810R90106
GROUND-WATER CONTAMINATION BY VOLATILE ORGANIC COMPOUNDS:
    SITE CHARACTERIZATION, SPATIAL AND TEMPORAL VARIABILITY

                            Year One Summary Report
                      for Cooperative Agreement CR815681-01

                                  July, 1990
                                    By:

            H. Allen Wehrmann               Michael J. Barcelona
            Ground-Water Section             Institute for Water Sciences
            Illinois State Water Survey          Western Michigan University
            Champaign, Illinois               Kalamazoo, Michigan
                                    To:

                           Jane Denne, Project Officer
                       Advanced Monitoring Systems Division
                      Aquatic & Subsurface Monitoring Branch
                        USEPA-EMSL, Las Vegas, Nevada

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Background

This report is intended to summarize the activities and accomplishments of the first 11A year of
Cooperative Agreement 815681-01.  A meeting was held in Las Vegas with Project Officer Jane
Denne (USEPA-EMSL), Doug Bedinger (DRI), Project Manager Allen Wehrmann (ISWS), Tom
Starks (UNLV-ERC, statistical consultant), and Mark Varljen (ISWS) in March 1990 at which an oral
presentation of the first year's activities was given. This report  includes some material which was
discussed at that meeting as well as a discussion of work accomplished since then.

A major focus of CR815681-01 is to improve the overall reliability of site characterization methods,
particularly as relates to ground-water contamination by volatile organic compounds.  Work is being
focused on a comparison between the concentrations of volatiles found on aquifer solids samples, in
monitoring well water samples, and in water samples collected by hydraulic probe (i.e., HydroPunch*).
Major concern regards estimating the contribution of sampling, analytical, and natural (or source)
variability to the overall variability of samples collected by these methods. Previous work (Barcelona,
et al., 1989) demonstrated how this can be done for the major inorganic and surrogate organic (e.g.,
TOC, TOX) ground-water quality parameters. Work under this cooperative agreement is deliberately
focused on volatile organic compounds.

Another  major focus of this  cooperative agreement is that of spatial and temporal variability of
VOC's in ground water within a "large" setting, i.e., several square miles (as opposed to an individual
site covering several square feet to several acres, e.g., Roberts, et al., 1990).  The field site chosen
is located in Rockford, Illinois (figure 1).  The area geology is principally characterized as outwash
sand and gravel lying within the Rock Bedrock Valley  which trends north-south  generally beneath
the present Rock River [for further discussion of the geologic setting, see previous progress reports
or Wehrmann, et al., 1988]. Background,  regional information  is being assessed from approximately
25 square miles (figure 2)  in the southeast quadrant of the city. The eastern one-third of the study
area is characterized as bedrock upland -  depth to bedrock (Silurian dolomite) is  often less than 50
feet. As the river is approached, however, the bedrock surface declines sharply and is overlain by up
to 250 feet of unconsolidated  glacial materials, principally outwash sand and gravel. Land use within
the area is mixed residential/industrial ~ heavy industry has marked the area for the past century.
Historical waste management  practices have led to numerous ground-water contamination problems
in the area (Colten and Breen, 1986).

Detailed  hydrogeologic and  chemical data collection activities  are  being concentrated  in  an
approximate ten  square mile area centered within the larger study area boundary.  The presence of
a variety of VOC's has been documented in numerous  private and public water supply wells  in the
area.  The principal components of contamination are trichloroethylene (TCE), trichloroethane
(TCA), dichloroethylene (DCE), and dichloroethane (DCA).
Summary of Project Activities

As mentioned in previous progress reports, efforts were being made to collect and assimilate as much
previously collected hydrogeologic and chemical data for the study area as possible. Other state and
local agencies (i.e., county and state health departments, Illinois EPA USEPA-Region V, Rockford
Water Department) were contacted and a variety of their data have been entered into basically four
related databases (figure 3).  Obviously, as we and these agencies collect new data, new information

                                             1

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Figure 1. General location of southeast Rockford study area.

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                 SE ROCKFORD  STUDY AREA
AREA OF
ENLARGEMENT
                                                       STUDY AREA
                                                       BOUNDARY
                           SCALE
                          0   0.5   1 mile
             Figure 2. Detailed view of southeast Rockford study area.

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will need to be added to the existing databases. Analysis of certain sets of these data have been
completed, however, and a summary of an evaluation of the quality of the historic ground-water
chemistry data is presented as an appendix. This includes a discussion of the types of chemical data
we have assembled and control chart analyses of VOC  data collected by the Illinois State Water
Survey (ISWS) and the Illinois Department of Public Health (IDPH) in previous studies in Rockford.
                            MASTER LOCATIONAL DATABASE
                                      Street addresses
                                  Digitized XY coordinates
   GEOLOGIC DATABASE
 [Aquifer Physical Properties]
          Well logs
       Bedrock surface
      Aquifer thickness
HYDROLOGIC DATABASE
[Aquifer Hydraulic Properties]
      Slug test results
  Ground-water elevations
  Historical pumping data
 CHEMICAL DATABASE
[Contaminant Distribution]
  Analyses from:
      Public wells
      Private wells
      Monitoring wells
                     Figure 3. Information contained in Rockford databases
Digitizing of private well sampling locations coupled with the water quality database has allowed us
to map VOC concentrations in a portion of the study area.  Contour maps of the principal VOC
components are presented in a following section entitled VOC Contaminant Distributor. In addition,
the results of our April sampling of the monitoring wells we drilled last fall are presented in the next
section aptly entitled April Sampling Results.  Other sections  of this report also include discussions
of geophysical work we conducted in June (and which we hope to continue later this summer), a brief
discussion of our summer drilling program, and other project-related activities.
April Sampling Results

The project staff jointly sampled five wells in April which are at the western edge of the known area
of contamination.  Results of sample analysis on these wells (#2, 4, 7, 8,  12) are summarized in
Tables 1 through 3.  The data show some evidence of ground-water contamination by a previously
detected contaminant, 1,1,1-trichloroethane, although the overall levels of the organic contaminants
appear to be quite low.

The apparent dissolved oxygen  concentrations  shown in Table 1  are clearly at or well above
equilibrium-saturation values for the in-situ temperatures. These were determined by iodometric
titration by the Winkler method and may be influenced by the presence of other dissolved oxidizing

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species acting as interferants, or a systematic error due to the low ambient temperatures experienced
in the field. We will explore these possibilities in detail in future sampling operations utilizing both
iodometric and electrometric (oxygen-electrode) methods.
   Table 1. Results of field chemical measurements for ground water sampled on April 17-18, 1990
Well
No.

2
4
7
8
12
Temperature (°C)


Down-hole Cell
11.5 13.0
11.5 12.5
13.0 12.0
10.2 11.5
11.4 12.7
Eh
(volts)

0.433
0.503
0.347
0.502
0.204
PH


7.30 - 7.58
7.34 - 7.60
7.14 - 7.39
7.35 - 7.56
7.62 - 8.02
Alkalinity
(mg/L as
CaCO3)
301.58
254.06
287.90
303.90
223.38
Dissolved
Oxygen8
(mg/L)
34.83
45.06
13.60
9.11
22.02
       8 Dissolved oxygen concentrations were determined by the Winkler titration method.


The volatile organic compound determinations (Table 2) reflect the area-wide halogenated solvent
contamination (i.e., trichloroethane) of the ground water.  The levels of approximately 15 ju-g/L
observed in the wells are at the very low end of the range of previously encountered contamination.
The observations of other chlorinated compounds and toluene are very near their respective detection
limits with  the exception of well #2.  Well #2 samples showed evidence of contamination with two
halogenated methanes as well as tetrachloroethylene though these observations need to be confirmed.
The dissolved inorganic and nutrient results (Table 3) reflect the levels commonly observed  in the
regional sand and gravel aquifer.   These preliminary  results will require  more in-depth  future
examination in order to correlate major ionic constituents distributions with regional water quality.

