3 residents in this

area were interviewed.


The study found more health complaints  in the Hemlock area than in the comparison

area.  Health problems most frequently  reported in the Hemlock area included:

          1.) skin rashes                      7.) visual problems
          2.) numbness                         8.) nausea
          3.) arthritis                        9.) urine sugar
          4.) injuries                         10.) thyroid problems
          5.) dizziness                        11.) strokes.
          6.) arm, leg, and lower back  pains

                                     10

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Differences in reported health complaints  could  not  be attributed  to  differ-



ences in age or sex between the two areas.  Occupational  or agricultural  exposure



to chemicals and the use of private well water supplies were also  considered in



the epidemiological study, but these factors were not  associated with  differences



in the incidence of health complaints.





In summary, investigations by the Saginaw  County  Health Department, MDA,  MUPH,



and MDNR did not produce evidence of groundwater contamination  or  indicate the



presence of toxic chemicals in the environment which would  cause animal or human



health problems.
                                     11

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IV.   EPA INVESTIGATION



.A.  Introduction



In July 1979, EPA was  requested  to  assist the State of Michigan by conducting



a more extensive investigation to assess whether a contamination problem existed



in Hemlock and the surrounding area.   In response to that request, Region V staff



members met with representatives of the MDA, MDPH, MDNR, and the center for Disease



Control to consider plans  for further  evaluation of the Hemlock problem.





In September 1979, EPA and MUNR  representatives jointly conducted a reconnaissance



survey of various sampling sites and homes  in the Hemlock area.  During the period



from October 1979, to February 1980, representatives from these agencies collected



a variety of environmental  samples  including water, soil, dust, sediment, and



sludge samples.  These samples were collected from 12 residential sites, the public



water and wastewater systems of  Hemlock, the Dow brine production and injection



system, and other selected locations near the Dow brine system.  Tissue samples



from domestic and wild animals were also collected during this time.





During October, a 30 day fish bioconcentration study was conducted using private



well water from one of the residential sites.  A similar bioconcentration study



was conducted in May 1980  using  water  from  the Hemlock public supply.  Fish tissue



samples were collected from these studies and analyzed for the presence of low-



level contaminants which would accumulate in the fish but would not be detected



by analyses of the water.





All samples were analyzed  using  current state-of-the-art methodology.  Docu-



mentation of methods used are available through the Toxic Substances Office,



Region V, U.S. EPA, Chicago,  Illinois.





To insure the reliability  of the data  generated, a rigid quality assurance program



was conducted for all samples.   Numerous duplicate samples were taken, and blanks





                                     12

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(samples which contain no contaminants) were prepared and analyzed.   Spiked  water,

sediment and tissue samples from U.S. EPA, Region V's Central  Regional  Laboratory

were shipped to and analyzed by the analytical  laboratory.   Additionally,  in

those cases where questions were raised, such as in some of the volatile organic

samples, sites were resampled.


The environmental and tissue samples were analyzed for a wide  variety of

parameters including:

                1) Arsenic               8) Fluoride
                2J Cadmium               9) Iodide
                3) Lead                 10) Purgeable organic  compounds
                4) Calcium              11) Nonpurgeable organic compounds
                5) Sodium               12) Pesticides
                6) Bromide              13) Polychlorinated biphenyls
                7) Chloride             14) Polybrominated biphenyls

These samples were also "scanned" for other organic chemical compounds  using gas

chromatography coupled with mass spectrometry (GC/MS).


Tissue samples and selected environmental samples were also analyzed  for 2,  3,

7, 8-tetrachlorodibenzo-p-dioxin, commonly known as dioxin, for a number of

reasons.  First, dioxin is a highly toxic chemical.  Secondly, Dow Chemical

produces certain pesticides, including 2,4,5-T, silvex,  and trichlorophenol

at their facility in Midland, fourteen miles north of Hemlock.  Dioxin may

be formed as a by-product during the production of these chemicals (Federal

Register, August 2, 1978).  And, thirdly, dioxin has been detected in fish

collected from the Tittabawasee, Saginaw, and Grand Rivers  in  Michigan,  in 1978

(EPA study, 1978).


In addition to collecting and analyzing samples from the Hemlock area,  EPA staff

evaluated the design and construction methods used by Dow Chemical Company for

their brine production and injection wells.  Documents and information  supplied

by Dow were reviewed to assess  whether the construction of these wells  would allow

contamination of upper-lying aquifers.

                                     13

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B.  Environmental  Samples from Residential  Sites
Samples were collected from 12 residential  sites  in  the  Hemlock  area.  A map
which is located on page 15, designates  the location of  these  residential sites
and identifies them by site number.   Table  1,  page  16, gives the number and
types of samples collected from each  of  these  sites.
1.  Water
A total of 15 water samples were collected  from the  12 residential sites.  All
samples were analyzed for nine inorganic chemicals.   Results from the  analysis
of these samples are given in Table  2,  page 17.  In  general, these chemicals
were at levels which are not known to be harmful  to  health.

The quality of the water did appear'to  be affected  at some  locations by sodium
chloride.  This condition is probably due to natural  causes since wells deeper
than the glacial drift layer in this  area typically  contain saline water
 (Michigan Water Resources Commission, 1963).  According  to  U.S.  Geological Survey
geologist, Floyd Twenter (personal communication, July 9, 198U),  salty water  is
frequently found in aquifers of rock formations below the glacial drift layer
and in nearby aquifers.  Since the depth of the glacial  drift  in this  area ranges
from 115 to 250 feet (MDNR, 1979), wells near or  below the  depth of  the glacial
drift for a specific area, would tend to be salty due to the natural conditions
of the aquifer.  What effect, if any, other factors  have had in  contributing
to the saline condition, especially  in wells of shallow  depth, can not be deter-
                                                                  /
mined with available information.
 Dr. Renate Kimbrough, a toxicologist at the Center  for Disease Control in Atlanta,
 (personal communication July 5, 1980) recommended that well water at site number
 7 should not be used for drinking because of the  high sodium level.  Consuming
 two  liters of water each day (a typical amount for  adults)  from  this water
 supply and ingesting salt from food  would result  in the  ingestion of roughly
                                     14

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                                  FIGURE  1

                    MAP OF HEMLOCK AREA AND  SAMPLING SITES
	 Brine line
 •  Brine injection well
 *  Brine production well
T)-(12)  Private Residences  (9  is  located within  Hemlock)
 A -  Fish  collection  point in  Marsh  Creek         H  -
 B -  Fish  collection  point in  Williams  Creek      I  -
 C -  Fish  collection  point in  McClellan Run       J  -
 D -  Brine injection  well                         K  -
 E -  Smith Drain  (collection point of creek bed   R  -
       sediment)
 F -  Brine injection  well                         S  -
 G -  Sample collection  point from brine line
Sandpit near brine line
Brine injection well
Brine injection well
Brine production well
Location from which the deer was
  taken
Location from which the squirrel
  was taken
                                     15

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                                                            17

-------
twice the recommended daily salt  intake.   Based on  personal communication on
July 23, 1980 with Dr. Stephen Hessl  (Head,  Section of Occupational Medicine
at Cook County Hospital),  increased  sodium intake may be detrimental to persons
suffering from various kidney and heart  ailments and hypertension.  But, accord-
ing to Dr. Hessl, there is  no evidence that  a  normal, healthy person would
develop health problems from the  sodium  levels present in the water samples.

Analysis for organic compounds indicated  the presence of methylene chloride,
toluene and two types of phthalates  in some  of the  water samples.  The presence
of these compounds appeared to be due to  laboratory contamination, based on the
control samples and the fact that these  compounds were not found when the water
supplies were resampled.

The GC/MS scan identified  three organic  compounds,  which are sometimes associated
with fecal contamination,  in five of the water samples.  Fecal coliform tests,
which are more reliable indicators for this  type of contamination, were con-
ducted by MDPH and MDNR on water  from these  locations.  These tests did not
indicate fecal contamination.

The following material in  this section gives a more detailed evaluation of these
water samples.
Arsenic levels
Arsenic levels in the water samples  ranged from below detection  [5 parts per
billion (ppb)] to 19 ppb.   All levels were below the EPA maximum contaminant  level
of 50 ppb.
Cadmium levels
Cadmium levels ranged from below  detection (1  ppb)  to 1.2  ppb and are below
the EPA maximum contaminant level of 10  ppb.  During the original analysis of
these samples, the cadmium level  for the water sample from site  number 11 was
reported to be 70 ppb, and from site number 12 the  cadmium  level was  reported to  be
                                     18

-------
17 ppb.  Because both of these levels  exceeded the EPA standard  for cadmium  in
drinking water, the residents were advised not to drink the water until  the
wells were resampled.  The results of  the second analysis  indicated that
the cadmium levels in the water were normal  and below the  standard for both
locations.  Apparently a laboratory error was  responsible  for the higher  levels
reported initially.  MDPH and MDNR also collected and analyzed water  from these
two locations to recheck the cadmium levels.   Their results  also indicated that
the cadmium levels in these two wells  were not elevated.
j-ead levels
Lead levels in the water samples ranged from .95 to 18 ppb and are below  the EPA
standard of 50 ppb.
Calcium levels
Calcium levels ranged from 29 to 160 parts per million (ppm).  There  is  no
EPA health-related standard for calcium in drinking water.  Calcium is an essen-
tial nutrient and, by being in the water, may  beneficially contribute to  the
body's daily nutritional needs (National  Research Council, 1979).  Although
calcium in drinking water is not harmful  to  health, high levels  may affect water
by causing it to be hard.  Water containing a  level of calcium ranging from  75
to 150 ppm is generally considered to  be moderately hard and would affect the
quality of the water by interfering with the cleaning ability of certain  soaps.
Sodium levels
Levels of sodium ranged from 49 to 1,175 ppm with an average level of 293 ppm.
The one extreme value of 1,175 ppm was detected in the sample from site  number
7 as compared to the second-highest value of 500 ppm detected from site  number 11.
There is no EPA standard for sodium in drinking water; however,  the American Heart
Association recommends that a person on a sodium-free diet should not continually
drink water containing more than 20 ppm of sodium.  It is  also recommended that a
person on a moderately restricted sodium diet  should not continually  drink water

                                     19

-------
containing a sodium level  greater than 270  ppm.   Doctors will sometimes  place
people with heart, circulatory,  or kidney illnesses  on  sodium restricted diets.
Persons whose water supplies had levels  of  sodium above 270  ppm  and who  had a
medical history of such illnesses were encouraged to check with  their  physicians
to determine whether they  should limit the  amount of this water  they drink.
Bromide levels
The bromide levels in the  water  samples  ranged  from  below detection   (less
than U.OL ppm) to 0.82 ppm.  Bromide is  seldom  found in water at detectable
levels other than sea water, brines, and water  affected by salt  formations
(Sneed, et. al., 1954).  The salt content in the upper  bedrock formations
(MOHR, 1979) appears to be the source of the bromide levels  in the upper-lying
aquifers.  According to Dr. Renate Kimbrough (personal  communication,  July 7,
1980), the levels of bromide detected in the water samples are not known to
cause health problems.
Chloride levels
The chloride levels ranged from  19 to 1,550 ppm with an average  of 314 ppm and
a median of 135 ppm.  The one extreme value of  1,550 ppm was detected  in the
sample from site number 7.  One  would expect to find high sodium and high
chloride levels in the same sample since high sodium and chloride levels are
often associated with one another.  There is no health-related standard  for
chloride in drinking water; however, there is an EPA secondary standard  for
chloride of 250 ppm.  Secondary  standards exist for  parameters which affect
the aesthetic quality of the water, such as its taste,  odor, color, or appear-
ance, rather than affect health.  Many people object to a salty  taste  in water
when chloride is above 250 ppm.   In addition to affecting  its taste, high
chloride levels may cause plumbing to deteriorate more  quickly.
Fluoride levels
The fluoride levels ranged from below detection (less than 0.1 ppm) to 2 ppm.
These  levels do not exceed the EPA standard of  2 ppm for that  geographic area.
                                     20

