United States
Environmental Protection
Agency
Technology Transfer
September 1989
CERI-89-224
xvEPA
Seminar on Site
Characterization for
Subsurface Remediations
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INTRODUCTION/SEMINAR OVERVIEW
I. INTRODUCTION
A. Purpose and Scope of Seminar
B. Speakers
C. Seminar Format
II. DATA COLLECTION GOALS
A. Determine Nature and Extent of Contamination
1. Important processes
a. advection
b. dispersion
c. sorption
d. degradation
e. volatilization
2. Data requirements
a. flow conditions
b. chemistry
B. Determine Remedial Option
1. Type of contaminant
a. nonaqueous phase liquid
b. dissolved compounds
c. natural chemistry
2. Contaminant distribution
a. vadose zone
b. saturated zone
3. Type of media
a. porous
b. fractured
III. SOURCES OF DATA
A. Existing Site-Specific Data
1. Source type and history
2. Previous studies
3. Regulatory reporting
B. General Data
Regional
a. U.S. Geological Survey
b. state reports
c. other government agencies
Chemical specific
a. chemical handbooks
b. research papers
C. Collection of Site-Specific Data
1. Stratigraphy
2. Lithology
3. Structural geology
4. Water-level data
5. Hydraulic conductivity
6. Chemical distribution
7. Source(s)/receptor(s)
IV. DATA COLLECTION TECHNIQUES
A. Indirect Methods
1. Geophysical techniques
2. Soil gas survey
B. Direct Methods
1. Soil borings
2. Piezometers
3. Monitoring wells
V. DATA COLLECTION STRATEGIES
A. Network Design
1. Source(s)
2. Pathway
3. Receptor
B. Phased Approach
1. Spatial variability
2. Temporal variability
VI. DATA ANALYSIS
A. Graphical Analysis
B. Scoping Calculations
C. Statistical Analysis
D. Modeling
1. Analytical
2. Numerical
VII. CASE HISTORY
A. Site Characterization
B. Analysis
C. Remediation
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SITE CHARACTERIZATION PHASES
FORM SYSTEM
BEHAVIOR HYPOTHESIS
DESIGN DATA
COLLECTION »ROGRAM
COLLECT DATA AND
OBSERVE SYSTEM
NO
(ANALYZE AND TEST
HYPOTHESIS
MAKE MANAGEMENT
DECISIONS
Bouwer et al. (1988)
CONTAMINANT TRANSPORT
PROCESSES
• MASS TRANSPORT
— advection
— diffusion
— dispersion
• CHEMICAL MASS TRANSFER
— radioactive decay
— sorptlon
— dissolution/precipitation
— acid-base reactions
— complexatfon
— hydrolysis/substitution
— redox reactions (biodegradation)
• BIOLOGICALLY MEDIATED MASS
TRANSFER
— biological transformations
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A Summary of th« Processes Important in Dissolved
Contaminant Transport and Their Impact on Contaminant Spreading
Process
Definition
Impac t on Transpor t
MASS TRANSPORT
1 Advectior
consequence of ground
water flow
Most important way of
transporting mass awav
2 . Diffusion
3. Dispersion
Mass spreading due to
molecular diffusion in
tration gradients .
Fluid mixing due to
effects of unresolved
heterogeneities in the
permeability distribution.
An attenuation
mechanism of second
order in most flow
systems where advection
and dispersion dominate.
An attenuation
Mchanism that reduces
contaminant concentra-
clon in the plume.
However, it spreads to a
greater extent than
predicted by advection
alone.
CHEMICAL MASS TRANSFER
4. Radioactive
decay
5. Sorption
Irreversible decline in
the activity of a
radionuclide through a
nuclear reaction.
Partitioning of a
contaminant between the
ground water and mineral
or organic *allds in the
aquifer.
An Important mechanism
for contaminant attenua-
tion when the half-life
for decay is comparable
to or less than the
res idence time of the
flow aystem. Also adds
complexity in production
of daughter products,
An Important mechanism
that reduces the rate at
which the contaminants
are apparently moving.
Hakes It acre difficult
to remove contamination
at a site.
NRC (1989)
Process
Definition
Impact on Transport
6. Dissolution/ Tht process of adding
precipitation contaminants to or
removing them from
solution by reactions
dissolving or creating
various solids.
7 Acid-base
reactions
Reactions involving a
transfer of protons (H*).
Complexation Combination of cations
and aniona to form a
Bore complex ion.
9. Hydrolysis/
substitution
10. R*dox
rttctloru
(blod«gr>-
cUclon)
Reaction of a
halogenated organic
compound with water or a
component ion of water
(hydrolysis) or with
another anion
(substitution).
Reactions that involve a
transfer of electrons and
include elementa with more
than one oxidation state.
Contamin*nt precipitation
is an important
attenuat ion me en am sni
that can control the
concentration of
contaminant in solution.
Solution concentration is
•ainly control led
either at the source or at
a reaction front
Mainly an indirect
control on contaminant
transport by controlling
the pH of ground water
An important mechanism
resulting in increased
solubility of metals ir-
ground water, if
adsorption is not
enhanced. Major ion
coBplexation will in-
crease the quantity of a
solid dissolved in
solution.
Often hydrolysis/
substitution reactions
make an organic compound
•or* susceptible to
biodegradation and more
soluble.
An extreaely important
family of reactions in
retarding contaminant
spread through the
precipitation of metaLs.
BIOLOGICALLY MEDIATED MASS TRANSFER
11. Biological Reactions involving the
transforma- degradation of organic
tions compounds and whose
rate is controlled by
the abundance of the
microorganisms, and
redox conditions.
Important mechanism for
contaminant reduction, but
can lead to undesirable
daughter products.
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HYOROLOOIC STITCH COMPONENTS
Diamncm Irem Conlmuou* ConUfwwni Soura
Dvunca horn Slug-Raton* Conumram Soun«
Th* I
of
Keely et al. (1986)
HASS BALANCE
ELEMENTS
PKOCESSCS
TRANSPORT
VOLATILIZATION
PLANT UPTAKE
DIFFUSION
SOLUTION
CAFILLAIY FLOW
NACROF-OIIC FLOW
TRANSFORMATION
BIOLOGICAL
CHEMICAL
PHOTO
STORAGE
SOLUTION
SORFTION
(MINCKALS)
SOUPTTON
(OHCANIC1)
BlOACCUMULATIOH
ATMOIPHlm
SOIL/ ROOT
ZONE
UNSATURATCO
ZONE
1 SATURATED
1 ZONE
| SURFACE
1 WATER
|
L
K-trU of phy.lc.l eo^,«rt««it. vxl proc..... .ff.cting .trazln..
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Explanation
Corn and soybean region
Atrazine detections
in percent
(MDO-10
ESS 10-20
Wi 20-50
£3 50-70
f J insuflcienl samples
Atrazine detections by
land resource area (LRA)
Alrazine detections by
Hydrologic Unit (HU)
• Potential study areas
Subregions selected by
!RA/HU/atrozine detections
Regional, aubreglonal and area delineation* for factor verification
or further study by a geographic Information aysten.
SOURCES OF INFORMATION
• EPA AND STATE ENVIRONMENTAL
OFFICE FILES
COUNTY OR REGIONAL PLANNING
OFFICES
• CITY OFFICES
• COMPANY FILES AND RECORDS
UTILITY COMPANIES
• U.S. GEOLOGICAL SURVEY
• U.S. DEPARTMENT OF AGRICULTURE
• STATE GEOLOGICAL SURVEYS
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SOURCES
1. EPA and State Environmental Office flits
RCRA permits and applications
Waste Generators and Transporters
TOSCA
NPOES permits and applications
Uncontrolled waste disposal sites
Spills of oil and hazardous materials
Water supplies
Enforcement actions
Surveillance reports
2. County or Regional Planning Agencies
for Areawide Waste Treatment Mgnt.
(CWA - Section 208 Agency)
3. Other County offices
Health Department
Planning and zoning
Assessor
4. City offices
Chamber of Commerce
Clerk
Engineer
Fire Department
Law Enforcement
TYPES/COMMENTS
for:
EPA Identification numbers
Generator annual reports
May require special clearance
for reviewer
Liquid waste types
Treatment processes
Production information
Nearest water supply
Problem history
Previous findings
Plans, concerns, and
past problems
Problems, complaints,
analytical results
Land use restrictions
Plat maps and land owners
Information and local indus-
tries Incl. number of employ-
ees, principal products, and
facility addresses
Foundation and Inspection reports
Survey benchmark locations
History of flrei and/or explo-
sions at facility
Complaints and violations of
local ordinances
Water and Sewer
5. Company files and records
6. Contractors
Bui 1di ng
Soil exploration and foundation
Water well drillers
7. Utility Companies
Gas
Electric
Water
Petroleum or Natural Gas Pipelines
8. U.S. Geological Survey
9. Remote Sensing Imagery
10. Computer Data Bases
11. U.S. Department of Agriculture
12. State Geological Surveys
13. U.S. Department of Labor
Occupational Safety and Health Admini-
stration (OSHA)
14. National Oceanic and Atmospheric Admini-
stration (NOAA)
15. National Ocean Survey
Location of buried mains and
lines
Confidential records require
special handling and storage
Local soils, geology, and
shallow water levels
Local soils, geology, hydro-
gology, water levels, regu-
lations, and equipment avail-
abi1ity
Location
of
buried lines
Technical geologic and hy-
drologic reports, naps,
aerial photographs, and
water monitoring data
Drainage patterns, land use,
vegetation stress, historical
land development, and geo-
logic structure
Wide variety of reference
data and bibliographies
Soil maps, types, physical
characteristics, depths
association, and uses
Technical geologic and hydro-
logic reports, State geologic
•aps, and monitoring data
Processes
Hazards
Protective equipment needs
Climatic data
Tidal data; historic,
recent, and projected
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ACTIONS TYPICALLY TAKEN
install a few dozen shallow monitoring wells
sample ground-water numerous times for 129 +
priority pollutants
define geology primarily by driller's logs and drill
cuttings
i evaluate local hydrology with water level contour
maps of shallow wells
• possibly obtain soil and core samples for chemical
analyses
Action* Typically Taken
• Install a lew dozen shallow monitoring wells
* Sample ground-water numerous times tor 129 +
priority pollutants
* Define geology primarily by driller's logs and drill
cuttings
* Evaluate local hydrology with water level contour
maps of shallow wells
* Possibly obtain soil and core samples for
chemical analyses
M— ej—
oonernS
* Rapid screening of the site problems
* Costs of Investigation are moderate to low
• Reid and laboratory techniques used are
standard
• Data analysis/Interpretation Is straightforward
• Tentative Identification of remedial alternatives (a
possible
Shortcomings
' True extent of site problems may be
misunderstood
• Selected remedial alternatives may not be
appropriate
* Optimization of final remediation design may not
be possible
• Clean-up costs remain unpredictable, tend to
excessive level*
• Verification of compliance rs uncertain and
difficult
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RECOMMENDED ACTIONS
• install depth-specific clusters of monitoring
wells
• initially sample for 129+ priority pollutants,
be selective subsequently
• define geology by extensive coring/sediment
samplings
• evaluate local hydrology with well clusters
and geohydraulic tests
• perform limited tests on sediment samples
(grain size, clay content, etc.)
• conduct surface geophysical surveys
(resistivity, EM, ground-penetrating radar)
• Install depth-specific dusters of monitoring wells
• Initially sample tor 129+ priority pollutants, be
selective subsequently
* Define geology by extensive coring/sediment
samplings
• EvsJuate local hydrology with well dusters and
geohydraulic tests
• Perform limited tests on sediment sample* (grain
size, day content, etc.)
• Conduct surface geophysical surveys (resistivity.
EM, ground-penetrating radar)
Conceptual understandings of site problems are
ore
plete
• Prospect* are Improved for optimization of
remedial actions
• Predictability of remediation effectiveness to
Increased
• Clean-up cost* are lowered, estimates e/e more
reliable
• Verification of compliance) I* more soundly based
Shortcoming*
• Characterization costs are somewhat higher
* Detailed understandings of site problems are still
difficult
* Full optimization of remediation Is still not likely
* Reid tests may create secondary problem*
(disposal of pumped waters)
• Demand for specialists I* Increased, shortage I* a
key limiting factor
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IDEALIZED APPROACH
• assume state-of-the-art as starting point
• conduct soil vapor surveys for volatiles, fuels
• conduct tracer tests and borehole geophysical
surveys (neutron and gamma)
• conduct karst stream tracing and recharge studies,
if appropriate to the setting
• conduct bedrock fracture orientation and
interconnectivity studies, if appropriate
• determine the percent organic carbon and cation
exchange capacity of solids
• measure redox potential, pH, and dissolved
oxygen levels of subsurface
• evaluate sorption-desorption behavior by
laboratory column and batch studies
• assess the potential for biotransformatlon of
specific compounds
fuels
• Assume stste-of-the-art as starting point
* Conduct soil vapor survey* for volatlles, s
• Conduct tracer tests and borehole geophysical
survey* (neutron and gamma)
* Conduct karst stream tracing and recharge
studies, H appropriate to the setting
* Conduct bedrock fracture orientation and
InterconnectMty studies, H appropriate
• Determine the percent organic carbon and cation
exchange capacity of solids
• Measure redox potential, pH, and dissolved
oxygen levels of subsurface
* Evaluate sorptlon-desorptlon behavior by
laboratory column and batch studies
* Aasess the potential for blotransformation erf
specific compounds
• Thorough conceptual understandings of site
problems are obtained
* Full optimization of the remediation Is possible
• Predictability of the effectiveness of remediation
It maximized
* Clean-up costs may be lowered significantly,
estimates are reliable
• Verification of compliance Is assured
Shortcomings
* Characterization cost* may be much higher
Few previous applications of advanced theories
and methods have been completed
Field and laboratory techniques are specialized
and are not easily mastered
Availability of specialized equipment Is low
Need for specialists la greatly Increased (H may
be the hey limitation overall)
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GEOLOGICAL ASPECTS
OF
SITE REMEDIATION
GEOLOGICAL FACTORS
GEOLOGY
SITE
REMEDIATION
- STRATIGRAPHY
- LITHOLOGY
- STRUCTURAL GEOLOGY
- HYDROGEOLOGY
QUESTIONS
. WHAT GEOLOGIC FACTORS ARE SIGNIFICANT
TO REMEDIATION?
. HOW ARE GEOLOGIC DATA COLLECTED?
. HOW ARE GEOLOGIC DATA INTERPRETED?
STRATIGRAPHY
• Formation, composition, sequence and
correlation of stratified rocks and
unconsolidated surficial materials (clays,
sands, silts, gravels).
• Necessary to Identify pathways of migration,
estimate extent, and to define hydrogeologic
frame work.
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ROCHESTER
IHALC
Section from north to south through S-Area
showing generalized geolocical conditions:
thickness of fractures and bedding planes
exaggerated to illustrate concepts.
STRATIGRAPHIC CONSIDERATIONS . REMEDY
Before
RAIN
u u
RAIN
LAGOON LEAKS II II
-J-
LEAKAGE THRU
CLAY & TILL
BEDROCK WATER LEVEL
GW & NAPL
'
After
CLAY
;. .. 1
p.. .1
-d
£";J
!^;:.;:;;;i;:bRAiN
^WALL::;;rn;;;;
•..7^*^,
i:i:::::::::::^3
-1
SS"^^:]
£&&£:fi
....]
^^*
WARD LEAKAGE^ x';m-
(. :-«— — " : :S_^,
^;;;;;;;;i;;;;;i;;;;i;;;i;;;N^
pffillii!?*^
:::::::::::::::::::::::::::::::::: ::^
;;1
.:::::::::::::::::::|*|rW^ :-f
if
G«neralii«d north-south »«etion throuch.
Northern Offsite and S-Area showing ^he
impact of remedies on water levels and
ground-water tnd NA?L flow directions.
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STRUCTURAL GEOLOGY
LITHOLOGY
Features produced by movement after
deposition-faults, folds, fractures
Fractures or faults may provide preferential
pathways for contaminants to move and require
special attention during remediation
Important where surficial deposits are thin or
very permeable
COMPOSITION OF UNCONSOLIDATED
DEPOSITS OR ROCKS
- MINERALOGY
- GRAIN SIZE
- GRAIN SHAPE
- PACKING
2 WATER TABLE
V INDICATES RECHARGE
I INDICATES WASTE PLUME
BOREHOLE BH-3A
BH-IS
MECHANISMS OF WASTE FLOW
(•) GRAVITY
® GRAVITY.NO PRESSURE.SOME ADVECTION
© ADVECTION. DISPERSION. DIFFUSION
RECHARGE AREA
LACKAWANNA RIVER
AREA OF
MINIMAL
INFILTRATION
DUE TO
MINE FLOW
>» BEDROCK
INFILTRATION
UNKNOWN CONNECTIVITY
WITH DIAMOND COAL
NOTE: Conceptual diagram -nol lo teal*, vertical aiaggarailon
diilorlt tha actual alopa ol lha coal taatf (actual-SX).
Major mechanisms of liquid wist* transport from the Keyser
borehole lo the Mater table.
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RELATIONSHIP OF MOVEMENT OF SUB-
SURFACE WATERS TO GEOLOGY
DIRECTIONS AND RATES OF
GROUNDWATER FLOW
TIES STRATIGRAPHY, LITHOLOGY,
STRUCTURAL GEOLOGY TO THEORY OF
GROUNDWATER HYDRAULICS
ESSENTIAL TO ANY GROUNDWATER
REMEDIATION, GROUNDWATER MONITOR-
ING OF SURFACE CLEANUP (I.E., EXCAVA-
TION, VACUUM EXTRACTION)
Trtn*plra!k>n
u
Hydrologlc cycle.
GeoTrans (1989)
WASTE FACILITY
(a)
WASH FACIUTT
(b)
Seasonal variations 1n recharge and pumping can reverse flow
directions during the year (a) late fall water-table with no
significant pumping and low recharge fb) early suraner after
spring recharge and significant pumping for •oi"f«-ui*ur-«
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HYDROGEOLOGIC INVESTIGATIONS
EXPLANATION
C««te*Untlcl I In*
DELINEATE EXTENT OF CONTAMINATION IN
SUBSURFACE
DETERMINE FLOW DIRECTIONS PATHWAYS
AND RATES FOR GROUNDWATER AND
POTENTIAL CONTAMINANTS
PROVIDE FRAMEWORK FOR DESIGN OF
GROUNDWATER REMEDIAL PROGRAM
— wells - where and how many
— pumping rates
— treatment facility influent
PROVIDE BASIS FOR SELECTING FROM
ALTERNATIVE REMEDIAL STRATEGIES AND
NO ACTION
— concentrations of contaminants at point of
use or property boundary
Pot*ntlone trie surface and flow lines.
GeoTrans {iyH9)
-------
FIELD METHODS
GEOLOGICAL INFORMATION
— borehole exploration
— mapping surface features
— geophysical methods
surface
downhole
GROUNDWATER FLOW INFORMATION
— monitor water elevations in wells,
adjacent surface waters
— aquifer test
pump tests
- slug tests
— special methods
laboratory properties
- flow meters
GROUNDWATER CONTAMINATION
INFORMATION
— sample wells/analyze
- measure/pump free product
- soil sample analysis
GEOPHYSICAL METHODS
• SURFACE TECHNIQUES
— gravity survey
— infrared imagery
— ground penetrating radar
- induced electrical polarization
- resistivity
- metal detection
- magnetometer
— reflection seismics
- electromagnetic surveys
• BOREHOLE METHODS
— geothermetry
— electrical
— acoustic
- nuclear
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Tp Well Cap
, |-«—Steel Protector Cap with Lock!
Surveyor'* Pin (flu»h mount)
oncrete Well Apron
ontlnuou* Pour Concrete Cap
and Well Apron
(expanding cement)
Non-shrinking Cement
orehole Wall
••-Annular Sealant::::•'•.•::
•-Filter Pack (2 leet or
leaa above acreenV:•:'•:•
Screened Interval/ :
nSump/Sedlment Trap
Bottom Cap «°\". •,
A typical monicoring-uill dnign.
GeoTrans (1989)
METHODS OF ANALYSIS
DESCRIPTIVE
GRAPHICAL
QUANTITATIVE
- statistical
- analytical solutions or calculations
— numerical models
HYDE PARK LANDFILL
. PROBLEMS:
. GEOLOGY:
. REMEDY:
. METHODS:
Extensive contamination of
bedrock by immiscible
dense contaminants
Glacial deposits ~ 30 feet
thick above flat lying sed-
imentary bedrock
Groundwater pump and
treat with reinjection
Groundwater modeling to
design prototype program
and help set ACL s
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HYDE PARK
LANDFILL
nsffi^
iii""
THE
WHIRLPOOL
RESERVOIR
PUMP-GENERAT
PLANT
MOSES
NIAOARA
POWER PLANT
\ .TWIN CONDUITS
(COVERED)
\
I
PUMPED-STORAGE
RESERVOIR
1 ROBERT MOSES"! r ?
STATE PARKWAY
Generalized diagram showing the geologic formations and topographic features In the
BhovlAg locmclon of ctic Hyde Park
-------
o OFF lire ovtttunori vrui
inn tftoi
D OTF-9lTt OVtltVtWH VTUS
• Off SlTf MMOCI Will
HIT* tftoi
• OFF SIT! IIDtOCR »fllS
IIMf 1WS1
a orr-tirt OVCMUHOCK •tits
(1M1I
• Off Wft HMOCI VfllS
iitri ti«oi
• OFF SITE IfDIOCI VEILS
HMI IM5I
MSI HAP HOOirilO F»0«
l,ockp»rt Do] om( te plumes as def Ined by the Myile I1.irk surveys in ;n -cnnliinre with
the Settlement Agreement (Pecemher 1982 - Mny l(»fl 0.
Overhurden pi time 3 as def I ned hy the Hyde I'ark surveys In .icrnnhim e with t lie
-------
Before
Remedial
Pumping
HYDE PAR
LANDFILL
NAPL PLUME
After
Remedial
Pumping
Before
Remedial
Pumping
HYDE PAR
LANDFILL
NAPL PLUME (
r £ \ r
— «*• T «=3
After
Remedial
Pumping
ROBERT MOSES
STATE PARKWAY
-------
CONSERVATION CHEMICAL SITE
. PROBLEM:
. GEOLOGY:
. REMEDY:
. METHODS:
Contamination of a valley
fill aquifer near the Missouri
River
Alluvial aquifer ~ 100 feet
thick
Groundwater pump and
treat
- Statistical analysis of
groundwater flow directions
- Computer modeling to
design initial pump and
treat system
fit. g*omorphlc (••turts.
•It* location! and other Important landmarks.
IVM fOOO Ml IMS
GENERALIZED GEOLOGIC SECTION
BLUE MISSOURI
RIVER RIVER
ELEVATION
•"»":•.! •'a7.:-. •.t'is^.^-nL
LEGEND
SILTY SANO
gUCLAYEY SANO
3 SAND
123 SAND-GRAVEL INTERMIX
CLAY-SILT INTERMIX
BEDROCK
PROJECTION
OF
BORING
-------
N
W—
— E
Groundwater flow directions and gradients observed
1n piezometers 1C, 4C, 11C [from Larson (1986)].
SLURRY WALL WITH INTERIOR PUMPING
LEVEE
- ^ — *.< CAP
-/^•INTERMITTENT
RECOVERYv
-------
CONCEPT OF HYDRAULIC CONTROL
PLAN B1
~T~15,500-ftVd.
Gradient 090°
at o.ooa
Q each well
= 2.00 gpm
Mobay ujell
=-5oo;ooogpd
RUN
C\SfcG>2
500 0 5OO
SCALE IN FEET
100O
trans.
Steady-state simulation results for remedy based on
site pumping; Run IC1S6G2.
inc
-------
Mercer et al. (1987)
CONCLUSIONS
Three hazardous waste sites involving groundwater contamination
have been reviewed in an effort to summarize effectiveness and costs
of remedial actions. Several conclusions are made based on this
review:
(1) Hazardous waste sites involving groundwater contamination
generally require more time and effort to characterize and
remediate than sites not involving groundwater
contamination.
(2) Good pre-remedial site characterization is critical to both
selection and implementation of remediation. Because of
seasonal changes in groundwater. a minimum of one year
should be devoted to monitoring and characterization before
a remedy is selected. As the site complexity increases,
this time will increase proportionately.
(3) In order to minimize costs, both site characterization and
remediation should be performed in phases, such that later
phases may be modified based on knowledge gained from
earlier phases.
(4) As the scale of the observation increases, properties, such
as permeability, tend to increase because more
heterogeneities are encountered. Therefore, remediations
based on core-scale observations, may underestimate
groundwater flow rates.
(5) Site characterization and remediation tend to be costly at
sites involving groundwater contamination, with clean up
costs difficult to estimate accurately.
(6) Monitoring is critical for both site characterization and
remediation. Long-term monitoring should be an integral
part of any remedial action plan. In addition, it is
important to monitor before, during and after remediation in
order to evaluate effectiveness. Groundwater elevation
data, which is relatively inexpensive to obtain, can be
particularly useful 1n the evaluation of remedial
effectiveness.
(7) The effectiveness of various remediations varies from site
to site, and depends in large part on the site
characterization and analysis. Of particular importance at
hazardous waste sites is the lack of good bedrock
characterization prior to remediation. Apparent containment
can be lost because of unexpected flow through the bedrock
(1n addition to some cases presented In this pap«r. for
example, see Ozb1lg1n and Powers, 1984, concerning the site
in Nashua, New Hampshire).
REFERENCES
Bouwer, £., J. Mercer, H. Kavanaugh, and f. DiGiano, 1988. Coping with
groundwater contamination, Jour. Water Pollution Control
Federation (August), pp 1415-1427.
Cohen, R.M., R.R. Rabold, C.R. Faust, J.O. Rumbaugh III, and J.R.
Bridge, 1987. Investigation and hydraulic containment of chemical
migration: Four landfills in Niagara Falls, Civil Engineering
Practice. 2(l}:33-58.
GeoTrans, Inc., 1989. Groundwater monitoring manual for the Electric
Utility Industry, Edison Electric Institute, Washington, D.C.
Keely, J.F., H.D. Piwoni, and J.T. Wilson, 1986. Evolving concepts of
subsurface contaminant transport. Jour. Watpr Pollution Control
Federation (May), pp 349-357.
Mercer, J.W., C.R. Faust, A.D. Truschel, and R.M. Cohen, 1987. Control
of groundwater contamination: Case studies, froceedings of
Detection. Control, and Renovation of Contaminated Ground Water.
EE Div/ASCE, pp 121-133.
National Research Council, 1989. prpimd Water Models—Scientific a,nd
Regulatory Application*. National Academy Press, Washington, D.C.
-------
SESSION I
Characterization of Water Movement in the Subsurface
CHARACTERIZATION Of WATER MOVEMENT IN THE SUBSURFACE
James W. Mercer, President, GeoTrans, Inc.
Hernaon, Virginia
I. DETERMINATION OF WATER MOVEMENT IN SATURATED POROUS MEDIA
A. Data Pertinent to the Prediction of Groundwater Flow
1. Physical framework
2. Stresses on system
3. Observable responses
4. Other factors
B. Review of Terminology
1. Hydrologic cycle
2. Water balance
3. Aquifer
4. Hydraulic head
5. Hydraulic gradient
6. Potentiometric surface
7. Surface water features
8. Flow net
9. Groundwater flow
a. recharge effects
b. hydraulic conductivity effects
c. advective transport
d. surface water - groundwater interaction
e. multiple aquifers
f. pumping effects
C. Monitoring Well Construction
1. Well casing and screen material
2. Multi-level monitoring well design
3. Well development techniques
D. Drilling Methods
1. Auger
2. Rotary
3. Cable tool
E. Measurement of Hydraulic Head
1. Steel tape
2. Electric probe
3. Air line
4. Pressure transducer
5. Acoustic sounder
6. Tensiometry
7. Electrical resistivity
8. Thermocouple psychrometry
9. Thermal diffusivity
10. Well placement
11. Frequency of measurement
Measurement of Storage Properties
1. Pumping test
2. Slug test
3. Water balance
4. Laboratory
Measurement of Hydraulic Conductivity
1. Slug test
2. Permeameter
3. Pumping test
a. Theis solution
b. Jacob method
c. recovery
d. Hantush solution
e. boundaries
Dr. James W. Mercer
Measurement of Spatial Variability
1. Piezometer slug tests
2. Hydraulic conductivity from grain size
3. Surface geophysics
a. direct current resistivity
b. electromagnetic Induction
4. Borehole geophysics
5. Pumping tests
6. Facies mapping
7. Continuous core
8. Borehole flowmeter
9. Geo flowmeter
Analysis of Data
1. Mathematical modeling
2. Geostatistical methods
3. Time-series techniques
4. Graphical methods
5. Filtering/synthesizing techniques
Groundwater Remediation
1. Hydraulic containment
2. Physical containment
3. Innovative technologies
II. DETERMINATION OF WATER MOVEMENT IN THE VADOSE ZONE
A. Data Pertinent to the Prediction of Vadose Zone Flow
1. Soil characteristics
2. Soil chemistry characteristics
3. Vadose zone characteristics
B. Soil Characteristics
1. Soil particle sizes
a. mechanical-analysis method (sieve)
b. hydrometer
c. settling tube
2. Soil texture
a. soil cores
b. test pits
3. Mineralogical composition
4. Organic matter
5. Density
a. particle density
b. bulk density
6. Soil-water consistency (Atterberg limits)
a. 1iquid 1imit
b. plastic limit
c. plasticity index
7. Shrinkage and expansion of soils
8. Soil compaction
9. Elasticity and compressibility
10. Temperature
C. Review of Terminology
1. Capillary rise
2. Capillary fringe
3. Pressure head
4. Moisture content
5. Water table
6. Perched water
7. Infiltration
8. Recharge
9. Porosity
10. Relative permeability
11. Runoff
12. Evaporation
-------
D. Measurement of Moisture Content
1. Gravimetric
2. Neutron scattering
3. Gamma ray attenuation
4. Electromagnetic
5. Tenslometric
6. Porous plate
7. Vapor equilibration
8. Osmotic
9. Thermocouple psychrometer
E. Measurement of Unsaturated Hydraulic Conductivity
1. Constant-head borehole infiltration
Z. Guelph permeameter
3. Air-entry permeameter
4. Instantaneous profile
5. Crust-imposed steady flux
6. Sprinkler-imposed steady flux
7. Parameter identification
8. Empirical equation
9. Vertical permeability to air
F Measurement of Moisture Movement
1. Infiltration
2. Vadose zone flux
3. Vadose zone velocity
G. Vadose Zone Remediation
1. Soil venting
2. Fixation
3. Excavation
III. DETERMINATION OF WATER MOVEMENT IN SATURATED FRACTURED MEDIA
A. Geometry
1. Fracture trace analysis
2. Surface geophysics
3. Tracer (dye) tests
B. Flow Parameters
1. Aquifer tests
2. Slug tests
3. Spatial variability
C. Discrete Fracture vs. Dual Porosity Concepts
1. Matrix diffusion
D. Data Analysis
DETERMINATION OF
WATER MOVEMENT IN
SATURATED POROUS MEDIA
Water Storage
Water Movement
> Contaminant Storage
> Contaminant Movement
»Impacts on Remediation
-------
DATA PERTINENT TO THE PREDICTION
OF GROUNDWATER FLOW
• PHYSICAL FRAMEWORK
- Hydrogeologic map showing areal
extent and boundaries of aquifer
- Topographic map showing surface-
water bodies
- Water-table, bedrock-configuration,
and saturated-thickness maps
- Hydraulic conductivity map showing
aquifer and boundaries
- Hydraulic conductivity and specific
storage map of confining bed
- Map showing variation in storage
coefficient of aquifer
- Relation of stream and aquifer
(hydraulic connection)
• STRESSES ON SYSTEM
- Type and extent of recharge areas
(irrigated areas, recharge basins,
recharge wells, Impoundments,
spills, tank leaks, etc.)