Determinations of pH, temperature, redox potential, alkalinity, and dissolved oxygen concentration
were all made in the field. Other inorganic and nutrient parameters, and volatile organic compounds
were determined in Western Michigan University's (WMU) Water Quality Laboratory. Unfortunately,
the planned purchase of new GC and GC-MS equipment has not been completed yet and our current
GC with FID and BCD detectors did not  allow us to determine the more volatile compounds (e.g.,
chloromethane, vinyl chloride, chloroethane). This was due mainly to interference from the methanol
solvent peak  and poor chromatographic resolution. We are improving our instrumental capabilities
and hopefully the new  GC-MS will arrive  in the  next month  or two. We have taken extra samples
which may  be used for future analysis under improved analytical conditions.

As part of  our vigorous pursuit of the QA/QC program, samples were analyzed  in the laboratory
together with at least  10% quality control samples consisting of duplicates, blanks,  EPA quality
control standards and/or laboratory standards.   The Water Quality  Laboratory at WMU has
documented  method performance parameters on file and  QA/QC  procedures  for all  inorganic
constituents analysis. However, improved VOC  analytical capability has to be established. We are

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in the process of evaluating and incorporating relevant laboratory QA/QC data into our Rockford
database in order  to be able to  estimate the magnitudes of errors introduced in the analytical
procedures. We will establish and evaluate the method performance for the VOC analyses soon after
our new instruments arrive.
    Table 2. Volatile organic compounds detected in ground water sampled on April 17-18, 1990
Well
No.
2



4

7

8


Compound
1,1,1 -trichloroethane
tetrachloroethene
bromodichloromethane
dibromochloromethane
1,1,1 -trichloroethane
toluene
1,1,1 -trichloroethane
1 ,3-dichlorobenzene
1,1,1 -trichloroethane
1,1,1 ,2-tetrachloroethane
ethylbenzene
Concentration
15.2
12.8
1.82
21.2
15.2
0.2
16.2/15.3
0.82/0.30
15.1
0.15
0.23
        12                  1,1,1-trichloroethane                           14.3
a Duplicate concentrations indicate results of duplicate analysis.
b Samples were analysed by the Water Quality Laboratory-WMU using a GC-FID method.
Historic Data Evaluation

We have attempted to collect historic chemical concentration and QC data as well as those from
more recent  sampling by other agencies.  To  date, we have gathered data from several sources
including the Illinois Department of Public Health (IDPH); the Rockford Water Department; and
previous research projects conducted by the Illinois State Water Survey (ISWS).  Data quality is
unknown for most of these data.   Preliminary examination  of available QA/QC  data  from two
analytical laboratories have enabled us to assess errors in the analytical procedures.  A summary of
these data collection and evaluation results is given in the Appendix.

The  laboratory QA/QC data  appear to suggest varying analytical errors for different compounds
depending on a number of factors including method of analysis and detection mechanism (e.g., GC
vs. GC-MS; PID vs. ELCD), instrument stability, calibration standard stability and replicate frequency,

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    Table 3. Metals and nutrients determined from ground water sampled on April 17-18, 1990
                                 (concentrations in mg/L)
Well
No.
2
4
7
8
12
Ca

81.2
-79.1
72.9
76.0
51.0
Mg

35.6
30.8
45.0
35.5
17.7
Na

26.8
28.8
25.2
15.6
23.2
K

2.38
2.96
5.96
3.14
1.40
Mn

0.02
<0.01
0.04
0.01
0.01
Fe

0.03
0.01
0.04
0.01
0.53
Ba

0.04
0.03
0.17
0.06
0.03

Well
No.
2
4
7
8
12
Cu

0.01
0.01
0.01
0.01
0.02
Cd

<0.01
<0.01
<0.01
<0.01
<0.01
Pb

0.04
0.04
0.04
0.04
0.01
Zn

<0.001
0.002
0.003
0.002
<0.001
Cl

50.1
57.2
66.7
23.9 •
10.1
S04

32.1
31.3
44.5
32.9
9.32
NO3-N

1.69
8.24
2.42
1.19
1.07

Well
No.
2
4
7
8
12
NH3-N

0.24
0.27
0.31
0.39
0.22
TDS

465
475
495
460
290
Si

7.56
8.50
6.11
9.42
6.90
TC

90.9
78.6
89.5
90.5
73.6
1C

85.9
70.9
87.2
88.0
68.1
TOC

5.0
7.7
2.3
2.5
5.5







TDS: Total Dissolved Solids; TC: Total Carbon; 1C: Inorganic Carbon; TOC: Total Organic Carbon

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and contamination.  For example, private well samples collected in 1986 by the ISWS were analyzed
by the Survey's Aquatic Chemistry Section using a GC method with PID (photo-ionization detector)
and  ELCD (electrolytic conductivity detector) detection.  Control chart analyses  of laboratory
standards recovery data suggest different patterns and magnitudes of variation in the recovery for
compounds determined by the ELCD (chlorinated aliphatic  compounds) and those by the PID
(aromatic compounds). For the aliphatic compounds, control charts show relatively small fluctuations
in the percent recovery during the early stage of the two-month analytical project (for typical charts
see figure Al  for dichloromethane and figure A8 for trichloroethene in the Appendix). Variation
increased during the later stage,  suggesting  decreased analytical precision.  For  the aromatic
compounds, control charts (e.g., figure A13 for chlorobenzene) show more stable percentage recovery
over the entire project, but analysis No. 26 on June 25 had  extraordinarily high  average  results,
suggesting it is an outlier.  The increasing positive bias of dichloromethane (figure Al) may be due
to gradual absorption of dichloromethane, a common solvent in the  laboratory, from the laboratory
environment by the reagent water  and/or  standards.  While  mean recoveries of most standard
compounds may be satisfactory (e.g., within  ±20% of the true value), precision of the analysis for
most chlorinated aliphatic compounds is poor.

Another example is the IDPH/Springfield laboratory which analyzed private well samples in Rockford
in the winter  of 1989 using a GC-MS  method.  Laboratory quality assurance data on standard
compounds recovery were available.  Control charts for the standards recovery are constructed and
a typical chart is shown in figure A22 for chloroform. Examination of the control charts suggest no
obvious outliers for all compounds.  Mean recoveries are within  ±20% of the true value and standard
deviations of  the recovery are less  than 15% for all  compounds  except vinyl chloride and 1,2-
dichloroethane which have slighlty higher values.

A number of missing data  points were present in the 1986 ISWS laboratory standards  results,
presumably due to failure in recognizing the GC peaks.  This problem is solved if a GC-MS method
is used, as in the IDPH/Springfield laboratory.
Future Experimental Design: Error Identification and Comparison

There is a critical need  in site characterization studies to  identify and control major sources of
sampling and analytical error. The control of systematic (determinate) error is particularly important
since these  errors lead to consistently low or  high apparent contaminant levels.  They may go
undetected in routine  investigations.  Indeed, if site characterization efforts  employ a number of
sampling personnel, techniques and matrices, systematically-biased results may be interpreted as actual
trends in contaminant distributions.  In our previous work (Sampling Frequency and Ground-Water
Sampling projects), we identified major sources of error and their potential effects on temporal trend
analysis.  Depending on the duration of the investigation, it may be necessary to increase the level
of QA/QC in order to reference our study results to apparent trends in the past ten to fifteen years
of data in the  Rockford region.  With respect to spatial variability, it will also be important to
intercompare overall accuracy and precision of replicate synoptic sample analyses from wells, the
Hydropunch, soil gas and aquifer solids.