-------
Iodide levels
Levels of iodide in the v/ater samples  ranged from U.OU07  to  0.01  ppm.   In areas
with an average iodide content in the  soil,  the drinking  water usually  contains
approximately O.U01 ppm (Ermolenko,  1972).   Iodide levels  in water  vary depending
upon the location, soil and geological  formations. There  is  no EHA  standard for
iodide in drinking water, and the levels  measured in  the  water samples  are not
known to be harmful to health.  In fact,  iodide levels  in water may contribute to
the body's daily nutritional  needs.  Low-iodide waters  (around .001  ppm)  can pro-
vide around 1-2% of a person's daily requirements and high-iodide waters (0.018
ppm) can provide from 24 to 44% of a person's  daily needs  for iodide  (National
Research Council, 1979).
Furgeable Organics
The analysis for volatile organic compounds  (purgeable  organics)  indicated the
presence of methylene chloride and toluene,  common laboratory chemicals, in several
of these samples.  The quality control  samples, however,  indicated  that  these
results were due to contamination occurring  either during the shipment  of the
samples from the sampling location to  the laboratory  or due  to laboratory contami-
nation of the samples prior to analysis.   This was confirmed when new samples were
analyzed and yielded negative results.
Nonpurgeable Organic^
Two nonpurgeable organics, bis (2-ethylhexyl)  phthalate and  diethyl phthalate,
were detected in one of the water samples from site number 8 at levels  of 11 and
13 ppb.  Phthalates are a group of compounds which are  commonly found in the envi-
ronment because of their extensive use in the manufacturing  of plastics.  Conse-
quently, phthalates could originate  from  many  products  found in the home.  If
the phthalates were actually in the  water at the time of  sampling,  their pre-
sence could be due to the use of plastic  being used in  the plumbing,  such as in a
water softening device or plastic pipes.   It is also  possible that  contamination

                                    21

-------
of the water sample with phthalates  occurred  after  the  sample  was collected.
The possibility of sample contamination is  supported  by the  analysis  of  a
duplicate sample from site number 8  in which  no  phthalates were  detected.
Pesticides. PCBs, PBBs
The water samples were analyzed for  pesticides,  PCBs  (polychlorinated bi-
phenyls) and PBBs (polybrominated biphenyls).  These  chemical  compounds  were
not detected in any of the water samples  at a  detection limit  of 1  ppb.
Tentatively Identified Compounds
In five water samples, three organic  compounds (cholestanol, hexadecanol,  and
9-octadecen-l-ol) were tentatively identified.  These compounds  are found  in
fecal  material, and, therefore, may  be indicative of  fecal contamination.
Based on these tentative findings, MUPH and MDNR performed fecal coliform  tests
on water from these locations.   The  fecal coliform  test is a more reliable test
for detecting fecal contamination.  The results  of  the  fecal coliform tests
indicate that the wells were not contaminated  when  the  tests were made.

2.  Hater Distillation Residue
Some residents in the Hemlock area had been distilling  their water  and reported
that once they began this practice,  their health seemed to improve. The  residues
from the water which remained in the  distilling  devices were sampled  from  two
units used at residences numbered 4  and 6.  The  results from these  samples are
given in Table 3, on page 23.

Polychlorinated biphenyls (Arochlor-1254) were tentatively indicated  in  the residue
from site number 4 at a level of 5.7  ppb.   However, due to the low  level detected,
it could not be confirmed whether PC6 was actually  present.   Its presence  was in-
dicated when analyzed by electron-capture gas  chromatography  (GC-EC)  but it could
not be detected when the sample was  reanalyzed by gas chromatography  coupled with
mass spectrometry (GC/MS).  (GC-EC can detect  lower levels of  chemicals  than GC/MS,

                                     22

-------
Parameters
                              Table 3

                  RESIDUE  FROM WATER  DISTILLATION

                   UNITS  USED AT  RESIDENTIAL  SITES


                                     Site Number
Arsenic (ppb)
Cadmium (ppb)
Lead (PPb)
Calcium (pom)
Sodium (ppm)
Bromide (ppm)
Chloride (ppm)
Fluoride (ppm)
Iodide (ppm)
7
11
2
NA
NA
4.8
3820
1.5
0.014

Purgeable Organics
NA

Nonpurgeable Organics
ND

Pesticides (ppb)
PBBs (ppb)
PCBs (ppb)
PCBs (Arochlor 1254)
ND
ND

5.7*

Tentatively
Identified
Compounds
cholestanol
hexadecanol
8 !
13
33
NA
NA !
4.5
843
1.7
.04

NA

ND

ND
ND
ND


cholestanol
hexadecanol
9-octadecen-l-ol
          ppb  -  parts  per billion.
          ppm  -  parts  per million.
          NA - Not  analyzed  for  in  the  sample.
          ND - Not  detected  In the  sample.
          * -  Was detected by GC/EC but could  not
              be confirmed by GC/MS.
                              23

-------
but is not as accurate at identifying specific chemicals.)  Analysis of the water
sample from this location did not  show PCBs  to be present in the water.
In addition, a 3U-day, fish bioconcentration study using water from this location
was conducted.  If PCBs were present  in the  water, they should have accumulated
in the fish tissue and would have  been detected when analyzed.  Since PCBs were
not detected in the fish tissue samples collected from this bioconcentration
study, it can be concluded that PCBs  were  not present in the water from this
location.

Cholestanol, hexadecanol, and 9-octadecen-l-ol were tentatively identified in
the residue samples.  Since these  compounds  indicated the possibility of fecal
contamination, water samples were  collected  and tested for fecal coliform bacteria.
Results from these tests did not indicate  the presence of fecal coliform.
3.  Soil
Seventeen soil samples were collected from nine  residential sites.  These con-
sisted of scrapings up to 2-4 inches  in depth  from the soil surface.  Soil samples
were collected below gutter downspouts  to  help identify  atmospheric contaminants
which may have been present in the air. During  periods  of  rainfall, atmospheric
contaminants would be washed out  of the air with the  rain and would be concentrated
in the soil at these locations.   The  single soil sample  collected  near a basement
sump drain was expected to contain contaminants  similar  to  those found in soil
below gutter downspouts.  Garden  soil samples  and uncultivated soil samples were
collected to determine if chemical contaminants  were  present in the soil itself or
as a result of long-term deposition from the air, water  drainage,  or other routes.
The laboratory results from these samples  are  summarized on Tables 4 and b on
pages 25 and 26, respectively.  Because of the large  number of additional chemical
compounds identified by the gas  chromatography-mass spectrometry scan, these com-
pounds are summarized separately  in Table  6 on pages  27  and 28.

                                     24

-------
                                            Table 4

                                  DOWNSPOUT SOIL SAMPLES FROM
                                       RESIDENTIAL SITES

                                                     Site Number
PARAMETERS
(ppm)
Arsenic L (Leachable)
T (Total)
Cadmium L
T
Lead L
T
Calcium L
T
Sodium L
T
Bromide L
T
Chloride L
T
Fluoride L
T
Iodide L
T

Organics
Bis (2 ethyl hexyl )phthal ate
Pyrene

Pesticides
PCBs
PBBs

Tentatively Identified Com-
pounds (quantity detected)
1
3.9
9.0
0.64
1.7
120
120
6,700
7,100
70
4,300
3.2
< 10
800
4,460
12.8
480
0.8
< 1



0.24

ND
ND
ND

6
1 3
0.31
3.2
0.12
0.40
12
20
13,000
18,000
60
4,400
4
<10
1,800
1,800
20
72
0.2
<0.1

ND



ND
ND
ND

9
4 ! 5 ! 6
0.33
5
0.12
0.38
14
60
1,200
5,200
50
5,400
4.8
310
-650
670
5.6
<5
0.1
0.3


0.21


ND
ND
ND

3
0.33
0.98
0.12
0.15
4
7.4
2,000
4,700
80
3,700
< 2
<10
4,860
5,000
20
440
0.17
0.25


0.22


ND
ND
ND

4
0.51
1.9
1.1
1.8
10
100
5,000
7,200
70
4,700
< 2
<40
500
2,000
3.6
< 5
0.1
1

ND



ND
ND
ND

4
7
0.64
5.4
0.35
1.3
180
170
8,000
9,700
70
4,900
< 2
<10
510
500
6.4
90
^0.1
<0.1

ND



ND
ND
ND

1
9
0.91
3.2
0.2
0.35
19
30
30,000
29,000
60
4,800
11
180
400
400
8.8
9
0.2
0.2


2


ND
ND
• ND

0
11
0.44
6.8
0.27
0.66
52
65
9,800
11,500
50 "
4,800
9.6
< 10
940
1,000
3.2
< 5
0.02
0.2

ND



ND
ND
ND

4
12
0.24
1.4
0.06
0.17
8
18
470
3,60
50
4,70
6.4
< 10
18C
165
26
15
o.a
< 1

NE



N[
NC
NE

1
ND - Not detected in the sample.
ppm  . - All values are expressed in parts per million.
< - Actual  value, if present, is less than stated value.
Leachable - Amount extracted from the sample by dilute acid washing.
Total - Total  amount in the sample (Teachable plus remaining).
                                            25

-------
                                           Table 5

              GARDEN,  UNCULTIVATED,  AND SUMP  SOIL  SAMPLES  FROM RESIDENTIAL  SITES



                            Type of  soil  sample and location  of samples  taken by site number
Parameters
(ppm)
Arsenic L (Teachable)
T (total)
Cadmium L
T
Lead L
T
Calcium L
T
Sodium L
T
Bromide L
T
Chloride L
T
Fluoride L
T
Iodide L
T
Organics
Bis(2-ethylhexyl )phthalate
Pesticides
PCBs
PBBs
Tentatively Identified
Compounds (quantity detected)
4
1.4
6.2
0.07
0.23
14
23
2,000
4,000
50
3,600
6.4
200
190
230
3.4
<5
0.1
<072~1

1.5
ND
ND
ND
6
GARDEI*
5
1.4
4
0.15
0.21
9
23
3,200
6,000
70
3,000
6.4
<10
500
500
24
25
0.01
<0.1
ND

ND
ND
ND
3
1 SOIL
6 [ 9 :
i.i
5.8
0.13
0.21
12
18
4.200
5,200
40
3,700
1.6
<10
180
200
9.6
10
CO. 01
0.4
ND

ND
ND
ND
3
1.3
6.4
0.42
2.1
11
28
18,000
27,000
100
5,700
3.2
170
660
660
8
no
0.3
0.5
ND

ND
ND
ND
2
UNCULT
4
2.4
3.5
0.05
0.11
5
6.9
600
1,900
50
2,900
4.8
<10
260
270
10
35
<0.01
0.2
ND

ND
ND
ND
1
IVATED <
6
0.35
1.3
0.15
0.19
6.9
19
7,500
11,000
70
2,100
6.8
285
1,070
6,440
5.6
5
0.1
<0.5
ND

ND
ND
ND
7
SOIL
12
0.6
3.6
0.09
0.21
3
17
2,700
5,500
70
4,000
11
<10
1,260
1,480
10
10
0.2
0.1

1.1
ND_j
ND
ND
4

























SUMP
SOIL
12
0.93
2.0
0.22
0.53
47
55
6,000
6,000
160
4,400
2.6
<10
270
275
<0.8
<5
0.05
<0.1
ND

ND
ND
ND
4
(ppm) -  All  values  are  expressed  in  parts per million.
  <    -  Actual  value, if present,  is  less than  stated value.
Leachable - Amount extracted from the sample by dilute acid  washing.
Total - Total amount in the sample (Teachable  plus remaining).
ND - Not detected in the sample.
                                              26

-------
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CHEMICAL COMPOUNDS





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ALCOHOLS 2-ethylhexan-l-ol





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isoctanol










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hexadecanol


















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2-methyl -1 -hexadecanol



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heptadecanol























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nonadecanol



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eicosanol










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tetradecanal














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ALKANES 3,3-dimethylhexane




























X



2-methyl nonane
1
1



X


























2,6,11 ,trimethvl dodecane





X







X







X








X

octadecane










X




















x
0)
c
ro
in
O
u
cu














X

















cu
in
o
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X


X
X

X

















pentacosane












X



















hexacosane








X























octacosane













X


















pentatriacontane





X





X


X



X




x

X




X
X
hexatriacontane























X








O)
c
a
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c_
a
c
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LU
LU















X

X
X

X



X







hpxaderejie














X

















CARBOXYLIC pentanoic acid






X

X

x
X
x



















ACIDS hexanoic acid




X
X


x

X

X
X
X















x
X
octanoic acid





x
X

X

X
X
X

X

















•r—
CJ
13
CJ
O
C
to
a
o
c





X
X

X

X
X
X

X

















decanoic acid


















X













. 3-methyldecanoic acid, methyl ester
a.

