United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-81-241  Jan. 1982
Project Summary
Monitoring  to  Detect
Groundwater  Problems
Resulting  from  Enhanced
Oil  Recovery

Ron Beck, Bernard Aboba, Douglas Miller, and Ivor Kaklins
  A study that developed a four-stage
monitoring program to detect
groundwater contamination  events
that could result from enhanced oil
recovery  (EOR) projects was
conducted by Energy  Resources Co.
Inc. The monitoring system design is
based on a statistical analysis evolving
from a series of equations that model
subsurface  transport  of EOR spills.
Results of  the design include both
spatial  and frequency monitoring
intervals that depend on properties of
the local  geology and  dispersion
characteristics  of  the potential
contaminants. Sample results are
provided   for typical  reservoir
characteristics.    Selection  of
measures to be sampled is based on a
review  of  the  identity  of  likely
contaminants, on  the available
sample and analysis procedures, and
on the cost and time  constraints on
analysis.  Nonspecific indicator
measures are identified that can be
used to flag those intervals requiring
more intentisve and specific monitor-
ing.
  The  number of  independent
variables in the analysis dictate that
EOR monitoring systems be designed
on a site-specific basis. Sampling
designs can be easily formulated to
conform to the peculiarities of chosen
EOR  sites  based on  data already
available from federal and  state
geological  surveys  and  from  oil
company statistics.
  This  Project Summary was
developed by  EPA's  Municipal
Environmental Research Laboratory.
Cincinnati,  OH, to announce key
findings of the research project that is
fully documented in a separate report
of the same title (see Project Report
ordering information at back).


Introduction
  Since the end of World War II, various
new fluid-injection methods have been
researched that provide the potential to
recover  large volumes of oil left in
reservoirs after conventional recovery.
Little effort, however,  has been applied
to identification  of  environmental
problems.
  All enhanced recovery technologies
(both  oil and gas) involve potential
groundwater  concerns.  Those
technologies that require injection of
chemicals  into the reservoir  or
fracturing of formations hold the most
potential  for contamination.  In  situ
combustion is also of particular concern
because of the range of chemicals that
are  formed during  the  subsurface
combustion  process.   Table  1
summarizes the types of pollutant
problems that may occur.
  Relatively few  data  have been
collected from the aquifers that may be

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Table 1.  Summary of levels of risk anticipated from various activities
         carried out during enhanced recovery programs























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Low
  Legend:
    — Negligible risk
    + Potential for occasional pollutant events
    * Significant potential for regular occurrence of pollutant events if no measures
      are taken
contaminated  from  currently active
enhanced recovery programs.  Many of
the enhanced recovery projects  are
experimental in  nature,  and  all
available resources were  devoted  to
assembly of engineering performance
data. Many of the early EOR  projects
took place in sparsely populated areas
where  no  convenient  water wells
useful for  the  sampling  of  aquifer
quality existed.
  A  monitoring system- is needed for
use by research and policy groups such
as the USEPA, USDOE, and API. They
will  require nationwide data sets  that
can be used to detect long-term trends,
to identify regional problems, and to
determine how much attention should
be   paid   to  potential  hazards  to
groundwaters from EOR activities.
  This study aims at meeting the data
needs for  identifying the nature  and
extent of  groundwater contamination
due to EOR activities.
  The primary objectives of this study
were to develop and design an efficient
groundwater monitoring program  for
EOR  projects  and  to  provide  the
groundwork  for   development  of
standard  principles  to  be  used in
monitoring EOR projects.


Monitoring  Program Design
  Design of an effective yet  realistic
groundwater monitoring program  is a
difficult analytical  problem  and  is
impeded by lack of  information about
the baseline quality of aquifers and the
pollutant pathways that are required to
make informed decisions.
  The major problems to be addressed
in the  enhanced  recovery  environ-
mental monitoring  report summarized
here are as follows'

  1.  How should monitoring  stations
     be located so that discharges from
     the recovery processes are likely
     to be detected?

  2.  What combination  of measure-
     ments, number of stations,  and
     frequency of sampling  provides
     the best information  value  per
     dollar expenditure?

  3.   How  can  all  of  the   various
      monitoring   variables   be
     standardized sufficiently  so that
     different recovery projects can be
     compared and so that time-series
     analysis can be carried out?

  4.   Which procedures  need  to  be
     followed   to   ensure   that  the
      measurements taken  constitute
      meaningful information?