This task, which we will pursue in the next two quarters of the project, will begin with an initial error
survey to estimate the magnitude of the errors involved in various  sampling and analytical steps. This
will be followed by the intercalibration experiment employing sufficient replicates to permit control

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          Table 4.  Error Identification and Control Measures for Ground-Water Sampling and Analysis
Sample
Collection
Error Source Pumping/
purging
Grab sampling
Sample
Handling/
Storage
Handling
losses/gains
Sample matrix
effects
Analysis Overall
Precision &
Accuracy
Analytical
methods

                                           Storage losses/
                                           gains
Control
Samples
Replicate
samples as a
function of
pumping or
sampling
technique
Field standards/
blanks

Spiked sample
replicates,
sample
replicates
Lab
standards

Lab blanks

External •
reference
samples
Precison/
Accuracy
6C*, Rf
                                         6C+6H+6A=
                                         *
                                         °Total

                                         RC+RH+
   Precision in units of standard deviation
   Accuracy in units of percent recovery relative to standards (i.e., bias)

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over the errors so that techniques can be compared in a statistically significant manner. The
sources of errors inherent to steps in sampling and analytical operations are shown in Table 4
with reference to the QA/QC control samples and standards which will be used to estimate
accuracy as percent recovery or bias and precision.

Our analysis of the existing organic compound data (provided in the Appendix) disclosed that
accuracy and precision may not have been controlled adequately over the entire period of
individual investigations.  Therefore, our study will employ additional control samples and
standards as well as external reference standards for each step in sample collection and analysis.
It is also clear that we will have to employ field and lab controls/replicates over a range of
concentrations to determine if either accuracy or precision vary with concentration level. We
anticipate that the concentration range of interest will extend from the method detection limit
(e.g., generally less than 1 /Ltg/L) to approximately 1 mg/L for volatile organic compounds in
water).
VOC Contaminant Distributions

Figures 4 - 8 present contour maps of several VOC contaminant distributions within the enlarged
area shown in figure 2.  Total VOC's are shown in figure 4, followed by trichloroethane (figure
5), trichloroethene (figure 6), 1,1-dichloroethene (figure 7), and dichloroethane (figure 8).
Asterisks on the maps represent the 220+ private well locations sampled by IDPH.  Punctual
kriging was performed to interpolate VOC concentrations at the nodes of a 30 x 20 grid in order
to facilitate contouring (kriging was accomplished using GEO-EAS, contouring was accomplished
using SURFER®). Note a general lack of sampling points in a corridor starting in the northeast
corner of the figures and proceeding southwest to just east of center.

Total VOC's range from nondetectable to over 700 /ig/L (figure 4). The plume generally follows
the direction of ground-water flow, that is, from east to west. The location of private water wells
allows a fairly detailed delineation of the  plume especially to the south and in selected zones
within the plume itself. However, we are  much less confident in the configuration of the plume to
the north and east because of the lack of sampling locations in that area (i.e., north and east of
the figure).  It is important to note that our interpolations indicate three peaks in the plume of
total VOC's.  Two of these peaks occur in regions where relatively few samples were taken.
Therefore, it has yet to be determined if these peaks are real or an artifact of the
interpolation/contouring procedure.

One way to express confidence in the  kriged estimates is to look at the error or standard
deviation of the estimate. The error of the kriged estimate of the total VOC's (i.e., the standard
deviation of the kriged, interpolated values) in figure 4 was contoured and is shown in figure 9.
Contour values represent the ln(total VOC's) with a contour interval of 0.1. The greatest error in
our kriged estimates will be where we  have the least data.  This is easily seen in figure 9 to
encompass areas outside of our private well sampling locations.  Similar uncertainties exist for
contours of individual VOC compounds.  We intend to use these  uncertainty data as a guide for
future sampling ~ most likely through  drilling and hydropunching.

The trichloroethane (TCA) plume (figure 5) appears to be quite similar to the total VOC plume.
Peaks in the plume of total VOC's are also strongly evident in the TCA plume. Even though

                                             10

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Figure 4. Total VOC concentrations in enlarged map area of figure 2 (scale: 1" = 1000').




                                         11

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                        P   i<^ldrj
                        i   L^^rfM
Figure 5. Trichloroethane (TCA) concentrations in enlarged map area of figure 2 (scale: 1" = 1000').




                               12

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Figure 6. Trichloroethene (TCE) concentrations in enlarged map area of figure 2 (scale: 1" = 1000').




                                             13

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Figure 7. 1,1-Dichloroethene (DCE) concentrations in enlarged map area of figure 2 (scale: 1' = 1000').


                                              14

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Figure 8. Dichloroethane (DCA) concentrations in enlarged map area of figure 2 (scale: 1" = 1000').




                                             15

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Figure 9. Standard deviation of the kriged estimate of ln[TVOC], contour interval = 0.1(ln[TVOC]) (scale: 1" =  1000').




                                                        16

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some portions of the peaks occur in areas where there are few samples, other portions occur
where there are many samples (i.e., we have more confidence in the interpolations).  Interestingly,
the separation distance between peaks figures to approximately a one year travel time assuming a
ground-water flow velocity of one foot per day (Wehrmann et al., 1988).

The spatial distributions of the compounds trichloroethene (TCE) and 1,1-dichloroethene (DCE),
figures 6 and 7, respectively,  are much different than for the TCA plume.  The TCE plume
appears to look like the "classic" point source plume with the highest concentrations in an
upgradient location and lower concentrations fanning out downgradient. Again, however, the
contoured plot shows the highest concentration in an area where no actual data exists and care
should be exerted when examining the contour map.

On the other hand, confidence in the DCE plume (figure 7) is quite high, as there are many
sampling points equally distributed throughout the plume.  No DCE appears to exist within the
eastern portion of the volatile plume. DCE concentrations increase in the downgradient
direction. This manifestation is consistent with the production of DCE from the degradation of
TCE and TCA (Olsen and Davis, 1990).  The compound dichloroethane (3JCA) is also present
(figure 8).  Compound identification was more uncertain for this compound than many of the
others  and, therefore, the contoured concentrations are less well behaved -- the pattern  exhibited
is similar to that of the TCE plume.

Incidentally, the graphical overlaying of concentration contours, sample locations, and cultural
information (e.g., roads, etc.) was accomplished using a desktop geographic information system
(GIS) developed for  this project. The concept of this desktop GIS, which is based on the
computer aided drafting program AutoCAD® was the topic of a paper presented by Mark Varljen
last June in San Francisco at the ASTM International Symposium on Mapping and Geographic
Information Systems.  A paper using some of the figures in this report as examples will be
published as part of the ASTM Special Technical Publications (STP) series -- the paper  was
reviewed by Bedinger and  C.O. Morgan.
Geophysics

As part of the hydrogeological investigation, a good conceptual model of ground-water flow
behaviour across the study area is needed.  In particular, we feel more effort is needed to
determine where the sand and gravel aquifer pinches out along the eastern bedrock valley wall of
the Rock Bedrock Valley. Not only does the sand and gravel thickness decrease as the elevation
of the valley wall rises, the thickness is decreased from above as a sequence of till overlies the
sand and gravel along the eastern flank of the valley.  Some surface resistivity may be done this
fall  to help define the existence of the till overburden; however, last June with the assistance of
the State Geological Survey, we spent P/2 days conducting a series of seismic refraction lines to
better define the depth to the bedrock valley wall in eastern portions of the study area.  The
locations of the general areas of investigation are shown in figure 10.

Six 600-foot lines were run with shots placed at both ends of the lines. One 1200-foot line was
laid out but not completed because of difficulties with the detonator.  More work will be done
later this year in the locations indicated.  Preliminary results indicate the depth to bedrock in
some areas was from 60 to 80 feet and in others over 200 feet. A detailed  analysis will be

                                            17

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       LOCATIONS  OF  GEOPHYSICAL INVESTIGATIONS
             SCALE
             MHBI^=
             0   0.5   1 ml<
                                    PROPOSED
Figure 10. Locations of seismic refraction lines for geophysical investigations in SE Rockford.


                               18

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forthcoming in future reports.


Upcoming Project Activities

Drilling/Sampling

Just as this progress report was being finished, another group of monitoring wells was being
installed in Rockford.  In conjunction with this drilling program, Kent Cordry (QED Technical
Consultant on the HydroPunch) assisted with the collection of several HydroPunch samples.  The
next progress report will detail the results of this preliminary work.  Figure 11 shows the location
of all our monitoring wells  (20 total). Wells 13-20 were drilled most recently.  The location of
most of our monitoring wells in relation to the VOC plume is shown in figure 12.