03
to

cu
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 CU
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 rO
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 c         c
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+•> CU r— r—
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X


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X
X
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CARBOXYLIC dodecanoic acid



X
X
X
X
X
X
X
X
X













X




ACIDS(cont.) tetradecanoic acid
X





























tetradecanoic acid, methyl ester





X

X
X
X
X
X


















pentadecanoic acid

X
X
X
X
X
X

X
X
X
X

X



X
X
X





X
X
X
X
X
hexadecanoic acid
X





























methyl heptadecanoic acid, methyl ester













X
















•o
<_>
ro
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C
ro
U
CU
-a
ro
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o
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X





























eicosanoic acid, methyl ester
X
X












X



X






X




heneicosanoic acid, methyl ester





























X
KETONES trimethyl pentadean-2-one












X

















l,7,7,trimethyl-bicyclo(2.2-l)heptan-
2-one












X

















OTHER 1,1 dodecanediol diacetate
X





























ORGANIC hexadecanol acetate



















X





X
X



COMPOUNDS benzeneacetic acid



—









X
















cholesta-diene




























X

s_
cu
.C
+->
cu
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4->
(J
o
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X





























o
c
cu
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X

bis(2-methvlDroDvl) phthalate










X



















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a.
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                                                                                                                                      I
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                                                                                                                                      U

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                                                                                                                                      CU
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                                                                                                                                     X
                                                                               28

-------
Anorganic Elements
Leachable and total  levels of inorganics  were determined  during the analyses
of the samples.  The Teachable value of the sample  was  obtained by mixing the
sample with a weak acid,  in order to extract the  soluble  portion  of the sample
for separate analysis.   The total value given represents  the  Teachable portion
plus the amount which remained in the sample after  the  first  extraction.  In
a few instances, the total value was reported to  be slightly  less than the
Teachable value.  In these instances, the Teachable value was  actually the total,
with the slight differences caused by acceptable  experimental  variation during
the analyses.  The evaluation of the levels of inorganics  in  the  samples was
based on the totaT levels which were detected in  the samples.
The exact composition and characteristics of soil in a  given  location depend on
many factors such as climate, landscape,  and the  rocks  and minerals present in
the area from which  the soil was derived  (Townsend,  1973).  For this reason,
the levels of the inorganic elements will vary for  each area.  When evaluating
the levels detected, broad ranges rather  than averages  must be used in assessing
whether the levels detected indicate an excessive amount.
For the inorganic metals  (arsenic, cadmium, and lead),  the levels detected
in the samples from the Hemlock area are  comparable to  levels  which have been
detected in soil from other areas.  Natural background  levels  of  arsenic in
soil range from 1-70 ppm (Bear, 1964) with an average of  6 ppm (Lisk, 1972).
In other locations,  higher concentrations up to 158 ppm have  been detected
because of the addition of arsenic to the soil (Carey,  et. al., 1980).  The
arsenic levels in Hemlock area samples ranged from  0.98 to 9  ppm which are
typical of naturally occurring levels.

-------
The cadmium levels detected in the samples ranged from U.ll  to Z.I ppm.   Cadmium
generally ranges from U.U1 to 7 ppm in soil  (Bonn, et. al.,  1979).  Background
cadmium levels in rural soils normally average around U.I  ppm, while some agri-
cultural land and soils in urban areas have  concentrations around l.U ppm or higher
(EPA Health Assessment Jocurnent for Cadmium,  1979).   Except  for one sample,  the
cadmium levels of the garden and uncultivated soil samples were generally at
U.
-------
affected by limestone deposits, calcium may be at levels of 250,000 ppm,



which is equivalent to 2b% of the weight of the soil (Hausenbui Her, 1972).



iviore typical values characteristic of loam, silt, and clay soils in the humid



and temperate regions range from 10,000-20,000 ppm (dear, 19bb).





The measured sodium levels (2,100-b,700 ppm) also appear to be typical.



Bear (1%4) reports that the sodium content of many soils ranges from 1,UUU to



10,000 ppm, and Vinogradov (1972) reports the average sodium content to



be around 7,DUO ppm.





Levels of bromide which are found in soils vary, depending on the organic



content of the soil (Ermolenko, 1972).  Most bromide in soil originates



from the soil-forming rocks.  In the elemental state it is usually present



in only trace amounts since it is easily leached from the soil (Hesse,  1971).



However, bromide tends to accumulate in organic soils because of the presence



of humic substances which bind bromide.  Therefore, bromide levels depend more



on the amount of humic substances in a particular area than the type of soil



present.  Ermolenko (1972) reports that sandy soils may contain only 0.1-1 ppm



bromide as compared to humus-rich soils, such as peats, which may contain



bO-bOO ppm of bromide.  The bromides detected in the soil samples ranged



from below detection (less than 10 ppm) to 310 ppm.





Chlorides were detected in the soil  samples at levels from lob to 6,440 pprn.



Tne usual range of chloride levels is 50-bOO ppm; however, higher levels are



found in soils with accumulated salts (Hausenbuiller, 1972).  The soil  samples



collected from the gardens and uncultivated areas have more typical  levels of



cnloride, averaging around bbO ppm.   One exception to this is the uncultivated



soil  sample from site number 4 with  a concentration of 6,440 ppm.  This sample



was collected from a field located near a dirt road.  In the past, brine was

-------
sprayed on dirt roads in the county  for dust  control.   This  practice may  be
a contributing factor in the high chloride levels  in this  and similar  areas.
The higher chloride levels of the soils under the  downspouts would most
likely be due to chlorides which have been deposited from  the atmosphere.
A common source of atmospheric chlorides  is from the combustion of fossil
fuels such as coal and oil which contain  varying amounts of  chlorine (Eliassen,
1959).

Fluoride, another variable component of the soil,  was  detected at levels
ranging from below detection (less than 5 ppm) to  480  ppm.   These levels  appear
normal since fluoride levels typically range  from  10 to 1000 ppm (Bear, 1964).
Fluoride is a typical component of certain minerals common in soil.
Iodide levels detected in the samples (less than 0.1-1 ppm)  were below levels
typically found in soil.  Bear (1964) reports the  normal range for iodide in
soils to be 0.6 to 8.0 ppm.

Organic Compounds
Bis (2-ethylhexyl) phthalate was detected in  five  of the soil samples.  This
compound is widely distributed in the environment  because  of its widespread
use in products such as paints, varnishes, and rust preventatives (Initial
Report of the TSCA Interagency Testing Committtee, 1978).  The widespread use
of this chemical compound may be the cause of its  presence in the soil samples.

Pyrene, another organic compound, was detected in  downspout  soil from  site
number 1.  Pyrene belongs to a class of compounds  known as polycyclic  aromatic
hydrocarbons and  is most often found as a by-product of incomplete combustion
of organic matter (Hoffmann, Wynder, 1968).   The most  likely source of
pyrene at this location would be from the wood-burning stove used in the

-------
house.  The smoke produced from the stove  would contain  pyrene and similar
compounds and would distribute these compounds in  the  vicinity of the house.

Tentatively Identified Compounds
Thirty additional compounds were tentatively  identified  in  various soil
samples by the GC/MS scan and are listed in Table  6, on  pages 27 and 28.  The
types of compounds identified are those which are  commonly  found in soil or would
be expected to be present in soil samples.  Chemical compounds which would in-
dicate a contamination problem were not detected in these samples.

Most of these compounds probably originated from living  organisms, either
directly from the organisms or from the natural breakdown of their components
or by-products.  For example, dead plant tissue will undergo a complex decompo-
sition process by which its components  will be chemically changed or broken
down in the soil.  Buckman and Brady (I960) outlined the stages of decomposition
during which the original compounds in  plant  tissue (eg., oils, fats, resins,
starches, sugars, proteins) will eventually become the complex organic material
in soil known as humus.  During this decomposition, various compounds will be
formed and decomposed.  These compounds could account  for some of the alcohols,
aldehydes, carboxylic acids, and other  types  of compounds in the soil.

Small microorganisms themselves, such as bacteria, would also contribute to
the presence of these organic compounds.  Average  soils  may contain from 1U -
1UO million bacteria per gram of soil (Allison, 1973).   These bacteria contain
many biochemical compounds such as the  lipids in which a variety of carboxylic
acids have been identified (Shaw, 1974).

Several of these compounds may have originated from a  single natural compound
present in the soil.  It has been determined  that  microbial activity on a
                                     33

-------
specific organic compound will  yield a  variety  of  degradation  products.   For
example, carboxylic acids may undergo the following  reactions  when  being  decom-
posed by microorganisms (Meikle,  1972):
     1)  shortening of the carbon chain  by two  carbons  through beta-oxidation
         which would produce a different carboxylic  acid.
     2)  removal of the carboxyl  group  producing an  alkane  or  alkene.
     3)  replacement of the carboxyl group by a hydroxy group  resulting in  an
         alcohol.
Consequently, the breakdown of hexadecanoic acid,  for  instance, may  produce tetra-
decanoic acid, pentadecane, hexadecanol, and other products.   Similar  general  re-
actions are known to occur with alkanes, alkenes,  ketones,  esters,  and other types
of organic compounds.

4.  Dust
Seven vacuum cleaner dust samples and two furnace  filter dust  samples were  col-
lected from nine of the residential  sites.  These  samples were collected  to
identify contaminants which may have been deposited  within  homes  from outside
sources.  The results of the analyses of these  samples  are  contained in
Table 7, on page 35.
The arsenic content of these dusts do not appear high  compared to the  results
from one study in which 61 household dust samples  were analyzed for arsenic (Klemmer,
et. al., 1975).  Klemmer found levels of arsenic ranging from  1.1 to 1,U80  ppm.
The higher values were found in homes which had been treated for  termites or con-
tained lumber which had been treated with certain  preservatives.  The  arsenic
levels in the Hemlock samples ranged from 2.3 to 21  ppm.
Cadmium levels in these samples ranged  from 2 to 25  ppm. These cadmium concen-
trations appear to be typical based on  a study by  Solomon and  Hartford (1976)  in
which household dust was found to contain cadmium  levels ranging  from  7 to  48  ppm
with an average of 18 ppm.
                                     34

-------
                                               Table 7
                                 DUST SAMPLES FROM RESIDENTIAL SITES

                               Type of Dust Sample and Location of Sample
                                        Taken by Site NumbeF

                                              Vacuum Cleaner
Furnace
Filter
Parameters
(ppm)
Arsenic L(Leachable)
T(Total)
Cadmium L
T
Lead L
T
Calcium L
T
Sodium L
T
Bromide L
T
Chloride. L
T
Fluoride L
T
Iodide L
T

Organic Compounds
Bis(2-ethylhexyl)phtha-
ate
Butyl benzyl jihthalate
Di ethyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Phenol
Fluoranthene
Mapthalene
Pyrene
Pentachlorophenol

PBBs
PCBs
Arochlor 1232
Arochlor 1260
Pesticides
Chlordane

Tentatively Identified
Compounds (quantity
detected)
1

6.2
21
5.1
9.4
77
no
11,000
25,000
6,800
15,200
36
^.250
11,300
34,000
22
^.25
1.2
<2.4

160
50
6.6
33
26

3.3

4.1
0.6

ND
ND


ND


13
3

2.4
2.7
10
11
230
280
100,000
110,000
4,500
11,000
4.0.8
460
1,500
23,300
14
5
0.1
^2.5

280
61
1
10





0.4

ND


0.45*
ND


10
4

2.5
5.9
4.8
4.0
60
62
30,000
30,000
4,400
7,200
50
-1250
3,060
146,000
30
<50
2
^2.5

800
35
4
19







ND


1*

0.3*|

10 !
5

2.2
2.6
17
25
170
280
75,000
83,000
4,600
9,200
<.4
4150
18,500
77,500
9.6
OO
1.0
1.9

24
4.3



1 .1





ND


2.4*
ND


9
7

5.4
2.9
20
21
230
220
48,000
66,000
3,500
5,700
32
<120
2,900
9,700
5.6
<5
1.1
^1.2

100
31
1.8
14

.92
1
28
1.7


ND

8.5*
"6.6*
ND


11
10 4
!
4.6
4.9
6.9
20
56
61
20,000
25,500
10,000
12,000
64
<500
29,500
87,000
7.2
r
1.2
^5

240
12









ND
ND


ND


3
11

2.5
2.3
3.4
3.6
37
46
23,000
32,000
68,000
86,000
<4
<200
13,200
52,000
16
^20
^0.04
^2.1

49
5.4
0.42
6.6





0.42




0.3*



10































6

5
14
3.3
3.7
50
51
7,000
72,000
2,600
55,000
8
1,500
2,420
2,610
14
^20
0.2
•^1.5

1,630
91

20

610








5*

4*

7
9

1.2
4.7
2.2
2
140
170
7,500
53,000
2,200
78,000
24
25
1,970
1,970
5.6
6
0.24
4.8

42
3












0.35*



11
ppm   - All values are expressed in parts per million.
ND  -  Not detected in the sample.
4-  -  Actual value, if present, is less than stated value.
*  -  Was detected by GC/EC but could not be confirmed by GC/MS.
Leachable - Amount extracted from the sample by dilute acid washing.
Total - Total amount in the sample (Teachable plus remaining).
                                               35

-------
Lead concentrations in the Hemlock dust samples  ranged from 4b  to  2BU ppm.   These

levels are slightly lower than those reported by Solomon and Hartford (iy7b)  who

found average levels of bUU ppm with a range of  1/U  to l,44u ppm.