  The design of an efficient  monitoring
program requires that  the  benefits of
monitoring be  identified.  Benefits of

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 EOR   groundwater   monitoring  will
 include  detection and  prevention  of
 environmental  risks  and evaluation of
 environmental   control  investments.
 Table  2  summarizes the categories of
 costs  and benefits that enter into the
 design of an EOR/EGR (enhanced gas
 recovery) monitoring program
   This analysis considers (1) selection
 of pollutant  indicators, (2) placement of
 stations  and frequency of monitoring,
 and  (3)  development   of  a   simple
 generalized  monitoring  program.
 "Detection"  and  "event-monitoring"
 programs  are  considered  as  two
 separate cases with  detection systems
 considered  in  more  detail  in  the
 analysis.
 Pollutant Indicators
   Enhanced  recovery activities use a
 wide variety of chemicals. Comprehen-
 sive  monitoring  for  each  potential
 pollutant will  require  extensive
 budgetary   commitments.   The
 measurement of  indicator parameters
 rather than specific chemicals provides
 less detailed and precise information,
 but is  a more certain way of obtaining
 useful  returns for  a given  level  of
 investment.
   Various indicators  used  to detect
 relevant pollutants are:
     1.  Individual Contaminants. GC/MS,
         gas chromatography,  and  high
         pressure   liquid  chromatograhy
         (HPLC) measures for organics, and
         atomic absorption  or inductively
         coupled argon plasma (ICAP) for
         metals are detection tests used for
         the  various  contaminants
         associated  with enhanced
         recovery.

     2.  Total Organic Carbon. This test
         measures  the  presence  of all
         chemicals  soluble  in  a  given
         solvent,   such  as  methylene
         chloride. Monitoring TOC in the
         vicinity of  EOR  projects  can be
         expected to detect the presence of
         organic   polymers,  organic
         biocides,   hydrocarbons,  and
         miscellaneous  other  organic
         additives used in oil operations.

     3.  Methylene  Blue  Active  Sub-
         stances. The MBA test quantifies
         the presence of a  large class of
         surfactants.

     4.  Conductivity.  The  conductivity
         test is a  surrogate measure to
         determine  the general presence
         of  salts and  brines  in  water
         bodies

     5.  Reservoir Pressure.Jhe pressure
         maintained within the oil-bearing
Table 2.  EOR/EGR Environmental Monitoring Costs and Benefits

                Costs                               Benefits
Dollar costs of monitoring tests

Manpower costs of monitoring
Identification of public-health risks

Detection of violations of regulations

Identification of ecosystem risks

Identification of other environmental risks
  (aesthetics, resource preemption,
  synergistic effects, intermedia effects)

Identification of previously unrecognized
  pollutants

Detection of degradation trends at levels
  below currently recognized risk
  thresholds

Detection of chemical or hydrocarbon
  losses (economic benefit)

Evaluation of the effectiveness
  of control investments
      formation provides a monitor on
      escape of fluids away  from the
      intended  pathways. These
      monitoring  activities  are usually
      carried  out  as  part  of   good
      reservoir engineering practices.
Placement of Monitoring
Stations and Frequency of
Sampling
  The key issues involved in developing
a monitoring program are  selection of
sampling  sites and frequencies.  The
considerations  affecting  spatial
placement of  monitoring stations are
different before and after a pollutant
event has occurred. Before a pollutant
event occurs, the emphasis is on early
detection  leading  to  monitoring for
contamination  close  to  possible
sources, whereas  after  an event the
emphasis is on determining the extent
of contamination,  which may  require
monitoring far from the  source. For
these reasons, the design of a detection
and  an event-monitoring  system has
only  a  weak linkage.   Because  a
detection   system  requires   greater
accuracy, higher sampling frequencies,
and  fewer  stations than an   event-
monitoring system, data collection by
well samples is  appropriate  For an
event system, however, less expensive
methods will suffice.
  Chemical-fate models fall into two
categories:  miscible and  immiscible
pollutant  models.  While  brines  and
biocides are  soluble in water,  oil and
surfactants   are   not,  necessitating
equations in mathematical models of
fluid flow. Briefly,  in the immiscible
case, equations must be written for the
movement of both  the water and non-
water phases, while in the miscible case
an equation for transport  only  in the
water phase is developed.
  The design of a detection system has
two  phases:  the first  is a "baseline"
analysis characterizing total  dissolved
solids (TDS), BOD, organic carbon, etc.,
and other levels before an event, and
the second phase is the design  of the
system itself.
  The  purpose of the first phase  is to
take  out  all  "trends"  or explicable
variations in  groundwater quality so
that residual variation is uncorrelated (a
white   noise).  Seasonal  trends in
groundwater quality have  been noted
frequently  in  the  literature;  other
possible trends include a straight-line
time  dependence, correlation  among