As the drilling progressed, Mike Barcelona and Western Michigan University staff with the
assistance of IDPH personnel, collected 80+ samples for VOC analysis from a selected group of
homes within the affected area.  All of the wells at these homes will be abandoned because City
water has been extended to the area through Superfund Emergency Response.  Sampling was
deemed highly desirable as a last chance to secure high-density coverage of the plume to evaluate
temporal changes in the plume configuration.  Again, a more detailed discussion of the results of
this effort will follow in our next progress report.
Budget

As of 7/20/90 accounting, the project is operating within budget for the first two budget
increments totaling $300,000. Progress on the WMU subcontract work had been substantially
slowed due to the inordinately long delay in processing the budget revision submitted in
December 1989.  It appears that the negotiations over equipment transfers slowed the processing
somewhat, yet the successive four month delay resulted from office difficulties at Agency
Headquarters.  As of this writing, the subcontractual agreement with the University of Illinois
should be in the final stages of approval. Is is clear that avoidance of future delays will be
necessary to keep their work on  schedule. Submission for an $85,000 third increment was made
last April. We have not received any word of the status of this funding.

The status of budget line items within the  $300,000 limit of the first two incements is shown on
the next page.  Outstanding obligations exist in the amount of approximately $11,000 which have
not yet cleared accounting (principally drilling costs).  The subcontractual line of $126,490 will  be
obligated when final subcontract arrangements have been made (Barcelona does have a letter of
intent from the U of I which basically allows him to spend against this amount). As you can see,
while we are within budget, once the $126,490 is obligated, our balance is only $7,333.
Considering the $11,000 outstanding, the $85,000 increment is sorely needed, particularly to
balance out our travel and supply lines.  These lines are especially  hard-hit during our summer
field work. Frankly, an additional increment will be needed to get us through the remainder of
the field season this fall.
                                             19

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                                               Budgeted        Balance

       Personnel                                $ 60,362
       Fringe Benefits                              7,908
       Travel                                      7,197
       Equipment                                 18,405
       Supplies                                    11,615
       Contractual                                 13,836
       Subcontractual (WMU)                     126,490
       Other                                       2,279
       Indirect Costs                               51.908

       Total Budget                             $300,000       $133,823
Project Staff

There have been no major changes in project staff during the past quarter.  Mark Varljen was
added to the staff of the Water Survey as a full-time permanent employee upon graduation last
June. He has been involved with the project from the start as a graduate assistant working part-
time during the school year and full-time last summer (1989). Mark is responsible for the
geostatistical interpretation and most of the hydrologic, geologic, and master locational database
development.
                                            20

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                                                  Sandy Hollow  Rd
Figure 11. Location of 4 municipal and 20 monitoring wells in SE Rockford study area.
                                    21

-------
                                        Harrison  Ave.
                              Sandy Hollow  Rd
Figure 12. Location of monitoring wells in relation to known VOC plume in SE Rockford study area.
                                  22

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                                    REFERENCES

Barcelona, M.J., H.A. Wehrmann, M.R. Schock, M.E. Sievers, and J.R. Karny. 1988. Sampling
Frequency for Ground-Water Quality Monitoring. Final Contract Report to USEPA-EMSL
(Grant No. CR12165-092), Las Vegas, NV. 194 p.

Colten, C.E., and G.E. Breen. 1986. Historical Hazardous Waste Disposal Practices in Winnebago
County, Illinois: 1870-1980. Illinois Hazardous Waste Research and Information Center Research
Report Oil, Champaign, IL. 125 p.

Olsen, R.L., and A. Davis. 1990. Predicting the Fate and Transport of Organic Compounds in
Groundwater Part I.  Hazardous Materials Control v. 3, no. 3 (May-June), pp. 39-64.

Roberts, P.V., G.D. Hopkins, D.M. Mackay, and  L. Semprini. 1990.^4 Field Evaluation of In-Situ
Biodegradation of Chlorinated Ethenes: Part I, Methodology and Field Site Characterization.
Ground Water, v. 28, no. 4, pp. 591-604.

Varljen, M.D., and H.A. Wehrmann. 1990. Using AutoCAD as a Desktop GIS for Hydrogeological
Investigations. ASTM Symposium on Mapping and Geographic Information Systems. June 21-
22,1990. San Francisco. In Press.

Wehrmann, H.A, T.R. Holm, L.P. Le Seur,  C.D. Curtiss III. 1988. A Regional Ground-Water
Quality Characterization of the Rockford Area. Winnebago County. Illinois. Illinois Hazardous
Waste Research and Information Center Research Report 027, Champaign, IL. 114 p.
                                          23

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                                        APPENDIX
  Summary of Collection and Evaluation of Historic Data on Rockford Groundwater Chemistry
                                       May 28, 1990
A. Historic Data Collection

Historic data on  Rockford ground water chemistry are available as a result of several  previous
sampling and monitoring efforts made by the Illinois Department of Public Health (IDPH), the
Illinois State Water Survey  (ISWS),  and other  state and municipal  agencies.   To date,  we have
collected a considerable amount of data from these sources on a number of chemical parameters.

Historic samplings were undertaken for a variety of reasons. Each set of data sources generally had
a different set of chemical parameters which were determined under different field and analytical
conditions.  In  certain cases, samples from  one sampling event were analyzed by more than one
laboratory  and  no external reference or inter-laboratory calibration data were available.  These
problems have resulted in data incompleteness and data quality inconsistencies.  In most cases, data
quality estimations (analytical precision and bias) were not supplied.  We were successful, however,
in obtaining relevant raw QA/QC data from some analytical laboratories.

Original data were supplied to us in hard copy and all have been through a preliminary examination.
In some cases this involved data reduction before manual entry into a PC-based database in the form
of ten Lotus spreadsheets. Table Al lists the Lotus spreadsheets and their contents. Codes and/or
abbreviations used in the database are provided  in Table A2.

The data  collected fall into  either organic (volatile organic compounds or VOC)  or inorganic
categories.  The following list shows specific parameters for which we have data for at least one
sample:

Inorganic Parameters: pH, alkalinity, SO42', NH4+, Ag, Al, As, B, Ba,  Ca, Cd, CM", Co, Cr, Cu, Fe,
       Hg, K, Mg, Mn, Na, Ni, Pb, Se, Sr, Zn.

Organic    (VOC)   Parameters:   vinyl   chloride,    bromoform,  bromodichloromethane,
       chlorodibromomethane, dichloromethane, trans-1,2-dichloroethene, 1,1-dichloroethane, 1,1-
       dichloroethene,cis-l,2-dichloroethene,chloroform,l,2-dichloroethane,trichloroethane,carbon
       tetrachloride, trichloroethene, 1,1,2-trichloroethane, tetrachloroethene,  benzene, toluene,
       chlorobenzene,  ethylbenzene,  1,3-dichlorobenzene,   1,4,-dichlorobenzene,   and  1,2-
       dichlorobenzene
B. Inorganic Data

Inorganic data collected are stored in file MASTER1.WK1. A major portion of the data was from
the 1986 private well sampling by the ISWS. Data from various other sources also are included with
sampling dates back to 1955 (1984, '82, '79, '78, '74, etc.).
                                            Al

-------
 C. Organic rVOQ Data

 Organic data are contained in file MASTER2.WK1.  These are primarily from the following sampling
 events:

 a. Private Well Sampling by IDPH. Sampling was conducted in Fall and Winter, 1989. Samples were
 analyzed in two laboratories, IDPH/Springfield Laboratory and IDPH/Chicago Laboratory.