- Surface-water diversions
- Groundwater pumpage (distributed
in time and space)
- Stream flow (distributed in time and
space)
- Precipitation and evapotranspiration
• OBSERVABLE RESPONSES
- Water levels as a function of time
and position
• OTHER FACTORS
- Economic information about water
supply
- Legal and administrative rules
- Environmental factors
- Planned changes in water and land use
-------
(PUCCMWIOW
+ IRRIGATION)
C«OUNDW»TfH FLO*
Simplified Landfill Water Balance
(A)
«B
C
_o
«
>
UJ
9
* 600
0
o
•g 550
0
* 500
V
E
!
,
0
B
2C
)0 4(
; : •/ •'• h-.'s7o
dh
30 d?'
; . + . '.
h • 590
20
. 0
200
' + '. T<
h'.610 '.'
10
Hydraulic Head
r™i Land Surface
Piezometric Surface
p/pg pressure
head
elevation
head
Datum (mean sea level)
Z=0
| 650
• 600
o a
= > 550
UJ •> 500
«
E 450
(C)
nmn
(D)
0 1 2
.
J •' i-'K«610
h.-630
dh 30
— . — • 0.40
dl 50
D»tirBin«tlon of flov dir*ccloni «nd hydraulic gradienti froa
n««ctd pitioMttrs (fro» Fr««t« and Ch«rry, GROUND WATER. (c)1979,
pp. 24. R«print«d by p«rml»iion of Prtncict Hall, Inc.,
Englivood Cliff*. N«w Jersey.)
Component, of hydraulic h«.d (modifi.d from Freeze and
Cherry, GSOUHDUATER. (c)1979, pp. 22. Englewood Cliffs,
H«w J.TT..,.)
-------
aROUNOWATEM
FLOW DIRECTION
•ATI R - ItVf I
PIEZOMETER ELEVATION
42110
PI 42711
P4 420.M
PO 427 OS
PS 422.M
P7 417 SB
PO 41013
PO 417.10
PIS 41121
PII 410 a
P11 41010
P11 410.01
P14 42001
PtO 420.71
MS 4J1.4S
DATE
RECORDED
1WOS
iri/n
mm
vim
3I2IK
3/itn
1/1/06
mm
i/i/ra
1/2/H
i/i/n
1/2/OS
t/vtt
mm
LEOEND
4tO_ POTENTIOHf THIC OUHFACE (NOVDI
-^ PIEZOMETER LOCATION
•PI
«MX4I?J4 KNCH MARK
TIM TEMPORARY BENCH MARK
® 417.17
• PROPERTY LINE
POTf NTIOMETRIC SURFACE MAP
•ILL AMD tCREEN
« «• PLOW LINE
• — — ~ POTEMT1OMETRIC SURFACE
IOUIPOTINT1AL LINE
AN EXAMPLE OF A FLOW NET DERIVED FROM PIEZOMETER DATA
EXPLANATION
OENEftAL FLOW DIRECTION
V WATER TABIE
Us. of .urf.c.-wat.r features to supplement hydraulic-head data from monitoring well.
-------
ELEVATION
NOVD
WO' n
F1EZOMETER PIEZOMETER
3 2
PIEZOMETER
HASTE DISPOSAL
UNIT
GROUND-WATER FLOW
K • 7 0 « \{T3tm/ite •
K-8.o» io-1
--_-_- CLAV ------------------
iwr so- o 5
-------
w
MAP VIEW
W
>'-;\^ 'VO 'Vlv -" -v.v ^ ^'-^'-'" 'x''• « i o c K'-V
^^^V^'^X^'v^^^fcO
.
Two-Aquifer System Wtth Opposite Flow Directions
Production
VERTICAL CROSS SECTION
Groundwater How Affected by a Pumped Well
Conraon facilities for observing water levels 1n
aquifers (from McUhorten and Sunada. 1977).
-------
WELL CASING AND SCREEN MATERIAL
Qaa Vent Tube
Tp—wen cap
, !••—Steel Protector Cap with Lock!
Surveyor's Pin (tlush mount)
Concrete Well Apron
Continuous Pour Concrstt Cap
and Well Apron
(expanding cement)
Non-ahrlnklng Cement
Borehole Wall
^7 ^*^. Pptentlometrlc
'-::-; .':'::•' :.v. •'-:•'."•. -V'-V-V-'-raurf ace .'.v'.v:-'.
[••-Filter Pack (2 feet or
• above *er«en> I
Scr
eened Interval/.!:
,".".'''•'/•.'/.%•';_«;.",' Vy •*CT\1 Sump/Sadlment_ Trtpl","•;;•".'•'I -,*
;,-','.'•", '.•,'•",".•".".*: T V'liaiiaaii' mill Cap'. •/.."„; ///- •'•/•*.'.'•',*
'/••'/.'•'.-'• ''_•'•• ".'i •'».'. -'.'.'•' t ".'•.'-.''.'.-•'••.''-• -' . .'r .' •' •
A typical aonitorlng"v«ll deaign.
• FLUORINATED ETHYLENE
PROPYLENE (FEP)
• POLYTETRAFLUORETHYLENE (PTFE)
OR TEFLON
• POLYVINYLCHLORIDE (PVC)
• ACRYLONITRILE BUTADIENE
STYRENE (ABS)
• POLYETHYLENE
• POLYPROPYLENE
• KYNAR
• STAINLESS STEEL
• CAST IRON & LOW-CARBON STEEL
• GALVANIZED STEEL
-------
Hell casing «nd screen material advantages and
Tvoe Advantages
Fluorinated Ethylene
Propylene (FEP)
Polytetrafluoroethylene •
(PTFE) or Teflon
Polyvlnylchlorlde (PVC)
Acrylonltrile Butadiene •
Styrene (ABS>
Polyethylene
Good chemical resistance to
volatile organlcs
Good chemical resistance to
corrosive environments
Lightweight
High-Impact strength
Resistant to Most chemicals
Lightweight
Resistant to weak alkalis,
alcohols, aliphatic hydro-
carbons and oils
Moderately resistant to strong
acids and alkalis
Lightweight
• Lightweight
disadvantages in monitoring wells.
pisadvantages
• Lower strength than steel and
Iron
• Weaker than most plastic Material
• Weaker than steel and Iron
• More reactive than PTFE
• Deteriorates when In contact
with ketones, esters, and
aromatic hydrocarbons
• Low strength
• Less heat resistant than PVC
• Lower strength than steel and
Iron
• Not commonly available
• Low strength
• More reactive than PTFE, but less
reactive than PVC
• Not commonly available
Polypropylene
Kynar
Stainless Steel
Cast Iron I Low-Carbon
Steel
Galvanized Steel
• Lightweight
• Resistant to Mineral acids
• Moderately resistant to
alkalis, alcohols, ketones and
esters
High strength
Resistant to most chemicals
and solvents
High strength
Good chemical resistance to
volatile organlcs
High strength
• High strength
• Low strength
• Deteriorates when in contact with
oxidizing acids, aliphatic hydro-
carbons, and aromatic hydrocarbons
• More reactive than PTFE, but less
reactive than PVC
• Not commonly available
• Poor chemical resistance .to ketones,
acetone
• Not commonly available
• Hay be a source of chromium In low
pH environments
• May catalyze some organic reactions
• Rusts easily, providing highly
sorpttve surface for many metals
• Deteriorates In corrosive
environments
• Hay be a source of zinc
• If coating is scratched, will rust,
providing a highly sorptive surface
for many metals
-------
Multiple Port
Samplers
Multiple Well*
Single Borehole
Multiple Well*
Multiple Boreholes
MULTI-LEVEL MONITOR WELL DESIGN
• MULTIPLE-PORT SAMPLER
NESTED SAMPLER/SINGLE
BOREHOLE
• NESTED SAMPLER/MULTIPLE
BOREHOLES
Opan
Borahola
Flint pick
-Packar or
Annular Saal
-Sampling
Porli
-Borehola-
W.ll
-Annular 8*ala -
•Bcraana•
-Filler Packa-
A conceptual comparison of three multl-ltval aampllng designs.
Multi-level monitoring well design - advantages and disadvantages.
Jvoe Advantages
Multiple-Port • Large number of sampling
Sampler zones per borehole
• Smaller volume of Mater
required for purging than
12 and 13
Disadvantages
• Potential for cross contamination
among ports
• Potential for sampling ports
becoming plugged
• Lower drilling costs than 13 • Special sampling tools required
Nested Sampler/
Single Borehole
• Lower drilling costs than 13
• Low potential for screens
becoming plugged
• Potential for cross contamination
among screen Intervals
• Number of sampling Intervals
limited to three or four
• Larger volume of water required
for purging than II or 13
• Higher Installation costs
Nested Sampler/ • Potential for cross-
Hultlple Boreholes contamination minimized
• Volume of water required for
purging smaller than 12
• Low installation costs
Higher drilling costs
• Low potential for screens
becntntnq pluqqed
-------
FIELD INSTALLATION
GROUND
WATER
k
•END CAP
MALE a FEMALE]
COUPLINGS
SURFACE
TABLE
•PVC PIPE
— COUPLING
> SAMPLING
/ POINTS
END CAP
CROSS SECTION OF
SAMPLING POINT
— TUBING
X
ONE-HOLE
RUBBER
STOPPER
:PVC PIPE
— SCREEN
WELL DEVELOPMENT TECHNIQUES
OVERPUMPING
BACKWASHING
MECHANICAL SURGING
HIGH VELOCITY JETTING
Multi-level tanpler (Cherry et al., 1981).
-------
Hell development techniques - advantages and disadvantages.
|ypq
Overpimplng
Backwash Ing
Hechanlcal Surging
Advantages
• Minimal tine and effort
required
• No new fluids Introduced
• Remove fluids Introduced
during drill Ing
• Effectively rearranges filter •
pack
• Breaks down bridging In filter •
pack
• No new fluids Introduced •
• Effectively rearranges filter •
pack
• Greater suction action and •
surging than backwashlng
• Breaks down bridging In filter
pack
• No new fluids Introduced
Disadvantages
Does not effectively renove
fine-grained sediments
Can leave the lower portion of
large screen Intervals undeveloped
Can result In a large volume of
water to be contained and disposed
Tends to push fine-grained
sediments Into filter pack
Potential for air entrapment U
air 1s used
Unless combined with pumping or
balling, does not remove drilling
fluids
Tends to push fine-grained
sediments Into filter pack
Unless combined with pumping or
balling, does not remove drilling
fluids
DRILLING TECHNIQUES
AUGER
• ROTARY
• CABLE TOOL
High Velocity Jetting
Effectively rearranges filter
pack
Breaks down bridging In filter
pack
Effectively removes the mud
cake around screen
Foreign water and contaminants
introduced
Air blockage can develop with
air Jetting
Air can change water chemistry
and biology (iron bacteria) near
well
Unless combined with pumping or
balling, does not remove drilling
fluids
-------
Auger, rotiry and cable-tool drilling techniques advantages and disadvantages for
construction of Monitoring wells.
Type
Auger
Rotary
Cable Tool
Advantages
• Minimal damage to aquifer •
• No drilling fluids required
•
• Auger f1ights act as temporary
casing, stabilizing hole for
well construction •
• Good technique for unconsoli-
dated deposits
• Continuous core can be collected
by wire-line nethod
• Quick and efficient Mthod •
• Excellent for large and snail
diameter holes •
• No depth limitations
• Can be used In consolidated
and unconsolidated deposits
Disadvantages
Cannot be used In consolidated
deposits
United to wells less than 150 feet
in depth
Hay have to abandon holes If
boulders are encountered
Continuous core can be
collected by wire-line
ethod
• No limitation on well depth
• United amount of drilling
fluid required
• Can be used In both consoli-
dated and unconsolidated
deposits
• Can be used In areas where
lost circulation Is a problem
• Good Kthologlc control
• Effective technique In boulder
environments
Requires drilling fluids which
alter water chemistry
Results in a mud cake on the
borehole wall, requiring
additional well development, and
potentially causing changes In
chemistry
loss of circulation can develop
in fractured and high-permeability
material
Hay have to abandon holes if
boulders are encountered
Limited rigs and experienced
personnel available
Slow and inefficient
Difficult to collect core
Air. Witor
or Drilling Fluid
Auger
Flight
Hollow-Stem Auger
Direct Rotary
Cable Tool
A conceptual comparison of the hollow-item auger, the direct-rotary, and the
cable-tool drilling Methods.
-------
SUMMARY OF METHODS TO MEASURE HYDRAULIC HEAD
Method
Application
Reference
Steel Tape
Saturated zone. Most
precise method.
NoncontInuous measurements.
Slow.
Garber and Koopman
(1968)
METHODS TO MEASURE
HYDRAULIC HEAD
Electric Probe
Saturated zone. Frequent
measurements possible.
Simple to use. Adequate
preci slon.
DHscoll (1986)
• STEEL TAPE
• ELECTRIC PROBE
AIR LINE
Air Line
Pressure
Transducer
Saturated zone. Continuous
measurements. Useful for
pumping tests. Limited
accuracy.
Drlscoll (1986)
Saturated or unsiturated
zone. Continuous or
frequent measurements.
Rapid response to changing
pressure. Permanent
record. Expensive.
Garbar and Koopman
(1968)
PRESSURE TRANSDUCER
ACOUSTIC SOUNDER
TENSIOMETRY
• ELECTRICAL RESISTIVITY
• THERMOCOUPLE PSYCHROMETRY
Acoustic
Sounder
Saturated zone. Fist;
permanent record.
Imprecise.
Tensiometry Saturated or unsaturated
zone. Laboratory or field
method. Useful range 1s 0
to 0.85 bars capillary
pressure. Direct
•easurerwnt. A widely used
method.
Davis and OeHlest
(1966)
Cassel and Klute
(1986);
Stannard (1986)
Electrical Unsaturattd zone.
Resistivity Laboratory or field method.
Useful range 1s 0 to 15
bars capillary pressure.
Indirect measurement.
Prone to variable and
erratic readings.
Campbell and Gee
(1986);
Rehm et al. (1987)
THERMAL DIFFUSIVITY
Thermocouple Unsaturated zone.
Psychrometry Laboratory or field method.
Useful range 10 to 70 bars
capillary pressure.
Interference from dissolved
solutes likely in calcium-
rich waste.
Raw]ins and
Campbell (1986)
Thermal Unsiturated zone.
Diffuslvlty Laboratory or field method.
Useful range 0 to 2.0 bars
capillary pressure.
Indirect measurement.
Phene and Beale
(1976)
-------
J^J SOMUMCENTOMtTt fLlWOEDMTflfHOlE
Q UTOHAMCNT MOMiTOfMPM Wf IIIMWI
• DOffMOHADIfNTMOMITOIIIMavCLLM*T|
Q ntZOMfTEHIfl
H "fit AMD ICHEIM
y TOTtHTIOMCTHIC IIMFACI Of Umft
lANOUMlT
POTIHTWMf THIC lUFlFACt Of lOWf H
J— I AMD UNIT
HOOOFWILL IM 1.IM IFIITt
MONITORING Hill PLACEMENT AMD KHECN LENGTHS IN A GLACIAL TERRAIN
SPRING - SUMMER
IntermHtent
Stream
x r
FALL - WINTER
Dlipoul Site
Empty
Streem
Channel
- flow direction
ttlict at Miionil fluctuations In aurfaci-water flow on groundwattr-flow
dlractiona.
J»w. iO *-T M J««- «1 **T •' J*1' *2
Hydrograph varaua uranlua conc«ntratlona (Bodlflad from
Good.,
-------
LU
>
111
_i
<
LU
CO
z
<
LU
2
LU
>
O
LU
LU
LU
X
O
cc
Q
t- to
aiu
QUARTERLY
MONTHLY
/\
METHODS TO MEASURE
STORAGE PROPERTIES
• PUMPING TEST
• SLUG TEST
• WATER BALANCE
• LABORATORY
SUMMARY OF METHODS TO MEASURE STORAGE PROPERTIES
DAILY
;l I,
j.
i
,il|i i
LI,
L,
li ... , -
Dally HaiuriMntl of praclplcaclon versus dally, monthly, and
quarcirly MaaureMnti of hydraulic head (modified from
Bcardan. 1974).
Method
Pumping Test
Slug Test
Hater-Balance
Laboratory
Appl ication
Can be used to measure
storage values for
unconfined or confined
aquifers. Multiple-well
tests are more accurate
than single-well tests.
Tests a relatively large
volume of the aquifer
Single-well tests for
confined or unconfined
aquifers. Test highly
influenced by well
construction and borehole
conditions.
Measures specific yield
only. Requires several
observation wells around
pumping well to accurately
determine the cone of
depression. Tests a
relatively large volume of
the aquifer.
Obtain a maximum long-term
value. Fractures,
macropores, and
heterogeneities of geologic
material may not be
represented. Only specific
yield can be deter-mined-
Reference
Bureau of
Reclamation (1977);
Stallman (1971);
Driscoll (1986);
Lohman (1979)
Hvorslev (1951);
Bouwer and Rice
(1976);
Lohman (1972);
Cooper et al .
(1967)
Nwankwor et al .
(1984);
Neuman (1987)
Nwankwor et al .
(1984)
-------
METHODS TO MEASURE SATURATED
HYDRAULIC-CONDUCTIVITY
• SLUG TEST
• PUMPING TEST
• STEADY-STATE PERMEAMETER
• FALLING-HEAD PERMEAMETER
SUMMARY OF METHODS TO MEASURE SATURATED HYDRAULIC-CONDUCTIVITY
VALUES IN THE FIELD AND LABORATORY
MinomcMr TubM
Method
Slug Test
Application
Reference
Confined aquifers with
fully-penetrating wells
screened along the entire
aquifer thickness. Single-
well test for wells not
Intended for sampling.
Hvorslev (1951);
Bouwer and Rice
(1976);
Lohman (1972)
Pumping Test Complex multiple-well test Bureau of
for confined or unconfined Reclamation (1977);
aquifers with fully pr Stallman (1971);
partially penetrating Driscoll (1986);
wells. Used for wide range Lohman (1972)
of aquifer permeabilities.
Test wells can be used for
sampling. Tests a
relatively large volume of
the aquifer.
e Dlagru of Cor*
«ooro«: 1099* «t •!.
K Ijnum
Steady-State Laboratory method to
Permeameter determine sample hydraulic
conductivity within a range
from 1.0 cm/sec to 10"s
cm/ sec.
Klute and Dirksen
(1986)
Falling-Head Laboratory method to
Permeameter determine sample hydraulic
conductivity within a range
from 10° cm/sec to 10'9
Klute and Dirksen
(1986)
-------
WELL TW3
SLUG TEST DATA-0
NEGATIVE DISPLACEMENT
10
10'
TIME (seconds)
Theoretical type curve and observed data for the negative displacement slug test
conducted In well TW3.
METHODS TO MEASURE
SPATIAL VARIABILITY
• PIEZOMETER SLUG TESTS
HYDRAULIC CONDUCTIVITY FROM
GRAIN SIZE
• SURFACE GEOPHYSICS
• BOREHOLE GEOPHYSICS
c-
o
£
c
j
0
•o
$
o
AU
35
30
25
20
15
10
5
shin = 1.1513 f— - log (-t) + 1.9 /
I m \ f 5/ J f
\ 29'8 loa / 63° \ t fll jT
*1'1513[12.5 ^ \(1/36) 0.2/ J /
« -0.9 X
" T= 264° y
i = j
m »
. 264«30 ^ S1hr=29.8ft
12.5 J7
'. -63ogPdm ,7 m = 12.5 ft _
/'
0.01 0.1 1.0 10 100 " 1,OOO
• LARGE-SCALE AQUIFER TESTS
(PUMPING TESTS)
• GEOLOGICAL MAPPING OF
SEDIMENTOLOGICAL FACIES
• CONTINUOUS CORE
• BOREHOLE FLOWMETER
Time (minutes)
test result
-------
SUMMARY OF METHODS TO MEASURE SPATIAL VARIABILITY
Method
Piezometer Slug
Tests
Hydraulic
Conductivity
from Grain Size
Surface
Geophysics
Borehole
Geophysics
Large-Scale
Aquifer Tests
(Pumping Tests)
Geological
Mapping of
Sedinen-
tological
Fades
Continuous Core
Borehole
Flowmeter
Application
Localized measurement,
Influenced by well
disturbed zone. Efficient
and easy to conduct.
Samples of aquifer material
required. Empirical and
poor accuracy, especially
for silt and clay
fractions.
Direct current resistivity,
electromagnetic induction,
streaming potential.
Difficult to Interpret and
poor accuracy.
Natural gamma, gamma-gamma
density, single-point
resistance, neutron.
K-f(tf), accuracy?
Provides bulk parameters
over relatively large
region.
Problems with
extrapolation --geological
sections above water table
and away from site.
Split-spoon sampler,
samples are disturbed.
Grain size analysis,
laboratory K.
Most promising. Equipment
difficult to obtain.
Reference
Hvorslev (1951);
Bouwer and Rice
(1976);
Lohman (1979)
Hazen (1892);
Krumbein and Monk
(1942);
Masch and Denny
(1966);
Seller (1973)
Zohdy et al .
(1974);
Sendlein and
Yazlclgal (1981);
Yazicigal and
Sendlein (1982)
Serra (1984);
Wheatcraft et al .
(1986);
Wyllle (1963);
Patten and Bennett
(1963)
Bureau of
Reclamation (1977);
Stallman (1971);
DHscoll (1986);
Lohman (1972)
Wolf (1988)
Rehfeldt et al .
(1988);
Hufschmled (1983,
1986)
HYDRAULIC CONDUCTIVITY
FROM GRAIN SIZE
K =Xd2
K = hydraulic conductivity (cm/sec)
d = representative grain diameter (cm or mm)
X = proportionality factor (a function of the
uniformity coefficient, U)
U = deo/dio
deo = diameter such that 60% of the sample
(by weight) is of diameter less than deo
dio = diameter such that 10% of the sample
(by weight) Is of diameter less than dio
Seller (1973):
K = X(U) d?o (cm) 5 £ U ^ 17
K = X(U)df5 (cm) U2>17
Hazen (1892):
K = d?0 (mm) U < 5
-------
Three-dimensional geometry of braided stream deposits.
HYDRAULIC coNDOcnvrrr (CM/SCC)
Ol Ol Ol 5| Ol
Ol
M
1°
a
3J
on of th« Hydraulic ConductiTity Profil«« liom
Laboratory Mm n ••mi i in Cor* Bo la C-ll and Borehole
r lln i 11 aMiii i in Mil E-11A.
|» • t I IllonU abundanl f7~r~l Vij.loM 6« ««lch-«illo», >«d?i
|. ^ t| >|»uc« I . • I ho1CT2cm/s) zones
in borehole flowmeter test wells.
-------
\
Flow Dlr«ctlon
\
N
\ \ \
\ \ \
\ \ \
\ \ x \
\ \\\
\ \ \ \ v
\ \ \ \ \
v\ \ \\\ \
x\\\\\
\ \ \ \ \ \ \
\ \ \ \ \ x
»
*
\
\
\
\
:« \
Direction
\
Currtnt
Source
Currtnt Mater
Currtnt Flow
Through Earth
Surfact
Hl*c*lcul*clon of |roundw«c«r-flaw dir«ccton» cau*«d
by unr*co|nizcd h«t«rot«n«lcy
DIMWM mama IABIC OCHCIPT or wmrwrrt
»«e>« IIT-U*
o
•flOUMO LIVtk
•^ — COMH iam
SECONOMT FIELDS
CURKENT LOOPS
SENSED VI
nctnt* COIL
. IKTTtl »»C •»!»
rvjwnwaU s«tuD tor th« G«o nowmetor
•LOCK OIAOIAH SHOUIMO (H PIUKIPU Of OPIUTiaMS
-------
ANALYSIS OF DATA
Ackul Syifam
• MATHEMATICAL MODELING
• GEOSTATISTICAL METHODS
• TIME-SERIES TECHNIQUES
• GRAPHICAL METHODS
• FILTERING/SYNTHESIZING TECHNIQUES
2.800
2.600
2.400-
2,200-
2.000
1.800
I I CU». •» m»n»«.i 04 Hmnic<«a.
I | WNMOid •» EJ
K'«'- J Smdimmbm
Side
Boundary
Walar TaUa
Top Boundary
Inpu
t Rogion Shap«
2. Hydraulic ConductMty
3. Boundary Condition*
4 Modal Control Paramatara
Oupul: Pradlctad HydnuUc Haad
NoFkM :
- lO-nn/i
SfncUtod
No Flow
K - 10 cm/i
K - 10 cm/1
*" example of how (a) a "real" ayateei la repreaented by (b) a aodel system, wlilt-h la defined by a
region ahape, boundary condltlona, and hydraulic paraeatara. The e»a«ple section cones from Freeze ll')69j).
Ttta ccwponanca of a a»dal: Input daca, • governing
aquaclon aolvad In che coda, and cha predicted dlacrlbuclon. which for
chla asaopla la hydraulic head.
-------
REGIONAL
\\ixii™
5y 10 f5 30 35
IQA/VC
120*
International Ground W»t«r Modtllng Ctnttr
Holcomb Research Institute
Butlar University
Indiinipolls, Indiana 46208
210*
180'
2/7/86 to 5/0/86
-------
FLOW DIRECTION FLUCTUATIONS
in
T3
N
ra
c
o
•*—•
o
T3
(0
fc_
O
REGULAR WELLS
ON A 4X4
HEXAGONAL GRID
REGULAR
WELLS
4X4 RECTANGULAR
3X3 RECTANGULAR
4X4 HEXAGONAL
16
9
14
R41
R31
H41
OVER WHOLE
AREA
R42
R32
H42
STRATIFIED
R43
R33
H43
ONLY IN MIDDLE
25% OF AREA
middle 25% ol area
RANDOM WELLS
=0^
FM mtttaodml planting
on 1-acralMt tit*.
1
3
5
7
9
11
13
15
17
19
21
33
33
55
36.5
255 I
290
38.6
258
35.8
43.8
33
55
36.1
30.6
22.4
Map showing optimal C: DBerenea between '
ataa at 21 wall*, average dttanca
batmen wall palraand
Htetogram showing no required lag for ad *i
of observation! for 3 m Interval*.
dlatance between wal '
pain.
Vv
H
/v
*•
•
-------
10,000
GROUNDWATER REMEDIATION
• HYDRAULIC CONTAINMENT
- Pump-and-treat technology
• PHYSICAL CONTAINMENT
- Slurry walls
• INNOVATIVE TECHNOLOGIES
- Soil venting
- In situ heating
- Bioreclamation
- Fixation
PROBLEMS WITH PUMP-AND-
TREAT TECHNOLOGIES
NOTE: Conversion Factor
Ippb ' IjtgL'1
1 10
TIME (days)
100
1000
• MATRIX DIFFUSION
• DESORPTION
• RESIDUAL SATURATION (IMMISCIBLE
FLUID)
LEADS TO LONG CLEAN UP TIME FRAMES
PROBLEMS WITH SLURRY WALLS
DIFFICULT TO ACHIEVE DESIGN
PERMEABILITY
DIFFICULT TO PREVENT UNDER FLOW
LEADS TO LOSS OF CONTAINMENT
-------
BIORECLAMATION
CONSISTS OF INJECTING OXYGEN INTO
A CONTAMINATED ZONE TO ENHANCE
NATURAL BIODEGRADATION
- Hydraulics (delivery) problem
IN SITU BIOREACTION
CARSON ADSORPTION/
NUTRCNT » OXYGEN MOTION
AIR STRIPPING TOWER
(REMOSUL OF DISSOLVtO COMPONENTS
WITH OXYGEN «DC«IDNI
PIT
OBSERVATION
WELL INFILTRATION
GALLERY
RECOVERED PRODUCT
RECOVERY HYDROCARBONS
WELL CONTROLS
'N
x>S**w*»v,
y APPROXIMATE VWTER
\ TABLE LEVEL
ACCELERATED MOOEGRADATON
OF ADSORBED AND DISSOLVED
HYDROCARBONS
—Af) SPARGER (OXYGEN AOOTIONI
DECONTAMINATED SOL AND WATER
CONE OF
DEPRESSION
WATER
PUMP
CONTAMINATED VWTER AND
SOIL WITH DISSOLVED AND
ADSORBED HYDROCARBONS
HYDROCARBON
RECOVERY
FLOATING
HYDROCARBONS
SATURATED ZONE SUMMARY
no subsurface characterization technique provides
perfect information; use several techniques in
combination
• determine data thresholds (phased approach) for
remedial decisions; decisions will have
uncertainty; importance of monitoring
• presented general data requirements and
characterization techniques; each application of
techniques is unique and site specific
• data interpretation is just as importnat as data
collection; need to understand data analysis and
why data are collected
-------
DETERMINATION OF WATER MOVEMENT IN SATURATED POROUS MEDIA
References
Bouwer, H. and R.C. Rice, 1976. A slug test for determining hydraulic
conductivity of unconfined aquifers with completely or partially
penetrating wells, Hater Resources Research. 12(3):423-428.
Bureau of Reclamation, 1977. Groundwater Manual. A Water Resources
Technical Publication. Bureau of Reclamation, U.S. Government
Printing Office, Washington, DC.
Campbell, G.S. and G.W. Gee, 19B6. Water potential: Miscellaneous
methods, in Methods of Soil Analysis, A. Klute, ed., Soil Science
Society of America, Agronomy Monograph no. 9, 2nd edition, pp.
619-633.
Cassel, O.K. and A. Klute, 1986. Water potential: Tensiometry, in
Methods of Soil Analysis, A. Klute, ed., Soil Science Society of
America, Agronomy Monograph no. 9, 2nd edition, pp. 563-596.
Cooper Jr., H.H., J.D. Bredehoeft, and I.S. Papadopulos, 1967.
Response of a finite-diameter well to an instantaneous charge of
water, Water Resources Research. 3(l):263-269.
Davis, S.N. and R.J. DeWiest, 1966. Hydrooeologv. John Wiley i Sons,
Inc., New York, 463 pp.
Oriscoll, F.G., 1986. Groundwater and Wells. Johnson Division, St.
Paul, MN, 1089 pp.
Freeze, R.A. and J.A. Cherry, 1979.