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levels of chemical constituents, corre-
lations  among  nearby  wells,  and
relations of concentrations to the level
of the groundwater table and volume of
water pumped.
  To determine which chemical  tests
should be  performed to detect  EOR
chemicals for accidents  at site, it is
important  to collect  the following
information:

  1.  A table of "likely" concentration
     levels of EOR chemicals in every
     EOR  process   in  injected and
     produced waters, in addition to
     levels in the reservoir formation.

  2.  A  table  of   contamination
     scenarios, listing for  each
     scenario the groups of pollutants
     that are likely  to  be  released
     together,  concentration  esti-
     mates, and relative mobilities.

  3.  A summary of the relevant EOR
     chemical degradation processes
     and by-products.

  4.  A  table of  "likely"  background
     values  for IDS,  BOD,   TOC,
     Methylene   Blue  Active   Sub-
     stances, etc., in the local  aquifers.
  The above information will allow one
to discern which chemical tests have
high detection power for a particular
pollutant event.
  The  progress  of  a contamination
plume will resemble Figure 1. As can be
seen, the "center of gravity" of the
plume progresses at a speed of V in the
x direction, while the width of the plume
in the y direction is proportional to the
dispersion coefficient 0. Figures 2 and 3
illustrate the variations in locations and
frequencies  as  a  function  of spill
volume and diffusion rate for a set of
hypothetical conditions.


A Sample Program to Monitor
EOR Projects
  Particular monitoring activities and
intensities   of  sampling  will be
associated  with   different   EOR
technologies and with each stage of an
EOR project.  Table 3 depicts a general
scheme for  monitoring. The  scheme
involves assembly of  background and
baseline  information during the  early
stages  of  a project, with  routine
monitoring during the course of the
project and, in some cases, follow-up
monitoring for 5  years after the project
                                                              V = .01 cm/sec.
 Figure  1.  Progression of burst leak; dispersion rate = 6 times groundwater velocity.
  1400
*7200
t
1/000
   800
 .
5
®  600
I
5
8
$400
   200
                   40
80           120
   Volume of spill
160
200
Figure 2.  Volume of spill (m3) for different dispersion coefficients.

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_  5 x JO4

|
 2  5x10*
 u>_

 £  4 x 104
I  3 x 104

I        .
>c  2 x 104
                      40
80           120

  Volume of spill (m3)
160
200
Figure 3. Sampling frequency as a function of spill volume and for different
          dispersion coefficients
is  completed.  For relatively low-risk
technologies  such   as  thermal  oil
recovery, less monitoring  is required.
  Table 4 and Figure 4 summarize the
overall concept of EOR/EGR monitoring.
     Figure 4 gives a step-by-step outline of
     the tasks to be carried out in an environ-
     mental   monitoring  program.  The
     approach is a hierarchical one, in which
     the  simplest,  broadest  monitoring
activities are performed first and then
only those analytical tests relevant to
specific  environmental  problems are
incorporated  in the detailed and com-
prehensive  phases  of  a monitoring
program. Table 4 characterizes each of
four hierarchical stages in a monitoring
program.
  To show how the general scheme in
Table 3 should be applied to a particular
project,  two typical  monitoring
programs are outlined—for a  polymer
flood (Table 5) and for  a steam flood
(Table 6).

Recommendations
  The report summarized here presents
only   a  preliminary   outline  for
groundwater monitoring programs, The
following  are recommendations  for
further  work  needed  regarding  the
assembly   of  groundwater   quality
information  for  enhanced  recovery
projects:

  1.  Identify  Projects   That  Require
     Monitoring. Review ongoing and
     planned EOR, EGR, and tar sands
     projects. Select those  projects
     that  are most  likely to  impose
     groundwater quality degradation.

  2.  Identify  Susceptible OH Regions.
     Review  the regional distribution
Table 3.  General Scheme for Monitoring of EOR Impacts on Groundwater
^N\^ Stage of
^•x. Project
Type ^X^
of X.
Project ^\
Steam soak.