 The Springfield Laboratory analyzed samples collected on: 11/06/89,       12/05/89,       12/1289,
 for the following (quantitative) parameters (using  capillary GC-MS method): vinyl chloride, 1,1-
 dichloroethene,  chloroform,  1,2-dichloroethane,   1,1,1-trichloroethane,  carbon  tetrachloride,
 bromodichloromethane, trichloroethene, benzene, dibromochloromethane, 2-chloro vinyl ether, and
 1,4-dichlorobenzene.

 The Chicago Laboratory analyzed samples collected on: 09/12/89, 09/19/89, 09/26/89,       10/17/89,
 10/25/89, 11/06-07/89, 11/28/89, 12/04/89, and 12/11/89.

 b.  Private Well Sampling by ISWS, 1986  (Wehrmann/Holm principal investigators).  Sampling was
 conducted in the Summer of 1986 and all samples were analyzed by ISWS Aquatic Chemistry Section
 using capillary GC-ELCD/PID. Parameters determined were as follows: dichloromethane, trans-1,2-
 dichloroethene, 1,1-dichloroethane, cis-l,2-dichloroethene, chloroform,  1,2-dichloroethane  plus
 trichloroethane (coeluting  on   GC  column),  carbon  tetrachloride,   trichloroethene,  1,1,2-
 trichloroethane,  tetrachloroethene,  benzene,  toluene,  chlorobenzene,  ethylbenzene,  1,3-
 dichlorobenzene, 1,4,-dichlorobenzene, and 1,2-dichlorobenzene.

 c. ISWS 1988 Pump Test on Municipal  Well 7A and VOC Sampling from Observation Wells.  Samples
 were analyzed  by ISWS for five  compounds: chloroform, benzene, toluene, trichloroethene and
 tetrachloroethene. Limited data.

d.  Miscellaneous Sources.  These include data from municipal well sampling conducted by the
Rockford Department of Water and others.
D. Data Quality Evaluation

A major problem encountered with the historic data are the data quality unknowns.  In most cases,
no error limits were given in the original data reports supplied to us.  We are unaware of any
vigorous QA/QC programs carried out with the sampling procedures (except limited data on travel
blanks) and cannot evaluate  overall data quality.  However,  by direct contact with the analytical
laboratories involved in the  sample analysis,  we were able to obtain  some  specific  analytical
information and laboratory quality assurance data, which would allow us to estimate  analytical
uncertainties.  The discussion below is restricted to the VOC analysis in two laboratories of which
we have so far obtained relatively complete sets of QA/QC data.

a. 1986 ISWS VOC Analysis.  Samples from the 1986 ISWS private well sampling were analyzed in
the Aquatic Chemistry Section, ISWS  between June 6 and  August 5, 1986.  Laboratory quality
assurance data on standard compound recovery are available for this period (file QAQC2.WK1).
                                            A2

-------
According to laboratory records, at least one laboratory standard sample was analyzed on any day
Rockford samples were analyzed.  Concentration levels of the laboratory standards included 5, 20,
but mostly 10 /ig/L.

The analytical  facility  consisted of an HP 19395A static headspace sampler, a Varian 3700 gas
chromatograph equipped with a HNU PID and an Hall ELCD in tandem, and a Vista 401 data
system. The facility was automated with the auto-injection feature of the sampler and a custom-made
timing/relay circuit  which,  upon  sample injection,  activates acquisition by the data  system  and
temperature programming on the GC.  All compounds were identified based on comparison of the
retention time  with  that of standard compounds.   1,4-Dichlorobutane was  used as the internal
quantitation standard for chlorinated aliphatic  hydrocarbons detected by the ELCD, and a,a,o-
trifluorotoluene as the internal standard for the aromatic compounds detected by the PID.

Percent recoveries of each standard compound have been calculated and the complete data set is
contained in file QAQC2.WK1. Summary statistics  on the recovery data, subgrouped by compound
concentrations and as a whole data set, are  shown in Table A3. X-Control charts for each compound
are plotted in figures Al to A17.

As  indicated in Table A3, we  have data from a total of 4 determinations at the 5 /ig/L level.  All
compounds appear to have been recognized and quantified.  There are 33 determinations at the 10
/ig/L level and 8 determinations at the 20 /ig/L level. At the latter two concentration levels, several
missing values are present  for certain compounds presumably because these compounds were not
recognized in the analysis. The missing data points were excluded from statistical analysis (Table A3).

The majority of compounds have a mean recovery within ±20% of the true value.  Positively biased
compounds exceeding 120% recovery include dichloromethane (5,10,20/igTL and overall), trans-1,2-
dichloroethene (10,  20 /ig/L  and overall),  1,1-dichloroethane (10,  20 /ig/L and overall), 1,1,2-
trichloroethane (20 /ig/L), and carbon tetrachloride  (20 /ig/L).  Negatively biased compounds with a
recovery lower  than 80% include cis-l,2-dichloroethane (5 /ig/L) and  carbon tetrachloride (5 /ig/L).

Standard deviations of percentage recovery are significantly large for  most compounds in the 10, 20
/ig/L and the all standards  sub-data sets (Table A3). In contrast, the 5 /ig/L standards show small
standard deviations.   No obvious analytical relationships, however,  can be derived between the
standard deviation and the  mean of the recovery. Indeed, the 5 /tg/L standards were analyzed only
in the early stage of the project (prior to June 13).  Determination of other standards spanned over
a wider period of time when other factors may have caused greater analytical variances as illustrated
in the control chart analysis discussed next.

In general, control charts  for the halogenated aliphatic compounds (figures  Al to A10) show
relatively small  fluctuations in the early stage of the analysis period (prior to June 17). Variation
increased during the later stages.  For aromatic compounds (except  1,2-dichlorobenzene),  control
charts show more stable percentage recovery over the entire analysis  period, but analysis no. 26 on
June 25 had extraordinarily high concentration results, suggesting a possible outlier. After removal
of analysis no. 26, statistical analysis of both the 10  /ig/L sub-data  set and the  all-standards data set
gives considerably smaller values in standard deviations for the aromatic compounds (Table A3). The
larger errors  in the  aliphatic  compound analyses compared to the  aromatic  may be due to the
different detection mechanisms.  Furthermore, larger  errors for the  aliphatic compound analyses
experienced in the later stage of the analysis period may be due to increased detector or laboratory

                                             A3

-------
standard instability.

The control chart for dichloromethane (figure Al) shows a significant increasing trend with time
starting from approximately June 16. The highest recovery reached 710.4%.  This increasing positive
bias may be attributed,  at least in part, to the gradual absorption of dichloromethane, a common
solvent in the  laboratory, from the laboratory environment by the reagent water and/or standards.

Based on the statistics  for the 5 /ig/L standards, Method Detection Limit  (MDL) and  Method
Quantitation Limit (MQL) are estimated  (Table A4). As the 5 figfL standards were all analyzed at
a period of best analytical performance, these estimates should be considered as the lowest possible
limits. Estimation of the 95% confidence interval for the overall percentage recovery is also given
in Table A4.

In summary, accuracy and  precision of VOC analysis by ISWS  in 1986 can be assessed from the
quality assurance data on the standard compound recovery. While mean recoveries of most standard
compounds  may be satisfactory (e.g., within ±20% of the true value), precision of the analysis for
most chlorinated aliphatic  compounds is poor. Control chart analyses suggest greater analytical
variability for the chlorinated aliphatic hydrocarbons during the later stage of the analytical season.
For the chlorinated aromatic hydrocarbons, precision is satisfactory if a highly likely outlier sample
is removed.  A number of factors may have influenced the  analytical accuracy and precision, including
detection mechanisms, instrument stability, calibration standard stability and replicate frequency, and
contamination.

b.  IDPHI Springfield Laboratory  VOC Analysis.  IDPH/Springfield Laboratory provided raw data on
GC-MS calibration check standards which were analyzed  together with the Rockford samples in the
winter of 1989. These raw QA data were reduced and entered into  Lotus  files QAQC3.WK1 and
QAQC4.WK1. Limited QA/QC data for  travel blanks and laboratory duplicates were also available
on the Springfield Laboratory analysis.