Englewood Cliffs, NJ.
Groundwater. Prentice-Hall, Inc.,
Garber, M.S. and F.C. Koopman, 1968. Methods of measuring water levels
in deep wells, United States Geological Survey, la Techniques of
Water-Resources Investigations, Book 8, Chapter Al, U.S.
Government Printing Office, Washington, DC, 23 pp.
Guthrie, M,, 1986. Use of a geo flowraeter for the determination of
ground water flow direction, Ground Water Monitoring Review.
Hazen, A., 1892. Experiments upon the purification of sewage »nd water
at the Lawrence Experiment Station, Massachusetts State Board of
Health, 23rd Annual Report.
Hufschmied, P., 1983. Die Ermittlung der Durchlassigkeit von
Lockergersteins-Grundwasserleitern, eine vergleichende
Untersuchung verschiedener Felnethoden, Doctoral Dissertation no.
7397, ETH Zurich, Switzerland.
Hufschmied, F., 1986. Estimation of three-dimensional statistically
anisotropic hydraulic conductivity field by means of single well
pumping tests combined with flowmeter measurements, HvdroaeoloQie.
no. 2, pp. 163-174.
Hvorslev, M.J., 1951. Time lag and soil permeability in ground-water
observations, U.S. Army Corps of Engineers Bulletin, no. 36.
Kerfoot, W.B., 1984. Darcian flow characteristics upgradient of a
kettle pond determined by direct ground water flow measurement,
Ground Water Monitoring Review. 4(4):188.
Klute, A. and C. Dlrksen, 1986. Hydraulic conductivity and
diffusivity: Laboratory methods, ia Methods of Soil Analysis,
Part 1, A. Klute, ed., Soil Science Society of America, Agronomy
Monograph no. 9, 2nd edition, Madison, WI, pp. 687-734.
Krumbein, W.C. and G.D. Honk, 1942. Permeability as a function of the
size parameters of unconsolidated sand, Petroleum Technology.
July.
Lohman, S.W., 1972. Groundwater hydraulics, U.S. Geological Survey
Professional Paper 708, U.S. Government Printing Office,
Washington, DC.
Hasch, F. and K. Denny, 1966. Grain size distribution and its effect
on the permeability of unconsolidated sands. Water Resources
Research. 2(4):665-677.
Neuman, S.F., 1972. Theory of flow in unconfined aquifers considering
delayed response of the water table. Water Resources Research.
8(4):1031-1045.
Nwankwor, G.I., J.A. Cherry, and R.W. Gillhaa, 1984. A comparative
study of specific yield determinations for a shallow sand aquifer,
Ground Water. 22(6).-764-772.
Patten Jr., E.P. and G.D. Bennett, 1963. Application of electrical and
radioactive well logging to ground-water hydrology, U.S.
Geological Survey Water Supply Paper 1544-D, 60 pp.
Phene, C.J. and D.W. Beale, 1976. High-frequency irrigation for water-
nutrient management In humid regions, Soil Science Society of
America Journal. 40, pp. 430-436.
Rawlins, S.L. and G.S. Campbell, 1986. Water potential: Thermocouple
psychrometry, in Methods of Soil Analysis, A. Klute, ed.. Soil
Science Society of America, Agronomy Monograph no. 9, 2nd edition,
pp. 597-618.
-------
Rehfeldt, K.R., L.W. Gelhar, J.B. Southard, and A.M. Dasinger, 1988.
Interim analysis of spatial variability of hydraulic conductivity
and prediction of macrodispersivity, Electric Power Research
Institute Research Project 2485-5.
Rehfeldt, K.R., P. Hufschmied, L.W. Gelhar, and M.E. Schaefer, 19B8.
The borehole flowmeter technique for measuring hydraulic
conductivity variability, Draft of a topical report prepared by
MIT for Electric Power Research Institute, Research Project 2485-
5.
Rehm, B.W., B.J. Christel, T.R. Stolzenburg, D.G. Nichols, B. Lowery,
and B.J. Andraski, 1987. Field Evaluation of Instruments for the
Measurement of Unsaturated Hydraulic Properties of Fly Ash.
Electric Power Research Institute, Palo Alto, CA.
Sendlein, L.V.A. and H. Yazicigal, 1981. Surface geophysical
techniques in ground-water monitoring, Part I, Ground Water
Monitoring Review. Fall, pp. 42-46.
Seller, K.F., 1973. Durchlassigkeit, Porositat und Kornverteilung
quartarer Keis-Sand-Ablagerunger des bayerischen Alpenvorlandes,
6as-und Wasserfach. 114(8) :353-400.
Serra, 0., 1984. Fundamentals of well-log interpretation, 1, the
acquisition of logging data, in Developments in Petroleum Science,
ISA, 423 pp., Elsevier Science Publishing Co., New York.
Sisk, S.W., 1981. NEIC manual for groundwater/subsurface
Investigations at hazardous waste sites, National Enforcement
Investigations Center, EPA-330/9-81-002.
Stallman, R.W., 1971. Aquifer-test design, observation, and data
analysis, in USGS Techniques of Water-Resources Investigations,
Book 3, Chapter Bl, U.S. Government Printing Office, Washington,
DC.
Stannard, D.I., 1986. Theory, construction and operation of simple
tensiometers, Ground Water Monitoring Review. 6(3):70-78.
U.S. Environmental Protection Agency, 1986. RCRA ground-water
•onitoring technical enforcement guidance document, OSWER-9950.1.
U.S. Environmental Protection Agency, 198Ba. Guidance on remedial
actions for contaminated ground water at superfund sites, Advance
copy, OSUER Directive no. 9283.1-2.
U.S. Environmental Protection Agency, 1988b. Guidance for conducting
remedial investigations and feasibility studies under CERCLA,
Interim final, OWSER Directive 9355.3-01.
Wheatcraft, S.W., K.C. Taylor, J.W. Hess, and T.H. Morris, 1986.
Borehole sensing methods for ground-water investigations at
hazardous waste sites. Desert Research Institute, University of
Nevada System, Water Resources Center, Pub. no. 41099, January, 69
PP-
Wolf, S., 1988. Master of science thesis, Department of Civil
Engineering, MIT, Cambridge, HA, in preparation.
Wyllie, M.R.J., 1963. The Fundamentals of Well Log Interpretation.
Academic Press, 1963, 238 pp.
Yjzicigal, H. and L.V.A. Sendlein, 1982. Surface geophysical
techniques in ground-water monitoring. Part II, Ground Water
Monitoring Review. Winter, pp. 56-62.
Zohdy, A.A.R., G.P. Eaton, and D.R. Mabey, 1974. Application of
surface geophysics to ground-water investigations, Book 2, Chapter
01, in Techniques of Water-Resources Investigations of the United
States Geological Survey, 115 pp.
-------
SESSION I
Part 2: Determination of Water Movement in Fractured Media
DETERMINATION OF
WATER MOVEMENT IN
SATURATED FRACTURED MEDIA
Water Storage
Water Movement
Contaminant Storage
Contaminant Movement
Impacts on Remediation
SHEAS ZC
JOINTS
SOUD ROCK
ELEVATION
NOVO
PIEZOMETER flEZOMETER
1 4
PIEZOMETER PIEZOMETER
3 2
2W-J
>
•.•.?-;...;.
• r .' '' '• '."•
ii*g;
-.-'?'.*".-'• -
^T
i i
-. -L L
-1 1 ' 1
-rh-1-
-r-S-1-
' i ' i
-V-T
T^T^
i^v"
11^1
Spss;:<
J
;• •*"|*>-*^ *;••••".-»— :
r^K^
Lii1 ! ' ! ' J
p LIMESTONE -f
I K • 16 « 10~se
'-: » \ < .' ' : '
1 1 1 i ' '
W^rf
[T^L'^-^
J
'.'X WASTE DISPOSAL y/T''-
••'."•:. X, u|g|T /''•'••.'•'••
;/.'•;•'•-: '•':•::. SILTY SAND vv':!.-'V • '•
::" '•-.•;•':•'. K- 1.4 M 1O~4cin/Me -.'•.'' '-.••:''
•.-''r:'.'• • v:: ' ',•
:. • '•.•''•'•'; XW FAULT LINE ^' .'..-• ••••
e^KbsycSEll '•••*••'-*•>"• ^s. •• " '•"
Jrx\^^p^j>.-:
JL ! ' ! j\ ' ! ; ! ' ! ' ! i ! r ,Ljg
••I'M' HYDRAULIC -H
•j ' | ' | 1 | 1 \l , CONDUCTIVITY -
' ' ' ' ' \ FOR LIMESTONE
J- 1 1 1 T-h-H- ALONG FAULT LIN
!'!'!'!'!'!\[i!iStii3
fe^V^-r''^-^'!'!'.!1
;\5.-.'- "/.-SANDSTONE '.^"J.V -....-,. .;•:•• v.
;:.i;;>':V:-v-:^;.r::.^:v:i:'.^.vV\Y '•^v-;.:v:^
y^y:! K • n, lo^cm/M ^^;-:;::^;;:^
1, V
^
V1 '
\ 1
'3d
-H*^
311/IK -^
-T-M
t
1 1 1
1 1 1
1 1 1
I'l'l1
^>x
1 1 I
1 1 J
^ 1 ' ! ' 1
POTENTIOMETRK
SURFACE
I I ' ' ' I I I
iw so- o so- MO-
AN EXAMPLE OF HYDRAULIC COMMUNICATION CAUSED BY FAULTING
FMACTUMC
V PLOW
* * /"
o.rrt,^
PONOUS
MOCK MATRIX
CALCIUM
BENTONITE
PLUGGED
BOREHOLE
Conceptualization of di«contlnuicl»* In * fractured nadiua.
Flow through fracturai and diffusion of contaainonc* from
fraccuraa Into th» rock matrix of « dual-poroaity ••diua.
-------
DEPTH
IN
Te.lurol and
Compositional
/-lj Variation
100 --
200 --
300 -L
(After Lottman ond Parlitk 1964)
Localization of water-yielding openings along bedrock fractures In
carbonate aquifers.
FRACTURE MAPPING
ORIENTATION
APERATURE
SPACING
50
as
eo
86
70
u
-. — — — MAPPED BY aeOTRANS
— MAPPED BY LEAVY (IBiSI
DARKENED AREAS INDICATE
BROKEN ROCK AND VOID SPACE
OR ZONES THAT DRILL RODS
DROPPED THROUGH
DARKENENED AREAS INDICATE
APPROXIMATELY FOUR FEET
OF VOID SPACE
CONTOUR INTERVAL IO fEET
NATIOHM. GCOMTIC VERTICAL DATUM al 1979
-------
^
i-V^5
i "* ' "il
. ' -3- J 3-"
','" '-V-
^fe
CL»ir
CL4V S LIW
LIMf STONE
W/ SHALE
LIMESTONE
W'SHALE
••o
• 90
140
83O
— LIMESTONE
SOLUTION
DEVELOPMENT
ALONG MORE
RESISTANT BED
CONTACTS
CLAY L'NED VCHD
OR WASHED OUT
CLAY OR SHALE
HORIZON
WELL A CeOLOCK LOG
•O* POLYCTHTLCNC CLJOW
vrTH !/• ' N P T
Schematic maoram ol a slx-poit multUev»l assembly and detailed
VIEWS ot a packer and sampling port systems.
TSP
WELL B €£OLOGiC LOG
-------
Prajtirt buildup data exhibiting a thr« ••gm+nt pattern
CXmcnoonM
distnbuttd-paramMar model at a naturaity tracturad formano
March 26 27 28 29 30 31 April 234
Tracer-diagram
Model of a network of panagei
Hydrological
limit of a karst
area ~
Va:vaOosezone
Vo Base leve
Pi Piezometnc surface
Ph:Ptireaticzone
Thr«« dlf(ar*nc eoncapcuallzaclona of fraccura iwcworlu
Hydrologicil limit of a kant area-
-------
porous media
fractured
Tpm
porous media
REV
REGION I Ports I
fractured media
REV !
REGION ! tt>)
(Froeturtil j
(Cj "
XBL
Conceptual wdel for overlapalng coijtln.ua,, curyfl («) Is s
the plot of a property * measured, for different yo|vm« (Ktvj i.
of porous Mdlili curve (b) iJ*^ P-lot of a ^P«rt»*
for different volumes (REy>, I5'9? f:'-»c*u:«d.P°r^Ll
region rfLL
MIL KHUN
fOTINTKMMTHK IDdFACt
fHAOIMIIP in*ci
OUHIM or e*vm>i irum v»w
mil 4 Mill
VMUICTiOMMin
UONITOniNQ MtLL PLACEMENT *NO ICREEN LENQTHt IN A MATURE KAR1T TERRAIN/FRACTURED BEDROCK SETTING
-------
LOCATION OF GEOPHYSICAL SURVEY LINES
TO OCAU
0 660 1320FEET
0 200 400 METERS
I STRONG
STRENGTH OF
EXPRESSION
0 660 1320 FEET
HH—I
0 200 400 METERS
FRACTURE TRACES NEAR ROMP WELL 120
-------
CONDUCTIVE:
CO
CO
a CPPC
+ CCPP
CPCP
>y
DISTANCE--
RESISTIVE:
— CONDUCTIVE
SHEET
45'
I
2SN
I- +
CO
(0
a CPPC
+ CCPP
0 CPCP
OW4
COUNTv'nOAD 32l'
OWt (ACTUAL)
ROMP 120->«
y^ UNE 2
0^«-OW2 (ACTUAL! UNE *
DISTANCE--
I
25W
I
2SE
I
50
I
79
OW1 (PROPOSED)
I I
H)0 125
I
1SOE
•25S
U—RESISTIVE
V///// SHEET
w///,
DISTANCE M METERS
TRI-POTENTIAL DATA
UNE 1: SOUTH SIDE 328
ANOMALY A / -^-ANOMALY 'B
f
-N-
INTEASECT1ON LOCATION
75M
SOUTH
EDGE OF AOAD
|17M
Location of four observation wells In the vicinity
of ROHP 120.
4O
-10O -60 -20
O CPPC
6O
1OO 1*O 180
DISTANCE (M)
+ CCPP o CPCP
-------
OiOTRANS
LOQQCR
uy t ii
NAME "OMP 120 |
ILOQ rtrtl (CALIPERI ICAUPERI INEUTRONI IQAUMA-OAMUAI ICALIPERI (NEUTRON) lOAyUA-QAMyAI ICALIPERI INEUTRONI INOQAUUA- ICAUPERI INEUTRONI IOAUUA-QAUMA1
- -~X=sS;TJijitS«__ ~£r C.Ung-^- -^. Um..!.^^ io^iO— t Ci.Tng -^ Ci.Tnr
i^-^-ii. ^ssiLi>^:i«:^^L~L. 9^ •J^_Eti_u^.i«;3^^_jr- ~> ~I^S~
^S«nd 8lr««k ~--
400
6 8 tO 12 2 4 660 80 100 2000 4000 6000 2 4 6 8 100 120 HO 2000 4000 6000 8000 2 4 6 80 100 120 140
INCHES CPM CPM INCHES CPU CPU INCHES CPM
4 6 I 80 1002000 4000
INCHES CPM CPM
Geophysical log Interpretation of observation
wells.
-------
OW1 (deep) Drawdown
Jacob Approximation
i.oo -
I
a
o
o.oo
Q - 180 gpm
to - 0.0045
r - 136 ft
10-*
10'
vF—
TIMf (•!*>
10'
10*
10
10
10
18"
10
OW1 (deep) Drawdown
Thels Analysis
W (u) - 1
1/u - 3.5
S - .11 II
I > .42 ml*
-i-U
Q - 100 gpm
r - 136 ft
to
10*
TIME (mln)
10
10
-------
HEAD ((eat)
10
30
TIME (»«c)
HEAD ((eel)
30 40
TIME (»«c)
FRACTURED MEDIA SUMMARY
heterogeneity Is important to characterize, but is
especially important in karst and fractured media
characterization techniques are somewhat limited:
coring, aquifer tests, tracer tests, geophysical
tools, and fracture trace analysis
difficult to characterize and predict behavior:
equivalent porous media, discrete fractures, dual
porosity, and stochastic approach
-------
DETERMINATION OF WATER MOVEMENT IN SATURATED FRACTURED MEDIA
References
Bogli, A., 1980. Karjt Jydroloov and Phy5l»1 Speleology. Springer-
Verlag, New York, 284 pp.
Boulton, N.S. ind T.D. Streltsova, 1977. Unsteady flow to a pumped
well In a fissured water bearing formation. Journal of Hydrology.
35, pp. 257-270.
Cherry, J.A. and P.E. Johnson, 1982. A multilevel device for
monitoring in fractured rock. Ground Mater Monitoring Review.
2(3):41.
Engelman, R., Y. Gur, and Z. Jaeger, 1983. Fluid flow through a crack
network in rocks, Journal of Applied Mechanics. 50, pp. 707-711.
Giffin, D.A. and O.S. Ward, 1989. Analysis of early-time oscillatory
aquifer response, New Field Techniques, NWWA Conference, Dallas,
TX, March 20-23.
Gringarten, A.C., 1982. Flow-test evaluation of fractured reservoirs
in Recent Trends in Hydrol geology, T.N. Narasimhan, ed.,
Geological Society of America. Special Paper 189, pp. 237-263.
Gringarten, A.C., 1984. Interpretation of tests 1n fissured and
aultllayered reservoirs with double porosity behavior: Theory and
practice, Journa.1 _of Petroleum Technology, pp. 549-564.
International Association of Hydrological Sciences, 1988.
Hvdrogeology and Karst Environment Protection. IAHS Publication
No. 176, 1261 pp.
Long, J C S , J.S. Remer, C.R. Wilson, and P. A. Witherspoon, 1982.
Porous media equivalents for networks of discontinuous fractures,
Water Resources Research. 18(3), pp. 645-658.
Marsily, G. de, 1985. Flow and transport in fractured rocks:
Connectivity and scale effect, IAH International Symposium on the
Hydrogeology of Rocks of Low Permeability (January 7-12), Tucson,
AZ.
Mickaa, J.T., B.S. Levy, and G.W. Lee, Jr., 1984. Surface and borehole
geophysical methods in ground water Investigations, Ground Miter
Review. 4(3):167.
Moriham, T. and R.C. Dorrier, 1984. The application of television
borehole logging to ground water monitoring programs, Gjojpq
Monitoring Review. 4(4):172.
Quinlan, J.F., 1982. Groundwater basin delineation with dye-tracing,
potentiometric surface mapping, and cava Happing, Maanoth Cave
Region, Kentucky, Beitrage zur Geologie dir Schweiz, Hydrolooie.
28, pp. 177-189.
Quinlan, J.F. and E.C. Alexander, Jr., 1987. How often should samples
be taken at relevant locations for reliable monitoring of
pollutants from an agricultural, waste disposal, or spill site In
a karst terrain? A first approximation. Proceedings of the
Hultidlsciolinarv Conference on Sinkholes and the Environmental
Impacts of Karst (2nd, Orlando, FL), Balkema, Rotterdam, pp. 227-
286.
Quinlan, J.F. and R.O. Ewers, 1985. Ground water flow in limestone
terrains: Strategy rationale and procedure for reliable,
efficient monitoring of ground water quality in karst areas,
Proceedings of the National Symposium and Exposition on Aquifer
Restoration and Ground Water Monitoring (5th, Columbus, OH),
National Water Hell Association, Dublin, OH, pp. 197-234.
Schwartz. F.W., L. Smith, and A.S. Crowe, 1983. A stochastic analysis
of macroscopic dispersion in fractured media. Mater Resources
fifiifiarcJl, 19(5), pp. 12S3-J265.
Streltsova, T.D., 1988. Well testing 1n heterogeneous formations ifl An
Exxon Monograph, John Wiley t Sons, New York, 413 pp.
Streltsova-Adams, T.D., 1978. Well hydraulics in heterogeneous aquifer
formations IQ Advances in Hydroscience, V.T. Chow, ed., 11, pp.
357-423.
Way, S.C. and C.R. Mckee, 1982. In-sltu determination of three-
dimensional aquifer permeabilities, Ground Water. 20, pp. 594-603.
Weeks, E.P., 1969. Determining the ratio of horizontal to vertical
permeability by aquifer-test analysis, Hater Resources Research.
5(1):196-214.
Uilke, S., E. Guyon, and Marslly, G. de. 1985. Water penetration
through fractured rock: Tests of a tridlmenslonal percolation
description, Mathematical Geqloqv. 17(1), pp. 17-27.
Wilson, C.R., et al., 1983. Large scale hydraulic conductivity
measurements In fractured granite. International Journal of Rock
Mechanics Mineral Science Geomechanical Abstract. 10(6), pp. 269-
2/6.
-------
SESSION I
Part 3: Determination of Water Movement in the Vadose Zone
DETERMINATION OF
WATER MOVEMENT
IN THE
VADOSE ZONE
Water Storage
Water Movement
Contaminant Storage
Contaminant Movement
Vapor Movement
Impacts on Remediation
American Society
for Testing and Mrtenets
American Association
of State Highway Officials
\J£. Department
of Agriculture
Federal Aviation
Administration
Corps of Engineers,
Bureau of Reclamation
Colloids'
Colloids'
Clay
Clay
Clay
Silt
Silt
Silt
Clay
Silt
Fine
sand
Fine
sand
Very
fine Fine
sand sand
Fines (silt or cleyl"
Fine
sand
Medium
sand
Coarse
sand
? T)
ium 5 c
sand 38
Fine
sand
O Q O O C
Sieve sizes R 8 * T *
i
fN o v
888
to Qp *~ (N O V
000 0 0 S
B
8?
V
Coarse
sand
Medium
sand
1 ?
3
^
c
•"
Coarse
sand
Gravel
Fine Medium
grave! yave*
Coarse
Fine Coarse
grave! sand
Boukton
CobblM
Gravel
Coarse
sand
2
Fine
(i- eve!
r ;ff is
coop*-; nnvioooo o o o o o o o
Coarse
gravel
r
Cobblti
i
8 §2 §
Particle size, mm.
'Colloid! included in clay fraction in tatt reports.
"The LL and PI of "Silt" plot below the "A" line on the plasticity chart. Table 4.
and the LL and PI for "Clay" plot above the "A" line.
Soil-separate size limits of ASTM, AASHO, USD A, FAA. Corpt of Engineers, and USSR.
-------
-gA.A A^r^
CLAY LQAMN
PERCENT SAND
Triangular chan showing the percentage* of sand, lilt, and clay
in the basic soil textural claim.
Bouwer (1978)
aoa
PARTICLE DIAMETER IN MM
Particle-size distribution for a uniform sand
and a well-graded soil
Bouwer (1978)
Land Surfact
Belt of Soil Water
Intermediate Belt
Capillary Fringe
Water Table
Ground Water
o
c
o
N
e
o
o
••»
o
o
M
DIVISIONS OF SUBSUR-
FACE WATER.
'1 "'2 * '3
h, > hj > hj
-120
il -100
-80
-60
-40
-20
Captttwy Aiw Equaaon
015
0 SO 100 ISO 200
DIAMETER OF TUBULAR PORE, r
R«laclocuhip b«tw««n pot*
praaiuz* haad (h) .
(r) on capillary rli« and
-------
NEGATIVE
PRESSURE
POTENTIAL
POSITIVE
.PRESSURE POTENTIAL
Illustration of pressure potential and matric
potential below and above a free water surface
The capillary tube represents an idealized son
void.
METHODS TO MEASURE
PRECIPITATION
• SACRAMENTO GAGE
• WEIGHING GAGE
• TIPPING-BUCKET GAGE
PRECIPITATION
I * I I I
EVAPOTRANSP1RAT10N
SUMMARY OF METHODS TO MEASURE PRECIPITATION
Idealized block diagram illustrating typical geometry of
the siream-aquifer system and ihe relation beiween water movement
and water quality.
Method
Sacranento Gage
Weighing Gage
Tipping-bucket
Gage
Application
Accumulated precipitation.
Manual recording.
Continuous measurement of
precipitation. Mechanical
recording.
Continuous measurement of
precipitation. Electronic
recording. Recommended.
Reference
Finkelstein et al .
(1983);
National Weather
Service (1972)
Finkelstein et al .
(1983);
Kite (1979)
Finkelstein et al .
(1983);
Kite (1979)
-------
METHODS TO MEASURE EVAPORATION
CLASS-A PAN
SUMMARY OF METHODS TO MEASURE EVAPORATION
Method
Application
Reference
Class-A Pan Evaporation from surface of
free liquid.
Veihmeyer (1964);
National Weather
Service (1972)
METHODS TO MEASURE OR ESTIMATE
EVAPOTRANSPIRATION
• WATER BALANCE METHODS
— pan lysimeter
— soil moisture sampling
— potential evapotranspirometers
— cl" tracer
— water-budget analysis
— groundwater fluctuation
• MICROMETEOROLOGIC METHODS
— profile method
— energy budget/Bowen ratio
— Eddy covariance method
— Penman equation
— Thornwaite equation
— Blaney-Criddle equation
-------
SUMMARY OF METHODS TO HEASURE OR ESTIMATE EVAPOTRANSP1RATION
Method
Application
Reference
yATER BALANCE
METHODS
Pan
Lysimeter
Direct field method;
accurate; moderate to low
cost.
Veihmeyer (1964);
Sharma (1985)
Soil
Moisture
Sampling
Direct field method;
accurate; moderate to low
cost.
Veihmeyer (1964)
Potential Direct field method of PET. Thornthwaite and
Evapotrans- Moderately accurate and low Mather (1955)
pirometers cost.
V Tracer Indirect combined field and
laboratory method; moderate
to high cost.
Shanna (1985)
Water-Budget Indirect field estimate of Davis I Dewiest
Analysis ET; manageable to (1966)
difficult; moderate to low
cost.
Ground-water
Fluctuation
MICROMETEORO-
LOGIC METHODS
Profile
Method
Energy
Budget/
Bowen Ratio
Indirect field »ethod; Davis & Dewiest
«oder»te to low cost. (1966)
Indirect field method. Shanna (1985)
Indirect field method; Veihmeyer (1964);
difficult; costly; requires Sharma (1985)
data which is often
unobtainable; research
oriented.
Eddy
Covanance
Method
Indirect field method;
costly; measures water-
vapor flux directly; highly
accurate; well accepted;
research oriented.
Veihmeyer (1964);
Sharma (1985)
Penman
Equation
Indirect field method;
difficult; costly; very
accurate; eliminates need
for surface temperature
measurements; research
oriented.
Veihmeyer (1964);
Sharma (1985)
Thornwaite Empirical equation; most
Equation accepted for calculating
PET; uses average monthly
sunlight; moderate to low
cost.
Veihmeyer (1964);
Sharma (1985)
Blaney-
Criddle
Equation
Empirical equation; widely
used; moderate to high
accuracy; low cost; adjusts
for certain crops ind
vegetation.
Stephens & Stewart
(1964)
-------
SUMMARY OF METHODS TO MEASURE OR ESTIMATE INFILTRATION RATES
Method
Application
Reference
Infiltrometers
Measures the maximum
infiltration rate of
surface soils. Useful for
determining relative
infiltration rates of
different soil types;
however, infiltration rates
determined by this method
tend to overestimate actual
rates.
Dunne and Leopold
(1978);
Bouwer (1986)
METHODS TO MEASURE OR
ESTIMATE INFILTRATION RATES
• INFILTROMETERS
Sprinkler
Infiltrometer
Measures the potential
range of infiltration rates
under various precipitation
conditions. Tends to be
expensive and non-portable.
Sprinkler Infiltrometers
have typically been used
for long duration research
studies.
Dunne and Leopold
(1978);
Peterson and
Bubenzer (1986)
SPRINKLER INFILTROMETER
AVERAGE INFILTRATION METHOD
EMPIRICAL RELATIONS
INFILTRATION EQUATIONS
Average Method for estimating the
Infiltration average infiltration rate
Method for small water sheds.
Provides an approximate
estimate of infiltration
for specific precipitation
events and antecedent
•oisture conditions.
Empirical
Relations
Dunne and Leopold
(1978)
Methods to approximate the
infiltration for large
watersheds. These methods
can be useful when combined
with limited infiltrometer
measurements to obtain a
gross approximation of
infiltration.
Husgrave and Hoi tan
(1964)
Infiltration Analytical equations for
Equations calculating infiltration
rates. Parameters required
in the equations can be
readily measured in the
field or obtained from the
literature. Probably the
least expensive and most
efficient method for
estimating infiltration.
Bouwer (1986);
Green and Ampt
(1911);
Philip (1957)
-------
t-0 FOR V VERSUS t
(RUNOFF
INFILTRATION
Infiltration and runoff for r»in of uniform intensity.
Bouwer (1978)
liM-u«nirM in"
tin..Matured lev"
Cross section of hypothetical cover design
300
water utiUiatiom from tariaut depth layers
Predicted distribution of pressure head
1*1
; 200
30 hr
90
-223
-ae
2H
.10 20 .X .40
Wmreomm.* (em1 /cmjI_ —
Predicted distribution of soil water content
-------
METHODS FOR MEASURING
MOISTURE CONTENT
• GRAVIMETRIC
• NEUTRON SCATTERING
• GAMMA RAY ATTENUATION
• ELECTROMAGNETIC
• TENSIOMETRY
SUMMARY OF METHOD FOR MEASURING MOISTURE CONTENT
Method
, To an •molif i«f ana Klltr wnicn monitors
V neutron collisions
. ACCESS TUBE
Electromagnetic
Tensioaetry
Application
Reference
Gardner (1986);
EPRI (1984)
Gravimetric Laboratory measurements of
soils which should be dried
at 110'C. The standard
method for moisture
content determina-tion.
Recommended.
Neutron In situ measurements via
Scattering installed access tubes.
Widely used. Requires
calibration curves.
Recommended.
Gamma Ray In situ measurements via
Attenuation installed access tubes.
Difficult to use. Not
recommended for routine
use.
In situ measurements fron
implanted sensors. Not
widely used. Not
recommended for routine
use.
HOW a neutron moisture meter operate*. The probe, contajiung a source
at fast neutrons and a slow neutron detector, i) lowered into the toil through an access
lube. Neutronj are emitted b> the source dor eiimple. radium ot amencium-bervUiumi
at a very aj(h speed. When tlxxc neutron* collide with a smaJI atom such as hydrogen
conuined in soil water, their direction of movement u changed and they lose pan ot
Ibav energy These "slowed" Detilrotu an meaaurad by a dcteoor tube and a acaiw.
g B related u> ux aoii oaovni
In situ measurements
inferred from moisture-
•atric potential
relationship. Prone to
error resulting from
uncertainty of moisture-
oatric potential
relationship. Not
recommended.
van Bavel (1963)
Gardner (1986)
Schmugge et al.
(1980)
Gardner (1986)
-------
SAND
PERCHED WATER ZONES
A.