Among the organic compounds detected, the phthalate  compounds were the most  com-

mon.  Their presence is expected because of the  number of household products  which

would contain such compounds.   Perhaps the largest use of these compounds  is  in

manufacturing plastics.  Some  plastics may contain up  to bU% phthalates

(EPA Duality Criteria for Uater, 1976).  other products  containing phthalates

which would make them common in the home include:

     paints                                   adhesives
     varnishes                                cleaning agents  and compounds
     rust preventatives                       household aerosols
     flame retardant chemicals                floorwaxes
     chemical deodorizers

(Initial  Report of the TSCA Interagency Testing  Committee,  1978)


Phenol was detected in two of  the dust samples.   It  is  an organic  compound

which can originate from many  sources including  chemical  oxidation processes,

human and other organic wastes, microbial  degradation  of pesticides  and  other

naturally occurring sources (EPA Duality Criteria for  Water,  iy7b).   The large level

of phenol detected in the furnace dust from site number 6 may have originated

from the filter itself.  To collect the dust,  the fiberglass material  contained

in the filter had to be removed and included in  the  sample.  Phenol,  which is

also used in many chemical processes, could have been  used in the  manufacturing

of the filter or have been in  a coating which may have been present on the filter.
                                                                   I


In two dust samples, three compounds normally associated with by-products of

incomplete combustion were detected in small amounts.   These compounds are fluor-

anthene, napthalene and pyrene.  Although these  compounds are widely  distributed

in the environment and can be  found in the air,  water, soil,  sediments,  and  plant

-------
and animal tissues (EPA Ambient Water Ljuality Criteria,  PAH),  their presence  at

these detectable levels suggest that they were formed during combustion  processes

in these homes.  At site number 1, a wood-burning stove  was  used  occasionally.

This stove is a likely source for these compounds.  Although a specific  source

was not identified at site number 7, these compounds could have been produced

from a variety of sources such as the burning of methane gas (Hoffman, Wynder,

1968), coal, oil and wood.  The compounds can also be found  in cigarette smoke

(EPA Ambient Water Quality Criteria, Fluoranthene).


Pentachlorophenol, a chemical compound commonly used as  a pesticide and  as  a

wood preservative, was found in trace amounts in three of the  dust  samples.

Additional sources of pentachlorophenol  in the home environment may include such

products as:

     adhesives               textiles
     oils                    carpet shampoos
     paints                  fabrics
     rubber                  (Conklin, Fox, 1978).

These products are sometimes treated with pentachlorophenol  because of its  effec-

tiveness as a fungicide and bactericide, and in preventing mildew.


Two types of PCBs (polychlorinated biphenyls), designated as Arochlor 1232  and

Arochlor 1260, were identified by electron capture gas chromatography (GC/EC) in

7 of the dust samples at levels ranging from 0.3 to 8.5  ppm.  However, these

compounds could not be detected by gas chrornatography/mass spectrometry  when

the samples were reanalyzed.  These PCBs, if actually present  in  the samples,

are believed to be at background levels  for dust.  PCBs  were once widely used

in many products and would still  be found in some products within the home.

Arochlors 1232 and 1260 were used in adhesives, surface  coatings, paints,

sealants, and textiles, and as  a de-lustering agent for  rayons (Interdepartmental

Task Force on PCBs, 1972).  Other possible sources of PCBs in  the home environment
                                     37

-------
include older fluorescent lights, and appliances  and electrical  equipment which
nave components containing PCds (iiacLeod, iy?y).

ur. Thomas Hurphy, of LiePaul  university,  recently completed  a  study  in  which
dust samples collected from homes and buildings  in the Lake  Michigan area were
analyzed for FCBs.  Preliminary results  (letter of April  k!b, lybU  from  Jr.
1'iurphy) snowed PCd levels in  the dust samples  to  range from  1.2  to bb ppm with  a
median level of y ppm.  In an unpublished report, Dr.  Hurphy states  that  these
levels of PCds in dust appear to be representative of  background levels  of
PCbs found in the air from various  sources.

une pesticide, chlordane, was detected by GC/EC  in two of the  dust samples.   The
presence of chlordane in the  samples  could not be confirmed  by tJC/i"1S analysis.
£ven if present, the levels of cnlordane  detected in the  two samples did  not
appear to be high.  Une study (Starr, et. al.  iy74) found chlordane in 4b house-
hold dust samples at levels ranging from  1.7y  to  41.Jb ppm with  an average of
/.by ppm.

Twenty-two additional compounds were  tentatively  identified  in the dust samples.
These are listed in Table b,  on pages Z7  and  iib.   As was  discussed on pages 33  and
34 in the section on the soil samples, these compounds most  likely originated from
natural organic matter present in these types  of  samples.  Chemical  compounds indi-
cating a contamination problem were not detected.

b.  Sediment and sludge
Sediment samples were collected from two  wells,  no longer in use,  from  sites
numbered b and /.  Also a sludge sample was  collected  from the septic tank
located at site number I'd.  The results from these samples are listed in
Table d, on page 3y.  The levels of inorganics found in these  samples do  not
appear to be significant or to indicate a contamination problem.

-------
                                   Table 8

             SEDIMENT AND SLUDGE SAMPLES FROM RESIDENTIAL SITES
                                              Site Number
PARAMETERS
  (ppm)
Well Sediment
  6      7
Septic Tank Sludge
     12
Arsenic L (Leachable)
T (Total)
Cadmium L
T
Lead L
T
Calcium L
T
Sodium L
T
Bromi de L
T
Chloride L
T
Fluoride L
T
Iodide L
T
Organic Compounds
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Diethyl phthalate
Di-n-butyl phthalate
Acenaphthalene
Benzo(a)anthracene
Chrysene
Fluoranthene
Benzo (b+k) fluoranthene
Pyrene
Benzo(a)pyrene
Pesticides
PCBs
PBBs
Tentatively Identified Compounds
(quantity identified)
10.8
9.2
0.33
0.28
12.7
18
46,000
59,200
890
6900
<3.3
<80
42,800
42,800
<80
<80
0.89
<0.8
ND











ND
ND
ND
3
8.2
44
3.3
2.9
58
56
12,000
13,800
960
6460
<110
<110
470
10,100
40
89
<1
<1




0.49
0.24
1.6
2.3
1
1.1
2
1.3
ND
ND
ND
4


































4.6
9.8
1.2
3.1
11
67
5670
82,500
1180
2100
<10
<250
27 ,800
35 ,600
1,550
1,550
0.77
<250

2.6
14.2
1.6
1.9







ND
ND
ND
7
Leachable - Amount extracted from the sample by dilute acid washing,
Total - Total amount in the sample (leachab.le plus remaining).
ppm   - All values are expressed in parts per million.
ND - Not detected in the sample.
< - Actual value is less than given value.

-------
ut the organic compounds detected in the samples,  4 phthalates  were found
in the septic tank sludge.  The presence of these  compounds  in  sludge is probably
due to the fact that phthalates are contained in many household products.

In the well sediment from site number 7, a phthalate and seven  other compounds,
known as polycyclic aromatic hydrocarbons, were found.   The  most likely source
of these compounds is contamination from surface water runoff.   A cracked con-
crete cap was used to cover the well.  This would  be inadequate protection
because the crack would have permitted water runoff to enter the well.

Additional compounds identified by the JC/ViS scan, listed in Table t>, on pages 27
and Zb are chemical compounds which would occur naturally in these samples and are
not associated with contamination.

o.  Tests for dioxin
Seven environmental samples from the residential  sites  were analyzed for dioxin.
Tiie following are the samples which were analyzed:
        1) well  sediment (site #o)
        Z) still residue (site # b)
        JJ septic tank sludge (site #\'
-------
C.  Samples From Hemlock's Municipal  Mater And Sewage Treatment  Systems
1.  Water
The results of the water sample collected from the Hemlock  municipal  system
are listed in Table 9, on page 42.

The levels of the inorganics present  in the water sample did not exceed  existing
EPA standards.  The inorganic parameters, for which EPA does not have standards,
were not at levels known to he harmful  to health.  Each of  these inorganics
in water were discussed previously beginning on page 14.

The organic compound, methylene chloride, was detected at a level  of  25  parts
per billion.  This compound was detected in several of the  other water samples
collected (See page 21).  Quality assurance procedures used indicate  that  its
presence is due to laboratory contamination.

Three organic compounds, which sometimes indicate fecal contamination of the
water, were detected by a GC/MS scan.  However, fecal contamination was  not in-
dicated by fecal coliform tests performed by MDPH.
2.  Sludge
A sludge sample was collected from the  sewage treatment facility in Hemlock.
The results from this sample are listed in Table 9, on page 42.
The results of the analysis of the sludge sample does not indicate evidence
of a contamination problem.  Levels of  arsenic and lead appear to be  low
according to Lisk's data on sewage sludge (1972), which found the average  con-
centration of arsenic to be 90 ppm and  lead to be 1,690 ppm.  The cadmium  level
also appears to be low since cadmium levels in sewage have  been  found to average
16 ppm, and range from 3 to 3,1)00 ppm (CAST, 1976).  The levels  detected for the
remaining inorganics  are believed to  be typical.
                                    41

-------
                                  Table 9

                        WATER AND  SLUDGE  SAMPLES  FROM
                         HEMLOCK'S MUNICIPAL SYSTEMS
                                    MATER
Inorganics
Arsenic
Cadmium
Lead
Calcium
Sodium
Bromide
Chloride
Fluoride
Iodide


Inorganics
Arsenic

Cadmium

Lead

Calcium
Sodium
Bromide

Chloride

Fluoride

Iodide

7 ppb
0.6 ppb
2 ppb
1 04 ppm
75 ppm
< 0.01 ppm
48 ppm
0.5 ppm
< 0.0003 ppm
SLUDGE
(All values are in parts
Leachable Total
7.4 11

1.3 0.83

16 27

43,000 45,800
890 7,700
< 2.9 < 2.9

192 42,400

< 14 < 14

< 0.3 < 0.3
Organ ics
methyl ene chloride 25 ppb*
Pesticides ND
PCBs ND
PBBs ND
Tentatively Identified Compounds
cholestanol
9-octadecen-l-ol
hexadecanoic acid, 2-oxo, methyl


per million)
Organ ics
bis(2-ethylhexyl) phthalate
di-n-butyl phthalate

Pesticides
PCBs
PBBs

Tentatively Identified Compounds
eicosanol
heptadecanol
undecane
2-butanone
tetradecanoic acid
hexadecanoic acid
heneicosanoic acid








ester




4.9
0.86

ND
ND
ND









                                                  benzeneacetic acid
ppm - parts per million
ppb - parts per billion
ND  - Not detected in the sample
 *  - Value may be attributed to laboratory contamination.
<   - Actual value, if present, is less than stated value.
Leachable - Amount extracted from the sample by dilute acid washing.
Total - Total amount in the sample (Teachable plus remaining).
                                      42

-------
The detected organic  compounds  included  two  phthalates.  Because of their wide-
spread use in many products,  their presence  is  expected.  The remaining com-
pounds which were identified  by the GC/HS scan  are thought to originate from bio-
logical sources  and are not known  to indicate a contamination problem.
                                    43

-------
D.  Biological Samples
Plant, fish and other animal  tissue samples  were collected  from the Hemlock
area and analyzed.  The results  from these samples  are  listed  in Table 10,
on pages 45 and 46.  Also in  this  table are  numbers  or  letters which designate the
location from which the samples  were collected.  These  numbers or  letters are
plotted on the map located on page 15.