Data from a total of 18  determinations on standard samples were supplied to us, most of which are
2 /ig/L standards (Table A7).  Other concentration levels were 0.4, 4, 8, and 20 /ig/L but the number
of data points  is  insufficient for subgroup statistical analysis. For this reason, statistics are only
obtained on percentage recovery data of  all standards (Table A5).

As shown in Table A5, the mean recovery of  all compounds  are within  ±20% of the true value.
Standard deviations of recovery for all compounds are less than 15% except vinyl chloride  and 1,2-
dichloroethane which have slightly higher values.

Examination of control charts (figures  A18 through A29)  suggests no obvious  outliers for all
compounds. However, short term (hours) drifts are obvious for most  of the  compounds (e.g., figure
A19,vinyl  chloride; figure  A20, bromoform).   It would appear that the analytical/instrumental
condition was  not sufficiently stable (not unusual for GC-MS quantitation) but well maintained
calibration/quality assurance procedures have ensured satisfactory results.
                                            A4

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     Table Al. Directory of Lotus Spreadsheets for Rockford Ground-Water Quality Data


MASTER 1  -  Inorganic chemistry master database

MASTER2  -  Organic chemistry master database

PUMPTEST -  VOC results from ISWS 1988 pump test on Municipal Well 7A

INQAQCl  -  Inorganic QA/QC data for 1986 private well sampling conducted by
              Wehrmann/Holm

QAQC1     -  Organic QA/QC results and calculations of % recovery for 1988 pump test

QAQC2     -  Organic QA/QC data for 1986 private well sampling conducted by
              Wehrmann/Holm

QAQC3     -  Organic QA/QC data for 12/5/89 private well sampling - IDPH Springfield

QAQC3A   -  Percent recovery calculates for lab standards - IDPH Springfield, 12/5/89

QAQC4     -  Organic QA/QC data for 12/12/89 private well  sampling - IDPH Springfield

QAQC4A   -  Percent recovery calculations for lab standards - IDPH Springfield, 12/12/89
                                         A5

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Table A2. Codes Used in Rockford Ground-Water Quality Databases
Well Type


Use
Aquifer Type


Site



Data Source



Concentration
             SP
              D
              P
           PWS
              M

            S-G
              B
            R.#
            SWS
         IDPH-C
         IDPH-S

              #
             ND
Sand Point
Drilled

Private
Commercial
Public Water Supply
Monitoring

Sand & Gravel
Bedrock

Rockford Group Well
Rockford Unit Well
Loves Park

State Water Survey
Dept. Pub. Health/Chicago Laboratory
Dept. Pub. Health/Springfield Laboratory

Compound detected but not quantified
Not detected
                             A6

-------
Table A3. Summary Statistics of Percentage Recovery of Laboratory Standards, ISWS
                            (June to August, 1986)1>2
Number of
Compound Observations
5 pbb standards (4 analyses)
dichloromethane
trans- 1 ,2-dichloroethene
1,1-dichloroethane
cis-l,2-dichloroethene
chloroform
1,2-dichloroethane
+ trichloroethane
carbon tetrachloride
trichloroethene
1 , 1 ,2-trichloroethane
tetrachloroethene
benzene
toluene
chlorobenzene
ethylbenzene
1 ,3 -dichlorobenzene
1 ,4-dichlorobenzene
1 ,2-dichlorobenzene
10 ppb standards (33 analyses)
dichloromethane
trans-l,2-dichloroethene
1 , 1 -dichloroethane
cis- 1 ,2-dichloroethene
chloroform
1,2-dichloroethane
+ trichloroethane
carbon tetrachloride
trichloroethene
1 , 1 ,2-trichloroethane
tetrachloroethene •
benzene

toluene


4
4
4
4
4
4

4
4
4
4
4
4
4
4
4
4
4

32
32
29
31
28
33

28
33
31
32
33
(32)
33
(32)
Minimum

115.8
77.4
82.0
73.2
83.4
83.1

64.8
73.6
76.0
75.6
99.0
87.0
96.2
90.8
95.6
91.6
98.6

15.1
83.1
86.5
45.6
65.3
18.4

83.3
53.8
71.9
58.7
89.9

63.0

Maximum

124.4
87.6
99.2
81.4
99.8
95.4

77.2
88.2
85.0
85.6
102.2
91.2
103.8
96.0
100.4
106.2 .
100.4

710.4
294.5
226.3
177.5
222.3
374.5

200.3
128.1
131.2
122.8
244.9
(149.4)
193.5
(107.9)
Mean

120.4
82.7
91.0
77.5
93.0
90.4

72.2
82.6
81.3
80.3
101.0
89.5
98.6
94.4
97.5
96.0
99.4

316.6
128.7
135.9
98.5
116.0
119.0

120.7
100.9
106.5
95.9
108.0
(103.7)
88.6
(85.3)
Standard
Deviation

4.64
5.06
7.04
3.40
6.89
5.25

5.79
6.47
3.79
4.66
1.47
1.77
3.50
2.42
2.10
6.84
0.90

173.82
40.34
35.43
27.06
32.75
59.74

31.35
16.20
11.54
13.04
26.46
(9.96)
20.99
(9.42)
                                                                           (continued)
                                      A7

-------
(Table A3. continued)
Number of
Compound Observations
chlorobenzene

ethylbenzene

1,3-dichlorobenzene

1 ,4-dichlorobenzene

1 ,2-dichlorobenzene
20 ppb standards (8 analyses)
dichloromethane
trans- 1 ,2-dichloroethene
1 , 1 -dichloroethane
cis- 1 ,2-dichloroethene
chloroform
1,2-dichloroethane
+ trichloroethane
carbon tetrachloride
trichloroethene
1 , 1 ,2-trichloroethane
tetrachloroethene
benzene
toluene
chlorobenzene
ethylbenzene
1 ,3-dichlorobenzene
1 ,4-dichlorobenzene
1 ,2-dichlorobenzene
All standards (45 analyses)
dichloromethane
trans- 1 ,2-dichloroethene
1,1 -dichloroethane
cis- 1 ,2-dichloroethene
chloroform
1 ,2-dichloroethane
+ trichloroethane
carbon tetrachloride
trichloroethene
33
(32)
33
(32)
33
(32)
33
(32)
29

8
8
8
8
8
8

8
8
8
8
8
8
8
8
8
8
7

44
44
41
43
40
45

40
45
Minimum
74.8

67.4

66.5

66.3

73.0

97.7
88.2
90.3
90.5
94.4
91.3

86.3
91.6
102.2
88.9
96.1
91.8
101.5
105.0
94.8
95.7
97.5

15.1
77.4
82.0
45.6
65.3
18.4

64.8
53.8
Maximum
207.5
(104.4)
182.2
(109.6)
177.2
(105.1)
155.2
(104.4)
151.8

397.3
166.7
157.8
133.7
139.7
146.4

169.9
139.9
155.6
131.6
113.2
98.5
107.7
118.0
107.4
110.2
109.0

710.4
294.5
226.3
177.5
222.3
374.5

200.3
139.9
Mean
98.1
(94.7)
98.7
(96.1)
92.8
(90.2)
92.4
(90.5)
93.9

235.1
122.2
120.7
109.4
111.6
114.0

124.6
112.4
123.4
106.8
104.8
94.1
104.2
112.9
100.8
102.6
103.9

284.0
123.3
128.6
98.5
112.8
115.5

116.6
101.3
Standard
Deviation
20.96
(7.43)
17.76
(9.67)
17.40
(8.71)
14.60
(9.44)
13.61

135.23
29.89
26.16
14.51
16.36
20.17

31.22
19.38
18.09
15.91
6.46
2.69
2.29
5.10.
3.99
5.12
4.47

168.8
38.7
34.6
25.0
29.0
52.2

32.9
17.5
                                                                                    (continued)
                                             A8