POTENTIOMETRIC
SURFACE
^ SURFACE UPPERMOST
' ^-».^. r _ AQUIFER
SAND
K - 1.0 «
PERCHED WATER ZONES AS PART OF THE UPPERMOST AQUIFER
SOIL-WATER SYSTEMS
Saturated Unsaturated
-Piezometer
Tensiometer'
Porous CUD
j [,—Piezom
Tygon tubing jacket
Insulated lead wire
Epoxy resm
Copper lead wire
Copper - constantin
thermocouple
Teflon plug
Chromel • constantan
thermocouple
Screen cage
Median longitudinal section of a screen-enclosed
thermocouple psychrometer (after Meyn and White,
Refcrencc level
A diagram of the relationships between hydraulic
head, H, pressure head, h, and gravitational head,
Z. The pressure head 1s measured from the level of
termination of the piezometer or tensiometer in the
soil to the water level in the manometer and is
-------
METHODS FOR DETERMINING
MOISTURE CHARACTERISTIC CURVES
• POROUS PLATE
VAPOR EQUILIBRATION
OSMOTIC
SUMMARY OF METHODS FOR DETERMINING MOISTURE CHARACTERISTIC CURVES
Method
Application
Reference
Porous Plate Standard laboratory method Klute (1966)
for measurement of soils.
Can be used to characterize
both wetting and drying
behavior.
300,
200
VOLUMETRIC WATER CONTENT
Schematic equilibrium water-content distribution above a water table (left) for a coarse
uniform sand (A), a fine uniform sand (B). a well-graded fine sand (C), and a clay soil (D). The
right plot shows the corresponding equilibrium water-content distribution in a soil profile consisting
of layers of materials A, B, and D.
Bouwer (1978)
Vapor
Equlibration
Best suited for matric
potentials less than -15
bars.
Klute (1986)
Osmotic
Similar to porous plate
method. Requires long
equilibration times. Not
recommended.
Klute (1986)
-------
WATER-EWTRY
WM.UE
o.i o.z 0.3 0.4 as
VOLUMETRIC WATER CONTENT
Schematic of water-content distribution above a water table
after the water table was falling (soil pores drained) and rising
(soil pores filled).
Bouwer (1978)
-200
-150 -100 -50
PRESSURE HEAD IN CM WATER
Hysteretic relations between h and 8 for Rubicon sandy loam.
UJ
(-
O
o
I
o
cc
UJ
0.2 §
O
0
METHODS TO MEASURE
UNSATURATED HYDRAULIC -
CONDUCTIVITY VALUES
• CONSTANT-HEAD BOREHOLE
INFILTRATION
• GUELPH PERMEAMETER
• AIR-ENTRY PERMEAMETER
• INSTANTANEOUS PROFILE
• CRUST-IMPOSED STEADY FLUX
• SPRINKLER-IMPOSED STEADY FLUX
• PARAMETER IDENTIFICATION
EMPIRICAL EQUATIONS
-------
SUMMARY OF METHODS TO MEASURE UNSATURATED HYDRAULIC-CONDUCTIVITY
VALUES IN THE FIELD AND LABORATORY
Method
Application
Reference
Constant-Head
Borehole
Infiltration
Field method in open or
partially cased borehole.
Host commonly used method.
Includes a relatively large
volume of porous media in
test.
Bouwer (1978);
Stephens and Neuman
(1982a,b,c);
Arooozegar and
Warrick (1986)
Guelph Field method in open,
Permeameter small-diameter borehole (>5
cm). Relatively fast
method (5 to 60 minutes)
requiring small volume of
Hater. K,, K(|J) and
sorptivity are measured
simultaneously. Many
boreholes and tests nay be
required to fully represent
heterogeneities of porous
•edia.
Reynolds and Elrick
(1986)
Air-Entry Field method. Test per-
Permeameter formed in cylinder which is
driven into porous media.
Snail volume of material
tested; hence, many tests
•ay be needed. Fast,
simple method requiring
little water (-10 L).
Bouwer (1966)
Instantaneous
Profile
Field or lab method. Field
method measures vertical
K(t,t) during drainage.
Measurement of moisture
content and hydraulic head
needs to be rapid and non-
destructive to sample.
Cooionly used method,
reasonably accurate.
Bouma, Baker, and
Veneman (1974);
Klute and Dirksen,
(1986)
Crust-Imposed
Steady Flux
Field method. Measures
vertical K((S) during
wetting portion of
hysteresis loop. Labor and
time intensive.
Green, Ahuja, and
Chong (1986)
Sprinkler-
Imposed Steady
Flux
Field method. Larger
sample area than for crust
method. Useful only for
relatively high moisture
contents.
Green, Ahuja, and
Chong (1986)
Parameter
Identification
Results of one field or lab
test are used by a
numerical approximation
method to develop K(f),
K(*), and t(8) over a wide
range of f and ^.
Relatively fast method;
however, unique solutions
are not usually attained.
Zachmann et al.
(1981a.b, 1982);
Kool et al. (1985)
Empirical
Equations
Each empirical equation has
its own application based
upon the assumptions of the
equation. Relatively fast
technique.
Brooks-Corey
(1964);
van Genuchten
(1980);
dual em (1986)
-------
Piezometer
Land surface
Layer 4
Layer 3
Layer 2
Layer I
Capillary fringe
.M h*»*r**m !?£
J .
Piezometer nest used to determine pneumatic head differences In the
unsaturated zone
Rcdicllr »rmm«nc ngioo for «xnf l«-v*ll ui flow modal
Elbow
eniscus
Hose connecting manometer reservoir and tube
Vented plug
(Atmospheric
pressure)
Petcock valve
- Pipe-to-hose
connection
— Atmosphere
vent
Globe valve
NOTE: All pipe tittings, vol
and hoses ore stand
i/4-inch items
Land surface
NOTE: Connection shown 1s thet used
when the downhole pressure 1s
greater than that at land surface
and the valve settings are those
for reading piezometer K
I 2345
Cement grout
Piezometer
number (pipa)
-400
-300 -ZOO -100
h IN CM WATER
O.S
Schematic relations between AC, (expressed as KJK) and h for sand, loam, and clay.
-------
£
•J5
rmea
Sandy Clay Loam y -r
Sandy Loam +. 1
D
—
(U
q
o
0.2
0.3
0.4
Water Saturation
0.03 -
0.02 -
O 0.01 -
-300 -200
-100
200
300
PRESSURE HEAD (cm H2O)
Exupla of th» r«l«clotubip« b«cw««n prxiur* h«ad «nd
hydraulic conductivity for an unsacuzacad aoll
u
z
a.
UJ
O
_WETTED
ZONE
-WETTING
FRONT
Geometry and symbols for piston-flow infiltration system.
Bouwer (1978)
VOLUMETRIC WATER CONTENT
0 O.I 0.2 0.3
IOO -
150 -
Calnilitnd walei-conteat
profiles in sand at various times (in
minutca on the curves) after cessation
of infiltration.
Bouwer (1978)
-------
PRE-TREATMENT SHALLOW SOIL
GAS CONCENTRATION
SOIL VENTING
OR STRIPPING INVOLVES THE FORCED
MOVEMENT OF AIR THROUGH SOILS
CONTAMINATED WITH VOLATILE
ORGANIC COMPOUNDS
- Increases volatilization of residuals
VMW2
E
CL
D.
o
PILOT STUDY APPARATUS
3900:
3600-
3300 -
3000
2700-
2400
2100
1800
1500
1200
900
eoo
300
0-4
VMW3
POST-TREATMENT SHALLOW
GAS CONCENTRATION
1 Electric Air Flow Healer
2 Forced Drall Injection Fan
3 Injection Air Bypass Valve
4 Injection An Sampling Port
i Injection An Flow Melur
I Extraction Manifold
7 Injection Manilold
1 Slotted Vertical Extraction Vent Pipe (lyp)
9 Slotted Vertical Injection Vent Pipe (lyp)
10 Extraction Air Sampling Porl
11 Extraction Air Flow Meter
12 Extraction Air Bypass Valve
13 Induced Oral! Extraction Fan
14 Vapor Carbon Package Tiealment Unit
VMW3
VMW2
VMW4
O
-------
RF HEATING SYSTEM
WELLHEAD TCE CONCENTRATION VS TIME
1000 F
E 100
Q.
Q.
= 10
CO
^
'c
ID
o
o
UJ
J2 0.1
0.01
EXTRACTION WELL #1 '
Y - 159.33* EXP(-O.OSX)
Curve Coefficient R2 - 0.62
I
20 40 60 60 100
Day of Active Treatment
Transition section
RF power feed point
Vapor barrier
Concrete pad
Pea gravel
Vapor collection
manifold
Electrodes
IN SITU HEATING
FIXATION
• INVOLVES HEATING CONTAMINATED
SOILS TO VAPORIZE HYDROCARBONS
- For example using radio-frequency
electromagnetic energy
PHYSICAL CHARACTERISTICS
, (BECOMES LESS WATER
SOLUBLE AND TOXIC) AND DECREASES
SURFACE AREA OF POLLUTANTS AVAIL-
ABLE FOR LEACHING
-------
OWest
Palm
BMch
HOUJNQ51
"*ttLA"of"-L'OFort
LaudenUI*
•4
PEPPER'S STEEL AND ALLOY SITE
PROBLEM - PCB S IN A SHALLOW SOIL
GEOLOGY
- Surf icial sands ~ 5 feet thick
- Limestone bedrock
REMEDY
- Fixation of oil soaked fill
- Monitor bedrock groundwater quality
METHODS
- Kriging (statistical) - determine cleanup areas
- Groundwater modeling - set ACL s
-------
Lateral Extent
of Oil Above
Water Table
V
I I I I
I I I I
I I I
I I I I I . l~ 1 I
I I I I I I I
' ' ' '
1 I ( I I
ABOUT 500 FT.
'.'Ill
' I I I I
I I I ZT
SCHEMATIC SW-NE SECTION THROUGH SITE
-------
LIMESTONE^-''^Vl1 V
-------
fee - MOCCD IMP M UPK* nu. uatn (Mmom TOP J n)
mn MO. » 0*1 ei/ar/M wtt ii:i»;*»
-------
TREATMENT OF CONTAMINATED SOILS
rm
QraundSulan
ZOM
•cr«*fl*d •>«« P0*n1 -
• drn*n fito unOHtuDM
*MOM tO(M MOMMflll
Th« flow of • noiuqiuoiu phai* liquid ch*c 1« (•) !••«
d«n«* Chan water (oil), and (b) nor« d*n«* Chan wacar
(chlorohydrocarbon) in th« unaacuracad and taturacad zonaa. In boch
caati cha eoncaainanca ara al*o cranaporcad aa diaaolvad coaqiounda in
cha (round vacar (froa Schwllla, 1914).
-------
E X P 0 S D
T MOD1LIHS
fcobert B. Aaferoee, Jr., P.I.
Manager
Ccnt.tr for Izpomr* Aa**iu>ent Modeling
Office of laiearch and Development
Q.I. brirotattntal Protection Agency
Athens, OA 30*13
1
| Distribution
| Mutual*
1..
Training
in
Model
Application*
—
1
Expert |
Advice |
on |--
Sclviosl
a |
Problem |
1
In-depth |
Participation |
ip PI Boning |
and Conducting
Priority |
Project* !
1
Cxpoiurt Kvmluation OlTlaion (BD) of OPTS
Graphical Expooun Modeling SyMaa (GDIS)
SE5OIL seasonal SOIL co«partm«nt model
XT123D
RISK OF UNSATURATZD/SATURATED TRANSPORT AMD
TRANSFORMATION IHTERACTIDHS FOR CHEMICAL
COHCENTRTATIONS (RUSTIC)
PRZM
(1-D Flow ind Tr»iwpon)
VADOSE
ZONE
MODEL
m
VADOFT
(1—0 Flow ind Transport)
SATURATED ZONE MODEL
SAFTMOD
(2-0 Flow *nd Tran*x>n|
JOE WILLIAMS
KERR ENVIRONMENTAL RESEARCH LABORATORY
ADA, OKLAHOMA
MODELS:
RITZ
PESTAN
BIOPLUME II
CHEMFLO
-------
VADOSE ZONE SUMMARY
more difficult to characterize than the saturated
zone
• vadose and saturated zones are part of a
continuous subsurface system; remediation
decisions must address both zones
- treatment trains
• can have greater sorption capacity than saturated
zone and can thus act as a source of
contamination even after site surface is cleaned
• can be a zone of significant biodegradation
• it is a pathway for the transport of gases and
volatile organics
-------
Catalog of Methods for Monitoring Water Content in the Vadose Zone
Method
Principle
Advantages
Disadvantages
References
1. Gravimetric
a. Oven drying
b. Carbide method
Core samples are obtained
from the vadose zone us-
ing tube sampler* for shal-
low depths and hollow
stem auger plus core sam-
pling for greater depths. A
core sample is weighed.
oven dried at 105 C for 24
hours, and rewelghed. The
water content Is deter-
mined by difference In
weight. Results expressed
on a dry weight or volume
basis. The difference in
water content values of
successive samples repre-
sents change In storage.
A field method. Solids sam-
ples are placed In a con-
tainer with calcium car-
bide. The calcium carbide
reacts with water, releas-
ing a gas. The gas pressu re,
registered on a gage. Is
convened Into water con-
tent on a dry weigh t basis.
1. A direct method.
Z The most accurate
of available methods.
a Simple.
1. More rapid than
oven drying.
2 Initial capital invest-
ment Is lower than for
oven drying.
1. A large number of repli-
cate samples are required
for each depth Increment
(necessitating several
holes) to account for spa-
tial variability of water
holding properties.
Z Expensive If large num-
bers of samples are re-
quired.
3. Adestructlve method—
I.e.. additional measure-
ments cannot be obtained
at the same sues.
1. May not be as accurate
as oven drying
2. Other disadvantages
are the same as for oven
drying.
Gardner II965L
HUld(1971J.
Schmugge. Jackson
andMcKlmll98OI.
Reynolds 1197Oa.
1970b). Brakenslek.
Osbom and Rawls
11979).
2. Neutron moisture
logging (neutron
scatter method)
A source of high energy
neutrons le.g_amereclum-
beryillum) In a down-hole
tool Is lowered Into an
access well. Water In the
vadose zone slows down
the fast neutrons, which
are captured by a detector
In the tool. Counts are
measured by a surface
sealer, ratemeter. or re-
corder. Counts are con-
verted Into volumetric
water content by an appro-
priate calibration relation-
ship. Successive readings
show temporal changes In
water storage at successive
depths.
1. Rapid.
Z An In-sltu method.
a Can be conducted in
cased or uncased holes
(for safety In unstable
material should install
casing).
4. Can be Interfaced
with portable data col-
lection system.
5. Successive readings
are obtained In the
same profile at the
same field location.
6. Can be used to locate
perched ground-water
zones. I*- valuable for
positioning monitoring
wells for sampling
perched ground water.
1. Expensive, requiring
the purchase or lease of
equipment.
Z Water content Is mea-
sured In a sphere. Cannot
relate results exactly to a
specific depth.
3. Fast neutrons are
moderated by other con-
•tltuenls besides hydro-
gen In water, eg., chlorine
or boron. Accuracy may be
affected.
4. During Installing of
access wells, cracks or cavi -
ties may be formed caus-
ing leakage along the cas-
ing wall.
5. An Indirect method re-
quiring calibration. Cali-
bration Is a difficult pro-
cedure.
6. Accurate readings are
not possible within 6 In. of
soil surface.
7. Cannot be used to Infer
water movement In re-
gions where storage
changes do not occur.
Holmes. Taylor and
Richards 11967L van
Baveil 1963). Keys
and MacCary U971).
McGowanand
Williams II980L
Schmugge. Jackson
and McKlm(198OL
Wilson (1980LHUld
(197 U Brakenslek.
Osbom and Rawia
(19791. Vlsvallngum
arxl Tandy (1972).
-------
Method
Principle
Advantages
Disadvantages
Reft
3. Gamma ray
attenuation.
a, Transmission
method.
b. Scattering
method.
Two parallel wells ins tailed
at precise distances apart
arc required. A probe with
a gamma photon source
(tg. cesium 13711s lowered
In one well. A second probe
with a detector Ifrg. sodium
Iodide scintillation crystal I
is lowered at the same rate
In the second well. Acces-
sories tndude a high-volt-
age supply, amplifier.
sealer, timer, spectrum
analyzer, pulse height
analyzer and photomulti-
pller tube. The degree to
which a beam of monoen-
ergetlc gamma rays Is
attenuated depends on the
bulk density and water
content. Assuming that
the bulk densiry remains
constant, changes be-
tween readings reflects
changes In water content.
A single probe is used, con-
taining a gamma source
and a detector, separated
by * lead shield. Gamma
ray* beamed Into the sur-
rounding media are ab-
sorbed by the solid media
and water. Back-scattered
rays are detected and mea-
sured. Knowing the dry
bulk density of the media.
the water content can be
calculated. Requires
empirical calibration
1. A rapid. !n-»!tu
method.
2. Water content Is ob-
tained In a narrow
beam—depth-wise
measurement can be
obtained as doae as one
Inch apart
3. Measurements can
be obtained within one
Inch of surface.
4. Nondestructive and
successive measure-
ments are obtained at
same locations.
5. Can be Interfaced
with portable data col-
lection system.
1. Rapid.
2. NondtstrucUve.wtth
successive measure-
ments obtained at
same depth.
3. In contra* to the
transmisaion method
only one access well Is
required. Reading can
be obtained at great
depth In vadoaeione.
1. Limited to shallow
depths because of difficul-
ties in Installing precisely
parallel wells, particularly
In rocky material.
2. Instabilities In count
rate may occur.
3. Expensive.
4. Changes In bulk densiry
In shrlnklng-swelllng
material affects accuracy
of water content readings.
S Variatlonslnwatercon-
tent and bulk density
occur In stratified soils.
6. Care must be taken In
handling radioactive
source.
1. Requires a source of
higher strength than
transmission method.
2. Not as accurate as trans-
mission method because
water content measured
In sphere and not a beam.
3. Expensive.
4. Changes in bulk density
In shrinking, swelling
material changes cali-
brations.
Brakenslek. Osbom
andRawis(1979).
Gardner I1965L
Bouwer and Jackson
11974). Reglnato and
van Bavd (19641.
Reglnato and Jackson
(1971), Schmugge.
Jackson and McKlm
(I960).
Keys and MacCary
(197 H Brakenslek.
Osbom and Rawts
<1979),PaeUoid
(1979).
4. TenslometerB
A terakxneter consists of
a porous ceramic cup ce-
mented to ngld plastic
tube, containing small
diameter tubing leading
to a surface reservoir of
mercury. Alternate version
uses strain gage trans'
ducer In lieu of mercury
manometer. The body tub-
Ing Is filled with water.
ftrres In cup form contin-
uum with pores In exterior
medium. Water moves Into
or out of body tube until
equilibrium Is readied.
Measured water pressure
reflects corresponding
water pressure In medium.
By using appropriate soil
water characteristic curve.
pressure can be related to
water content
1. Provide continuous.
In place measurements
of water con tent
2. Successive measure-
ments are obtained.
3. Inexpensive and
simple.
4. Transducer units re-
spond fairly rapidly to
water content changes.
I. Units fall at theairentry
value of the ceramic cup.
generally about -0.8 atmo-
spheres.
2. Results are subject to
hysteresis, that Is. differ-
ent results are obtained
for wetting vs. drying
media.
3. If proper contact Is not
made between cup and
media units will not oper-
ate properly.
4. Sensitive to tempera-
ture changes.
5. Difficult to Install at
great depth In vadoae zone.
Brakenslek. Osbom
and Rawts (1979 L
Holmes. Taylor and
Richards 119671
Blanchl<1967).
Galronand Hadas
(19731 Schmugge.
Jackson and McKlm
(1980L Wilson 119001
Oaksford(1978(.
-------
Method
Principle
Advantages
Disadvantages
References
5. Electrical resistance
blocks
6. Thermocouple
psychrometers/
hygrometers
Blocks consist of elec-
trodes embedded In por-
ous material (plaster of
parts, nylon, doth, fiber-
glass). Water content of
blocks change with water
content or soli Electrical
properties ofbiodut change
with changing water con-
tent Electrical properties
are measured using a
meter. Calibration curves
must be obtained.
A psychrometer unit con-
sists of a porous bulb with
a chamber In which the
relative humidity of the
exterior media is sampled:
a sensitive thermocouple.
a heat sink, reference elec-
trode, and electrical cir-
cuitry. The unit operates
on the principle that a rela-
tionship exists between
soil water potential and
relative humidity. Two
types are available, the wet
bulb type and the dew
point type. Both types rely
on cooling of the thermo-
couple junction by the Pel-
tier effect. In the wet bulb
type, when the tempera-
ture of the junction is re-
duced bdow the dew point
cooling is discontinued. As
condensed water evapor-
ates, the temperature in-
creases to ambient Signal
from the junction at the
temperature plateau to pro-
parOana! to relative humid-
ity. In the dew point type.
the temperature at junc-
tion Is held constant at
dew point The thermo-
couple signal cor
to dew point depression.
and thus to the relative
humidity. Different meth-
ods are required for the
two rypes.The dew point
method Is more accurate.
Calibration curves relating
relative humidity to water
potential are required.
Water potential and water
content are related
through a characteristic
curve for each materlat
1. Can be Interfaced
with portable data col-
lection system.
2. Can be used at soil
water pressures less
than -0.8 atmospheres.
3. Gypsum blocks are
Inexpensive.
4. Precision Is good.
1. In-sltu pressure
measurements are pos-
sible down to -5O atmo-
spheres, permitting the
determination of water
contents in the very dry
range.
2. Permits continuous
recording of pressures
(and water contentstat
the same depth.
3. Can be interfaced
with portable or remote
data collection systems.
4. Some units have
been installed to great
depth (down to 3OO
(cell
1. Subject to hysteresis.
2. May be difficult to In-
stall at great depth In
vadose zone and main Lain
good contact.
3. Requires calibration for
each texturai type In
profile.
4. Lack of Insensltlvtty In
wet range.
5. Sensitivity to soil salin-
ity (except gypsum blocks I
6. Gypsum blocks deteri-
orate badly In certain
media.
7. Calibration curves of
some units shift with time.
a Time lag In response.
1. Results are subject to
hysteresis.
2. Good contact between
bulb and surrounding
media may be difficult to
obtain.
3. Provide point measure-
ments only.
4. May be difficult to ob-
tain accurate calibration
curves for deep regions of
the vadose zone.
5. Fragile, requiring great
care In Installation.
Brakensiek. Osbom
and Rawlsl 19791.
Holmes. Taylor and
Richards (1967).
Phene. Hoffman and
Rawilns(197H
Schmugge. Jackson
andMcKlm(19SOL
Galronand Hadas
(1973).
Rawilna and Dalton
(1967). Merrill and
Rawtlns U972L
Enfldd. Hsleh and
Warrlck(1973).
Schmugge. Jackson
and McKiml 19801
Hanks and Ashcroft
(1980). Brlscoe 119791.
Campbell. Campbell
and Barlow (1973L
-------
7. Heat dissipation
sensor
Heat dissipation sensors
operate on the principle
that the temperature gra-
dient to dissipate a given
amount of heat tn a porous
medium of low conductiv-
ity Is related to water con-
tent. In practice, the water
content of a soil can be
measured by applying a
heat sounr at a rentraJ
point within the sensor
and measuring the tem-
perature rise at that point.
Calibration curves of
matnc potential vs. tem-
perature difference are
obtaJ ned us! ng a pressure
plate apparatus with soils
from the site. The matnc
potential is related to water
content by preparing a
water characteristic curve.
Commercial sensors con-
sist of a miniature heater.
temperature sensors and
circuitry, embedded In a
cylindrical porous ceramic
block within a small-diam-
eter PVC tube, and a kad
cable.
I. Simple.
2. May be interfaced
with a data acquisition
system for remote col-
lection of data.
3. Measurements are
Independent of salt con-
tent of soil.
4. Calibration appears
to remain constant.
5. Can be used to mea-
sure soil temperature
as well as matnc poten-
tial.
& Useful for measur-
ing water contents in
the dry range.
1. Subject to hysteresis In
the water characteristic.
2. Calibration Is required
for each change In texture.
a May be difficult to In-
stall at depth In the vadose
zone and maintain good
contact between the sen-
sor and medium.
Phene, Hoffman and
Rawllns (1971a).
Phene. Rawllns and
Hoffman II97 Ib).
Schmugge. Jackson
andMcKlmll980).
-------
Catalog of Methods for Monitoring or Estimating Flux of Wastewater in the
Vadose Zone
Method
Principles
Advantages
Disadvantages
References
1. IntlJtraUon at land
surface
a, Impoundments
(1) Water budget
method
(U) Instantaneous
rate method
(111) Seepage
Entails solving for the
seepage cuiiipuiieiit of the
water budget equation.
That is:
Inflow - Outflow = ± AS
Su=(I + P)-(D+E)±Aa
Where SL= seepage loss
I = Inflow from all
P = precipitation
D = discharge
E = evaporation
S = storage
Measurements of L P. D. E.
AS are required: requiring
flumes, ralngages. evapor-
ation pan. and staff gages
or water stage reLaiuers.
Calibration curve or table
of head vs. surface area is
required.
By shutting down aD In-
flows to a pond and an
discharges from a pond.
the water level win recede
primarily as a result of
infiltration. That Is. an the
components of the
budget equation are set
ftyial to zero ejiuept for
Infiltration, evaporation
and change In storage.
Measuring AS for a short
time provides a value for
Infiltration rate
Ing evaporadonl
meters are cylin-
ders. capped at one end
and open at the other end.
The open end of the cylin-
der Is forced into the pond
surface and seepage is
equated to the outflow
from the cylinder when
pressure heads Inside and
outside the cylinder are
equal Types Include: the
SCS seepage meter, the
USSR seepage meter and
the Bouwer-Rice
meter.
1. Averages intake rate
for the entire surface
area of the pond
(sides and bottom 1.
2. Measurements do
not Interfere with
normal pit operation.
1.Simple and tiKA|icn-
stve.
2. Errors in measuring
auxiliary compon-
ents do not enter
Into calculations.
3. Estimates average
Intake rate (or entire
surface area of pond.
1. Inexpensive.
2. Simple to operate.
3. Uses only one piece
of equipment. I.e..
reduces the overall
error compared to
using several mea-
suring devices as
with writer budget.
l.Tlme consuming and
expensive.
2. Errors in measurements
of auxiliary parameters
affect accuracy In esti-
mating seepage.
Bouwer (19781
I.May cause inconveni-
ence to pond operator.
2. The measured Instan-
taneous rate does not
account for rate fluctua-
tions caused by fluctua-
tions in Inflow and out-
flow components.
1. Measures seepage at
discrete points and a
large number of mea-
surements are required
to obtain 'average' In-
take rates (Including
both sides and bottom
points).
2. Operator will need to
swim underwater to in-
stall units In bottom
Of |MlTfl
Bouwer (19781
Bouwer and Rice
(1963). Kraanl 1977.
b. Land treatment
areas and
Irrigated flekJs
(I) Water budget
method
See impoundments: Water
budget method. Inflow and
outflow from fields are
measured by flumes, weirs.
etc Evaporation equated
to that from a free surface.
See Impoundments:
water budget method.
See Impoundments: water
budget method.
-------
Method
Principles
111) Inflltrometers
An Inflltro meter Is an open
ended cylinder driven Into
the ground. The amount of
water added to maintain
a constant head In the
cylinder Is equated to In-
filtration rate. Types tn-
dude single-ring and dou-
ble-ring Inflltrometers. In
double-ring type both the
outer and Inner annular
areas are flooded, ostens-
ibly to minimize diverg-
ence in flow from inner
area Intake measurements
are taken in the inner area.
1. Simple
2. Inexpensive
a Portable
[.Provides point measure-
menooniy.
2. Because of spatial vari-
ability In soli properties
a large number of read-
ings required to estimate
"avenge" infiltration.
a Shallow, flow Impeding
layers affect results.
4. Divergence In subsur-
face flow occurs because
of unsaturated now
(Bouwer recommends
using single, large cylin-
der to minimize this
prooiem).
5. Leakage along side walls
may cause anomalously
high rates.
Bouwer (1978). Dunne
and Leopold (1978).
Burgevand Luthln
(19561 US.
Environmental Pro-
tection Agency. US.
Army Corps of Engi-
neers and US.
Department of Agricul-
ture (1977).
(Ill) Test basins
Large basins (e.g. 20 feet
by 20 feet I are constructed
at several locations in a
field. The basins are flood-
ed and Intake rates are
measured. Results are re-
lated to "average" Intake
rate for the field. (The water
source to be used for field-
sized operations should be
used during testing.)
1. Provides more repre-
sentative Intake rates
than infUtrometers-
results can be used
to design full-scale
projects.
2. Simple.
1. Expensive.
2. Time consuming.
a May be difficult to trans-
port water to sites.
4. Shallow lenses of fine
material will affect re-
sults by causing diver-
gence of flow.
5. Spatial variability in soil
properties affects results.
U.S. Environmental
Protection Agency,
U.S. Corps of Engi-
neers, and US. Depart-
ment of Agriculture
(1977).
2. Flux In the vadoae
zone.
a. Water budget with
soil moisture
accounting.
The water budget method
of Thornthwalte and
Mather (1957) Is applied
to a given soil depth (eg.
root zone of an irrigated
field: final soil cover on a
landfill). Inflow compon-
ents Include rainfall and
Irrigation. Outflow com-
ponents include runoff.
evmpotranspi ration, drain-
age, and deep percolation
(Dux). Change in storage
equals water content
change In depth of Interest
Flux equated to known In-
flow and outflow compon-
ents and AS. Evapotran-
splratlon may be most dif-
ficult component to mea-
sure (see Jensen. 1973 for
alternative methods).
1. Estimates flux for
entire area and not
only points.
2. Computer programs
are available to sim-
plify calculations l&g.
WATBUG. WUlmott.
1977L
1. Errors In measurement
or estimation of com-
ponents accumulate in
estimates of flux.
Thornthwalte and
Mather (1957).
WUlmott (19771
Mather and
Rodrtquez(1978L
Fenn. Hartley and
DeGeare(1975L
Jensen 11973 L
-------
Method
Principles
Advantages
Disadvantages
References
b. Methods relying
on water content
measurements
(e-g_ draining pro-
file methods).
O dt
Flux is related to water
content changes in a given
depth of the vadose zone.
The relationship between
flux and water content is
expressed as follows:
Where J = flux. B = water
content, z = depth, and t=
time. (This method is
actually a profile-specific
water budget with all terms
except flux and storage
change set equal to zero).
Water content changes are
measured by neutron log-
ging, tenslometers. resist-
ance blocks and psychro-
meters.
1. Simple.
2. Compared to meth-
ods relying on data
for hydraulic gradi-
ents, a large number
of measurements can
be obtained with
minimal cost and
labor needs.
3. A large number of
measurements us! ng
simple methods is
more amenable to
statistical analyses.
1. Errors In measuring
devices affect results.
2. Spatial variability In soil
hydraulic properties re-
quires that a large num-
ber of measurements be
obtained to obtain an
"average" value.
3. Costly.
4. May not be suitable for
measuring flux below
Impoundments of land-
nils because of difficul-
ties in installing measur-
ing units.