1.  Pish
Fish samples were collected from Marsh  Creek,  Williams  Creek,  and  McClellan
Run in the Hemlock area.  Additional fish samples were  taken from  two loca-
tions on the Tittabawassee River near Midland, Michigan.  The  fish collected
from the Tittabawassee were caged  fish  which were being monitored  by the MUNR.
One location on the Tittabawassee  was upstream from the Dow Company plant site
and the other was downstream  from  Dow.   The  caged fish  from the Tittabawasee
were included in this study to determine if  chemical contamination was still
present in fish downstream of Dow  Chemical.  The MDPH previously had issued a
warning against consuming fish from this river because  of chemical contamination.

The levels of arsenic, cadmium and lead found  in the fish were not excessive.
Lisk  (1972) reports average levels of these  metals  in fresh water  fish to be
O.U3-0.5 ppm, 0.02-0.15 ppm,  and 0.5-2  ppm,  respectively.

Phenol, an organic compound,  was found  in 4  of the  samples.  The presence
of phenol in fish tissues could be due  to a  number  of reasons  since it is
a compound widely found in the environment from both natural and anthropogenic
sources.  One source of phenol is  the microbial breakdown of certain pesticides.
However, this appears to be an unlikely source, in  this case,  because no pesticides
were found in the fish.  If pesticide degradation was the source of phenol, the
pesticides would have accumulated  and been found in the fish tissues.  Other pos-
sible sources of phenol in fish are natural  sources. The natural  sources
                                     44

-------
                                             Table  10
                                PLANT AND ANIMAL  TISSUE  SAMPLES
Fish Fish Fish Fish Fish Fish Goose
Alqae 11 12 #3 14 IS 16 Fat
Location
Parameters
Arsenic
Cadmum
Lead
Organic Compounds (pom)
phenol
di-n-butyl phthalate
diethyl phthalate
Pesticides (ppm)
PCBs (ppm)
PBBs (ppm)
Oioxin fontl
Tentatively Identified Compounds
(Alconols)
heptaaecanol
4-methyl phenol
glycerol
cholest-5-en-3-ol
(Aldehydes)
tetradecanal
octadecanal
octadecenal
2,4,nonadiena1
(Carboxylic Acids)
butanoic acid
3-methyl butanoic acid
octanoic acid, methyl ester
8-methyl decanoic acid, methyl ester
undecanoic acid, methyl ester
cyclopentane undecanoic acid, methvl ester
tetradecanoic acid
tetradecanoic acid, metnyl ester
pentadecanoic acid, metnyl ester
14-methylpentadecanoic acid, methyl ester
hexadecanoic acid
hexadecanoic acid, methyl ester
14-methyl hexadecanoic acid, metnyl ester
15-methvl hexadecanoic acid, methyl ester
heptadecanoic acia, methyl ester
16-metnvlheptadecanoic acid, ^ethyl ester
octacecenoic acid
ocCiCece-.oic aci-L methyl ester
9-octadecenoic acid
10-octadecenoic acia, .retnvi este"
14-octadecenoic acia, metnyl ester
17-octadecenoic acid, methyl ester
10,13-octadecadienoic acid, metnyl ester
eicosanoic acid, rretnyl ester
heneicosanoic acid, metnvl ester
Other Compounds
VJ-dodecanediol diacetate
nonadecane
1 ,1-dimethoxyhexane
benzoic acid
NA
MA
NA
A
<0.15
0.06
NA |<0.02

0.17

0.18


NO
ND
NO
NA



X









X

X


X


X

1


















0.07
NO
NO
NO
NO







X













X





X





X







B
<0.15
0.023
< 0.02

0.02


NO
NO
c
<0.15
0.026
<0.02

0.9


NC
NO
NO ! NO
NO





NO





c
<0.15
0.037
0.11


2

NO
NO
*

-------
                                                                       Table 10

                                                                       (continued)

Goose Chicken Chicken Chicken Chicken Cow Cow Cow Deer Deer Squirrel Squirrel
Liver Fat Fat Liver Liver Fat Liver Kidney Fat Liver Muscle drains
Location
Parameters
Arsenic
Cadmi urn
Lead 	
Organic Compounds (oDm)
phenol
di-n-butyl phthalate
diethyl phthalate
Pesticides (ppm)
PCBs f
PlBs
ppm
ppm)
Dioxin fDDtl _. . .
Tentatively Identified Compounds
(Alcohols)
heptadecanol
4-methyl phenol
4
<0.15
0.36
0.10
,10



5
<0.5
<0.004
0.2$
ND


5
<0.5
0.006
0.25
ND



ND NO i ND
ND
;JD
ND : ND
ND ' NO
itD ; ND NO



!

glycerol
cholest-5-en-3-ol X X X
(Aldehydes)
tetradecanal
octadecanal
octadecenal
2,4,nonadiena]
(Carboxylic Acids)
butanoic acid
3-methyl butanoic acid
octanoic acid, methyl ester
8-methyl decanoic acid, methyl ester
undecanoic acid, methyl ester
cyclopentane undecanoic acid, methyl ester
tetradecanoic acid
tetradecanoic acid, methyl ester

X
x _,





1


5
<0.15
0.34
0.15'
ND



ND
ND
ND
ND



5 6
<0.15
0.62
— or"*
ND



ND
ND
ND
ND





X

X












<0.15
0.03?
0 11

0.'3


NO
NO
ND
ND^










i i
6 6
<0.15
2.2
• o h l

.75


ND
ND
" ND
ND
















<0.15
0.70
— irtr~
ND



ND
ND
ND
ND





X










X


X
pentadecanoic acid, methyl ester ,
14-methylpentadecanoic acid, methyl ester X X
hexadecanoic acid X


X

hexadecanoic acid, methyl ester X
1 4-methyl hexadecanoic acid, methyl ester
15-methyl hexadecanoic acid, methyl ester
heptadecanoic acid, methyl ester
16-methylheptadecanoic acid, methyl ester
octadecenoic acid
octadecenoic acid, methyl ester
9-octadecenoic acid
10-octadecenoic acid, methyl ester
14-octadecenoic acid, methyl ester
17-octadecenoic acid, methyl ester
10,13-octadecadienoic acid, methyl ester
eicosanoic acid, methyl ester
heneicosanoic acid, methyl ester
Other
Comoounds
U-dodecanediol diacetate
nonadecane
1 ,1-dimethoxyhexane
ben zo ic acid 	 . 	 .



X







X

X
X




X




'



















X L X
X

X




X
XXX



X









X
X








X i







X


X











R , R
<0.5
<.004
( 05

0.06

0.02
NO
ND
M
NO





X

X






<0.15
0.11
Ol3

.02


ND
ND
ND
ND














	 ; 	 -^ 	 i
S i S
!
<0.15
0.008
	 0 14


























X '
i X
|
X
X
X
1 X


x ;

X X
X
X



X X



i X










x x !



X
X























!












<0.15
0.22
— tn —

.36


ND
NO
ND
NO


X

X


X











X

X
X
X








X

X
X
X





ppm - parts per million.
ppt - parts per trill ton.
NA - Not analyzed for in the sample.
ND - Not detected in the sample.
<  - Actual value,  ff present,  is less than stated value.
*  - Caged fish from upstream Tittabawassee.
** - Caged fish from downstream Tittabawassee.
X  -  Indicates  the compound was tentatively identified in the sample.
                                                                   46

-------
include certain aquatic plants which produce phenol  and the  decomposition
of vegetation such as oak leaves, which enter the water (Hoak,  1957).   Another
potential  source may be industrial  discharges.
Two phthalates were also present in three fish samples.  As  mentioned  previously,
phthalates are used in many products and have been found throughout  the environ-
ment and are commonly present in waterways and aquatic  life  (EPA  Initial Report
of the TSCA Interagency Testing Committee, 1978).   The  levels of  phthalates
found in these fish samples are not believed to be unusual.  One  type  of
phthalate was reported to be present in fish, collected from various locations
across the country, at levels ranging from 0.2 to 10 ppm (Stalling et.  al.,  1973).

Dioxin was detected in a fish sample from site number 6, at  a level  of  23  parts
per trillion.  This sample was from the caged fish located downstream  from
Dow on the Tittabawassee.  In 1978, 2b out of 35 fish samples,  collected from
the Tittabawassee, Saginaw, and Grand Rivers, contained dioxin  (EPA  Memo on
Dioxin, December 20, 1978).  Levels detected in the  fish from the 1978  study
ranged from 4 to 695 parts per trillion.  Dioxin was not detected in the other
fish samples.
A number of additional organic compounds were identified in  the fish samples
by the GC/MS .scan.  These compounds, are believed to be part of the  normally
occurring background compounds which one would expect to be  present  in  these
samples.  They are not known to indicate chemical  contamination of the  fish.
2.  Animal Tissues
Tissue samples were analyzed from a goose, two chickens, three  cows, a  deer
and a squirrel, taken from the Hemlock area.  Arsenic was not detected  in
any of the samples.  Based on personal communication (July 2, 1980)  with Val
Beasley, D.V.M., of the University of Illinois, College of Veterinary Medicine,

                                     47

-------
the levels of cadmium and lead found were at  background  levels  and  do  not  indicate
a contamination problem.  Dr. Beasley commented that  the highest cadmium level
detected in cow liver (2.2 ppm) was  slightly  above  levels  normally  found.   However,
he believed that it was not high enough to cause health  problems in cattle.
The organic compound, phenol, was detected in 5 of  the tissue samples.   The
phenol levels detected are not uncommon according to  Dr. Fred Oehme (personal
communication on July 2, 1980), who  is a veterinarian-toxicologist  at  Kansas
State University.  Dr. Oehme stated  that phenolic compounds  are naturally
found in animal and plant tissues.   Also, levels of phenol can  increase  in
animal tissues if the animal feeds on lush vegetation.

Diethyl phthalate was also found, in trace amounts, in the deer fat sample.
Because of the widespread distribution of phthalates  in  the  environment, it
does not seem unusual that this compound would be found  in some animal tissues.

Other chemical compounds which were  detected  in the samples  appear  to  be back-
ground compounds which naturally occur in tissues.  Pesticides, PCBs,  PBBs,  and
dioxin were not detected in these samples.
In addition to those samples listed  in Table  10 on  pages 45  and 46, two  more
cow fat samples from site number 6 were analyzed for  dioxin.  Dioxin was not
found in either of these samples.
3.  HI ant
Algae, growing at the base of a water well at residence  number  6, were analyzed
for organic chemical compounds.  The  results  of the analysis  are contained in
Table 10, on  pages 45 and 46.
Evidence of chemical contamination was not found in the  plant sample.   The
phenolic and  carboxylic acid compounds detected are believed to be  naturally
present in plant tissues.
                                      48

-------
E.  Evaluation of Goose Wing Deformity
A goose from site number four was  born with a deformity  of  one  wing  which  made
it appear to be attached backwards to the body.   The goose  was  autopsied  and
tissue samples were analyzed (Table 11), pages 45 and 46) to determine  if  a
chemical contaminant may have caused this deformity.  The goose was  examined
by a Michigan State University veterinarian, and according  to the  autopsy
report (November 28, 1979), the deformity was actually an increased  flexibility
of the joints close to the base of the wing.  This  allowed  the  wing  to  rotate
to the extent that the feathers appeared to point in the wrong  direction  when
the wing was flexed.  Based on personal communications (July 2, 1980)  with
Dr. Val Beasley (a veterinarian from the University of Illinois, College  of
Veterinary Medicine), this type of deformity may have been  caused  by a  mal-
position of the unhatched bird during the development process,  a genetic  dis-
order, or a chemical contaminant.   However, chemical contaminants  were  not
observed in the tissues analyzed.   According to  Dr. Roland  Winterfield  (personal
communication, July 2, 1980), a specialist in avian diseases at Purdue  University,
the wing disorder is most likely due to a genetic defect.  Dr.  Winterfield stated
that it was most likely not related to a chemical contaminant since  other
deformities or problems were not found in the goose.
                                     49

-------
F.  Fish Bioconcentration Studies



Two fish bioconcentration studies  were  conducted  in the Hemlock area.  These



studies involved placing fathead minnows  in  tanks, filled with water from the



test sites, for a 30-day period.   Two fish samples were collected before the



studies began (day 0) to serve as  controls,  and on day 15 and day 30.  These



samples were analyzed to determine if trace  chemical contaminants were present,



which would accumulate in the fish from the  water.