-------
(Table A3. concluded)
Compound
1,1,2-trichloroethane
tetrachloroethene
benzene

toluene

chlorobenzene

ethylbenzene

1 ,3-dichlorobenzene

1 ,4-dichlorobenzene

1 ,2-dichlorobenzene
Number of
Observations
43
44
45
(44)
45
(44)
45
(44)
45
(44)
45
(44)
45
(44)
40
Minimum
71.9
58.7
89.9

63.0

74.8

67.4

66.5

66.3

73.0
Maximum
155.6
131.6
244.9
(149.4)
193.5
(107.9)
207.5
(107.7)
182.2
(118.0)
177.2
(107.4)
155.2
(110.2)
151.8
Mean
107.3
96.5
106.8
(103.7)
89.7
(87.3)
99.2
(96.8)
100.8
(99.0)
94.6
(92.8)
94.6
(93.2)
96.2
Standard
Deviation
16.3
14.5
22.8
(8.91)
18.1
(8.79)
18.1
(7.44)
16.4
(10.8)
15.3
(8.75)
13.3
(9.71)
12.3
1. Missing data were excluded from the statistical analysis.
2. Values in parentheses are statistics of data sub-set obtained by removal of the outlier (analysis
    no. 26).
                                              A9

-------
          Table A4. Method Detection Limit (MDL), Quantitation Limit (MQL), and
            95% Confidence Interval for Percent Recovery of VOC Analysis, ISWS
                                 (June to August, 1986)
 Compound
MDL
MQL1
95% Confidence Interval2-3
From (%)      To (%)
dichloromethane
trans-l,2-dichloroethene
1,1-dichloroethane
cis-l,2-dichloroethene
chloroform
1,2-dichloroethane
+ trichloroethane
carbon tetrachloride
trichloroethene
1,1,2-trichloroethane
tetrachloroethene
benzene

toluene

chlorobenzene

ethylbenzene

1 ,3-dichlorobenzene

1 ,4-dichlorobenzene

1 ,2-dichlorobenzene
1.1
1.1
1.6
0.8
1.6
2.4

1.3
1.5
0.9
1.1
0.3

0.4

0.8

0.6

0.5

1.6

0.2
2.3
2.5
3.5
1.7
3.4
5.3

2.9
3.2
1.9
2.3
0.7

0.9

1.8

1.2

1.1

3.4

0.5
-222.4
7.3
24.9
23.6
25.8
-41.2

17.8
48.7
58.4
53.0
38.4
(77.0)
35.5
(60.9)
45.0
(74.4)
51.7
(66.6)
48.8
(66.5)
54.6
(64.1)
59.3
790.3
239.3
232.3
173.5
199.9
272.3

215.4
154.0
156.2
139.9
175.3
(130.4)
143.8
(113.7)
153.4
(119.1)
149.9
(131.3)
140.5
(119.0)
134.5
(122.3)
133.2
1. Estimation of MDL and MQL are based on statistics on the 5 ppb standards (Table A3),
    where:
             MDL=4.541  x (5o)
             MQL=10 x (5o)

             where, o =standard deviation of recovery

2. Estimation of 95% confidence interval is based on statistics on all standards (Table A3),
    from Mean - 3o to Mean + 3o.

3. Values in parentheses are estimates based on statistics after removal of the outlier,
    analysis no. 26.
                                         A10

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     Table A5. Summary Statistics of Percentage Recovery of Laboratory Standards,
                         IDPH/Springfield (December, 19S9)
                             Number of                                       Standard
Compound                 Observations   Minimum   Maximum     Mean   Deviation

carbon tetrachloride               18           74.5       114.0        93.8      12.80
vinyl chloride                     18           56.6       111.9        83.2      16.03
bromoform                       18           89.1       130.5       110.3      11.14
bromodichloromethane            18           75.0       113.2        95.0      11.99
chloroform                       18           71.6       103.2        90.9       9.86
chlorodibromomethane            18           89.2       113.9       102.1       8.15
1,2-dichloroethane                18           63.0       112.4        91.7      15.95
1,1,1-trichloroethane              18           72.8       114.1        91.7      11.02
benzene                         18           82.3       104.3        93.7       6.98
1,4-dichlorobenzene               18           90.9       123.5       106.8       9.65
1,1-dichloroethene                18           60.8       102.4        81.3      13.34
tetrachloroethene                 18           80.8       107.7        95.9       7.81
                                        All

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Table A6. Analysis Sequence Number, Date of Analysis, and Laboratory Standard Concentration
             Plotted in Control Charts in Figures Al to A17 (ISWS 1986 Data)
Analysis
Sequence
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Analysis Laboratory Standard
Date Concentration
(1986) (Mg/L)
06/06
06/06
06/09
06/09
06/10
06/10
06/11
06/11
06/12
06/12
06/13
06/13
06/16
06/16
06/16
06/17
06/17
06/23
06/23
06/24
06/24
06/24
06/24
20
20
10
10
5
5
20
20
5
5
10
10
10
10
10
10
10
10
10
10
10
10
10
Analysis
Sequence
Number
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
Analysis Laboratory Standard
Date Concentration
(1986) (pg/L)
06/25
06/25
06/25
06/25
06/27
06/27
07/28
07/28
07/29
07/29
07/30
07/30
07/31
07/31
08/01
08/0-1
08/04
08/04
08/04
08/04
08/05
08/05
10
10
10
10
10
10
10
10
20
20
10
10
20
20
10
10
10
10
10
10
10
10
                                         A12

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     Table A7. Analysis Sequence Number, Time of Analysis, and Laboratory Standard
Concentrations Plotted in Control Charts in Figures A18 to A29 (IDPH/Springfield 1989 Data)
Analysis
Sequence
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Time
Date
(1989)
12/04
12/04
12/04
12/04
12/04
12/05
12/05
12/06
12/06
12/07
12/08
12/08
12/08
12/15
12/16
12/16
12/17
12/17
of Analysis
Hour
9
10
11
13
14
13
14
9
22
20
0
3
7
20
7
15
5
9
Compound
Concentration
(Mg/L)
0.4
2
4
8
20
2
2
2
2
2
4
8
20
2
2
2
2
2
                                        A13

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Figures Al to A17. X-Control Charts of Percentage Recovery Data of Laboratory Standards,
        ISWS (June to August, 1986).  Dashed lines indicate mean and mean ± 3o.
                                    Symbol code:

                                    5 At-g/L Standard
                                    10 /ig/L Standard
                                   20 fjifL Standard
                                        A14

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                        Dichloromethane—ISWS
CD

o
o

CL
CD
o
       900


       800  t
                                           - +3o
                                                                  : Mean
           0
10    15    20    25    30    35    40    45
                            Analysis Sequence Number
                  Figure Al. Dichloromethane Control Chart
                                 A15

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                  trans-1,2-Dichloroethene—ISWS
CD

O
o
CD
cc

-t—*

CD
O
      300
      250  -
          0
10    15     20     25     30    35    40    45
                           Analysis Sequence Number
               Figure A2. Trans-1,2-Dichloroethene Control Chart
                                A16

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                      1.1 -Dichloroethane—ISWS
CD

O
O
CD
cc



CD
       300
       250  -
200  -
           0
10    15    20    25     30    35    40
                                                          45
                           Analysis Sequence Number
                 Figure A3. 1,1-Dichloroethane Control Chart
                                A17

-------
CD

5
o
CD
CC

"c
0)
o
200
150  -
100  -
 50  -
  0
             cis-1,2-Dichloroethene—ISWS
                                                            - +3o
                                                            . -3o
    0     5     10    15    20     25     30    35    40    45
                     Analysis Sequence Number
          Figure A4. Cis-l,2-Dichloroethene Control Chart
                          A18

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                           Chloroform—ISWS
       300
       250  -
CD

O
O
CD
cc



CD
O
           0
10    15    20    25     30     35    40    45
                            Analysis Sequence Number
                     Figure A5. Chloroform Control Chart
                                 A19

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           1,2-Dichoroethane & Trichloroethane—ISWS
CD