Ubardlet all 1980).
Nielsen. Blggar and
Ern(1973).Warrick
and Amoozegar-Fard
(1980). Bouwer and
Jackson (1974).
Wilson 11980).
c. Method requiring
measurements of
hydraulic
gradients.
d. Method based on
assumption that
hydraulic gradi-
ents are unity.
The method Is based on
solving Dairy's equation
for unsaturated flow.
J=K(0)I
where K10) designates that
hydraulic conductivity Is
a function of water content
ft I = hydraulic gradient
Hydraulic gradients are
measured by Installing
tenslometers. blocks or
p^ichronietera.Cabbndon
curves are required to
relate negative pressure
measurements to water
content, and water content
to unsaturated hydraulic
conductivity. Separate
curves are required for
each textural change.
Same as above except that
unit hydraulic gradient Is
assumed so that J= Kiel.
Only one pressure meas-
uring unit Is required
at each depth of Interest
to permit estimating 8
from a pressure vs. water
content curve KW) Is esti-
mated from a separate
curve (For a more complex
version of this method see
Nielsen. Blggar and Erh.
1973.) An alternative ap-
proach Is to use the rela-
tionship J= K(*_Lwhtch
requires a curve showing
the changes in nydrauttc
conductivity with matrtc
potential I*.). Bouma.
BakerandVeneman<1974)
described the so-called
•cruet test' for preparing
• Kl») v*. *. curve. This
o^**T procedure v cvncd
outoncyUndrtcalc
1. A very precise
method.
1.Simpler and less
expensive than meth-
ods requiring grad-
ients.
l.More complex than
methods using water
content values.
2. Results are subject to
hysteresis in the calibra-
tion curves.
3. Expensive to Install the
requisite number of
units for statistical
analyses.
4. May not be suitable for
ponds or landfills.
5. Generally restricted to
shallow depths in the
vadose zone.
1.Assumption of unit hy-
draulic gradients may
fall particularly in lay-
ered media.
2. Results are subject to
hysteresis In calibration
curves.
a May not be suitable for
ponds or landfills.
4. More complex than
methods requiring soil
moisture evaluation.
5. Large number of units
required to offset spatial
variability In soil prop-
sties.
LaRue, Nielsen and
Hagan (1968). Bouwer
and Jackson 11974).
Wilson (1980 L
Nielsen. Blggar and
Erh (1973L Bouwer
and Jackson (19741
Warrlck and Amooze-
gar-Fard (19801. and
Bouma, Baker and
Venneman(1974L
-------
Metbod
Principles
Advantages
e. Flowmeters
f. Methods based on
estimating or
measuring hy-
draulic conductiv-
ity. K.
(I) Laboratory
methods.
(aa)Permea-
metera
(bb) Rdatlon-
shlps be-
tween
hydraulic
conduct-
ivity and
grain-size.
(cc) Cata-
log of
hydraulic
proper-
ties.
constructed In a test pit
Each column Is Instrument-
ed with a tenslometer. a
ring Inflltrometer. and
gypsum-sand crusts. A
series of crusts are used
during different runs to
Impose varying resistances
to flow. During each run.
Infiltration rates and ten-
slometer values are mon-
itored
Flux ts measured directly
using flowmeters- Princi-
ples of two available types
are as follows: ID direct
flow measurement using
a sens! tlve flow transducer.
and (2) flow is related to
movement of a heat pulse
In water moving In a por-
ous cup buried In the soil.
Calibration curves are re-
quired for second type.
The premise of these
methods Is that If K values
are available the flux can
be estimated by assuming
hydraulic gradients are
unity, and that Darcy s law
Is valid.
Cylindrical cores of vadose
zone sediments are placed
In tight fining metal or
plastic cylinders. Water ts
applied to the cores and
outflow is mctered. The
head of water applied to
cores may be either con-
stant head or falling.
Appropriate equations are
solved to determine K.
knowing head values, ap-
plication rates and dimen-
sions of the container.
Primarily for saturated K.
Grain-size distribution
curves are obtained for
samples of vadose zone
material. The hydraulic
conductivity Is calculated
from equations which ac-
count for a representative
graln-slzedlameierorfrom
the spread In the gradation
curve. Primarily for satur-
ated K.
A catalog of hydraulic pro-
perties of soils, prepared
by Mualeml 19761 Is con-
sulted for soli types sim-
ilar to vadose zone sedi-
ments. Both saturated and
unsaturated K values are
reported.
l.Do not require In-
formation on hy-
draulic conductivity
or hydraulic gradi-
ents.
1. Simple
2. May be used to deter-
mine variations In K
values because of
stratifications.
l.A "first cut" method
If other data are un-
available.
2. May be used to esti-
mate relative varia-
tions. In K because of
stratification.
1. Simple.
2. A quick method.
3. May be used to estlm-
mate relative varia-
tions In K because of
stratification.
4. Inexpensive—provi-
ded that grain-size
data are available.
1. Disturbance of soil dur-
ing installation may af-
fect results.
2. Convergence/divergence
problems arise In the
flow Held.
3. Limited range of soil
types and fluxes.
4. Calibration procedures
are tedious.
5.Applicability to deeper
regions of (he vadose
zone is questionable.
1. Expensive If a large
number of samples are
required.
2. Accuracy of method Is
questionable because of
wail effects.
a Not an In-sltu method-
results will be affected
by spatial variability of
hydraulic properties in
vadose zone.
1. Accuracy Is question-
able.
2.A disturbed method-
results may not be repre-
sentatlve of In-sltu
values.
3. Expensive If grain-size
values are unavailable.
4. Requires trained per-
sonnel
1. Problems arise because
of hysteresis In unsatu-
rated K.
2. Because of errors In
measuring K (61 values
for •particular soil type
may not be transferable
to similar types. To ob-
tain a doser estimate
Kit] must be evaluated
(breach soil I Evans and
Warns*. 19701
Gary (1973). Dlrtoen
(1974al. Dirksen
(1974b).
Bouwer (19781 Freeze
and Cherry (1979).
Freeze and Cherry
(1979) and references
therein.
Mualem(1976L
-------
Method
Principles
Advantage*
Disadvantage*
Rcfcni IM t M
111) Field methods.
(aa) Shallow
methods.
(aal) Methods
for meas-
uring sat-
urated K
In the
absence
of a water
taKU
A portion of the soil zone
is brought to saturation
and saturated K Is esti-
mated for the flow system
thus created. Appropriate
measurrments and equa-
tions are used to solve for
K. Alternative methods
Include: (1) pump-in meth-
od. (2) air-entry permea-
meters. (3) Infiltration
gradient method, and (4)
double tube method.
1. Each method has Its
own advantages—see
Bouwer and Jackson
(1974).
l.Each method has Its
own disadvantages—see
Bouwer and Jackson
(1974).
2. Because of air entrap-
ment during tests com-
plete saturation Is not
possible. Measured K
values maybe 1/2 actual
values (Bouwer. 1978).
3. Several of the methods
are based on the assump-
tion that flow Is entirely
vertical—a false premise.
Bouwer and Jackson
(1974).
(aa2) Instantan-
eous profile
method.
(bb) Deeper
methods.
(bbl)USBR single
well method.
The basis of this method
Is the Richards equation.
rewritten as follows:
In practice, a soil plot In
the region of Interest is
Instrumented with a bat-
tery of tensiometers. with
Individual units terminat-
ing at depths of Interest.
for measuring water pres-
sures: and with an access
tube for moisture logging.
The soil is wetted to sat-
uration throughout the
study depth. Wetting is
Mopped and the surface is
covered to pi event evapor-
ation. Water pressure and
water content measure-
ments are obtained during
drainage. Curves of *k vs. z
and 8 vs. t are prepared.
Slopes of the curves at the
depths of Interest are used
to solve for KJ0). Values of
KIS) at varying times can
be used to prepare K(*l vs.
8 and Kiik.) vs. *. curves:
(for a detailed description
of the method, including
step by step procedures.
see Bauma. Baker and
Veneman. 1974).
Water is pumped Into a
borehole at a steady rate
such that a uniform water
level Is maintained In a
basal test section. Satu-
rated K la estimated 6cm
appropriate curves and
equations, knowing dimen-
sions of the hole and Intet
pipes, length In contact
with formation, height of
water above base of bore-
hole, depth to water table.
and Intake rate at steady
Mate. Two type* of teaOc
(1) open-end casing tests.
In which water flows only
out of the end of thecaamg.
and (2) open-hole testa, In
which water ftows out of
1. Method can be used
In stratified soils.
2. Simple.
3. Reasonably accurate.
at least at each mea-
suring site.
I.May be used to cad-
mate K at great
depths In vadose
2.A profile of K values
may be obtained.
1. Provides hydraulic con-
ductivity values only for
draining profiles. Be-
cause of hysteresis, these
values are not represent-
ative of the hydraulic
conductivity during wet-
ting cycles.
2. Because of spatial vari-
abilities In soil hydraulic
properties, a large num-
ber of sites must be used
to obtain mean values of
hydraulic conductivity.
3.Time consuming and
relatively expensive.
Bouma. Baker and
Veneman (19741.
1. Solution methods are
based on assumption
that flow region Is en-
tirety saturated (free sur-
face theory*—this is not
true.
X Ass consequence of l.K
to underestimated.
a Expensive and time con-
suming.
4. Requires stoUed person-
nel to conduct testa.
US. Bureau of
Reclamation (1977).
-------
Method
Principles
tbb2)USBR
multiple veil
method.
(bb3l Stephens-
Neuman
single well
method.
Used to estimate K In vicin-
ity of widespread lenses of
slowly permeable material.
An Intake well and series
of piezometers are in-
stalled. Water is pumped
into well at a steady rate
and water levels are mea-
sured in piezometers. Ap-
propriate curves and equa-
tions are used to deter-
mine K.
Stephens and Neuman
(1980) developed an em-
pirical formula based on
numerical simulations
using the unsaturated
characteristics of four
soils. That Is. this approach
accounts for unsaturated
flow.
1. Results can be used
to estimate lateral
flow rates in perched
ground-water regions.
l.The formula can be
used to estimate the
saturated hydraulic
conductivity of an
unsaturated soil wl th
Improved accuracy.
2. No need to wait for
steady state condi-
tions—the final flow
rate can be estimated
from data during
transient stage.
1. Expensive and time con-
suming.
2. Requires trained per-
sonnel
1. Needs field testing.
US. Bureau of
Reclamation (1977).
Step hens and
Neuman (19801
(bb4) Air per-
meability
method.
a Velocity in the
vadose zone.
a. Tracers
b. Calculation using
flux values.
Air pressure changes are
measured In specially con-
structed piezometers dur-
ing barometric changes at
the land surface. Pressure
response data are coupled
with information on alr-
flUed porosity to solve
equations leading to air
permeability. If the Mlnken-
berg effect is small air
permeability Is converted
to hydraulic conductivity.
A suitable tracer
-------
Method
Principles
Advantages
Disadvantages
References
c. Calculation using
long-term Infil-
tration data.
e e
The long-term infiltration
rate. 1. of the facility Is
assumed to equal the
steady state flux J in the
vadose zone. Conseq uently.
Also assumes the (1) hy-
draulic gradients arc unity.
(2) average water content
= 9. (3) flow Is vertical, and
(4) homogeneous media.
1. Simple.
2. Probably satisfactory
as first estimate of
velocity.
3. Inexpensive.
1. Velocity will be higher
In structured media
than calculated.
2. Method assumes vertical
flow only. Perching layers
cause lateral flow.
3. For mululayered media
an average 6 and v may
be difficult to obtain.
Bouwer(1980l.
Wamck(1981).
-------
Catalog of Methods for Monitoring Pollutant Movement
in the Vadose Zone
Method
Principles
Advantage*
Disadvantages
1. Indirect methods
a. Four probe
electrical
method.
b. EC probe.
c. SallnJty
sensors.
2. Direct methods.
a. Solids sampling
followed by
Laboratory ex-
traction of pore
water. Inorganic
constituents.
Used for measuring soil
salinity In situ. Basically
the method consists of
measuring soil electrical
conductivity using the
Wenner four probe array.
The apparent bulk soil
conductivity Is related to
the conductivity of the
saturated extract using
calibration relationships.
The EC (electrical conduc-
tivity! probe consists of a
cylindrical probe contain-
ing electrodes at fixed spac-
ing apart. The probe Is
positioned In a cavity and
resistivity Is measured at
successive depths. Calibra-
tion required. Primarily
used for land treatment
areas and Irrigated fldds.
An alternative version con-
sists of Inexpensive probes
which can be permanently
implanted for periodic
measurements.
Sensors consist of elec-
trodes em bedded In porous
ceramic. When placed In
soil the ceramic comes In
hydraulic equilibrium with
soil water. Electrodes
measure the specific con-
ductance of the soil solu-
tion. This method Is most
suitable for land treatment
areas and Irrigated fldds.
although sensors could be
Installed below ponds be-
fore ponds are pu t In opera-
tion. Calibration curves are
required-
Solids samples are obtain-
ed by hand or power auger
and transported to a labor-
atory. Normally samples are
taken in depth-wise incre-
ments. Samples are used
to prepare saturated ex-
tracts (see Rh cades. 1979a,
for method L Extracts are
analyzed to determine the
concentrations of specific
constituents.
1. An in-piace method.
2. Readings are ob-
tained quickly and
Inexpensively.
3. Can be used to de-
tect the presence of
shallow saline
ground water.
4. Can be used to de-
termine lateral tran-
sects of salinity.
5. By varying electrode.
spacing can be used
to determine verti-
cal changes in salin-
ity.
6. The salinity in larger
volumes of soil are
measured compared
to other methods.
1. Changes In salinity
are measured at dis-
crete depths in stra-
ti/led soils.
2. Measurements are
obtained at greater
depth than fourdec-
trode method.
3. The In-piace units
permit determining
changes In salinity
with time.
1. Simple, easily read
and sufficiently ac-
curate for salinity
monitoring.
2. Readings are taken
at same depths each
time.
3. By Installing units
at different depths
chronological salin-
ity profiles can be
determined.
4. Output can be Inter-
faced with data
acquisition systems.
1. Depth-wise profiles
of specific pollutants
can be prepared.
2. Variations In Ionic
concentrations with
changes In layering
are possible.
3. Solids samples can
be used for addi-
tional analyses such
as grain size, cation
exchange capacity.
etc.
1. Obtaining calibration
relationships may be
tedious.
2. Accuracy decreases in
layered soils.
3. Chronological In situ
changes cannot be
measured except by
taking sequential trav-
4. Prl manly used for shal-
low depths of the vadose
zone.
5. Does not provide data
on specific pollutants.
1. Individual calibration
relationships are re-
quired for each strata—
time consuming and
expensive.
2. Variations In watercon-
lent may affect results.
a Prt manly used for shal-
low depths at the vadoae
4. Does not provide data
on ^Jectfkc pollutants.
1. More subject to calibra-
tion changes than four
electrode method.
2. More expensive and less
durable than four elec-
trode method
3. Time lag In response to
changing salinity.
4. Cannot be used at soil
water pressures less
than -2 atmospheres.
5. Soil disturbance during
Installation may affect
results.
6. Does not provide data
on specific pollutants.
1. Because of the spatial
variability of soil prop-
erties an Inordinate
number of samples are
required to ensure rep-
resentativeness.
2. Expensive, if deep
sampling is under-
taken.
3. Changes In soil water
composition occur
during preparation and
extraction.
4. Samples should be ex-
tracted at prevailing
water content Le_ Ionic
composition changes
during saturation.
Rhoadea and HaJvorson
(19771. Rhoadea (1979a).
Rhoades (1979b).
Rhoades and Hatvorson
11977). Rhoades and van
Schilfgaarde U976).
Rhoades ( 1 979a).
Rhoades 11979c).
Rhoades (1979a). Oster
and Ingvalson (1967).
Richards (1966). Oster
and WUlardsonl 1971).
Rhoades (1979aL Rlble et
ai. (1976). Pratt Wameke
and Nash (1976).
5. A destructrt* method— variability In sediments
samples cannot be re- precludes comparing
taken In exactly the successive results.
same location
-------
Method
Principles
Advantages
Disadvantages
References
b. Solids sampling
for organic and
mlcroblaJ con-
stituents—dry
tube coring pro-
cedure.
c. Ceramic type
samplers (suc-
tion lysi meters I.
(I) Vacuum
operated
type-
Vacuum-
pressure
type.
A hole is augered to above
the desired sampling
depth. A dry-tube core
sampler of special design
Is forced Into the sampling
region. Separate sub-
samples are obtained for
analyses of organlcs and
microorganisms. Extreme
care must be exercised to
avoid contamination.
A ceramic cup is mounted
on the end of a small
diameter PVC tube. A one-
hole rubber stopper is
pushed into opening in
tube. A small diameter tube
is forced through stopper.
terminating at base of
ceramic cup. Unit Is placed
In shallow soil depth. A
vacuum Is applied to the
small tube and soil water
moves through the cer-
amic cup. Sample is
sucked out the small tub-
Ing Into a collection flask.
Samples are analyzed In
the laboratory. When using
such samplers extreme
care must be exercised to
prepare cups to remove
aorbed Ions. An add treat-
ment is recommended for
this purpose. A variation
of this type uses a filter
candle In lieu of a suction
cup.
A ceramic body tube con-
tains a two hole rubber
stopper. A small diameter
tube is pushed Into one
opening, terminating at the
base of the cup. A second
tube pushed Into the other
opening terminates below
the rubber stopper. The
long line Is connected to a
•ample bottle. The short
line Is connected to a pres-
sure-vacuum source. When
the unit is In place, a
vacuum Is applied to draw
In exterior solution. Pies-
sure is then applied to blow
the sample into a flask.
1. Contamination of
samples is mini-
mized c.f. other core
sampling methods.
2. Additional sub-
samples could be
taken for chemical
analyses.
1. A direct method for
determining the
chemical character-
istics of soil water.
2. Samples can be ob-
tained repeatedly at
the same depths.
3. Inexpensive and
simple.
4. Can be installed
below shallow im-
poundments and
landfills prior to con-
struction, for later
monitoring of seep-
age-
1. Can be used at
depths below the
suction lift of water.
2. Several units can be
Installed in a com-
mon borehole to de-
termine depth-wise
changes In quality.
Also: See advantages
for vacuum operated
type.
1. Expensive and time Dunlapet aL (1977)
consuming.
2. Difficult to obtain sam-
ples at great depth in
vadosezone.
3. Samples cannot be ob-
tained directly below
Impoundments.
4. A destructive method.
5. Results are affected by
spatial variabilities In
properties of the vadose
zone.
1. Generally limited to soil
depths less than 6 feet.
2. Limited to soil water
pressures less than air
entry value of the cups
(-1 atmosphere).
3. Point samplers—be-
cause of the small vol-
ume of sample obtained
representativeness of
results Is questlon-
nable.
4. Pore water in the soil
blocks is sampled. In
structured soils, water
moving through cracks
may have different Ionic
composition than water
In blocks.
5. Suction may affect soil-
water flow patterns.
Tensionmeters must be
Installed to ensure that
the proper vacuum is
applied.
6. Samples may not be
representative of pore
water because tech-
nique does not account
for relationships be-
tween pore sequences.
water quality and
drainage rates (Hansen
and Harris. 1975L
1. When air pressure Is
applied some of the
solution Is forced
through the walls of the
cup.
Also: See disadvantages
2 through 6. vacuum
operated type.
Rhoades 11979a). England
( 1974). Hoffman
et all 1978).
Rhoades (1979aL England
(1974). Partzek and Lane
(1970). Apgar and Lang-
muir (1971L Johnson and
Cartwrtght(19eOL
-------
Method
Principles
Advantages
Disadvantages
(111) High
pressure-
vacuum
type-
A Sampling
perched
ground water.
The sampler Is divided Into
two chambers. The tower
chamber is a ceramic cup.
Upper and lower chambers
an connected via tubing
with one-way valve. A plug
In the upper chamber has
two openings. One opening
is connected by tubing to a
pressure-vacuum source.
The second opening is con-
nected to a line within the
upper chamber. This line
contains a one-way valve.
The line also extends to
the surface, terminating In
a collection flask. When
vacuum is applied to one
tube, soluuon Is drawn into
the upper chamber. When
pressure Is applied the one-
way valve In base prevents
sample from being forced
out of cup. Sample Is forced
up the outlet line Into col-
lection flask.
Perched ground-water re-
gions frequently are ob-
served In vadose zones, for
example. In alluvial valleys
In the west. Water samples
may be extracted from
perched ground-water
regions for analyses. For
shallow perched ground
water, samples can be
obtained by installing
wdK piezometer nests or
multilevel samplers. For
deeper perched ground
water, two possibilities
exist! 11 sampling cascad-
ing water In existing wells.
or (2) constructing special
wefls.
1. Prevents air pres-
sure from blowing
sample out of cup.
2. Can be used at great
depths.
a Several units can be
Installed in a com-
mon borehole.
Also: See advantages
for vacuum operated
type-
Same as for vacuum-
pressure type except for
disadvantage No. 1.
Wood (1973). Wood and
Signer (19751
1. Large sample vol-
umes are obtain-
able: particularly de-
sirable when sam-
pling for organlcs
and viruses.
Z Samples reflect the
integrated quality of
waterdralnlng from
an extensive portion
of overlying vadose
zone—more repre-
sentative than point
samples.
a Cheaper than Install-
ing deep wells with
batteries of suction
samplers.
4. Can be located near
ponds and landfills
without concern
about causing leaks.
5. Nested piezometers
and multilevel
samplers can be
used to delineate
vertical and lateral
extent of plumes and
hydraulic gradients.
1. Perched zones may not
be present In source
2, Detection of perched
ground water may be
expensive, requiring
test wells or geop nyslcal
methods.
3. Some perched ground
waterregions are ephem-
eral and may dry up.
4. The method is moat
suitable for diffuse
sources, such as land
spreading areas or irri-
gated fields.
5. Multilevel sampling Is
restricted to regions
with shallow water
tables permitting
vacuum pumping.
Wilson and Schmidt
(1979). Schmidt (1980).
Graf (198OI. Pickens et at.
(1981). Hansen and Hams
(1974. 1980).
-------
DETERMINATION OF WATER MOVEMENT IN THE VADOSE ZONE
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-------
Ubardl, P.L,, K, Relchardt, D.R. Nielsen, and O.K. Blggar, 1980.
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-------
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-------
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-------
SESSION II
Determination of Extent and Magnitude of Contamination in the Subsurface
Dr. Michael J. Barcelona
Michael J. Barcelona received the B.A. and M.S. degrees in Chemistry from St. Mary's College (Winona,
MN) and Northeastern University (Boston, MA) in 1971 and 1973, respectively. He received the Ph.D.
degree in Marine Chemistry from the University of Puerto Rico (Mayaguez, P.R.) in 1976. He served as
an instructor of marine chemistry and chemical oceanography while he completed his thesis on the
interactions of natural organic compounds with gypsum in seawater. Following nearly three years as a
research postdoctoral fellow in Environmental Engineering Sciences at Caltech (Pasadena, Ca) with Dr.
James J. Morgan, Dr. Barcelona joined the Water Survey Division of the Illinois Department of Energy and
Natural Resources in 1979.
Since 1980 he has been head of the Survey's Aquatic Chemistry Section, building form a group of 5 to the
current 21 chemists and engineers. The Section provides research and services to State, Federal and
industrial sponsors. As a Principal Scientist, Dr. Barcelona is involved in environmental research on a wide
range of topics, including sampling, organic compound analysis, ground-water geochemistry and monitoring
network design. He has authored more than 25 peer-reviewed publications and over 50 technical reports,
many of which are in wide use in ground-water sciences.
PART 1. SUBSURFACE GEOCHEMICAL CONDITIONS: VARIABILITY, CONTROLLING
FACTORS AND SAMPLING CONSIDERATIONS
A. Nature of Variability in General
1. Discussion of error; systematic vs. random
2. Sources of error (sampling, analysis, siting, design, etc.)
B. Subsurface Variability (Aquifer Properties, Water Quality, Geochemistry)
1. Spatial (physical, chemicai, biological)
2. Temporal (physical, chemical, biological)
3. Equilibrium versus kinetic controls on subsurface
geochemistry - redox processes
4. Summary
C. Sampling Considerations
1. Environmental sampling in general
2. Sampling protocols for site characterization work
a. scope and magnitude of the problem/Relation to
sampling intervals and representativeness
b. interactions between contaminated and uncontami-
nated sub-areas within the site
c. choice of diagnostic parameters, analytes
d, sampling protocols based on hydrogeologic data
e. sampling experiments
f. refined sampling protocol
g. transition from characterization work to monitoring remediation efforts
-------
A. Nature of Variability in General
B. Subsurface Variability (Aquifer Properties,
Water Quality, Geochemistry)
C. Sampling Considerations
SITE
SELECTION
<-2 , e;2 . <-2
^g a VERT. * b HORI2.
SAMPLING
S2, S2
°i a SYSTEMATIC +
c-2 c2
0 RANDOM + 3 NAT'L.
MEASUREMENT
METHODS
REFERENCE
SAMPLES
DATA
HANDLING
Thus the overall variance * S2 - S2 + S2 + S2 + S2 * S?
fl t rn r o
Sourc** of arror involved in ground-w«t«r monitoring prognma contributing to tot«l »»riano»
-------
PURPOSE
OUTLINE BASIC INFORMATION NECESSARY TO MAKE
INFORMED DECISIONS ON: NATURE AND EXTENT OF
CONTAMINATION, REMEDIATION SCHEMES, LIFE CYCLE
COSTS, ETC.
PROVIDE REFERENCES ON SAMPLING (THE EYE OF THE
NEEDLE!)
RECOGNIZING THAT WE NEVER HAVE ENOUGH DATA
MONITORING SCALES
(DEGREE OF HOMOGENEITY AND BASIS
FOR INTERPRETATION)
REGIONAL (lO'l to lOO'l at UlomeUn)
LOCAL (kilometer)
SITE (meteri)
ASSUMPTIONS
WHAT YOU DON'T OBSERVE CANNOT BE REMEDIATED
ALL OBSERVATIONS ARE TIME DEPENDENT
HYDROGEOLOCY PROVIDES THE BASIS FOR JUDGING
REPRESENTATIVENESS AND THE BASIS FOR ANY
CHEMICAL INTERPRETATION
OBJECTIVES INCLUDE A CONTROLLED DATA
COLLECTION EFFORT
MONITORING SYSTEMS/PURPOSES
(EVOLVE TOWARDS INCREASING COMPLEXITY)
• DETECTION (SOURCE?)
I ASSESSMENT (APPROXIMATE MAGNITUDE)
I EVALUATION (SEVERITY, EXTENT, AND VAR1ABI1JTY)
I SCOPE (LIFE-CYCLE COST ANALYSIS)
'^f REMEDIATION (FINAL WASH)
CHEMICAL DATA RESOLUTION
REGIONAL (CARBONATE EQUILIBRIA IN LIMESTONE
AQUIFERS)
LOCAL (RECHARGE OF OXYGENATED WATER)
SITE (POLLUTANT OF THE MONTH IN THE
BACKYARD)
MAJOR MESSAGE.';
INCREASED VERTICAL RESOLUTION AND DETAIL OF
BOTH SUBSURFACE GEOCHEMISTRY AND CONTAMINANT
DISTRIBUTIONS
QUARTERLY SAMPLING AS A STARTING POINT, AND
HIGHER FREQUENCDIS FOR REACTIVE CHEMICAL
CONSTITUENTS
RECOGNITION OF MAJOR SOURCES OF UNCERTAINTY IN
FROBJLEM ASSESSMENT AND THE PROBABILITY OF
SUCCESS IN REMEDIATION (WE NEVE* HAVE ENOUGH
INFORMATION)
-------
A. Nature of Variability in General
1. Discussion of error; systematic vs. random
2. Sources of error (sampling, analysis, siting, design, etc.)
FIGURE 1
Water Research Centre Interpretation of the bull'sreye analogy
(or describing analytical error
(•) Large random errors,
no systematic errors
(e) Smafl random errors,
bug* systematic errors
(b) SmaJI random errors,
no systematic errors
(d) Large random errors,
large systematic errors
•Anatyte Signal (S«)-
Zero S,,
MeMe
Not Dated*)
Region of
Detection
Region
Quanttlj
Zero
S» -f 3
LOO
S»
LOQ
Signal (S,)-
Flgura 1. The Imtt of detection (LOO) b located 310o
recommended inference
anaJyte not detected
region of detection
region of quantitation
-------
CERTAINTY IN GROUND-WATER CHEHICAL MEASUREMENTS
MATURE OF UNCERTAINTY
SUBSURFACE ENVIRONMENTAL CONDITIONS
0 LACK OF KNOWN "TRUE" VALUES
IDENTIFICATION OF THE SAMPLE POPULATION
— H1T3RQGEOLOGIC INHCHCCEKEITY
— HIDROOEOLOCY AND SAMPLING WELL DESIGN
WELL DESIGN — DRILLING
CONSTRUCTION/SCREEN DESIGN/
DEVELOPMENT
MATERIALS
PURGING PROCEDURES
SAMPLING DEVICES
SAMPLING HANDLING/ON-SITI ANALYSIS
SAMPLING STORAGE/PRESENTATION
RECOGNITION Of UNCERTAINTY
MATURE OF UNCERTAINTY I* GBOUSD-WATER CHEHISTRI
— EKVISOSMEMTAL CONDI7IOKS
0 LACK OF KKOWN "TRUE" VALUES
0 COMPLEX, LIVING, DDiAMIC SfSTEMS
0 SPATIAL ANE TEMPORAL VARIABILITY
0 AJITHRQPOGEHIC DISTURBANCE
o EQUILIBRIUM VS. KINETIC CONTROL
— SAMPLING AS A SELECTION PROCESS:
PS'JTOCOL DE\'EU5P«EKT
— ERROR IDESTIFICATION AND CONTROL MEASURES
— SUMMARY
B. Subsurface Variability (Aquifer Properties, Water Quality,
Geochemistry)
1. Spatial (physical, chemical, biological)
2. Temporal (physical,
biological)
3, Equilibrium versus kinetic controls on subsurface
geochemistry - redox processes
4. Summary
-------
~ SUBSURFACE ENVIRONMENTAL CONDITIONS
O PHYSICAL VARIABLES: TEMPERATURE AND PRESSURE
EFFECTS NATURAL DISTURBED
T MIXING, REACTION PATHS AND RATES 3*-20«C 3*-35«C
SOLUBILITY CONSIDERATIONS (i 10-15 CM (A 10-25 C*)
(DEPTH VARIATIONS)
(SOURCE VARIATIONS)
t GAS SOLUBILITY 1-10 bar 1-1000 bar
PERMEABILITY AND POBOSITY
SUBSURFACE ENVIRONMENTAL CONDITIONS
O PHYSICAL VARIABLES (oont'd.)i FLOW VELOCITY
HYDRAULIC EFFECTS
NATURAL
HEAD DIFFERENCES/GRADIENTS
PUMPING <1-10
MIXING <1-1000
DISTURBED
O-JOO
<1-1000
SUBSURFACE ENVIRONMENTAL CONDITIONS
O BIOLOGICAL VARIABLES
NATURAL
BIOMASS CATALYTIC OH
TRANSFORMATION POTENTIAL lO'-IO8
ACTIVITY TURNOVER RATES
VMAX METABOLIC STATUS
Glucose
(Sp«clflo
activity)
DISTURBED
0.1 |ig-L~'-hr~' 7
(0.03-0.06 x ID"9
glucose-h"'*
cell"1)
SUBSURFACE ENVIRONMENTAL CONDITIONS
O CHEMICAL VARIABLES: RANGES
Ct ndi/ (••;)
Blssolved Oxygen (ag-L*1)
Alkalinity (ag-L'1 CaC03)
^ATURAL
5,5-9.5
*5,000 to 100
»600 to -100
-10 to <0.3
1,000 to 100
DISTURBED
3-12
>10,000 to 100
*600 to -250
>10 to <0.3
71,000 to <100
-------
SUBSURFACE ENVIRONMENTAL CONDITIONS
O CHEMICAL VARIABILITY: SPATIAL
SITE SCALE
LARGE SCALE
HORIZONTAL
02
Fe2*
Eh
VERTICAL
02
Eh
•0.01 to +0.5 0.3 to 1
(mg-L'Vm*1) (mg*L~1-km"2)
-3 to 1
(mv/nf
-0.2 to +0.77
-2 to -10
(mg«m~2)
-0.5 to -180
-------
Changes In Plumes and Factcr* Causing the Changes
Source: U.S. EPA, 1977
— — — Former boundary
. Prewnt boundary
• Watt« litv
j
ENLARGING
PLUME
t Increase in rat* of
discharged waste*
2. Sorplten activity
used up
3. Effects of changci
In water table
REDUCING
PLUME
1 Reduction in wastes
2. Effects of changes
In water table
3. More effective
lorption
4 More effective
dilution
5. Slower movement
and more time
for decay
^
0
0
NEARLY STABLE
PLUME
L Eitentially tame
wade Input
2. Sorp«len capacity not
fully utilized
1 Dilution effect
fairly (table
< SBght water-table
fkKtuatlon or effects
of water, table
fluctuation not
Important
SHRUNKCN
PLUME
SERIES OF
FLUMES
L Waste no longer 1, hfermlffenf or
ct abandcrted
waste ills
-------
DATA REQUIREMENTS FOR WATER SOURCE
DEFINITION AND AQUIFER REPRESENTATION
A. Drilling History
B. Well-Completion Data
C. Well-Pumping History
D. Effects of Well Construction, Completion
and Development of Water Quality
E. Effects of Sampling Mechanisms and
Materials on Water Quality Measurements
SAMPLING FREQUENCY
• NATURAL (OR SOURCE) VARIABILITY MAY EXCEED
CONTROLLED SAMPLING AND ANALYTICAL ERRORS
• GROUND-WATER QUALITY DATA ARE NON-NORMAL, HIGHLY
AUTOCORRELATED, AND USUALLY OF VERY SHORT DURATION
• QUARTERLY SAMPLING FREQUENCY IS A GOOD STARTING
POINT FOR MANY CONSTITUENTS
• REACTIVE CONSTITUENTS OR HIGHLY VARIABLE
HYDROGEOLOGIC SETTINGS MAY REQUIRE MORE FREQUENT
SAMPLING (i-t, MONTHLY OR BIMONTHLY)
-------
Temperature
(a)
Total Organic Carter
(b)
Ferrous Iron
(c)
Sulfide
(d)
Fig. 2. Time series of flow cell temperature (2a), total organic carbon (2b), ferrous iron (2c), and suIfide (2d) for the wells at the Sand Ridge site.