In situ combustion
Steam drive with
additives
CQz other
miscible gas
Advanced waterflood.
polymer flood
Alkaline flood
micellar/ polymer flood
Conception
^
<&
Q.
_ 
5 "-
1 i
* I
5 a
m 9)
3 5
* i
1
£
Field
management
(Rework or
seal old wells,
drill new wells)


9) 
S •$
5 i=
« 8
IB £
» !
s !
4) O
!s *
! i
1
Preflush
N.A*

N.A.
N.A.


Carry out
tracer studies

Injection of
chemical
slugs
N.A.

N.A.
Monitor for pres-
ence of chemicals
in produced oil
and water

Carry out
tracer studies

Production by
water or steam
injection


Perform diagnostic
monitoring only if
unusual reservoir
conditions are
noted


Conduct routine
monitoring of
nearby
groundwater
Post
production



None
required



Conduct routine
monitoring of
nearby
groundwaters
 N.A. = Not Applicable

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Table 4.   EOR/EGR Environmental Monitoring Overview Matrix*
                                                              Stages of Monitoring

Parameters to be
measured
Purpose of
monitoring
General
strategy
I
Develop
baseline
Indicators
Determine existing
conditions
a. Measure baseline
levels
b. Identify spatial and
temporal patterns
II
Monitor
trends
Indicators
Identify changes
in levels
a. Select key stations
b. Take periodic
measures
c. Look for changes in
identification
patterns
III
Specifically
evaluate flagged
problems
Specify chemicals
Identify problem
contaminants; identify
violations of standards
a. Perform specific tests a.
to determine contam-
inants that have
caused trends
b. Determine if criteria
have been violated
c. Determine spatial
extent of contamination
IV
Assess
effectiveness
of controls
Specify chemicals
Compare levels with
regulatory criteria;
check for reduction in
levels to below criteria
values
Evaluate contaminant
trends in response to
controls
 Major dimension(s)
 of analysis
 Spatial and temporal
Temporal for
representative sites
Profile of classes
of contaminants
Temporal for specific
problem zones
  * 777/s display summarizes the major characteristics of the four types of monitoring needed
    to evaluate environmental quality.
 1A
 Characterize Technology
 a. Type of Method
 b. Quantity of Chemicak
 c. Other Environmental
   Stresses
 1B
 Select Parameters
 to Be
 Monitored
 2A
 Characterize Environ-
 ment of the Site
 a. Geology
 b. Oil Reservoir
 c. Hydrology
 d. Other Activities That
    May Act
    Synergistically	
                                    1
2B
Evaluate Frequency of
Samp/ing, Spatial
Location of
Sample Sites
   3A
   Monitor the Recovery
   Project and Track
   Material Balances
    4A
    Identify Apparent Losses
    of Chemicals from Oil
    Reservoir
 3B
 Carry Out Monitoring
 Program Using Indicator
 Variables (TOC, MBA.
 Conductivity)
  4B
  Identify Generalized
  Pollutant Trends
  Develop Specific Trend
  Monitoring Program
                                                   3C
                                                   Carry Out Specific
                                                   Diagnostic Monitoring
                                                   Activities in Response
                                                   to Observed Pollutant
                                                   Events
                                                    4C
                                                    Characterize Pollutant
                                                    Eventfs)
Figure 4.  Monitoring program:  water-quality degradation from EOR/EGR.