The first bioconcentration study was  performed during October, 1979, using the



well water from site number 4.  The second fish bioconcentration study was



conducted during April, 1980, using water from the Hemlock municipal supply.



The results of the fish sample analyses are  listed in Table 11(a), on page 51,



and in Table ll(b), on page 52.  Based  on the chemical compounds identified



and the levels detected in the control  and the duplicate fish samples, there



appear to be no significant differences in the levels or types of chemicals



identified.  The bioconcentration  studies did not indicate contamination of the



water.
                                     50

-------
                                          Table ll(a)

                               FISH TISSUE SAMPLES FROM 30 DAY
                                BIOCONCENTRATION STUDY USING
                               WATER FROM RESIDENTIAL SITE #4
"ameters
Control  Control
 Day 0    Day 0   Day 15  Day 15  Day 30  Day 30
Drganics (ppm)
senic
Jmium
ad

ganic Compounds (ppm)
jnol
2thyl phthalate
-n-butyl phthalate

stlcides (ppm)
3s (ppm)
5s (ppm}
Dxin (pot)

itatively Identified Compounds
ycerol
Dlest-5-en-3-ol
tradecanal
tadecanal
:anoic acid, methyl ester
tradecanoic acid
tradecanoic acid, methyl ester
-methyl tetradecanoic acid, methyl ester
-methyl pentadecanoic acid, methyl ester
xadecanoic acid
xadecanoic acid, methyl ester
-methyl hexadecanoic acid, methyl ester
-methyl hexadecanoic acid, methyl ester
xadecenoic acid, methyl ester
-methyl .heptadecanoic acid, methyl ester
-methyl heptadecanoic acid, methyl ester
-octadecenoic acid, methyl ester
-eicosenoic acid, methyl ester
neicosanoic acid, methyl ester
idecane
0.32
0.068
0.81


1.0



ND
ND
ND
ND


X






X





X





^0.15
0.044
0.18




0.6

ND
ND
ND
ND


X



X
X



X

X
X





0.37
0.032
0.13



0.23


ND
ND
ND
ND







X

X


X





X
X

1.0
0.080
0.13

ND




ND
ND
ND
ND



X
X

X




X





X



0.53
0.13
0.12

ND




ND
ND
ND
ND


X




X

X






X




0.83
0.077
0.15


0.17
0.3
2.7

ND
ND
ND
ND

X



X

X
X
X
X
X







X
X
>m - parts per million.
 t - parts per  trillion.
 -  Not detected in the sample.
 < - Actual value,  if  present,  is  less  than  stated  value.
 X - Indicates the  compound was  tentatively  identified  in  the sample.
                                             51

-------
                                   Table ll(b)

                         FISH TISSUE SAMPLES FROM 30 DAY
                     BIOCONCENTRATION STUDY USING WATER FROM
                        HEMLOCK MUNICIPAL WATER SYSTEM .
Parameters
Control
 Day 0
Control
 Day 0
Day 15    Day 30
Blank
Inorganics (ppm)
Arsenic
Cadmi urn
Lead
Thallium

Organic Compounds (ppm)
phenol
di ethyl phthalate
di-n-butyl phthalate

Pesticides (ppm)
PCBs (ppm)
PBBs i.ppm)
Dioxin (ppt)

Tentatively Identified
Compounds
tetradecanoic acid
hexadecanoic acid
9-hexadecanoic acid
octadecanoic acid
0.16
0.33
0.88
<0.6

ND




ND
ND
ND
ND

X
X
X
X
0.21
0.45
1.3
<0.6

ND




ND
ND
ND
ND

X
X
X
X
0.20
1.1
0.94
<0.7


ND
0.4
0.7

ND
ND
ND
ND

X
X
X
X
0.33
0.33
<0.4
<0.4

ND




ND
ND
ND
ND

X
X
X
X
0.66
0.01
0.14
<0.07

ND




ND
ND
ND
ND





ppm - parts per million.
ppt - parts per trillion.
ND - Not detected in the sample.
 < - Actual value, if present, is less than stated value.
 X - Indicates the compound was tentatively identified in the sample:
                                       52

-------
G.  Samples  From Pow's  Brine System And  Areas  Located  Near  It
Samples were collected  from the brine system and  areas  located  near  it which
may have been affected  by past  spills  or leaks  in the  system.   The locations
and descriptions of the samples collected are  indicated in  Table 12,  page 54,
and the sample results  are listed in Table 13,  pages 55 and  56.

Four brine samples were collected from different  locations  along the  system.
The levels of the inorganic parameters detected,  appear to  be characteristic
of the brine and are not considered significant.   Two  organic compounds, which
probably resulted from  background or laboratory contamination,  were detected
in the brine samples.   Methylene chloride, detected  in one  of the brine samples,
was also found in control samples.   This indicates that sample  contamination
had occurred.  The other organic compound, tentatively identified by  the GC/MS
scan, was diethylene glycol.  This  is  a  chemical  compound which is used as a
solvent, plasticizer,  and surfactant,  and can  be  found in plastics, synthetic
sponges, paper products, cork compositions,  adhesives,  and  dyes (Hawley, 1977).
The sample in which diethylene glycol  was identified was originally collected
by a local resident and was stored  in  a  glass  jar.   Trace contamination of the
sample could have occurred from the jar  or lid before  the sample was  transferred
to an approved sample container.  Diethylene glycol was not  detected  in the
soil sample from the area where the spilled brine had  been  collected.

Soil and sediment samples were collected from  areas  near the brine system and
analyzed for specific  inorganic chemicals.  Significant levels  of these inorganics
were not found.  The organic compounds identified in these  samples, with the ex-
ception of di-n-butyl  phthalate, are believed  to  have  originated from natural
background sources.  Di-n-butyl phthalate and  similar  compounds, are  commonly
found in the environment and could  have  originated from many sources.
                                     53

-------
                                 Table 12
        DESCRIPTION OF SAMPLES COLLECTED FROM THE  DOW  BRINE  SYSTEM
                        AND AREAS LOCATED NEAR IT.
Type of Sample
brine
brine
bri ne
brine
soil
soil
sediment
sediment
sediment
sediment
sediment
sediment
Location *
F
F
G
**
F
G
H
E
D
I
J
K
Description
Waste brine collected from a
valve near the injection well.
Waste brine which had leaked
from the pipe and had collected
at the base of the well.
Brine which had been collected
earlier by one of the local
residents from a spill site.
Brine released from the filter-
ing system of the #6 lagoon loca
ted on the Dow plant site in
Midland. (Location not marked on
the mapl)
Surface soil near the injection
well.
Surface soil from a spill site
located along the brine system.
Sediment from a sandy area next
to the brine system.
Creek bed sediment taken from th
area known as Smith Drain.
Sediment from the injection we! i
pond.
Sediment collected from an injec
tion well head which was being
dismantled.
Sediment which was inside a brin
injection pipe at the horizontal
orifice plate near the well hea
Pipe scrapings from under a gas
separator located on a brine pr
duction well. This well is loc
ted in Midland County, one mile
South of Midland. The exact
location of the well is not mar
on the map. •
* - Locations indicated on map (page 15).
** - Location not marked on the map.
1  - Addition sample collected at Location  F
                                     54

-------
   h-
   00
   a: >->
   CO
      OL
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-------
EPA requested permission from Dow to  collect  sediment samples from the waste
brine lagoon located at the Midland plant  site.   Dow refused EPA's request
based on their rationale that the sediment samples would  not be representative
of the chemical  composition of the brine.   Dow indicated  that the waste brine
was sand-filtered,  thereby removing chemical  contaminants, before being released
from the lagoon to  brine transmission lines.   However, Dow did permit sampling
of pipe sediment within the brine well  injection  system.  As a result, three
pipe sediment samples,  two from brine injection wells and one from a brine
production well, were collected.

Four synthetic organic  chemical  compounds  were detected in sediments within
two of the pipes.  These pipes are located at the brine production and injection
wells near Midland.   Non-natural  chemical  compounds were  not detected in the in-
jection well near Hemlock.  The four  organic  chemicals detected were:
     1)  bis(Z-ethylhexyl) phthalate
     2)  di-n-butyl  phthalate
     3)  4-chloro-m-cresol
     4)  2-chlorophenol
In addition, a duplicate sample from  location J was analyzed at a second
laboratory.  From these analyses, two additional  synthetic chemical compounds,
hexachlorobenzene (2.5  ppb) and pentachloroanisole (4U ppb), were detected.
However, when analyzed  by GC/MS,  the  presence of  these compounds could not
be confirmed.
The three pipe sediment samples were  also  analyzed for dioxin.  Using current
state-of-the-art methodology, dioxin  was  not  found in these samples.'
                                     57

-------
H.  Evaluation of Dow's Brine We1J_ Design and Construction
EPA staff reviewed technical  data on the brine production and  injection wells
operated by the Dow Chemical  Company of Midland,  Michigan.   These  data were
reviewed to determine what impact Dow's brine wells  might have on  shallower
aquifers used for water supplies  in the Hemlock  area.   Part  of this  information
was originally requested through  the Freedom of Information  Act  and  was submitted
by Dow to the Congressional  Subcommittee on Oversight  of Government  Management
on June 25, 1979. This information was  later forwarded to EPA  on October  30,
1979 (Appendix 1, page 63).   EPA  staff  reviewed these  data and were  unable
to make a valid engineering evaluation  of the mechanical conditions  of the
wells because insufficient information  was provided.

During a meeting with Dow representatives on January 24, 1980, additional
information was requested by EPA  staff  (Appendix 2,  page 67).  In  response to
the request, Dow provided the necessary information  to EPA  (Appendix 3, page 69).
The information included details  on injection well number 42 (location  "J" on
the map) which is located near Hemlock.

Based on the available data, EPA  staff  concluded that  the program  followed by
Dow in the construction of their  brine  wells exceed  current  U.S. Geological
Survey, Division of Oil and Gas,  On Land Injection Standards.  In  addition,
no evidence was found to suspect  that these wells would be  responsible  for
cross-contamination between the geological formations.
A  limitation to EPA's evaluation  was that insufficient data  were available on
wells constructed before 1970.  Consequently, EPA was  unable to  make an evaluation
of these wells. It is Dow's position that, before 1970, the  best technology
available at that time was used to construct the wells.
                                     58

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V.  CUNCLUSION



Chemical  contamination was  not  detected  by analysis  of the  environmental and



tissue samples collected in the Hemlock, Michigan  area.  Based on available



information, the levels of  the  inorganic and  organic chemicals in these samples



appeared to be within normal  bounds.   Most of the  organic chemical compounds



identified are naturally occurring in  the environment.   Several synthetic



chemical  compounds were also present.  However,  these compounds are frequently



found in the home and ambient environment due to the presence of consumer



products  which contain them.  The quality of  water from  certain wells in the



area contained elevated levels  of sodium chloride  salt which can affect the



taste of the water.





In summary, based on results  from a large number and wide variety of samples,



the United States Environmental Protection Agency  has found no evidence of



chemical  contamination of the environment in  the Hemlock, Michigan area.
                                     59

-------
VI.  REFERENCES CITED


Allison, F. E., JSoT[ Organic Hatter and its  Role In Crop Production,  Elsevier
   Scientific Publishing Co., N.Y., 1973.