Temperoture
(a)
Total Organic Carbon
(b)
Ferrous Iron
(c)
Sulfide
W
4 • 11 1C » 34 V Jl
-------
SUBSURFACE ENVIRONMENTAL CONDITIONS
o CHEMICAL VARIABILITY: TEMPORAL CONCENTRATION VARIATIONS
SHORT-TERM (MINUTES TO DAYS)
N03- 13X
S0i4' 7X HS
NH3 3X
LONG-TERM (WEEKS TO YEARS)
SOi,
6X
7X
3X
Fe2
110X
15X
3X
Observations of temporal variations in ground-water quality: short-term variations
Constituents
(concentration variation)
Agricultural sources Se (±2 mg-L"')
NO,- (1-3X)
SO,' (3-7X)
NO," (MX)
NO,- (1-10X)
SO«- (1-1. 5X)
NO,- (0.5-2X)
Atrazine (1-5X)
Non-Agricultural or mixed HjS (1-5X)
sources SO," (1-I.2X)
NH, (1-3X)
NO, (1-13X)
SO,' (1-2X)
Fe (1-3X)
Mn (1-1.5X)
PCE, TCE, 1,2-t-DCE (1-10X)
TCE (2-1 OX)
Fe2* (1-110X)
S- (1-15X)
Volatile halocarbons (1-8X)
Nature of variability
Period
Monthly
Minutes
Minutes
Monthly
Hours to weeks
Minutes to hours
Minutes to hours
Minutes
Minutes
Monthly to weekly
Minutes
Probable cause
Irrigation/return/indeterminate
Pumpage/head changes and
leaching from unsaturates zone
Pumpage/venical stratification
Irrigation/fertilizer applications/
leaching; locationaJ differences
apparent
Surface runoff recharge
Pumping rate and well drilling
Pumping rate and purging
Purging
Pumping rate and purging
Pumping rate and development
of cone of depression
Purging
Reference
Crist (1974)'
Schmidt (1977)'
Eccles el at. (1977)'
Spalding and Exner (1980)
Libra et al. (1986)
Colchin et al. (1978)'
Humenick et al. (1980)'
Wilson and Rouse (1983)
Keely and Wolf (1983)'
McReynolds (1986)'
Barcelona and Helfrich (1986)
• Denotes variations observed in water supply production wells, PCE = perchloroethylene, TCE = trichloroethylene, 1,2-t-DCE = 1,2 trans-dichloroethykW
-------
Observations of temporal variations in ground-water quality: long-term variations
Agricultural sources
Non-Agricultural
sources
or mixed
Constituents
(concentration v&rifltion)
Cl- (+1.5X)
SO4- (2-»X)
NO," (3-6X)
SO4- (3-7X)
NO,' (±48mg-L-' jr"')
NO,' (1-12X)
SO4" (1-I.5X)
NO," (1-5X)
NO,' (1-1.5X)
Pesticides (1-1. 5X)
Conductance (2-3X)
SO4- (I-3.5X)
Hardness (2-6X)
Conductance ( + 2,000 uS-cm
NO,' (±55mg-L-' yr'1)
Cl- (1-3X)
PCE (±1-20X)
TCE(±1-3X)
* Denotes variations observed in water supply production
Nature of variability
Period Probable cause
Decades Irrigation/recharge
Seasonal Irrigation/precipitation
Seasonal Leaching/recharge
Seasonal Irrigation/fertilizer applications
Seasonal Recharge/fertilizer applications
Years-seasonal Infiltration/recharge
Seasonal H2O level fluctuations
freezing/thawing recharge
* ') Decades Irrigation/upconing of saline
water
Seasonal Sewage/fertilizer recharge and
applications
Seasonal Oil field brine/recharge
Seasonal Infiltrated surface water quality
variations
Seasonal Pumping rate and patterns in
well Held
wells, PCE = perchloroethylene, TCE = trichloroethlylene.
Reference
Evenson (1965)'
Tenorio et al. (1969)*
Tryon (1976)
SpaJding and Exner (1980)
Rajagopal and Talcott (1983)
Libra et al. (1986)
Feulner and Shupp (1963)
Handy et al. (1969)'
Perlmutter and Koch (1972)
Pettyjohn (1976), (1982)
Schwarzenbach et al. (1983)
McReynoIds (1986)'
Subjective estimate of strength of seasonality or trend in variables by location
PH
Cond
Temp C
Temp W
Eh
Sand Ridge
(1-4)
*
+
+
Probe O2
Wink O2
Alk
NHj
NO, N
NOjNOj
HS-
S04
SiO2
o-PO4
T-PO.
cr
Fe*
Ca
Mg
Na
K
Fe-r
MnT
TOX
VOC
NVOC
TOC
•
N
•
•
Beardstown Beardstown Number of
(upgradient) (downgradient) violations
0
+ + 2
+ + 6
+ + 4
1
0
0
+ • 1
3
1
0
0
• • 0
• 0
1
• I
+ 2
• 3
+ 1
2
3
• • 3
0
• + 0
2
6
• 4
• 3
* Indicates strongly seasonal.
• Indicates apparent trend or possible seasonality.
TOC = VOC + NVOC; Total Organic Carbon = Volatile Organic Carbon + Nonvolatile Organic
Carbon.
-------
ESTIMATED RANGES OF SAMPLING FREQUENCY (IN MONTHS) TO
MAINTAIN INFORMATION LOSS AT <10J FOR SELECTED TYPES OF
CHEMICAL PARAMETERS
Pristine background Contaminated
Type of parameter conditions
Water Quality
Trace constituents
«1.0 mg'L'1)
Major constituents
Geochemical
Trace constituents
«1.0 mg-L'1)
Major constituents
Contaminant Indicator
TOC
TOX
Conductivity
pH
2 to 7
2 to 7
1 to 2
1 to 2
2
6 to 7
6 to 7
2
Upgradlent
1 to 2
2 to 38
-2
7 to 11
3
21
21
2
Downgradient
2
2
1
1
3
7
7
1
to 10
to 10
to 5
to 5
-------
Average overall accuracy and precision for the chemical constituents determined in the study
Param.
NH,
T-P04
Fe*J
NO,-
s-
NOj
SiO,
o-PO4
ci-
so4-
Ca
Mg
Na
K
Fe
Mn
Ace.
95.90
99.64
96.07
82.17
NA
100.35
99.47
103.44
105.78
95.77
98.36
99.15
101.69
97.85
99.22
101.04
Overall
Prec.
23.49
8.60
18.80
36.29
NA
10.27
5.03
15.38
32.59
21.85
3.88
8.70
12.17
5.17
5.80
6.46
Sand Ridge
Ace.
91.99
100.95
NA*
81.07
NA
98.85
100.21
106.54
112.01
94.73
98.65
99.90
103.51
99.10
100.34
101.28
Prec.
29.80
9.28
NA
35.00
NA
7.82
2.97
20.77
46.55
6.58
3.76
10.72
16.16
5.15
7.20
8.17
Beardstown
Ace.
100.09
98.24
96.07
83.27
NA
101.97
98.71
100.12
100.18
97.24
98.07
98.42
99.95
96.63
98.04
100.79
Prec.
12.54
7.56
18.80
37.50
NA
12.17
6.41
2.32
1.52
33.07
3.98
6.03
5.87
4.89
3.46
3.92
* NA indicates that the number of observations for which accuracy and precision could be determined
was less than five, principally due to a larger number of below detection limit results.
Percentage of variance attributable to laboratory error, field error, and natural variability by chemical
and site
Type of
n&rstmptpr •
Sand Ridge
lab
field
nat
Beardstown
lab
field
(upgradient)
nat
Beardstown (downgradient)
lab
field
nat
Water quality
NO,-
so4-
SiO,
o-P04"
T-P04-
ci-
Ca
Mg
Na
K
Geochmicol
NH,
NO,-
s-
Fe*1
F*r
MnT
Contaminant
> •. .
0.0
0.0
0.0
1.2
0.0
7.2
0.0
0.0
0.0
0.0
0.0
NA
NA
NA
0.0
0.0
00.0
0.0
NA
1.2
NA
NA
45.7
20.0
NA
NA
0.0
NA
NA
NA
NA
NA
lab + field
TOC 15.4
TOX 0.0
100.0
100.0
100.0
97.6
100.0
92.8
54.3
80.0
100.0
100.0
100.0
NA
NA
NA
100.0
100.0
• •
84.6
100.0
0.1
0.2
0.0
0.0
2.8
0.0
0.0
0.0
0.0
33.9
0.0
0.1
NA
0.0
0.0
0.0
29.9
12.5
NA
NA
20.0
0.0
NA
3.3
2.3
2.2
0.3
NA
0.0
NA
NA
0.1
0.0
40.1
lab +
• 99.9
99.8
80.0
100.0
97.8
96.7
97.7
97.8
99.7
66.1
100.0
99.9
NA
99.9
100.0
59.9
field
70.1
87.5
0.2
1.4
0.0
0.0
0.9
0.0
0.0
0.0
0.0
87.1
0.0
0.3
NA
0.0
0.0
0.0
40.6
24.6
NA
0.1
6.8
0.0
NA
17.2
3.6
2.8
7.1
NA
0.0
NA
NA
5.9
NA
73.6
lab +
99.8
98.6
93.2
100.0
99.1
82.8
96.4
97.2
92.9
12.9
100.0
99.7
NA
94.1
100.0
26.4
field
59.5
75.4
• NA indicated that the number of observations on which the estimated variance was based was less
than 5. or the estimated variance was negative.
•• True field spiked standards no available for these constituents demanding combined estimates of
laboratory and field variability.
-------
BARCELONA ET AL.: AQUIFER OXIDATION REDUCTION CONDITIONS
TABLE I. Physical Characteristics of the Study Sites and Well Installations
Depth
Condition of
Groundwater
Site 1 , Sand Ridge
noncontaminated
Site 2, Beardstown
contaminated
Well No.
I
2
3
4
5
6
8
9
10
lit
12*
13
Meters Below
Land Surface
11
15
21
32
5.5
7.0
7.5
10
10.5
10
10
10
Screen Elevation
msl, m
142t
I37t
I33t
120t
131
129
131
129.5
128
129.5
129.5
129.0
Hydraulic Conductivity"
gpd/fT1
200-500
700-7000
600-900
500-&W
cm/s
0.01-0.024
0.033-0.33
0.03-0.042
0.02-0.038
Bulk Flow
Velocity, cm/day
10-30
30-50
20-30
40-55
40-55
40-55
40-55
40-55
40-55
Land surface 152 m above msl.
•Modified slug test results [Hvorslev, 1951].
tStainless steel well finished at 10 m depth along a perpendicular to the flow direction downgradient from the treatment impoundment.
tPoly vinyl chloride well finished at 10 m depth along a perpendicular to the flow direction downgradient from the treatment impoundment.
Parameter
Eh, mV*
ft'1, /iS/cm*
PH*
T, °C
TOC
TOX,
CH,
N02--N
NH3
Fe (II)
Fer
Mnr
s-
O2 (probe)*
O2 (Winkler)*
Alkalinity (as CaCO,)'
cr
(NO3- + NOj-)-N
so;
T-POT
Silica
Ca2*
Mg^
Na2*
K+
Depth
BARCELONA ET AL.: AQUIFER OXIDATION REDUCTION CONDITIONS
TABLE 2. Average Results for Groundwater Chemical Analyses
Well 1
Mean
s.d.
456
359
7.75
12.0
0.85
3.65
-O.I2!
0.00
-0.01
0.01
0.01
0.00
0.00
9.00
8.82
216
2.19
0.95
36.2
0.02
0.04
15.5
65.9
22.6
3.11
0.71
35 feet (11
91
11
0.53
0.9
0.26
5.0
0.8
0.002
0.014
0.04
0.03
0.009
0.03
0.50
0.86
12
0.71
0.2
5.8
0.02
0.074
0.4
3.3
1.25
0.49
0.08
m)
Well 4
Mean
s.d.
WellS
Mean
s.d.
110
225
7.80
12.2
0.57
3.07
0.01
0.00
0.06
0.50
0.44
0.15
0.00
0.61
0.46
132
1.67
-0.01
22.1
0.11
0.13
15.7
38.4
12.3
3.53
0.73
105 feet
50
II
0.37
0.3
0.2
4.0
0.08
0.001
0.04
0.08
0.10
0.03
0.005
0.27
0.06
5.4
0.72
0.07
4.49
0.023
0.05
0.62
2.36
0.62
0.54
0.09
(32m)
226
375
6.48
12.5
3.08
6.26
0.00
0.00
0.26
1.04
1.02
0.09
0.04
0.36
N.D.
65.5
66.6
-0.02
76.7
0.06
0.10
13.3
38.5
14.7
33.9
2-85
33
97
0.35
2.7
0.75
4.6
0.036
0.002
0.15
0.18
0.23
0.02
0.01
0.13
N.D.
5.7
38.9
0.023
13.1
0.03
0.05
1.08
8.6
3.1
11.9
n 87
upgradient 18
feet (5.5 m)
Well 8
Mean
102
1607
6.87
15.6
6.78
10.9
1.33
0.01
174
2.21
2.15
0.63
0.14
0.36
N.D.
690
141
1.89
35.6
14.6
14.7
19.0
44.1
17.5
117
22.7
downgradient
feet (7.5 m)
s.d.
27
173
0.20
1.6
1.17
7.6
0.71
0.004
51.3
0.82
0.78
0.10
0.07
0.18
N.D.
81
10,1
2.07
5.59
7.7
7.6
4.95
7.1
2.2
14.6
2.47
25
S.d., standard deviation in concentration or similar units; N.D., not detected. Values represent the results are given in milligrams per liter
unless otherwise specified for duplicate determinations on each of 39 sampling dates over the study period.
'Determined in the field.
tNegative mean values result from the reporting of actual sample results above and below the limit of detection as recommended by
ASTM[19&7}.
-------
BARCELONA ET AL.: AQUIFER OXIDATION REDUCTION CONDITIONS
0 100 ZOO 300 400 500 (mv) m Eh
10 Img-L'1! «PROBE ewNKLER. (
1 20 -
X
111
Q
0-5 (mg-L-'l
Fig. 2. Average profiles of Eh (solid squares), dissolved oxygen (solid circles, probe; open circles, Winkler) and
ferrous iron (solid triangle) gradients with depth at the uncomaminatcd site, Sand Ridge State Forest.
io-3
5 10-'
10-'
UPGRAOIENT
Eh
OS'
uA*<
COWNGRADIENT
-SOUMCE-
*
r
Eh
400
300
200
• 1.11, U 10 WELL No
. > t DISTANCE FROM SOUKCE
-17m -Km »J3m »SSm
Fig 3. Average concentrations of redox-active chemical spe-
cies with distance from the contaminant source (concentration in
logarithmic scale with reference tick marks on each margin. Eh scale
linear).
-------
e Pi*lom«(«r
e— W»l«r L»v»l
R«cord>r Willi
0 PTF E W»ll
0 Suintou StMl Will
A PVC w«n
(30) O»pth in FMI
Intermediate
Lagoon
Anaerobic
Lagoons
o
331 "13
Dominant Direction
of Ground-Water
Flow
Existing
Wall
O
Fig. 1. Plan diagram of the monitoring well locations at the
contaminated groundwater site at Beardstown, Illinois.
200
400 600
DAYS FROM 12-1-84
BOO
1000
Fig. 6. Time series plot of H2O2 concentration from December I, 1984, for oxic groundwater samples from depths
of 35 (11 m) (open circles), 50 (15 m) (solid circles), and 65 feet (21 m) (open triangles). Mean field blank level is shown
on the dotted line.
-------
BARCELONA ET AL.: AQUIFER OXIDATION REDUCTION CONDITIONS
0.8
. WELL3
0.7
0.6
0.5
0.4
0.3
0.2
0.1
-200
Theoretical-0-j
0*
Platinum Electrode
Sato-02
200 400 600 BOO 1000 1200
DAYS FROM 12-1-84
0.6
O.S
0.4
0.3
0.2
!"•'
£.
m 0
-0.1
-0.2
-0.3
-0.4
-O.S-
WELL4
N03/N02
f • N03/NH4
Fe3+/Fe2
5 «o° o o°°o °o 00°
SQ4/S ° o 0
100 200 300 400 500 600 700 BOO
DAYS FROM 10-1-85
0.6
0.5
0.4
- 0.3
I
£0.2
0.1
. WELLS
NO3/N02
5so4/s
-0.2 h
0.6
d
O.S
0.4
0.3
_0.2
|
£
" 0.1
WELL9
NO3/N02
f , , N03/NH4 ^
o o
o o°
O0 0
0000°
100 200 300 400 SCO 600 700 800
DAYS FROM 10-1-85
100 200 300 400 500 600 700 800
u-,or~u- . DAYS FROM 10-1-85
Fig. 5. Comparison of Eh potential measurement results with calculated Eh values during the study period for (a) well
3, (b) 4, (c) 5, and (d) 9.
-------
BARCELONA ET AL.: AQUIFER OXIDATION REDUCTION CONDITIONS
TABLE 4a. Spatial Gradients in Subsurface Oxidation- Reduction Conditions, Site Scale
Type of Environment
Redox Gradient
AO,, mg L~'
m~' AEh, mV/m
Contaminant?
Reference
Horizontal (Along General Groundwater Flow Path)
Unconfined sand
Unconfined sand
Unconfined
sand/gravel
Unconfined
sand/gravel
Unconfined sand
Confined sand/gravel
Confined sand/gravel
Unconfined sand
Unconfined sand
Unconfined
sand/gravel
Unconfined
sand/gravel
Unconfined sand
+ 1
-0.04 -2
+ 0.1
-3
-1.5*
-0.01 -2.5
+0.5
Vertical
-10 to -15
-0.34t -2 to -40t
-0.7 -30
-0.2 to 0.77* -2 to -301
-8 to -27*
landfill leachate
high organic carbon recharge
landfill leachate
inorganic fertilizer plume
anaerobic treatment leachate
high organic carbon recharge water
artificial recharge
(Increasing Depth)
background
landfill leachate
high organic carbon recharge water
background
anaerobic treatment leachate
Nicholson el al. [1983]
Jackson and Patterson [1982]
Baedecker and Back [19796]
Barcelona and Naymik [1984]
this study (Beardstown)
Jackson and Patterson [1982)
Van Beek and Van Puffelen
[1987]
Jackson et al. [1985]
Jackson el al. [1985]
Jackson and Patterson [1982]
this study (Sand Ridge)
this study (Beardstown)
"Eighteen month average between wells 8 and 10.
tVaJues available from two separate sampling periods.
^Thirty month average range between wells 1 and 3 and 3 and 4, respectively.
TABLE 46. Spatial Gradients in Subsurface Oxidation-Reduction Conditions, Large Scale
Type of Gradient
Horizontal (Along general
groundwater flow path)
Redox
Type of Environment AO2, mg L~' km
confined sandy clay/gravel (Patuxent)
confined sand/clay, lignite (Rarilan-
Magothy)
confined carbonate chalk (Berkshire) -0.30
confined limestone (Lincolnshire) -0.34
confined sandstone/siltstone none
(Foxhills-BasaJ Hell Creek)
unconfined sand/gravel (Tucson + 1
Basin)
Gradient
AEh, mV/km
-34
-57
-30
-180
-0.4 to +5
+ 23
Reference
Back and Barnes [1965]
Back and Barnes [1965]
Edmunds et al. [1984]
Edmunds et al. [1984]
Thorstenson el al. [1979]
Rose and Long [1988]
-------
SUBSURFACE ENVIRONMENTAL CONDITIONS
0 EQUILIBRIUM VS. KINETIC CONTROL OF SPECIES CONCENTRATIONS
la the reaction fast w.r.t. rates of flow/mixing?
Do equilibrium assumptions apply?
Can we use stepwise-equilibrium calculations within the
limits of solute-transport models?
-0.1
Fig. 4. Grouping of Eh-pH measurement results for the monitoring wells used in this study. The H:O,/Oj standard po-
tential line from Sato [I960! is shown on the diagram. Solid symbols are for data from Jackson and Patterson [1982].
-------
OXIDATION AND REDUCTION
INTENSITY - Eh POTENTIAL MEASUREMENTS,
RATIOS OF OXIDIZED AND REDUCED
SPECIES
Fe(III), Fe(ID
o2, HA
[As(V), As(III)]
• IDENTIFICATION OF IMPORTANT SPECIES,
BIOGEOCHEMICAL POSSIBILITIES
CAPACITY - REDUCTION OR OXIDATION CAPACITIES
• BEAR DIRECTLY ON THE POTENTIAL FOR JJ{
SITU OXIDATION OR REDUCTION OF
CONTAMINANTS
-------
HYPOTHETICAL IN SITU OXTDATTVE REMEDIATION
(100% EFFECTIVE)
ESTIMATED CHEMICAL COST (per m' of Aquifer)
HYDROGEN PEROXIDE (HjOJ $25 to $1,000
POTASSIUM PERMANGANATE (KMnOJ $50 to $2,000
POTASSIUM PERSULFATE (KjSjO,) $1,100 to $42,000
-------
C. Sampling Considerations
1. Environmental sampling in general
2. Sampling protocols for site characterization work
a. scope and magnitude or the problem/relation to
sampling intervals and representativeness
b. Interactions between contaminated and uncontaml-
nated sub-areas within the site
c,- choice of diagnostic parameters, analytes
d. sampling protocols based on hydrogeologic data
e. sampling experiments
L refined sampling protocol
g. transition from characterization work to monitoring
remediation efforts
-------
ENVIRONMENTAL SAMPLING
— A SELECTION PROCESS
o Objects within populations of increasing complexity
o Evolutionary approach and sampling experiments
o Isolate variables of importance in specific situations
o Ambient, contaminated, and exposure conditions must be
weighed in network design and sampling protocol
development
OBJECT POPULATION
OBJECT
DEGREE OF HOMOGENEITY HOMOG
OF OBJECTS
MATUM OF CHANGE IN QUALITY
THROUGHOUT OBJECTS
EXAMPLES
II WELL-MIXEt
1 WELL-MIXED
I
ENEOUS
3 GASES
LIQUIDS
PURE METALS
TRUE SOLUTIONS
MACROSCOPIC GRADIENTS
CHEMICAL NO
PHYSICAL NO
HETERO
DISCRETE
ORE-PELLETS
CRYSTALLINE
ROCKS
SUSPENSIONS
NO
NO
3ENEOUS
1
CONTINUOUS
REACTIVE
GAS MIXTURE
REACTIVE
SOLUTIONS
SUSPENSIONS
YES
POSSIBLE
1
DISCONTINUOUS
REACTIVE GAS PLUME
IN WIND FIELD
REACTIVE EFFLUENT MIXTURES
ENTERING TREATMENT PLANT
OREOGEO SEDIMENT
DISPOSAL OPERATION
YES
YES
Figure I. Typa uf miurwopic ubjrtK or suni/>lc origins
-------
SUBSURFACE ENVIRONMENTAL CONDITIONS
0 CHEMICAL CONCENTRATION VARIABILITY
SHORT-TERM; PUMPING, RECHARGE EFFECTS
LONG-TERM; SEASONALITY, TREND ANALYSIS
CALL FOR
• INTEGRATION OF HYDROLOGIC AND CHEMICAL DATA INTERPRETATION
• CAREFUL SELECTION OF SAMPLING FREQUENCY
(HOW OFTEN IN THE FLOW PATH )
-f
FIELD
CONTROL
SAMPLES
1
1
OBJECT _ _ OBJECT .— . OBJECT
(PARENT POPULATION)
INCREMENT INCREMENT OBJECT*
\ /
| SAMPLE SAMPLE SAMPLE ^"O^E"
\ /
[ (CROSS) SAMPLE ]
1 <• v " " ' ' SUBSAMfM f S
SUBSAMPLE
CONTROL
J 1
BLK t
STD
ST
DUPLICATE STORAGE ANALYSIS ANALYSIS ANALYSIS """"pARtVoR
!" ' ' £ ANALYSIS
1 1
ALIQUOT ' '
D
(i ANALYSIS PROCEDURE
7 |
1 1
LAIORATOR
CONTROLS
' 1
I EXTERNAL REFERENCE STANDARDS
Figure 2. Sample numroctufurr ovrrvinv.
-------
HYPOTHESIS
PROGRAM
PURPOSE
FORMULATE
QUESTIONS
AND DESIGN
!
1
OBSERVATION
SAMPLE
SAMPLING
— ^^ —
PROTOCOL
t
PROCEDURES
I
TECHNIQUES
t
METHODS
ANALYZE
^ ANALYTICAL_
PROTOCOL
t
PROCEDURES
!
TECHNIQUES
t
METHODS
INTERPRETATION
INTERPRET
^ RESULTS
RE-EVALUATE HYPOTHESIS/PURPOSE •• '
Figure J. Rrliil/onship nf program rturpme anil protocols to the uimlific method.
Table 1.1. Data Requirements for Water-Source Definition and
Aquifer Representation of Ground-Water Samples
(Modified after Claassen, reference 31)
A. Drilling history
1. Well depth and diameter
2. Drill-bit type and circulating fluid
3. Lithologic data from cores or cuttings
4. Well-development before casing
5. Geophysical logs obtained
B. Well-completion data
1. Casing sizes, depths and leveling information relative to both land surface and top of casing
2. Casing material(s)
3. Cemented or grouted intervals and materials used
4. Plugs, stabilizers, and so forth, left in hole and materials used
5. Gravel packing: volume, sizes, and type of material
6. Screened, perforated, or milled casing or other intervals which allow water to enter the borehole
7. Pump type, setting, intake location, construction materials, and pump-column type and
diameter
8. Well maintenance record detailing type of treatment and efficiency
C. Well pumping history
1. Rate
2. Frequency
3. Static and pumping water levels
D. Estimation of effect of contaminants introduced into aquifer during well drilling and completion
on native water quality
E. Effect of sampling mechanism and materials on the composition of ground-water sample
1. Addition of contaminants
2. Removal of constituents
a. Sorption
b. Precipitation
c. Degassing
-------
PARTI
SAMPLING IN GENERAL
A Guide lu ibc Selection of Materials for Monitoring Well Construction and Ground Water
Sampling. EPA 600/S2-84-024, U.S. Environmental Protection Agency, RSKERL: Ada, OK,
1983.
American Chemical Society Committee on Environmental Improvement. Analytical Chemistry
1980, J2, 2242-2249.
Baedcckcr, M. J.; Back, W. Ground Water U, -5, 429-437.
Barber, C; Diws, G. B. Ground Water 1987, 25. 5, 581-587.
Barcelona, M. J. In Principles of Environmental Sampling: Keith, L. H., Ed.; American Chemical
Society. Washington, DC, 1988; Chapter 1
Barcelona, M. J.; Garske, E. E. Analytical Chemistry 1983, ii, 6, 965-967.
Barcelona, M. J.; Gibb, J. P. American Society for Testing and Materials, Philadelphia, PA,
ASTM STP-963, 1988, pp 17-26.
Barcelona, M. J.; Hclfrich, J. A. Environmental Science and Technology 1986, 20,11, 1179-1184.
Barcelona, M. J.; Hclfrich, J. A. Proc. of the Ground Walcr Geochemistry Conference. National
Walcr Well Association, Denver, Colorado, February 16-18, 1988, pp 363-375.
Barcelona, M. J.; Hclfrich, J. A.; Garske, E. E. Analytical Chemistry 1985b, 52, 2, 46CW64
(errata: 51, 13, 2752).