O
O
CD
CC


~c
CD
O
                                                               •- +3o
                                                               : Mean
          0
10    15    20    25    30    35    40    45
                           Analysis Sequence Number
          Figure A6. 1,2-Dichloroethane and Trichloroethane Control Chart
                               A20

-------
                     Carbon  Tetrachloride—ISWS
o3

o
o
CD
CC

"c
CD
       300



       250
200  -
150  -
       100  -
        50  -
         0
           0
                10    15    20    25    30    35     40     45
                            Analysis Sequence Number
                 Figure A7. Carbon Tetrachloride Control Chart
                                 A21

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                        Trichloroethene—ISWS
       200
CD

O
O
CD
CL



CD
O
       150
100
        50
        0
           0
                10     15    20     25     30     35     40    45
                           Analysis Sequence Number
                   Figure A8. Trichloroethene Control Chart
                                A22

-------
              1,1,2-Trichloroethane—ISWS
CD

O
O
CD
QC


"c
CD
O
200
150  -
100  -
 50  -
  0
    0
                       10    15    20    25    30     35     40    45
                     Analysis Sequence Number
          Figure A9. 1,1,2-Trichloroethane Control Chart
                          A23

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                Tetrachloroethene—ISWS
200
o
o
CD
DC


CD
O
150  -
100  r
 50  -
  0
    0
                       10     15     20    25    30    35     40     45
                     Analysis Sequence Number
           Figure A10. Tetrachloroethene Control Chart
                          A24

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                           Benzene—ISWS
o
o
CD
CE


CD
O
      300
      250  -
      200  -
          0
10
15    20     25    30    35    40    45
                           Analysis Sequence Number
                    Figure All. Benzene Control Chart
                               A25

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                            Toluene—ISWS
CD

O
O
CD
CL



CD

e

8.
           0
10    15    20    25    30    35    40    45
                           Analysis Sequence Number
                     Figure A12. Toluene Control Chart
                                A26

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                        Chlorobenzene—ISWS
CD

o
o
CD
CL



CD
o
      300
      250  -
200  -
150  '-
       100  -*
       50  r
        0
          0
                10    15    20    25    30    35    40    45
                           Analysis Sequence Number
                  Figure A13. Chlorobenzene Control Chart
                                A27

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                         Ethylbenzene—ISWS
o
o
CD
CL



CD
                                           - +3o
           0
10    15    20    25    30    35     40     45
                            Analysis Sequence Number
                   Figure A14. Ethylbenzene Control Chart
                                 A28

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                      1,3-Dichlorobenzene—ISWS
o
CD
OC


0>
o
       300
       250  -
       200  -
150



100
        50  -
         0
- +3o
           0
                10     15     20     25     30    35    40    45
                            Analysis Sequence Number
                 Figure A15. 1,3-Dichlorobenzene Control Chart
                                A29

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                     1,4-Dichlorobenzene—ISWS
o3

o
o
CD
cr


CD
O
      300
      250  -
200  -
                                                           +3o
          0
                10    15    20    25    30    35    40    45
                           Analysis Sequence Number
                Figure A16. 1,4-Dichlorobenzene Control Chart
                               A30

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                     1,2-Dichlorobenzene—ISWS
o
CD
O
      200
       150  -
cc      100  rt-r:
       50  -
        0
          0
10    15    20    25    30    35    40    45
                           Analysis Sequence Number
                Figure A17. 1,2-Dichlorobenzene Control Chart
                               A31

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Figures A18 to A29. X-Control Charts of Percentage Recovery Data of Laboratory Standards,
     IDPH/Springfield (December, 1989). Dashed lines indicate mean and mean ± 3o.
                                    Symbol code:

                                   0.4 /ig/L Standard
                                     2 /ig/L Standard
                                     4 /ig/L Standard
                                     8 /xg/L Standard
                                    20 /tg/L Standard
                                        A32

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              Carbon Tetrachloride—IDPH/Springfield
       200
CD

s
o
CD
DC


"c
CD
o

CD
CL
       150
100
        50
           0  1  2  3  4   5  6  7  8  9  10  11 12 13  14  15 16 17  18  19 20
                            Analysis Sequence Number
                Figure A18. Carbon Tetrachloride Control Chart
                                 A33

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            Vinyl  Chloride—IDPH/Springfield
200
150
o
o
CD
cc


CD
O

CD
Q_
100
 50
    0   1  2  3  4  5  6  7  8  9  10  11 12 13  14  15  16 17 18 19  20
                     Analysis Sequence Number
            Figure A19. Vinyl Chloride Control Chart
                          A34

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             Bromoform—DPH/Springfield
200
CD

O
O
CD
DC


CD
O

CD
Q_
150
100
 50
   0  1  2  3  4  5  6  7  8  9  10 11  12 13 14  15  16 17  18  19 20
                    Analysis Sequence Number
             Figure A20. Bromoform Control Chart
                         A35

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      Bromodichloromethane—IDPH/Springfield
200
CD

O
O
CD
CL



CD
150
100
 50
                    i  i   I   I  I   i  i   i   i  i   i   i  i   i
   0  1   2  3  4  5  6  7  8  9  10 11  12  13 14  15  16 17  18 19 20
                    Analysis Sequence Number
        Figure A21. Bromodichloromethane Control Chart
                         A36

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                     Ch oroform—IDPH/Springf ie d
       200
                                            I   I  1  I   i   I  I
o3

o
o

-------
             Chlorodibromomethane—IDPH/Springfield
       200
                I  I   I   I  I   T  I   I
CD

O
O
CD
cc



CD
O
       150
100
        50
          0  1  2  3  4  5  6  7  8  9  10  11 12 13  14 15  16 17 18  19 20
                          Analysis Sequence Number
               Figure A23. Chlorodibromomethane Control Chart
                               A38

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         1,2-Dichloroethane—DPH/Springfield
200
CD

O
O
CD
CL


CD
O
CD
CL
150
100
 50
    0   1  2  3  4  5  6  7   8  9  10 11 12  13  14 15 16  17  18 19 20
                     Analysis Sequence Number
          Figure A24. 1,2-Dichloroethane Control Chart
                          A39

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       1,1,1 -Trichloroethane—IDPH/Springf ield
200
150  -
CD

O
O
CD
cc


"c
CD
O
100
 50
    0   1  2  3  4  5  6  7  8  9  10  11  12 13 14  15  16 17 18  19 20
                     Analysis Sequence Number
         Figure A25. 1,1,1-Trichloroethane Control Chart
                          A40

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                      Benzene—IDPH/Springfield
       200
CD
o
CD
CE


CD
O
       150
       100
        50
          0  1  2  3  4  5  6  7  8  9  10 11  12  13 14 15  16  17 18 19  20
                           Analysis Sequence Number
                     Figure A26. Benzene Control Chart
                                A41

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        1,4-Dichlorobenzene—IDPH/Springfield
200
       I  I   I   I   I  I   I   I  T
                                     I  I   I   I
CD

O
O
CD
CC


"c
CD
O

CD
Q_
150
100
 50
       I  i   i
                    I   I   I  I   I
                                       I   I   I   I  I   I   I
    01234567
                                      10 11 12  13  14 15 16  17  18 19 20
                    Analysis Sequence Number
          Figure A27. 1,4-Dichlorobenzene Control Chart
                         A42

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         1,1 -Dichloroethene—IDPH/Springfield
200
CD

s
o
CD
cr



CD
o
150
100
 50
    0  1  2  3   4  5  6  7   8  9  10  11 12 13  14  15  16 17  18  19 20
                     Analysis Sequence Number
          Figure A28. 1,1-Dichloroethene Control Chart
                          A43

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           Trichloroethene—IDPH/Springfield
CD

s
O
CD
CL

~c
CD
O
200
150
100
 50
          i  i   i   i   I  i   i   i'  i   i  i   i   I   I   i  I   i   i
    012345
                                    9 10 11  12  13  14 15 16 17  18  19 20
                     Analysis Sequence Number
           Figure A29. Trichloroethene Control Chart
                          A44

-------