Bear, F. E., editor, Chemistry of the Soil,  American Chemical  Society Monograph
  Series #12b, Reinhold Publishing Co., 1955.

Bear, f. E., editor, Chemistry of the Soil,  American Chemical  Society Monograph
  Series fflbU, Reinhold Publishing Co., 19b4.

Beasley, Val, D.V.M.; University of Illinois,   Veterinary Uiagnostic  Medicine
  Uept.  Personal communication on July 2,  198U.

Bohn, McNeal, U'Connor; Soil Chemistry, Wiley-Interscience Publication,  John
  Wiley and Sons, 1979.

Bucknian, H. U. and Brady, N. C.; The Nature  and Properties of  Soils  bth  Edition,
  Macmillan Co., U.Y. 19bO.

Carey, Uowen, Forehand, Tai, Wiersma; "Heavy Metal  Concentrations  in  Soils  of Five
  United States Cities, 1972 Urban Soils Monitoring Program.";  Pesticides Monitoring
  Journal, Vol. 13, No. 4, March, 198U; p.  lbU-154.

CAST; Application of Sewage Sludge t£ Cropland:  Appraisal  of  Potential  Hazards
  of the Heavy Hetals to Plants and Animals, Council  for Agricultural  Science and
  Technology, Report #64, 1976.

Conklin, P. and Fox, F. in Pentachlorophenol edited by  K.  Ranga Rao,  Plenum
  Publishing Co., NY  1978.

Eliassen,  R.  Domestic and Municipal  Sources of Air Pollution  in  U.S  P.H.S.
  Proceedings for the National Conference oil Air Polllution Nov.  18-2U,  1958;
  GPU; Washington, D.C., 1959.

EPA, Ambient Water Duality Criteria; Criterion Document for Fluranthene, Washington U.C.

EPA, Ambient Water quality Criteria; Criterion Document for Polynuclear  Aromatic
  Hydrocarbons; Washington D.C.

EPA, health Assessment Document for Cadmium, Office of  Research and  Development,
  EPA-6UU/8-79-UU3, January 19/9.

EPA, Initial Report of the TSCA Interagency  Testing Committee.  January 1978,  EPA
  5bU-lU-78/UUl, Washington, D.C.

EPA, Memo  of December 20, 1978 from Dr. Edward Qswald to Karl  Bremer. Subject:
  Summary of Results for Analyses of Samples of Fish from Michigan -  EPA Region V  -
  for 2,3,78-Tetrachlorodibenzoparadioxin  (TCDD).

EPA, quality Criteria for Watej:. 1976.

Ermolenko, N.K.; Trace Elements and Colloids in Soils.  Israel  Program for Scientific
   Translations, 1972.


                                       6U

-------
Kederaj Register.   Rebuttable Presumption Against Registration;  EPA,  Office  of
   Pesticides Programs;  Vol.  43,  Ho.  4,  August  2, 1978;  p.  34U3U.

Hausenbuiller, R.  L.; Sol1  Science Principles  and Practices,  W.M.C. Brown Co.,

Haw ley, G. G., Condensed Chemical  Dictionary,  9th Edition,  Litton  Educational
   Publishing, Inc., 1977.

Hesse, P. R., A Textbook of Soil  Chemical  Analysis.  Chemical  Publishing Co., NY, 1971.

Hessl, Stephen, M.D.; Head  Section of Occupational Medicine at Cook County Hospital and
   Assistant Professor of Environmental  and  Occupational  Health  Sciences, University
   of Illinois, School of Public  Health; Personal Communication  on July 23,  198U.

Hoak, R. U.; "The  Causes of Tastes and Odors in Drinking Water."  Proc. llth Ind.
   Waste Conf. Purdue University.   Eng.  Bull.  4:229.

Hoffman, D. and Wynder,  E.; in Air Pollution,  2nd edition,  edited  by  Arthur C. Stern,
   Academic Press, N.Y.  1968.

Interdepartmental  Task Force on PCBs,  Polychlorinated  Biphenyls  and the Environment,
   Washington, D.C., 1972.

Kimbrough, Renate, Dr.,  CUC toxicologist,  Atlanta, Georgia; Personal  communication
   on July 7, 1980.

Klemmer, Leitis, Pfenninger;  "Arsenic Content  of House Ousts  in  Hawaii," Bulletin,
   of Environmental Contamination  and Toxicology, Vol. 14,  No. 4,  1975, p. 449-4b2.

Lisk, U. J., "Trace Metals  in Soils,  Plants, and Animals,"  Adv.  Agron., 24:267-311.

i'lacLeod, K.; Sources £f  Emissions  of  PCBs  into  the Ambient  Atmosphere and Indoor
   Ai£, EPA report EPA-bOO/4-79-022,  MarchTSTs.

MDA, Final report  from the  laboratory examination of a goose  and two  chickens,
   Nov. 28, 1979,  Accession no. 200564-bbb.

MNDR, Investigation of Groundwater Quality j_n  the Hem!ock Area cjf  Saglnaw County,
   Water Duality Division,  Groundwater Compliance and  Special Studies Section, April,
   1979.

MDPH, The Hemlock  Area Study - An  Investigation Into Reported Health  Problems and
   Possible Water  Contamination,  Chemicals and  Health  Center, March,,  T9/9.

Heikle, R. W.; "Decomposition of  Organic Compounds"  in Organic Chemicals in the Soil
   Environment, edited by Gorhing, C.  A. and Hamaker,  J., Marcel Uekker, Inc., NY, T972.

I'lWRC; Water Resource Conditions and Uses In  the Shiawassee  River Basin; Michigan
   Water Resources Commission, October,  1963.

Murphy, T. J., Ph.D., Associate Professor of Chemistry,  DePaul Univeristy, Chicago;
   Letter dated April 25, 1980, and attached unpublished report  sent  to Region V,
   U.S. EPA, Office of Toxic  Substances.
                                     61

-------
National Resource Council ;  The Contribution  erf  Urinking Water ;t£ Mineral  Nurtition
  in Humans; prepared for EPA by the Nutrition  Subcommittee  of the Safe Drinking
  Water Committee, NRC; National Academy  of  Sciences,  Washington, D.C. 1979.

Uehme, Fred, ur.; Veterinarian-Toxicologist, Kansas State University, Toxicology
  Laboratory; Personal Communication on Junly Z,  198U.

Shaw, N.; "Lipid Composition as a Guide to the  Classification of Bacteria"  in Advances
  iji Applied Microbiology,  Vol. 17,  edited by D.  Perlman, Academic Press, N.Y. 1974.

Sneed, Maynard, Brasted; Comprehensive Organic,  Chemistry, Vol. _3 The Halogens;
     U. Van Nostrand Co.,  NY, 1954.

Solomon, R. L. and Hartford, J. W.  "Lead  and Cadmium  in Dusts and Soils in  a
  Small urban Community,"  Environmental Science and Technology,  Vol. 1U,  No. 8,
  August, 1970, p. 773-777.

Stalling, Hogan, Johnson;  "Phthalate Ester Residues -  Their  Metabolism and
  Analysis in Fish"; Environmental  Health Persp. ,  b:lb9-173  (1973).

Starr, Aldrich, McDougall,  Mounce;  "Contribution  of Household Dust to the Human
  Exposure to Pesticides";  Pesticides Monitoring  Journal, Vol. 8, No. 3,  Dec. 1974,
  p.
Swaine, D. J.; The Trace Element  Content  of  Soi 1 ,  Commonwealth Agriculture Bureau,
  Commonwealth Bur. Soil Technology Commun.  No.  48,  Harold Printing Works, England,
  1955.

Townsend, W. N.; An Introduction  to the  Scientific Study of the Soil; St. Martin's
  Press, NY, 1973.

Twenter, Floyd, geologist, U.S. G.S.,  Lansing,  Mich., Personal Communication on
  July 9, 198U.

Vinogradov's data in Soil  Chemistry, by  Bonn, MciMead, O'Connor,; Wiley  -Interscience
  Publication, 1979.

Winterfield, Roland, Dr.;  Professor of Avian Diseases,  Veterinary Diagnostic
  Laboratory, Purdue University;  Personal  communication on July 2, 1980.

-------
                                                                            APPENDIX   1
        AMAMAM nateerr. COM*. CHAIRMAN
 Haarr M. JACKSON. WASH.
 THOMAS r. EAOLITON. MO.
 UkWTON CHILIS, njt.
 SAM MONK, OA.
 JOHMOLCNN, OHIO
 JIM SASSOt. TXNN.
_ DAVID nmft, ARK.
CHARUS M. raev, ILL.
JACOB K. JAVrr», H.Y.
WILLUM V. BOTH, Jit. OIL.
TTO STRUM, ALASKA
CHARLES MC C. MATHIAS, JJfc, MO.
                  WILLIAM «. COHCN, MAINK
                  DAVID Dunoaaraai. MUM.
        CAUL LXVIH. MICH.. CHAIRMAN

DAVID urn*. AUK.      WILLUM s. COHCN. MAINI
                DAVID DUHDUCJIam. MIMM,

          snmCN H. KLITZMAN
      CMU* OOUNSCL AND «TAVP OIIUETOM
                                          COMMITTEE ON
                                      GOVERNMENTAL AFFAIRS

                                        SUBCOMMITTEE ON
                                OVERSIGHT OF GOVERNMENT MANAGEMENT

                                       WASHINGTON. D.C. 20810
                                       October  30, 1979
         Mr.  Karl Bremer
         Region V
         Environmental  Protection  Agency
         230  South  Dearborn Street
         Chicago, Illinois 60604

         Dear Mr. Bremer:

              Per our discussion of October  17,  I have enclosed a copy of the
         Subcommittee's correspondence requesting technical  data from  Dow Chem-
         ical Company relative to  the company's  brine production and injection
         wells.  When comparing the requests  to  information  received by the Sub-
         committee, you will note  that the response is in  fact only a  partial one.
         The  burden of a full response would  have been too large an imposition on
         the  company  at that time.

              I would also like to take this  opportunity to  thank you  for your
         appearance at and involvement in the Hemlock town meeting.  I found your
         input to be  quite helpful in clearing up residents'  impressions of EPA
         activities relative to that area.

              Please  don't hesitate to contact me if I can be of any further ser-
         vice to you  or EPA Region V.
                                        Sincere!
         RLT/fdv
         Enclosure
                      Richard  L.
                      Staff Investigator
                                         63

-------
              -ACS* * JAVI^S N.Y.
                 v.
              TD
JOHN Gwr^N OHIO

JIM GASSCIt. TEN*.
CMAffuCS MC C MATWIAS, JR^, MO.
JOHW C. OAWOWTM. MO.
W1LUAM C. COHCN, MAJNC
DAVIO OUMCMBC^OUl. MINN.
         UCVIN. MICH., CHXifl

D*VtO r~*YO*, AUK.     WILL!»M S
             OAVO Z'JKi.


        STCFMCN H K'_r*^KAN
     CHIEF COUN^e-AftO 6TAJF Omi
         miCHAJIO A, WECMAN
        COUNSEL AND BTA^T CM RECTO*
                                COMMITTEE ON
                             GOVERNMENTAU AFFAIRS

                               SUBCOMMITTEE ON
                        OVERSIGHT OF GOVERNMENT MANAGEMENT

                             WASHINGTON. D.C. 205 10
                                    June 25, 1979
     SPECIAL DELIVERY
     RETURN RECEIPT REQUESTED
     Mr. Paul F. Oreffice
     President and Chief Executive  Officer
     Dow Chemical Company
     2030 Dow Center
     Midland, Michigan  48640

     Dear Mr. Oreffice:

          The Subcommittee on Oversight of Government Management is
     conducting an investigation  into  governmental implementation
     of hazardous waste management  programs by the Environmental
     Protection Agency  (EPA), the EPA  regions  and state agencies.
     Pursuant to this investigation, we are interested in how govern-
     mental units have responded  to possible problems caused by the
     brine injection deep wells you are operating or have operated
     in the Midland, Michigan area.  The Subcommittee has been
     informed that some of these  wells  were constructed to extract
     sodium chloride from the earth for your chemical manufacturing
     processes in Midland, and that the brine  sludge residue was
     pumped back into reinjection wells.