Barcelona, M. J., Helfrich, J A.; Garske, E. E. In Verification of Sampling Method.} and
Selection of Materials for Ground-Waicr Copiamipalion Sludi»; CoUm. A. G Johnson A. 1
Eds.; STP 963; American Society for Testing and Materials: Philadelphia, PA, 1988c; pp 221-231.
Barcelona, M. J.; Holm, T. R.; Schock, M. R.; George, G. K. Water Resources Research. 1989,
25, 5, 991-1003.
Bibliography nf Ground Walcr Sampling - Internal Report. EPA/600/X-87/235, U. S,
Environmental Protection Agency, EMSL: Us Vegas, NV, 1987.
Battist* J. R.; Connelly, J. P. VOC Conlarninaiion al Selected Wisconsin landfills - Sampling
Results and Policy Implications. Wisconsin Deparlmen! of Natural Resources, Madison, Wi.
Publ. SW-094-89, June 1989, 74 pp.
Qunp, D. R.; Gulent, J.; Jackson, R. E. fan J F"'h Sciences 1979,1& 1, L2-23.
Cherry, J. A.; Gillham, R. W.; Anderson, F. G.; Johnson, P. E. J, HvJroL 1983, fii 31-49.
Cohen, R. M.; Rabold, R. R. r.rnund Water Mnnilnnng Rtricff 1988, 8. 1, 51-59.
Cowgill, U. In Principles of Environmental Sampling: Keith, L. H., Ed.; ACS Professional
Reference Books: Washington, DC, 1988; Chapter 11.
Davis, S. N.; DeWiest, R. J. M. Hydrology. Second Edition: Wiley: New York, NY, 1967;
463pp.
Driscoll, F. Ground Water and Wells. Second Edition: Johnson Division: St. Paul, MN, 1986;
1089 pp.
Evans, L. G.; Ellingson, S. B. Proc. of >he Ground Water Geochemistry Conference. National
Water Well Association, Denver, Colorado, February 16-18, 1988, pp 377-389.
Freeze, A. R.; Cherry, J. A. Groundwaler: Prentice-Hail, Inc.: EogJewood Cliffs, New Jersey,
1979.
Garske, E. E.; Schock, M. R. Ground Water Monitoring Review 1986, & 3, 79-84.
Ground Water Monitoring and Sample Bias. Report No. 4367, American Petroleum Institute,
Environmental Affairs Department, Washington, DC, June 1983.
Gschwcnd, P. M.; Reynolds, M. D. J. of Contaminant Hydrology 1987, 1, 1, 309-327.
Holden, P. W. Primer on Well Walcr Sampling for Volatile Organic Compounds: University
of Arizona, Water Resources Center Research, 19S4, 44 pp.
Holm, T. R.; George, G. K_; Barcelona, M. J. Analytical Chemistry 1987, 52. 4, 582-586.
Holm, T. R.; George, G. K.; Barcelona, M. J. Ground Water Monitoring Review 1988, g, 3,
83-#>.
Kent, R. T.; Payne, K. E. In Principles of Environmental Sampling: Keith, L. H., Ed.; ACS
Professional Reference Book, American Chemical Society: Washington, DC, 1988; Chapter 15.
Kobyashi, H.; Rittroann, B- E. Environmental Science and Technology 1982, J& 3, 170A-183A.
Lee, M. D.; Thomas, J. M.; Borden, R. C.; Bedient, P.B.; Wilson, J. T.; Ward, C. H. CRC
Critical Reviews in Environmental Control 1988,1& 1, 29-89.
Lrndbcrg. R. D.; Runnclls, D. D. Sflejjcc. 1984, 22i 925-927.
Marsh, J. M.; Uoyd, J. W. Ground Water 1980, IS, 4, 366-373.
Matthess, G. The Properties of Ground W.ler. J. Wiley A Sons, 1982.
Monitoring Ground-Water Quality: Monitoring Methodology. EPA-600/4-76-026, U. S.
Environmental Protection Agency, Las Vegas, NV, 1976.
Monilorin; Well Design and Construction. EPA 625/6-87/016, U.S. Environmental Protection
Agency, CER1, Cincinnati, OH, 1987.
Montgomery, R. H.; Loftis, J. C.; Harris, J. Ground Water 1987, 25, 2, 176-184.
Palmer, C. D.; Keely, J. F.; Fish, W. Ground Water Monitoring Review 1987, 2, 4, 40-47.
-------
Panko, A. W.; Earth, P. In Ground Water Contamination Field Methods: Collins, A. G.;
Johnson, A. I., Eds.; STP 963; American Society for Testing and Materials: Philadelphia, PA,
1968; pp 232-239.
Peyton, G. R.; Gibb, J. P.; LeFaivre, M. H.; Rilchey, J. D. Proc. 2nd Canadian/American
Copferept^ QD HyjrQgcoiogy "Hflriflrdous Wastes in QrflUfld Wfttcr: A Jjofoble Dajegjpia. Banff
AJberta, Canada, June 2S-29, 1985, pp 101-107.
Practical Guide for Ground Waler Sampling. Stale Water Survey Contract Report No. 374 (EPA
600/52-85/104), USEPA-RSKERL, Ada, OK, 1985.
Procedures for the Collection of Representative Waler Quality Data from Monitoring Wells:
Cooperative Ground Waler Report 7; Illinois Stale Water Survey and Stale Geological Survey:
Champaign, 1L, 1981.
Rehm, B. W.; Slolzenburg, T. R.; Nichols, D. G. Field Measurement Methods for Hvdrogeolopc
Investigations: A Critical Review of the Literature. EPRI-EA-4301, Electric Power Research
Institute, Palo Alto, CA, 1985, 328 pp.
Rabbins, G. A. Ground Waler. 1989, 22. 2, 155-162.
Robin, M. J. L.; Gillham, R. W. Ground Waler Monitoring Review 1987, "L 4, 85-93.
Smith, J. S.; Sleelc, D. P.; Malley, M. J.; Bryant, M. A. In Principles of Environmental Sampling:
Keith, L. H, Ed.; ACS Professional Reference Books, American Chemical Society: Washington,
DC, 1988; Chapter 17.
Stunun, W.; Morgan, J. J. Aquatic Chemistry. Second Edition: Wiley Inlenciencc: New York,
NY, 1981; 780 pp.
Towler, P. A.; Blakey, N. C; Irving, T. E.; Clark, I_; Maris, P. J.; Baxter, K. M.; Macdonald, R.
M. Hydrology in the Service of Man. Memories of the 18lh Congress. International Association
of Hydrogcologists: Cambridge, U.K_, 1985; pp 84-97.
Van Beck, C. G. E. M.; Van Puffclcn, J. Waler Resources Research 1987, 22, 1, 69-76.
White, D. C.; Smith, G. A.; Gehran, M. J.; Parker, J. H.; Fmdlay, R. H.; Martz, R. F.;
Frederickson, H. L. Dev. Ind. Microbiol. 1983, 24, 201-211.
Wilson, J. T.; Leach, L. E.; Henson, M.; Jones, J. N. Ground Waler Monitoring Review 1986,
fi, 4, 56-64.
Wilson, J. T.; McNabb, J. F. EQJ 1983, 64 33, 505-506.
GENERAL STATISTICAL CONSIDERATIONS
U.S. Environmental Protection Agency, 1989. "Guidance Document on the Statistical Analysis
of Ground-Water Monitoring Data at RCRA Facilities - Interim Final Guidance.' Office of
Solid Waste Management Division, April 1989 (VERY USEFUL LIST OF REFERENCES in
Appendix C).
-------
SESSION 2. DETERMINATION OF EXTENT AND MAGNITUDE OF CONTAMINATION
IN THE SUBSURFACE
PART 2. SOIL AND AQUIFER SEDIMENT SAMPLE COLLECTION
A, Solid Sample Collection
1. Sampling strategies/recognizing major sources of error
2. Hydrogeologic and source considerations
3. Statistical considerations
a. general
b. case studies
B. Solid Sampling in Practice
1. Program objectives and the preliminary Dimpling protocol
2. Analyte selection (Le., contaminants, soil or aquifer properties)
3. Sampling points and devices
4. Sampling experiment
5. Refined sampling protocol/refined hypotheses and objectives
C. New Methods for Solid-Associated Contaminant Investigations
1. Soil-Gas techniques
2. Hybrid samplers (Le., H2O and Soil)
PART 2. SOIL AND AQUIFER SEDIMENT SAMPLE COLLECTION
A. Solid Sample Collection
B. Solid Sampling In Practice
C New Methods for Solid-Associated
Contaminant Investigations
-------
A. Solid Sample Collection
1. Sampling strategies/recognizing major sources of error
2. Hydrogeologic and source considerations
3. Statistical considerations
general
b. case studies
-------
Rgure 3-2. Major Hydrochemlcal Proce»sen In the Soil Zone of Recharge Areas
.Source: R. Allan Freeze and John A. Cherry. Groundwater
(Englewood Cliffs, N.J.: Prentice-Hall. Inc.. 1979). p. 204
Horizon
The Soil
(Solum)
Abundant root* and
organic matter
Accumulated clay,
iron oxide, and
some humus
Oxidized, slightly
weathered geologic
materials, some
accumulation of
secondary minerals
j£> Saturated xone'&j
&&&&?&.:•&&#&.
02
Gaseous
diffusion and
aqueous
transport
into soil
-4-4-4-
Oj consumption
by organic
matter oxidation
Downward
movement of
water low or
deficient in O2
C02
Escape
to
atmosphere
f JL 4
1— ~~ r~* — i >
Production of COj
H2O+CO2*H2CO3
Downward
movement by
gaseous
diffusion and
water transport
f^$*^$&
Active leaching
and transport of
dissolved species
resulting from
interactions of
CO? -and O2-rich
water with mineral
constituents and
organic matter
-------
SOIL AND AQUIFER SEDIMENT SAMPLING
SAMPLING STRATEGIES:
• PURPOSES • STRATEGY QUESTIONS
- DETECTION - Is area/volume contaminated?
- ASSESSMENT - Is contamination widespread?
EVALUATION - Are H2O and solids contaminated?
What la the spatial distribution
of contamination?
SAMPLING STRATEGIES
_ SCOPE (EXAMPLES) ZONES OF INFLUENCE
SMELTERS -
USPs
NAPL's
Pb (Dallas, TX) -400 m "radius"
Zn, Cd, Pb, Cu (Palmerton, PA)
•5,000 m 'radius"
Solvents, Hydrocarbons (various sites)
~50 to 2,000 m "radius"
R-C1, (various sites)
-50 to 2,000 m; depths to 500 m
SOLID SAMPLING
DEVELOPMENT OF A SOLID'S MONITORING PROGRAM
NECESSITY OF A SAMPLING EXPERIMENT
AS A BASIS FOR MORE FOCUSSED OBSERVATION,
ANALYSIS, DECISION-MAKING
- MONITORING DATA ALONE WILL NOT ESTABLISH
UNEQUIVOCALLY "CLEAN" OF CONTAMINATED" AREAS
•WHAT IS THE PROBABILITY THAT THE AREA TO BE
TREATED HAS A CONTAMINANT CONCENTRATION LESS
THAN THE ACTION LEVEL?"
SOLID SAMPLING
PROTOCOL DEVELOPMENT
• Preliminary Sampling Experiment
Preliminary Sampling Array (i-t, grid size,
spacing and number of samples)
Sample type and device (U-, grab, composite, etc.)
Statistical analysis of Data (he, geostatlstlcs, Kriging)
Refined network design/hypothesis
-------
SOLID SAMPLING PROTOCOL
• Determine Spatial Distribution of Contaminants at known
precision
— Intensity of sampling depends on non-sampling variance
and spatial structure of the concentration data.
(ALWAYS EASIER TO COLLECT SOLIDS THAN TO
ANALYZE THEM - ARCHIVE)
• Preliminary Sampling Experiment provides these values.
SOLID SAMPLING PROTOCOL - SAMPLING ARRAY
• GRIDS - ALLOW PRECISE ESTIMATION OF SHORT
RANGE CORRELATIONS
• TRANSECTS - ALLOW PRECISE ESTIMATION OF LONG
RANGE CORRELATIONS
• COMBINATIONS OF THE ABOVE ARRAYS SHOULD
PROVIDE THE BASIS FOR MORE REFINED HYPOTHESES.
-------
STARKS ET AL ON METAL POLLUTION DESIGN
w—
FIG. 1—Palaerton Wind Ro«e 1978-1979 d«t«-
To 5 Mil**
1200' Pointi.
To South
' Lthighton
v\\
»\\ Lthigh Valley
III Tunnel
Sampling Locations
N
HO. 2—S*»pU pacccrn for the initial FalMrtoa Survey (1~ • 4250').
-------
2900.0
2100.0-
1300.0
Contour Map of Lead
Concentrations in PPM
2900.0 4500.0
6100.0
7700.0
FIG. 2—Contour map of the lead concentrations In ppn around
the smelter.
o>
u
I-
« M
li
•i
II
« «
I-0
o
o
Tickmark = 167 m (500 feet)
Lag. (the distance between sample locations)
• 1—A semlvarlogram of lead samples taken systematically
on a 230m (750 foot) grid "
-------
FLATMAN ON SOIL SAMPLING PROGRAMS DESIGN
11700.0-
500.0
MO.O 2100.0 37OO.O 5300.0 UOO.O BSOO.O 10100.0 11700.0
Kriging Error Map—RSP
FIG. 3—Contour map of atandard deviation* of the lead
concentrations In ppn.
-------
SOLID SAMPLING PROTOCOL - ERRORS
• AUTOCORRELATION (in space or time) POSITIVE OR
NEGATIVE
SYSTEMATIC SAMPLING RATHER THAN RANDOM
CONTOURING RATHER THAN V TESTING
SOLID SAMPLING PROTOCOL - SAMPLE TYPE
(AT LEAST)
• FOUR SPACED SAMPLING SITES ON TRANSECTS/GRIDS AT
DISTANCES BELOW THE EXPECTED RADIUS OF INFLUENCE
• DUPLICATE SAMPLES AT 5% OF THE SAMPLING
POINTS (HELP SORT OUT SHORT-RANGE VARIABILITY)
• SPLIT-SAMPLES AT 5% OF THE SAMPLING POINTS (PROVIDES
COMBINED SUBSAMPLING AND ANALYTICAL ERROR
VARIANCE)
PLUS
• COMPOSITING LARGER SAMPLES OFTEN IMPROVES VARIANCE
ESTIMATES (TRY TO AVOID SAMPLES LESS THAN 100 g)
-------
SOLID SAMPLING - ERROR
• AUTOCORRELATION (HIGH FOLLOWS HIGH AND V.V.)
• SUBSAMPLING ERROR (REPRESENTATIVENESS OF "SMALL-
SAMPLES)
• ANALYTICAL ERROR (INTERFERENCES, INCOMPLETE
RECOVERIES, ETC.
Detection Limit Values (Built-in Bias)
• SPATIAL 'REPRESENTATIVENESS'
— The Geographic Area defined by a radius centered at the sample
site and of a length (L) equal to that or the range
SOLID SAMPLING - REPRESENTATIVENESS
• SPATIAL VARIABLES (TIME OR SPACE)
— The range of correlation of the spatial correlation structure of the
contaminant distribution can be estimated by semivariograms
- The range of correlation
= MAX. L between sampling sites at which samples are
correlated.
» MIN. L at which samples are independent
— Semivariograms can provide this information.
-------
B, Solid SampUag in Practice
L Program objectives and the preliminary sampling protocol
2. Analyte selection (i.e-, contaminants, soil or aquifer properties)
3. Sampling points and devices
4. Sampling experiment
5. Refined sampling protocol/refined hypotheses and objectives
-------
SOLID SAMPLING PROTOCOL - ANALYTES
• INORGANIC - 'CRUSTAL" - Fe, Mn, Al, SI
- 'CONTAMINANTS' - Zn, Cd, Pb, As, Sc,
Cu, NI, Co
• ORGANIC - TIC,TOC
VOLATILE ORGANIC COMPOUNDS
SEMI-VOLATILE ORGANIC
COMPOUNDS
MICROBIOLOGICAL
PARAMETERS
• HYDROGEOLOGIC
PARAMETERS
- GRAIN SIZE DISTRIBUTION,
PERMEABILITY
SOLID SAMPLING PROTOCOL - SAMPLING DEVICE
• SOIL - HAND AUGER, BRACE AND BIT,
POST-HOLE, CORING DEVICES
• AQUIFER SOLIDS - SPLIT SPOON, SHELBY TUBE
- CONTINUOUS CORER
- DRIVEN OR PUSHED CORER
- DIAMOND CORE
- BAIL (CABLE TOOL METHOD)
-------
•OL CORE CUTTER
i i
Fig. I. Undisturbed soil core sampling tppannu.JAiycTli'c^W! /fff)
1
2
3
4
Teflon Wiper Disc,
Dr.is: Dushingi
Ncoprcnc Seals
Swivel
MODIFIED WIRELINE PISTON DESIGN
-------
ADVANCEMENT
(SAMPLING)
AUGER HEAD
BIT
-CLAM- SHELL
CLAM-SHELL FITTED AUGER HEAD
WIRELINE
HAMMER
BOREHOLE
DRILL RODS
HOLLOW-STEM
AUGERS
CORE BARREL
DRILL BIT
PLACEMENT^
M -DRILL RODS
-WIRELINE
- BOREHOLE
rj^~~DRILLING MUD
"<" FILTER CAKE
BARREL
LINER
PISTON
DRILL BIT
WIRELINE RECOVERY
DRILLING
MUD
SAMPLE
HOLE
-------
Flow
arul Indicator
Sample Tube
from Extruder
SOIL SAMPLING - CASE STUDY (Williams et al., 1989)
**Ra CONCENTRATIONS IN SOIL - URANIUM MILL TAILINGS
STANDARD - ^Ra < 5 pCI/gram above background in top 15 cm
< 15 pCi/gram above background in deeper
15 cm layers, both over 100 m2 area
BACKGROUND - 1 to 2 pCI/gram
Fi«ld Sampling Glove Box
2 I. D. S.S.
PARING CYLINDER
S.S. PLATE
COPE PARING TOOL
CASE STUDY - ^Ra
SAMPLING STRATEGY
10 - (50 g) composite
20 - (25 g) composite
1 - (500 g) grab
DATA ANALYSIS APPROACHES
• Single 20 composite
• Single 10 composite
• 5 to 20 random grabs
• 5 to 20 uniformly-spaced grabs
-------
CASE STUDY - **Ra
RANKED RANKED
APPROACH PRECISION ACCURACY
Single 20 composite 1 i
Single 10 composite 2 1*
Random grabs 2 2
Uniform grabs 2 2
* larger composites better
CASE STUDY - mRa
SUMMARY
80-90% confidence is achievable with a reasonable number
of samples if accuracy of 70 to 130% is satisfactory.
Single 10-composite samples would be within 30% of true
mean about 75% of the time.
TWO 10-composite «30% of true mean -90% of the time.
THREE 10-composite =30% of true mean -95% of the time.
GROSS GAMMA MEASUREMENTS ARE USEFUL IN
SAMPLING DESIGN AND EVALUATION; NOT
NECESSARILY AS PREDICTORS OF "'Ra.
-------
Monltiring Points
tloe-1000 rain.
tlne-2000 Bin.
tlme-3000 Bin.
Change In Hatric Potential with. Time Adjacent to a
Porous Cup Sampler Evacuated with a Constant Vacuum of
70 wt.
C New Methods for Solid-Associated Contaminant Investigations
1. Soil-Gas techniques
2. Hybrid samplers (Le^ H,O and soil)
-------
NEW METHODS FOR SOLID-ASSOCIATED
CONTAMINANT MONITORING
• EMPHASIZE DETECTION (May be difficult to reproduce)
• SOIL GAS
DYNAMIC (Pumped grab sample)
STATIC (Act Carbon, Curie Point Method for
"integrated" sampling)
HYDROPUNCH™
- DRIVEN SAMPLER (to collect H,O in saturated
zone)
BOURE1
Sotgas
trations under a variety of conditions •-•' V- "?>'{>"'* 'i. l
Depth
voc
concentration
Depth
voc
concentration
Depth
};•(*) Homogeneous porous material with sufficient air-filled porosity ' ., 3. ...-. - -,,r' ; /;,.
'- '
;• omogeneous porous matea wt sucen ar-e pry ., 3. ...-. - -,, ;
; (B) Impermeabte subsurface layw (e.g., day or perched water) , v;,.i.-V..;; '--.-jT-. ';• .;: . •.:
(C) ImpermeaWe surtace layer (e.g.. pavement) • •.•-••'.. ; -'.\: .;V •.''••-«- ' •'.
Zbrierth^rnicrc*)wtoc>cd activity (drctes and wavy .- • ;,-:;• '.•.••;-••' "'."'." JJ-:,
Ines indicate different compounds) .-.'• ..'.:."•;'. . "-. ••'..••.:,.•:.'>..; J'- ! •',.•--
.' -'•-' - ' ••' '•''•"•
-------
SOIL GAS-MEASUREMENTS
• AMENABLE TO VOLATILE ORGANIC COMPOUNDS
AND GASES
SOLVENTS - TCA, TCE, PER, DCE, CLF, CILCI,,
FREONS
FUELS - TOLUENE, BENZENE, ETHYLBENZENE,
XYLENES
FIXED GASES - COV CH<( Olt N2
• NOT DIRECTLY APPLICABLE TO SEMIVOLATILE ORGANICS
OR INORGANICS
SEMIVOLATTLES - NAPHTHALENE, PHENOLS, AMINES,
ETC.
NONVOLATILE - PCB's, BAP, "WEATHERED" FUELS, ETC.
INORGANICS - METALS, SALTS, ETC.
SOIL GAS-ANALYTES
• PORTABLE (NONSPECIFIC) SENSORS: PID, FID
• MOBILE LABORATORY: GC-PID, GC-FID, GC-ECD, ETC.
• ANALYTICAL LABORATORY: GC-PID, GC-FID, GC-ECD, ETC.
-------
u
tl
»-rrt
Figure 1. Soil gas sampling apparatus: (a) Close-up view of syringe
sampling through the evacuation line, (b) gas (low through a soil
tas probe (7fonftSO*J fa* MM/LlV, / If ?}
TABLE 3
Profiles of F-113 (1,1,2-TrichIorotrifluoroethane) and TCE (Trichloroethylene) in Soil Gas
Depth (m)
0.6
1.1
3.4
6.1
8.0
Case#l
(A)
F-113 fc/s/L)
0.004
OJ Soil
33 Gas
1800
81 Water
Depth (m)
3.0
7.6
15.2
27.4
310
Case #2
(B)
TCE fcg/L)
0.006
0.02
0.03
9
140
Ground water concentrations of the two halocarbons analyzed at the water table are shown. All concentrations are
presented in units ofpg/L frrfWSbJ *HO****»>..
-------
150m
SCALE
EPA-1
(30)
VERTICAL PROFILE BORINGS
^ GROUNDWATER MONITORING WELLS
243 • SOIL-GAS SAMPLING POINTS '
—n*—. TCE CONCENTRATION CONTOURS IN
SOIL GAS
(30) TCE CONCENTRATIONS IN GROUNDWATER
MONITORING WE~LLS (ppb)
,J0 383 380.373370
CU (280O)
Fifure 4. Concentration contours of Irichlonxthylene (TCE) In soil (u for CMC K
M-7 (4100)
MfaU,* / a f 7)
-------
•29
0 50 tOO
LEGEND
,0-Corc»ntrat)on Contours of
Jf^ Total Hydrocarbons in
Soil Gas (mq/L)
• 34 Soil Gas Sampling
Point 34
O*48 Groundwater Sampling
Point 48
•9
•10
•n
•16
Concentntion contours of toul hydroarbons in soQ t«» for Ca*« «4
-------
FIGURE 2
1,1,1-THchkxoetnane concentrations In soil
w-io
W-2,
.w-e
Gnxjndwaler flew
•w-7
Legend
Well*
1.1.1.-THchloroethane
contours In tot gaa G»g/L)
Scale
0 25
North
FIGURES
Correlation between 1J,1,-trkdiVxoethane concentrations In soil gas
and In gnxindwater samples from 11 wells
100-
10-I
I
I
£
C 0.1-1
5
0.0V
0.001-
0X01
R-0.88
• Wfl
0.01
0,1
10
100
1000 10.000
TCA concentratlcn in groonctwatw OigfL)
-------
FIGURE 4
Subsurface contamination from a leaking gasoline tank
(a) Product plume according to confirmatory borehole
results
(b) bccctane concentrations (ppb by volume) in sofl gas at
22 meters
(c) Butane concentrations (ppm by volume) in soil gas at
U meters •
Legend
Contour Ene
Scale
. Sampling point 0 50 100
^ (meters)
I Contamination from w«n and exploratory borehole data
Contaminated groundwater prediction
Enclosed low-concentration zone
-------
SOIL GAS SAMPLING
• RESULTS OF PRELIMINARY SAMPLING NEEDED?:
- AIR FILLED POROSITY >5%
- VOLATILE CONTAMINANTS PRESENT AT SIGNIFICANT
LEVELS
- SELECT OPTIMAL SAMPLING DEPTH
- INITIAL SAMPLING LOCATIONS, GRID/TRANSECT
• CO,, Ov CH4 SHOULD NOT BE IGNORED IN FAVOR OF
POLLUTANTS OF THE MONTH.
SOIL GAS AND HYDROPUNCH00 SAMPLING
ADVANTAGES:
• USED TOGETHER THEY CAN SUBSTANTIALLY IMPROVE THE
DESIGN OF MONITORING NETWORKS BEYOND THE
DETECTION STAGE
• COMPLEMENT EACH OTHER IN ESTABLISHING
CONTAMINANT MOVEMENT, PERSISTENCE AND
RECOVERABILnY
• MAY GIVE THE BEST PICTURE OF SHORT-RANGE
VARIABILITY IN SPACE
-------
SOIL GAS AND HYDROPUNCH™ SAMPLING
DISADVANTAGES:
• SOIL GAS - Difficult to reference directly to pore water or ground-
water contaminant concentrations
• MAY BE DIFFICULT TO REPRODUCE AND PROBABLY NOT VERY
USEFUL IN REMEDIATION EVALUATIONS
CAREFUL DECONTAMINATION AND QUALITY CONTROL MUST
BE DONE IN THE FIELD - DIFFICULT CONDITIONS TO
CONTROL
['FAST' KINETICS
'SLOW KINETICS
AGE OF
UNIVERSE
AOE OF
CAITH
FIRST All.
IIEATHINO
ANIMALS
RECENT '
OEOLOOIC
TIME
THREESCORE
I TEN YEARS
ONE
TEAR
ONE
MONTHl
ONE
PAT
HUMAN
ruiSE
PERIOD
FAST
DIFFUSION.
CONTROLLED
REACTION IN
WATER
HYDROOCN
IOND
FORMATION
MOLECULAR
HRIOD
VIIRATION
TIME FOR
FASTEST
ELECTRON
TRANSFER
REACTION
FASTEST
NUCLEAR
PROCESSES
II I* 14 12 10 .. •
bg«rtt«iac Um» teal* tor U poMftta
.2 .4 .* . -• .10 .12 -U .16 -II -20 .22 .24
1 '
*nd AnOom. ,
-------
PART 2
SOILS AND AQUIFER SOLIDS
Andreini, M, and T. Steenhuis, 1988. Preferential flow under conservation and conventional
tillage. American Society of Agricultural Engineers. International Winter Meeting of (he ASCE,
Dec 13-16, 1988. Paper No. 88-2633. pg. 12.
Bouma. J, C. Belmant, L. Dekker, and W. Jeurissen, 1983. Assessing the suitability of soils
with macropores for subsurface liquid waste disposal. Journal of Environmental Quality
12(3)305-311.
Bumb, A-, McKee, C, Evans, R, and L. Eccles, 1988. Design of lysimelcr leak detector networks
for surface impoundments and landfills. Ground Water Monitoring Review. 9:102-114.
Brown, K. W, 1987. Efficiency of soil core and soil-pore water sampling systems. USEPA-
RSKERL, EPA 600/S2-86/083.
Campbell. G., 1985. Soil Physics with Basic; Transport Models for Soil-Plant Systems. Elsevier
Press, pg. 150.
Dimem, and Watson, 1985. Stability analysis of water movement in unsaturated porous materials:
Experimental studies. Water Resources Research. 2L-979-984.
Fitchko, J, 1989. Criteria for Contaminated Soil/Sediment Cleanup. Pudvan Publishing
Company, Northbrook, IL.
Flatman, G. T, 1986. Design of Soil Sampling Programs: Statistical Considerations. In ASTM
STP 925, C. L. Perket, £i American Society for Testing and Materials, Philadelphia, PA.
Germann, P-, and K. Seven, 1981a. Water flow in soil macropores; I. An experimental approach.
Journal of Soil Science. 31:1-13.
Germann. P, and K. Seven, 1981b. Water flow in soil macropores; II. A combined flow model.
Journal of Soil Science, 32:15-29.
Germann, P., and K. Seven, 1981. Water flow in soil macropores; HI. A statistical approach.
Journal of Soil Science. 3231-39.
Glass, R, T. Steenhuis, and J. Partange, 1988. Wetting front instability as a rapid and far-
reaching bydrologic process in the vadosc zone. Journal of Contaminant Hydrology. 3:207-226.
Hill, D. and J. Parlange, 1972, Wetting front instability in layered.soils. Soil Science Society
of America Proceedings. 36:697-702.
Hillet, D, 1980. Fundamentals of Soil Physics. Academic Press, pg. 413.
Klule, A_, 1972. The determination of the hydraulic conductivity and diffusrviry of unsaturated
soils. Soil Science. 113:264-276.
Lhaor, M, 1988. Review of soil solution samplers. Water Resources Research 24(5)727-733.
Lohman, S. W., 1972. Definitions of Selected Ground-Water Terms - Revisions and Conceptual
Refinements. USGS Water Supply Paper, Washington, D.C., pp 039-053.
McKee, C., and A. Bumb, 1988. A three-dimensional analytical model to aid in selecting
monitoring locations in the vadose zone. Ground Water Monitoring Review. 9:124-136.
Miller, E, 1975. Physics of swelling and cracking soils. Journal of Colloid and Interface Science.
52<3):434-443.
Morrison, R., and B. Lowery, 1989a. Effect of cup properties, sampler geometry, and vacuum
on the sampling rate of a porous cup sampler, (in press).
Morrison, R., and B. Lowery, 198%. Sampling zone of a porous cup sampler, experimental
results, (in press).
Munch, J, and R. W. D. Killey, Winter 1985. Equipment and methodology for sampling and
testing cobesionless sediments. Ground Water Monitoring Review, pp. 38-42.
Myers, R. G., C. W. Swallow and D. E. Kissel, 1989. A method to secure, leach and incubate
undisturbed soil cores. Soil Sci. Soc. Amer. 53:467-471.
Parlange, J., el al., 1988. The (low of pesticides through preferential paths in soils. New York's
Food and Life Sciences Quarterly. 18:20-23.
C L Perket, 1986. Quality Control in Remedial Site Investigation: Hazardous and Industrial
Solid Waste Testing, Fifth Volume ASTM-STP 925. American Society for Testing and Materials,
Philadelphia, PA.