                                    6

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Table 5.  Monitoring Program for a Polymer Flood to be Conducted
          Over a 20-year Period
Stage of project
               Monitoring events
Design of project
1.   Identify all freshwater aquifers.
2.   Collect monitoring data on aquifer water quality;
    utilize "kriging" statistics to develop average
    values. Look for seasonal trends.
Rework oilfield wells
1.  Develop maps of all old and all sealed wells, and
    inventory the condition of all old wells.
2.  Monitor reworking procedure to detect any
    communication with aquifers.
Preflush
1.   Conduct tracer studies to determine dynamics
    of injected fluids.
2.   Monitor quality of preflush fluids.
Injection of chemical slugs    1.
                             2.
    Conduct tracer studies to determine dynamics
    of chemical slug.
    Inventory known degradation tendencies,
    toxicity, carcinogenicity of chemicals used;
    identify persistent potentially harmful
    components.
Production
    Monitor for unusual levels of indicators (Total
    Organic Carbon, Methylene Blue Active Sub-
    stances, Conductivity, Reservoir/Welltest
    Pressure, Resistivity,  and the Geophysical Logs)
    on a weekly to monthly basis, depending on the
    proximitiy of the aquifer to the producing zone.
    Sampling sites to be  spaced at not more than 4
    times well spacing if possible.
Post-production
1.  Monitor for unusual levels of indicators
    on a yearly basis.
2.  Monitor pressure for a statistically selected
    sample of oil wells.
Table 6.   Monitoring Program for a Steam Flood to be Conducted Over a
          20-Year Period
Stage of Project
               Monitoring Events
Design of Project
1.   Identify all freshwater aquifers.
2.   Collect monitoring data on aquifer water quality;
    utilize "kriging" statistics to develop average
    values. Look for seasonal trends.
Rework Oilfield Wells
1.   Develop maps of all old and all sealed wells,
    and inventory the condition of all old wells.
2.   Monitor reworking procedure to
    detect any communication with aquifers.
Steam-soak Selected Wells
    Monitor produced oil and water phases to detect
    heat-induced synthesis of hazardous organics.
Fieldwide Steam Soak
    Monitor produced oil and water phases to
    detect heat-induced synthesis of hazardous
    organics.
Post-production
    None
     of  EOR,  EGR,  and  tar  sands
     projects. Evaluate the  regional
     environmental  issues,  existing
     environmental  quality,  and
     groundwater use.

 3.  Select Trend Monitoring Sample.
     Develop  a   statistically  based
     sample  of  projects  based  on
     compartmentalization  of  the
     sample by region and by inferred
     pollution potential.

 4.  Select Initial  Sample. Select a
     small set of projects for sampling.
     This initial set of from one to five
     sites should  be selected based on
     the accessibility of the site, the
     availability of existing wells to use
     in the sampling effort,  and the
     anticipated costs of sampling  at
     that site.

 5.  Develop  Samp/ing   Plans   for
     Sample Set.  Design a site-specific
     sampling plan for the initial set of
     sites  based  on the  monitoring
     guidelines presented in this report.

 6.  Development  Cooperative
     Sampling  Procedure.  Working
     with the DOE and industry, the
     EPA should  develop a workable
     plan for conducing monitoring at
     the initial sample of stations and
     on a nationwide basis.

 7.  Training.EPA.  and  DOE  should
     jointly develop training programs
     for  federal,  state,  and  industry
     personnel who will  be responsible
     for  carrying   out   the   EOR
     monitoring programs.

  In addition to the work recommended
for the implementation  of a ground-
water monitoring  program. The follow-
ing more general activities should  be
undertaken to complement the topics
covered by this report:

 1.   Water   Usage   Monitoring.    A
     program needs to be developed to
     account  for water usage by EOR
     and EGR projects It will need to
     take  the  form  of  monthly
     tabulations  of water  usage  by
     projects  as  compared  with
     unallocated water supplies at that
     locality.

 2.   Produced  Water  Disposal
     Formations. An information base
     needs to be  developed and kept
                                                                           •&U. S. GOVERNMENT PRINTING OFFICE: 1982/559-092/3368

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         updated regarding the  usage of
         subsurface formations  for
         produced water disposal and the
         volumes  disposed  of  at  each
         formation.

      3-  Monitoring Programs for Related
         Technologies. (Tar Sands, Heavy
         Oil Mining). The EPA Las Vegas
         laboratory has developed detailed
         protocols for the  monitoring of
         wastewater from  oil  shale
         projects. These protocols, together
         with  this  report,  need  to  be
         extended to the tar sands  and
         heavy  oil   mining  technology
         areas.

      The  full report was submitted in
     partial fulfillment of  Contract No. 68-
     03-2648  with  Rockwell International
     under sponsorship of the U.S. Environ-
     mental Protection Agency.
           Ron Beck, Bernard Aboba, Douglas Miller, and Ivor Kaklins are with ERCO/
             Energy Resources Co.. Inc.. Cambridge, MA 02138.
           John S. Farlow is the EPA Project Officer (see below).
           The complete report, entitled "Monitoring to Detect Groundwater Problems
             Resulting from Enhanced Oil Recovery," (Order No. PB 82-119 074; Cost:
             $13.50, subject to change) will be available only from:
                   National Technical Information Service
                 5285 Port Royal Road
                   Springfield, VA 22161
                   Telephone: 703-487-4650
           The EPA Project Officer can be contacted at:
                   Oil and Hazardous Materials Spills Branch
                   Municipal Environmental Research Laboratory—Cincinnati
                   U.S. Environmental Protection Agency
                   Edison, NJ 08837
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use $300

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