          It is also our understanding  that the Michigan Department
     of Natural Resources (DNR) has performed  chemical analyses of
     surface pools in the Fremont-Richland area formed as a result
     of leaks and/or cracks in your company's  brine reinjection lines.
     The studies performed by DNR indicate that substances other than
     brine residues were present  in these  surface pools, such as
     flourides, ammonia, certain  phenolic   compounds and other
     materials.

          The Subcommittee is interested in the government's res-
     ponse to possible chemical contamination  of the groundwater by
     such substances in Midland,  Bay, Saginaw  and-Gratiot counties.
     In order to assist the Subcommittee in its investigation, we
     would appreciate your providing the following materials by
     July 9, 1979:
                                 64

-------
 Mr.  Paul F.  Oreffice
 President and Chief Executive Officer
 Dow  Chemical Company
 June 25,  1979
 Page 2

      1.  Copies of all groundwater and geological  studies  per-
 formed by or for Dow, or under the direction  of Dow,  covering
 any  part  of  the area within a 25-mile radius  of your  Midland
 facilities.   Please also supply any other documents which may
 indicate  geological groundwater flow patterns or  geologic
 subsurface conditions relative to the areas of deep well  in-
 jection  systems.

      2. Copies of all chemical laboratory analyses, performed
 since 1950,  of spent brines and brine spills,  as  well as  other
 liquids,  from Dow pipelines in the four  counties  mentioned
 above, which Dow may have  injected or is injecting into the
 ground.

      3. A copy of all well logs for deep well injection sys-
 tems, showing the volume of materials injected into those wells
 to date,  as  well  as injection pressures.   Please  include  with
 these logs a list and map  of all waste injection  wells, as
 well  as landfills and surface impoundments owned  or once  owned
 by Dow, whether or not these wells,  landfills  or  impoundments
 are  presently in  use.   How long does  Dow maintain such well
 log  information in its files?  What record keeping is required
 of Dow by  federal law with respect to these wells, landfills
 and  impoundments?

      4. Copies  of all  inorganic analyses  and  summary  data
 performed by  or for Dow, or under the direction of Dow, which
 indicate  the  presence  of any heavy and/or pseudo  metals in
 Dow's injected  waste  streams.                           »

      5. Copies  of all  analyses  of organic constituents in  the
 injected wastes,  specifically identifying their levels of
 concentration.

      In addition,  please respond  to the  following specific
questions:

      1.  How much waste  from the manufacture of trichlorophenol
and/or 2,4,5-T  has  been pumped  into Dow's reinjection wells
and/or placed in  Dow landfills  or  impoundments?  Which wells,
landfills and impoundments?

     2.  At what rates and pressures does Dow dispose of waste
material through  deep well  reinjection systems?   Is this rate
continuous.or intermittent,  and are there seasonal fluctuations
in these rates?  Are these  rates  low enough to insure the sta-
bility of the geologic  formations?
                            65

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 Mr.  Paul F.  Oreffice
 President and Chief Executive Officer
 Dow Chemical Company
 June 25, 1979
 Page 3

      3.  What types of high molecular weight and/or halogenated
 organics are present in the waste stream of materials being
 pumped to your reinjection wells?  Please specifically iden-
 tify types and concentrations of these materials.

      4.  Have EPA Priority Pollutant Analyses been  performed
 on Dow's waste streams?  If so,  please provide a copy to the
 Subcommittee.

      5.  Has  Dow performed any groundwater or well  water analyses
 of wells and water supplies within a 25-mile radius of your
 Midland  facilities within the last two years?  If  so, please
 supply these to the Subcommittee.

      6.  Does Dow have any information which would  indicate
 that groundwater contamination may be caused by abandoned or
 existing landfills and surface impoundments?  If so,  please
 supply^ such  information to the Subcommittee.

      7.  Has  Dow ever encountered any problems in operating
 injection systems, for example,  failure of the injection
 string within the groundwater aquifer?  If so, please describe
 fully.

      8.  Does Dow have any information which would  indicate
 that abandoned oil,  gas or brine wells or other sources may
 have contributed or are contributing to groundwater contami-
 nation?   If  so,  please supply this information to  the Subcom-
 mittee.
                                                          »

      Thanks  for your cooperation in this matter.   We  realize
 that this request is detailed.   However, the Subcommittee has
 scheduled hearings on governmental implementation  of  hazar-
 dous waste management programs for later in July and  we would
 appreciate a prompt response.  If there are any questions con-
 cerning  these requests, please contact Richard Tallman of the
 Subcommittee staff at (202)  224-3682.
•CL/rt
                               66

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                                                                 APPENDIX  2
       '  *     '                UNITED STATES

    "0                ENVIRONMENTAL PROTECTION AGENCY

     a                             REGION V

    ^                       230 SOUTH DEARBORN ST.

                            CHICAGO. ILLINOIS 60604
  JAN 3i 1980


Mr. D. Dick DeLine
Manufacturing Manager
Dow Chemical U.S.A., Michigan Division
47 Building
Midland, Michigan  48640

Dear Mr. DeLine:

Thank you for your cooperation on January 24, 1980 regarding our
meeting and the samples obtained from the brine production and injec-
tion system.  The day proved to be quite productive and will assist
in our evaluation of the Hemlock, Michigan area.

As you recall, Mr. Russell Diefenbach requested information during
the meeting on typical well records for the brine well injection
system.  Per your request, Mr. Diefenbach has determined that the
following information is needed to continue his evaluation of the
Dow injection system (records from the Hemlock, Michigan area are
more appropriate):

1.  Caliper Surveys for typical injection well(s) that are typical
    for area.

2.  Comparison of calculated cement volumes (w/o Caliper) v.s. cement
    volume from bond logs.

3.  Average % wash out used for cement calculations.  How established.

4.  Results of Cement Bond Log's cement top v.s. calculated cement
    tops.  (Temp, survey's for CBL if used in lieu of).

5.  Is the long casing string kept in tension during cement setting
    time?  After cement sets, is all casing weight set on braden-
    head or is it slacked-off?

6.  What casing accessories are used on long string of casing?  Is
    there pressure test after WOC?

7.  Is casing dressed with central izers to center allow 360° cement
    sheath?
                                67

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     -   '  -     •                     2
8.  Describe typical cement program for long string.
Your response may be forwarded to my office at your first convenience.
I anticipate completion of this part of the evaluation during February,
1980.
Thank you for your consideration.
Sincerely,
Karl E. Bremer
Toxic Substances Coordinator
cc:  Senator Carl Levin
                                   68

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                                                                   APPENDIX  3
                   DOW CHEMICAL  U.S.A.
February 29, 1980                                          MICHIGAN DIVISION
                                                      MIDLAND,  MICHIGAN 48640
Karl E. Bremer
Toxic Substances Coordinator
US EPA Region V
230 South Dearborn Street
Chicago, Illinois  60604
Dear Karl:

Enclosed is the information requested by Mr. Russell Diefenbach through
your letter of January 31, 1980.  I was pleased that your visit to the
Michigan Division was quite productive and will assist you in your
evaluation of the Hemlock area.

This information was supplied by Mr. David Cella, Manager of the Brine
Chemicals Section and our technical expert in the brine well area.
Mr. Cella has been with the Michigan Division since 1970 and his
responses to Mr. Diefenbach's inquiries relate to the procedures and
technology used over the past ten years.  Prior to 1970, the best
technology available at the time was used.

1.  Caliper surveys for typical injection well(s) that are typical
    for the area.

    Caliper survey and associated bond logs of three wells in the
    Hemlock area are enclosed.
         Production Wells #76 and #82
         Injection Well #42

2.  Comparison of calculated cement volumes (w/o Caliper) versus
    cement volume from bond logs.

    The number of sacks of cement and type of cement used in each
    well are shown on the enclosed "Cementing Service Reports."

        Production Wells #76 and #82
        Injection Well #42
              AN OPERATING UNIT OF THE DOW CHEMICAL COMPANY

                                 69

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C
             Karl E. Bremer
             February 29, 1980
             Page 2
3 .   Average % wash out used for cement~balculations .   How established.
                                       /               — — ^— — ^^^— _

    Since 1973, we have calipered the open hole.  Prior to that time,
    the normal practice was to use the volumetric difference between
    bit size and casing size plus 20-30% excess cement.

4.   Results of Cement Bond Log's cement top versus calculated cement
    tops.  (Temp, survey's for CBL if used in lieu of ).

    A comparison of the data recorded on the Cementing Service Report
    and the 3-Dimensional Velocity Log will give the actual results
    versus calculated.  Please see enclosed reports for production
    wells #76 and #82 and injection well #42.

5.   Is the long casing string kept in tension during cement setting time?
    After cement sets, is all casing weight set on bradenhead or is it
    slacked-off?

    The long string of casing is held in tension at the surface during
    cementing operations.  After the cement has set,  we pull one-half the
    weight of the free pipe and set the slips.

6.   What casing accessories are used on long string of casing?  Is there
    pressure test after WOC?

    The following accessories are used on long strings of casing:

        (a) regular pattern guide shoe,
        (b) cement float collar,
        (c) centralizers (3-5/well) .

    Surface casing and long string are tested at a minimum of 500 psig.

7.   Is casing dressed with centralizers to center allow 360° cement
                 Centralizers are used on the long string and are normally placed one
                 joint above casing shoe, below and above the Dundee zone, with one
                 or two between the Dundee and casing shoe.  A caliper log or the
                 geologists log is used for judgment when placing the centralizers.

             8.  Describe typical cement program for long string.

                 A typical long string casing cement program is the same for both
                 production and injection wells, except for casing size.  We consider
                 a cement fillup from 200' minimum to 500' above the Dundee zone an
                 adequate cement job.  Normally, the target cement top is about
                 2000' to 2500' from the surface, which is approximately 500-1000 ' above
                 the Dundee formation.  The supervisor on the job is given the latitude
                 to modify the cement program to fit the downhole conditions .  The
                 brine field is in the Sylvania formation which is about 1000' to
                 1500' below the Dundee top.
                                              70

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Karl E. Bremer
February 29, 1980
Page 3

8.  Describe typical cement program for long string,  (continued)

    The hole is drilled down to the top of the production zone, circu-
    lated and cleaned up.  A caliper log is run and determination is
    made as to where to place centralizers and what cement volume is
    required to bring the cement top to 2000' from the surface.  Depending
    on the condition of the hole, 10-20% excess cement over computed
    volume is used.

    The casing is then run by a casing crew using power tongs .  The bottom
    of the hole is tagged with the casing and the casing is then picked
    up two feet.  After the casing has been landed, circulation is
    broken by pumping down casing and getting returns to surface.

    A fresh water pad (50 barrels) is pumped ahead of the cement and the
    cement is pumped in.  When the cement reaches the bottom of the casing,
    the pumping rate is slowed down so as not to exceed 2-1/2 barrels /minute.
    The cement is displaced with water and drilling fluid, leaving 20-30 feet
    of cement in the casing.

    The well is shut in (WOC) and allowed to set 48 hours.  The hole is
    then nippled up to drill out below the casing.  After nippling up,
    the hole is run in with a drill pipe and top of cement tagged, drilled
    up to casing seat, and pressure tested to a minimum of 500 psig.

    If the test is approved, drilling is continued to total depth.  After
    the hole has been drilled to total depth and cleaned up, logs are run
    on the hole.  Almost all of our Sylvania wells are open-hole completion.

    Generally, the wells are "in gage," and no major problems have been
    encountered in the completion of our brine wells .  There have been
    very few changes in the cement program over the years , except for
    type of cements used and/or the method of cement placement.  We
    prefer the "slo-flo" technique of cementing rather than "turbulent
    flow," the merits of each being debatable.  Naturally, we rely on our
    Dowell Division for vendor technology in this field.

Karl, I am sorry for the delay in getting this information to you.  If you
have additional questions or comments, please give me a call.

Sincerely,
D. Dick DeLine
Manufacturing Manager
(517)636-0150

lej

Enclosures (9 )
cc:  (Letter only) Senator Levin, B. G. Caldwell, Dr. H. Tanner
                   Dr. M. Reizen, R. Ellison
                                 71

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