Petenen, R, and L. Calvin, 1986. Sampling. Methods of Soil Analysis. Part I. Physical and
Mineralogical Methods (2nd edition). Soil Science Society of American. Agronomy Monograph
N. 9, pp. 33-52.
Rials, P., 1973. Unstable welting fronts in uniform and nonunifonn soils. Soil Science Society
of American Proceedings. 37:681-684.
Richards, L, 1931. Capillary conduction of liquids through porous media. Physics. Vol. 1.
Scott, and Clothier, 1983. A transient method for measuring soil water diffisivity and imuturaled
hydraulic conductivity. Soil Science Society of American Journal. 47:1068-1072.
Simpson. T, and R. Cunningham. 1982. The occurrence of flow channels in soils. Journal of
Environmental Quality. 1(1):29-30.
Starks, T. H., K. W. Brown, and N. J. Fisher, 1986. Preliminary Monitoring Design for Metal
Pollution in Palmerton, PA. In ASTM STP-925, C. Perket, EjL pp. 57-66. American Society for
Testing and Materials, Philadelphia, PA.
Steenhuis, T, and J. Parlange, 1988. Simulating preferential flow of water and solutes on
hillslopes. Conference on Validation of Flow and Transport Models for the Unsaturated Zone.
Ruidoso, New Mexico., May 23-26, pg. 11.
Sleenhuis, R, J. Parlange, M. Parlange, and F. Stagenitti, 1988. A simple model for flow on
hillslopes. Agricultural Water Management. 14:158-168.
-------
Taylor, 1950. The instability of liquid surface when accelerated in a direction perpendicular to
(heir planet Proceedings of Ac Royal Society. 201:192-195.
USDA, 1980. CREAMS; A field sole model for chemic.li, runoff, and erosion bom agricultural
management systems. W. KinscJ, £4 USDA Conservation Research Report. No, 26. pp. 640.
van dcr Ploeg, R,, and F. Beete, 1977. Model calculations for the eflraclion of soil water by
ceramic cups and plates. Soil Science Society of America Journal. 41:466-470.
Warner, G, and J. Nieber, 1968. CT scanning of macroporec in toil columns, WuUer Meetiflg
of American Society of Agricultural Engineers. Paper No, 88-2632. Presented at toe
International Winter Meeting at tbe Hyatt Regency, Chicago, Dec. 13-16,1988. pg. 13.
Warrick, A., and A. Amoozegar-Pard, 1977, Soil water regime* near poronc cup water samplers.
Water Resources Research, v. 13. pp. 203-207.
Warrick, A., D. Myers, and D. Nielsen, 1986. Geostatistic*! Methods Applied to Soil Science,
method* of Soil Analysis. Put 1, Physical uul Mineralogical Method* (2nd edition). Soil Science
Society of Amnerka. Agronomy Monograph. No. 9, pp. 53-82.
White, R., 1985, The influence of macropores on (he transport of dissolved and suspended
matter through toil. Advance! in Soil Science, Vol. 3., Springer Verlag New York, Inc.,
pp. 95-10.
Williams, L. R. et al,, 1989. Optimization of sampling for tbe determination of mean radium-
226 concentration in surface mil. Environ. Monit. Assessment 12:83-96.
Yaron, B, Z. Gcrtd, and W. Spencer, 1985. Behavior of herbicide* in irrigated toils. Advances
in Soil Science, Vol \ Springer Verlag New York, Inc., pp. 122-190.
Zipico, M. M., S. Valet, 1, Cherry, Summer 1987, A wireline piston core barrel for sampling
cohensionless und and gravel below the water table. Ground Water Monit. Rev., pp. 74-82.
SOIL GAS
Dcvitt, D. A., R. B, Evans, W, A. Jury, T. H, Stark*, B, Eklund, and A, Ghalsan, January 1988.
Soil Gas Seru-mg for Detection and Mapping of Volatile Organic*, USEPA-EMSL, Las Vegas,
NV. EPA 600/S8-87/036, 265 pp.
Everett, L. G., E. W. Hoyunan, L. O, WUson, and L. G. McMillan, 1984. Constraint* and
calegoriet of vadoce zone monitoring devices. Ground Water Monitoring Review, 4{l):26-32.
Kerfoot, H. B., and L. J, Barrowt, 1987, Soil-Gas Meaturement for Detection of Subsurface
Organic Contamination. USEPA, Lai Vegas, NV,
Kerfoot, H, B., J. A. Kofaout, and E, N. Amnkk, 1986. Detection and Measurement of Ground
Water Contamination by Soil-Gas Measurement. Proc. Conf. Hazardous Wastes and Hazardous
Materials, Hazardous Materials Control Research Institute, Silver Spring, Maryland, pp. 22-36.
MaciCay, D., and W, Y. Shiu, 1981. A critical review of Henry's Law constants for chemicals of
environmental interest. Journal of Physical Chemistry Reference Data. 10(4):1175-H99,
Marrin, D, L., and G. M, Thompson, 1984, Remote Detection of Volatile Organic Contaminants
in Groundwater Via Shallow Soil Gas Sampling, Proc. Coof. Petroleum Hydrocarbons and
Organic Chemicals in Groundwater. National Water Well Association, Dublin, Ohio, pp. 172*
187,
Marrin, D, L., 1985, Delineation of Gasoline Hydrocarbons in Groundwater by Soil Gas
Analysis. Proceedings Hazardous Material Management Conf./Weit Tower Conf. Management
Co., Whealon, Illinois, pp. 112-119.
Marrin, D. L., 1987, Soil Gas Analysis of CH,. Delineating and Monitoring Petroleum
Hydrocarbons. In Proc. of tbe NWWA/API Conference on Petroleum Hydrocarbons and
Organic Chemicals in Ground WAter — Prevention, Detection and Restoration, pp. 357-367.
Hyatt Regency, Houston, TX.
Marrin, D. L., 1987. Proceedings of the First National Outdoor Action Conference on Aquifer
Restoration, Ground Water Monitoring and Geophysical Methods, Las Vegas, NV, National
Water Well Association, pp. 137-154.
Marrin, D, L, and H. B. Kerfoot, 1988. Environmental Science and Technology. 22<7);740-
745.
Marrin, D, L, and G. M. Thompson, 1987, Gaseous behavior of TCE overlying a contaminated
aquifer. Journal of Ground Water, 25(l);21-27.
Spittler, T, M, L. Rich, and S. Clifford, 1985. A New Method for Detection of Organic Vapors
in the Vadose Zone, Proc. Conf, Characterization and Monitoring of the Vadose Zone. National
Water Well Association, Dublin, Ohio.
Swallow, J. A., and P. M. Gschwend, 1983. Volatilization of Organic Compounds from
Unconfined Aquifers. Proc, Symp, Aquifer Restoration and Ground Water Monitoring, National
Water Well Association, Dublin, Ohio, pp. 327-333.
Voorbees, K, J., J. C, Hkkcy, and R. W, Kinsman, 1984. Analysis of groundwater contamination
by a new static surface trapping/mass spcctrometry technique. Analytical Chemistry. 56:2604-
2607.
HYDRQPUNCH1*'
Cordrv, K., 1986. Ground Water Sampling Without Wells. Proceedings of the Sixth National
Symposium and Exposition on Aquifer Restoration and Ground Water Monitoring. NWWA-
AGWSE, Columbus, OH.
Edge, R, W., and Cordry, 1C, 1989. The Hydropunch'*': An in-situ sampling tool for collecting
ground water from unomsolidated sediments. Ground Water Monit. Review, v. 9, Summer, pp.
177-183.
-------
PART 3. GROUND-WATER SAMPLE COLLECTION AND DATA INTERPRETATION
A. General Considerations
1. Sampling strategies/evolving a network design-
2. Hydrogeologic and statistical considerations
3. Development of a preliminary sampling protocol, QA/QC
B. Ground-Water Sampling in Practice
1. Objectives and the preliminary sampling protocol
2. Analyte selection (i.e., contaminants, major ionic
constituents)
3. Sampling points and devices
4. Sampling experiment
5. Refined sampling protocol/refined hypotheses
C. Interpretation of Geochemical and Water Chemistry Data
1. Analytical performance, QA/QC, consistency checks
2. Major ion, trace constituents and background conditions
3. Contamination problems and comparisons with background
4. Recognition of interferences, gross errors, etc.
5. Dealing with snapshot data in a dynamic environment
6. Case studies
-------
TABLE II
Chemical constituents of interest in ground-water monitoring
Cype of analyte Analyte
-itochemical pH. Eh
Conductivity
Temperature
Dissolved oxygen
Alkalinity
Ca**,Mg**
Na*. K*
a-, so4-. PO«-
Silicate
Vattr Quality Trace Metals
(Fe. Mn
Cr, Cd
Pb, Cu)
NO,-, NH4*
F-
TOC
TOX
TDS
Organic
Compounds
Laboratory /Field
determination L or F
F
F (Field Filtered, FF)
L (Field Filtered, FF)
L (Field Filtered, FF)
F (Field Filtered, FF)
L (Field Filtered, FF)
L
(FF)
L(FF)
LOT)
L
L
(FF)
L
Information applications
Water quality
X
X
X
X
X
X
X
X
X
X
X
Drinking H2O
suitability
X
X
X
X
X
X
X
X
X
X
Contamination
indicators
X
X
X
X
X
X
X
X
X
Possible source
impacts
X
X
X
X
X
X
X
X
X
X
Geochemical
evaluation of
data
X
X
X
X
X
X
X
X
X
GROUND WATER SAMPLING (FOR ANALYSIS)
o Sampling in the "dark" given significant unknowns
o Most efforts are regulatory, legal or assessment for
remedial action
o Trace organic and inorganic overemphasized
o Little or no treatment of "master" variables, major
ionic constituents
o Solids, colloids, hydrogeochemical effects virtually
ignored
-------
GROUND-WATER SAMPLING AS A SELECTION PROCESS: PROTOCOL DEVELOPMENT
o Preliminary-Establish Hydrogeologic Basis
(hydraulic gradient, velocity-magnitude and direction)
o Location of Sampling Points
o Well Design, Drilling, Construction/Development
o Purging of Stagnant Water
• Sampling
• Sample Handling/Field Analysis
• Sample Storage
o Refine Protocol on the Basis of New Information
— level of detail, time/resources, certainty required
TABLE I—Ground-water quality monitoring network design activities.
Stage
Activity
Detective work
Preliminary nctwort design
Working network design
Refine network design
and sampling protocol
Study site characterization
facility operations/land use
hydrogeologic
geochemical
Scope of network purpose and parameter selection
quality assurance/quality control
detection
assessment
Sampling points
well placement and construction
well development and performance evaluation
Preliminary sampling protocol
sampling mechanism and material selections
water level measurements
well purging
sample collection
sample filtration/preservation
field determinations, blanks, standards
sample storage/transport
Analytical operations
Interpret chemical and hydrologic results
-------
Table 1.1. Data Requirements for Water-Source Definition and
Aquifer Representation of Ground-Hater Samples
(Modified after Claassen, reference 31)
A. Drilling history
1. Well depth and diameter
2. Drill-bit type and circulating fluid
3. Lithologlc data from cores or cuttings
4. Well-development before casing
5. Geophysical logs obtained
B. Well-completion data
1. Casing sizes, depths and leveling information relative to
both land surface and top of casing
2. Casing material(s)
3. Cemented or grouted intervals and materials used
4. Plugs, stabilizers, and so forth, left in hole and
materials used
5. Gravel packing: volume, sizes, and type of material
6. Screened, perforated, or milled casing or other intervals
which allow water to enter the borehole
7. Pump type, setting, intake location, construction
materials, and pump-column type and diameter
8. Well maintenance record detailing type of treatment and
efficiency
C. Well pumping history
1. Rate
2. Frequency
3. Static and pumping water levels
D. Estimation of effect of contaminants Introduced into aquifer
during well drilling and completion on native water quality
E. Effect of sampling mechanism and materials on the composi-
tion of ground-water sample
1. Addition of contaminants
2. Removal of constituents
a. Sorptlon
b. Precipitation
c. Degassing
-------
— GROUND WATER SAMPLING: TOPICS OF SPECIAL INTEREST
Well Casing: Geochemical Disturbance, long-term Fe^* trends
Well Purging: Making the Hydrologic Connection, Gross Errors
Sampling Devices: Reproducibility and Minimizing Systematic Error
Tubing: Gas Permeability and Oxidation
Filtration: Truly Dissolved Constituents, Colloids, Artefacts
Storage: Keep it on ice!
-------
WELL CASING:
O SCREEN DESIGN AND DURABILITY MOST IMPORTANT.
O INEVITABLE DISTURBANCE DURING DRILLING.
O AVOID MUDS OR DRILLING FLUIDS.
O PLACE GROUTS AND SEALS CAREFULLY.
O LONG-TERM GEOCHEMICAL EFFECTS POSSIBLE.
O ALL MATERIALS SORB TO SOME EXTENT.
WELL PURGING:
JO --
Ft
Iti
orr*
O CALCULATED PURGE REQUIREMENTS; VERIFY BY MEASUREMENTS
OF pH, fl-1, T, (02, Eh).
O ESTABLISH HYDRAULIC CONNECTION BETWEEN SYSTEM AND
SAMPLING POINT.
O BE CONSISTENT AND DOCUMENT RESULTS.
-------
COA/C.
100
_ //L
IT
4 * it/net es
u-r«*
if
so
TABLE 3
METALS DETECTION LIMITS (PPM)
Cadnlum(O.Ol) Magne*iun(0.lO)
Ctlcium(O.lO) Nick«|(0.05)
Chroniuni(O.lO) Sodium(O.lO)
Copper(O.lO) Zinc(O.lO)
Lead(O.SO) Uraniun(O.S)
Iron(O.SO)
Monitor Well MSB 3A
Metal i Data In ppm
Well Volumes
Ca
F«
Mf
N2
Zn
0
2
*
6
8
10
6.70
8.57
8.37
8.27
8.09
8.47
0.22
0.30
1.08
0.26
0.3S
0.50
1.91
2.68
2.67
2.59
2.58
2.60
18.80
10.20
10.50
9.76
9.88
10.10
0.12
0.15
0.16
0.15
0.13
0.13
-------
100
80
ui 60
O
I-
ui
O
tr
ui
a.
40
20
620.0 m2/day
Q « 500 mL/min
DIAMETER = 5.08 cm
I I I
10 15 20
TIME, minutes
25
30
Figure 2.15. Percentage of aquifer water versus
time for different transmissivities
Example 2.4. Well purging strategy based
on hydraulic conductivity data
Given:
48-fbot-deep, 2-inch-diameter well
2-foot-long screen
3-foot-thick aquifer
Static water level about 15 feet below land surface
Hydraulic conductivity = 10"2 cm/sec
Assumptions:
A desired purge rate of 500 mL/min and sampling rate of 100 mL/
min will be used.
Calculations:
One well volume
(48 ft - 15 ft) x 613 mL/ft (2-inch-diameter well)
20.2 liters
Aquifer transmissivity
hydraulic conductivity x aquifer thickness
10"* m/sec x 1 meter
10-" mVsec or 8.64 m'/day
From Figure 2.15:
at 5 minutes ~95% aquifer water and
(5 min x 0.5 L/min)/20.2 L
= 0.12 well volumes
at 10 minutes ~100% aquifer water and
(10 min x 0.5 L/min)/20.2 L
• 0.24 well volumes
-------
RIGID MATERIAL RECOMMENDATION
PURPOSE OF PROGRAM
SUBSURFACE
CONTAMINATION
CONDITIONS
UNKNOWN
PTFE
SS
PVC
IMPORTANCE OF
TRACE LEVEL
ORGANICS
DETECTIVE
ASSESSMENT
HIGH
INORGANIC
SUSPECTED
PTFE
SS
PVC
HIGH ORGANIC
OR INORGANIC
SUSPECTED
COULD PPB LEVEL
ORGANICS BE IMPORTANT?
HIGH ORGANIC
NO ORGANIC
KNOWN
PTFE
PVC
SS
HIGH ORGANIC
AND/OR INORGANIC
KNOWN
PTFE
SS
YES/
jPTFEl
|ss |
PTFE - polytetrafluoroethylene
SS - stainless steel (316 or 301)
PVC - polyvinyl chloride
FIG. Ib—Example decision tree for recommended well-casing/screen materials (adapted from Kef 13).
SAMPLING MECHANISM RECOMMENDATION
LIFT REQUIREMENTS
FLOW RATE
VARIABILITY OF MECHANISM
(PURGING AND SAMPLING)
ARE
PARAMETERS Of
IKTEllEST
VOLATILE.
OH pH SENSITIVE?
IMITED
NO YES
NO GAS CONTACT
P-D BLADDER
P-D MECHANICAL
NO CAS CONTACT:
P-D BLADDER
P-D MECHANICAL
OR
GAS-DRIVE
CENTRIFUGAL
PERISTALTIC
SUCTION
THIEF
- INCOMPLETE -
FIG. 3—Example decision tree for recommended purge and sampling mechanism (adapted from Kef 13).
-------
Type or
constituent
Volatile
Organic
Coipounda
Organoew tall lea
Olaaolved Caaea
Mail-Purging
Parameters
Traea Inorganic
Natal Spec lea
Deduced Spec lea
Major Catloaa
A Anlona
Example of
constituent
Chloroform
TOX
OtjHg
Oj, C02
pH, O"1
CD
Fe. Cu
M0j~, S"
Ma*, r. Ca**
Mf**
cr, so.-
bladder pvaipa
t .
I
N
C
It
E
A
S
I
1
C
S
A
H
r
L
C
S
I
1
S
I
T
I
¥
I
T
I
Superior
perforaiance
for eoat
applleatlona
Superior
performance
for aoat
applleatlona
Superior
performance
for most
applleatlona
Superior
performance.
for moat
applleatlona
Thief, In al tu or
ballera
INCREASING HELIABI
Hay be adequate If
well purging la
aaaured
Hay be adequate If
well purging la
aaaurad
May be adequate If
well purging la
uaured
Adequate
Hay be adequate If
well purging la
aaaured
Mechanical poalttva.
displacement pumpa
Gaa~drl ve
devlcea
Suction
ITT OF SAMPLING MECHANISMS
May be adequate If
dealgn and operation
are controlled
Hay be adequate If
dealgn and operation
are controlled
Adequate
Adequate
lot
recommended
lot
recommended
Hay be
adequate
Adequate
lot
recommended
Not
recommended
May be ade-
quate If
•aterlala
are approp-
riate
Adequate
TABLE 2—Matrix of sensitive chemical constituents and various sampling mechanisms (from Kef 3).
SAMPLING DEVICES:
O MOST ACCURATE AND REPRODUCIBLE; BLADDER PUMPS
O MOST RELIABLE AND EASY TO DIAGNOSE MALFUNCTION
O DEDICATION TO THE WELL AVOIDS CROSS-CONTAMINATION AND
FIELD DECONTAMINATION
-------
200
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
TIME (min) TIME (min)
FIG- l—Concenn-ation of sorbed chlorinated organic*. The torbed concentration (\t-g-m'1 of the four lest
compounds from distilled water solutions is shown as a function of time in exposure to tubing materials: (a)
chloroform, (b) trichloroethane, (c) rrichloroethylene. (d) tetrachloroethylene. Dissolved concentrations were
initially between 90 and 120 ppb of each compound (from Kef 22).
SAMPLING TUBING:
o OXYGEN PERMEABILITY MAY GIVE RISE TO BIASED RESULTS
FROM DEEP INSTALLATIONS.
o RAPID SORPTION OF ORGANIC COMPOUNDS A CONCERN.
-------
Table 7-9. Frequency of Occurrence of Phthalate Esters
in Wastewater and Ground-Water Samples
N. Y. state "Superlund"
Industrial public water monitoring
Phthtlates westewtters supply wells tamp 195
bis-(2-ethylhexyl) phthalate 42% 98% 0%
Dibutyl phthalate 19 72 4.8
Diethyl phthalate 8 35 1.9
Butytbenzyl phthalate 8 26 < 1
Dioctyl phthalate 6 11 1.1
Number of Samples 2532-2998 56 1150
-------
"0153 5 7 9 11 15 18 24
TIME (HOURS)
Rjurr •». firU rr/rirrrolKm oftamfla with M«IT irr.
18
16
14
-. 1
gi
H 8
6
4
2
0 4 8 12 16 20 24 28
TIME (HOURS)
fijwr S. Santa /iirrj in rnoW Irr rhiM » •! *C «mJ mnH/mra w n» irr rkra
inrkilnl w*k Hue irr.
25
20-
15
a 10
12
24
Tlm» (hrs.)
36
SAMPLE STORAGE:
O CHILL WITH WATER, ICE OR MECHANICAL REFRIGERATION
IMMEDIATELY.
O TRANSPORT RAPIDLY AND OBSERVE CHAIN OF CUSTODY PROCEDURES.
O ARTIFICIAL ICE-PACKS ALONE DON'T WORK.
-------
TABLE 4—Potential contributions of sampling methods and materials to error" in ground-water chemical results.
ameter
C
ill)
litile
janic
impounds
Concentration,
units
5-9 pH units
0.5-25
mg-C-L-'
0.01-10 mg-L-'
0.5-15 u.g-L-'
80-8000 u,g-L-'
Drilling Grouts. Well Well
Muds Seals Purging Casing
... + , 4 to 5 units ± . 0. 1 to 4
cement units
-t- , 300* ... ± , 500* ± , 200*
- .» 500* - ,' 1000* + . 1000*
cement iron.
galvanized
steel
±. 10 to 100* ±, 200*
Sampling
Mechanism
gas lift + .
0.1 to 3
units
bailer + ,
150*
gas lift - .»
500*
suction - .'
1 to 15*
Sampling
Tubing References
10. 11. 14
Table 1 . 10
2. 10. 11.
14
10
- 10 to 75* 20. 21
1 Bias values exceeding > ± 100* denoted as gross errors (+ or -); other values expressed as percent of reported mean.
' No data available on the type and extent of error for this parameter.
CONCLUSIONS:
O SAMPLING ERRORS CAN BE CONTROLLED IF LOCATION, SAMPLING-POINT
DESIGN AND CONSTRUCTION ARE DONE PROPERLY.
O PURGING IS THE SINGLE-MOST IMPORTANT STEP IN SAMPLING.
O SAMPLING AND ANALYTICAL PROTOCOL DEVELOPMENT SHOULD BE PHASED
AND REFINED AS DETAIL REQUIRES.
O ANALYTICAL ERRORS CAN BE CONTROLLED WITH PROPER QA/QC.
O "NATURAL" VARIABILITY CAN BE ESTIMATED WITH QUARTERLY SAMPLING;
SEASONAL VARIATIONS MAY TAKE YEARS OF SUCH SAMPLING TO RESOLVE.
-------
TABLE 3—Generalized ground-water sampling protocol.
Step
Goal
Recommendations
Hydrologic measurements
WeU purging
Sample collection
Filtration/preservation
Field determinations
Field blanks/standards
Sampling storage/transport
establish nonpumping water level
removal or isolation of stagnant
HjO which would otherwise
bias representative sample
collection of samples at land sur-
face or in well-bore with min-
ima] disturbance of sample
chemistry
filtration permits determination of
soluble constituents and is a
form of preservation. It should
be done in the field as soon as
possible after collection
field analyses of samples will ef-
fectively avoid bias in deter-
minations of parameters/con-
stituents which, do not store
well: for example, gases, al-
kalinity. pH
these blanks and standards will
permit the correction of ana-
lytical results for changes which
may occur after sample collec-
tion: preservation, storage, and
transport
refrigeration and protection of
samples should minimize the
chemical alteration of samples
prior to analysis
measure the water level to ±0.3
cm (±0.01 fr)
pump water until well purging
parameters (such as pH, T,
n-'. Eh) stabilize to ±10%
over at least two successive
well volumes pumped
pumping rates should be limited
to —100 mL/min for volatile
organics and gas-sensitive pa-
rameters
filler, trace metals, inorganic an-
ions/cations, alkalinity
do not filter: TOC, TOX, volatile
organic compound samples;
other organic compound sun-
pies only when required
samples for determinations of
gases, alkalinity and pH should
be analyzed in the field if at all
possible
at least one blank and one standard
for each sensitive parameter
should be made up in the field
on each day of sampling. Spiked
samples are also recommended
for good QA/QC
observe maximum sample hold-
ing or storage periods recom-
mended by the Agency. Doc-
umentation of actual holding
periods should be carefully per-
formed
• 1 ft - 0.304S m.
B. Ground-Water Sampling in Practice
1. Objectives and the preliminary sampling protocol
2. AnaJyte selection (i-e., contaminants, major ionic
constituents)
3. Sampling points and devices
4. Sampling experiment
5. Refined sampling protocol/refined hypotheses
-------
STEP
Hydrologic
Measurements
Well Purging
Sample Collection
Filtration/
Preservation
Field Determinations
Reid Blanks/
Standards
Sampling Storage/
Transport
GOAL
Establishment of nonpumping
water level.
Removal or isolation of stagnant
H;,0 which would otherwise bias
representative sample.
Collection of samples at land
surface or in well-bore with
minimal disturbance of sample
chemistry.
Filtration permits determination of
soluble constituents and is a
form of preservation. It should be
done in the field as soon as
possible after collection.
Field analyses of samples will
effectively avoid bias in
determinations of parameters/
constituents which do not store
well: e.g., gases, alkalinity, pH.
These blanks and standards will
permit the correction of analytical
results for changes which may
occur after sample collection:
preservation, storage, and
transport.
Refrigeration and protection of
samples should minimize the
chemical alteration of samples
prior to analysis.
RECOMMENDATIONS
Measure the water level to ±0.3
cm (±0,01 ft).
Pump water until well purging
parameters (e.g., pH, T, IT1, Eh)
stabilize to ± 10% over at least
two successive well volumes
pumped.
Pumping rates should be limited
to ~ 100 mL/min for volatile
organics and gas-sensitive
parameters.
Filter: Trace metals, inorganic
anions/cations, alkalinity.
Do not Ulter: TOC, TOX, volatile
organic compound samples. Filter
other organic compound samples
only when required.
Samples for determinations of
gases, alkalinity and pH should
be analyzed in the field if at all
possible.
At least one blank and one
standard for each sensitive
parameter should be made up in
the field on each day of
sampling. Spiked samples are
also recommended for good QA/
QC.
Observe maximum sample
holding or storage periods
recommended by the Agency.
Documentation of actual holding
periods should be carefully
performed.
Rgura 2.16. Generalized ground-water sampling protocol
-------
STEP
PROCEDURE
ESSENTIAL ELEMENTS
Well Inspection
Well Purging
Sample Collection
Filtration*
Field
Determinations"
Preservation
Field Blanks
Standards
Hydrologic Measurements
I
Removal or Isolation of Stagnant Water
I
Determination of Well-Purging Parameters
(pH, Eh, T, IT')"
Unfiltered
Field Filtered*
\tolatile Organics, TOX
I
Dissolved Gases, TOC
I
Large Vtolume Sam-
ples for Organic
Compound Determi-
nations
Assorted Sensitive
Inorganic Species
NOr, NH,*, Fe(ll)
(as needed for good
QA/QC)
Alkalinity/Acidity**
Trace Metal Samples
S", Sensitive
Inorganics
Water-Level
Measurements
Representative Water
Access
Verification of
Representative Water
Sample Access
Sample Collection by
Appropriate Mechanism
Minimal Sample Handling
Head-Space
Free Samples
Minimal Aeration or
Depressurization
Minimal Air Contact,
Field Determination
Adequate Rinsing against
Contamination
Minimal Air Contact,
Preservation
Storage
Transport
Major Cations and
Anions
Minimal Loss of Sample
Integrity Prior to Analysis
* Denotes samples which should be filtered in order to determine dissolved constituents. Filtration
should be accomplished preferably with in-line filters and pump pressure or by N2 pressure
methods. Samples for dissolved gases or volatile organics should not be filtered. In instances
where well development procedures do not allow for turbidity-free samples and may bias analytical
results, split samples should be spiked with standards before filtration. Both spiked samples and
regular samples should be analyzed to determine recoveries from both types of handling.
** Denotes analytical determinations which should be made in the field.
Figure 3.1. Generalized flow diagram of ground-water sampling steps
-------
Table 3.1. Recommended Analytical Parameters for Detective Monitoring
Type ot determination
Type of parameter Lab. (L), Field (F)
Well-purging F
Contamination
indicators
Water quality*
Drinking water
suitability"
L
L
L
L
L
Anaiytes
Required by regulation
pH, conductivity (Q~')
pH, O-1
Total organic carbon (TOC)
Total organic halogen (TOX)
Cr, Fe, Mn, Na*, SCV
Phenols
As, Ba.Cd, Cr, F~, Pb, Hg,
NO,-, Se, Ag
Endrin, lindane, methoxychlor,
toxaphene
2,4-D, 2,4,5-TP (Silvex)
Radium, gross alpha/beta
coliform bacteria
Suggested lor
completeness
Temperature (T)
Redox poteniial (Eh)
Alkalinity (F) or
acidity (F)
Ca~, Mg~, K*.
P0«-, silicate,
ammonium
we;
10°-
10
2-
10
6-
_ X
o N
.-• — •
W 2
\
N
10
10
10
10
10
.10
r 10
. 1
(D)
100 '
80
60
40
20
10
1.0
.8
.6
.4
(N)
.05-
.08-
.10-
.15-
.20-
.30
.40
.50
F -ON
864 Ki
Example (clean sand)
K - 10'T
i « 10~*
N - 0.30
D • 0.4 meters
Figure 2.8. Sampling fr«qu«ncy nomograph
-------
C Interpretation of Geochemical and Water Chemistry Data
1. Analytical performance, QA/QC, consistency checks
2. Major ion, trace constituents and background conditions
3. Contamination problems and comparisons with background
4. Recognition of Interferences, gross errors, etc.
5. Dealing with snapshot data in a dynamic environment
6. Case studies
Sample type
Alkalinity
Anions
TOC
TOX
\folatiles
Volume
50 mL
1 L
Cations 1 L
Trace metals 1 L
40 mL
500ml
40 mL
Extractables A 1 L
Extractables B 1 L
Extractables C 1 L
' « 75.25 Water/Polyethylene
" • Glass Distilled Methanol
Table 2.10. Field Standard and Sample Spiking Solutions
Composition
Na*. HCCV
K*, Na*, Cr, SO.'
F-, NO,-, PO.-, SI
Na*, K*
Ca**, Mg**, Cr, NO3-
Cd**, Cu**, Pb**
Cr***, Ni2*, Ag*
Fe***, Mn**
Acetone
KHP
Chloroform
2,4,6 Trichlorophenol
Dichlorobutane, Toluene
Dibromopropane,
Xylene
Phenol Standards
Polynuclear Aromatic
Standards
Standards
as required
Glycol (400 amu) Mixture
Field standard
(concentration)
10.0; 25 (ppm)
25, 50 (ppm)
5.0; 10.0 (ppm)
10.0; 25.0 (ppm)
0.2; 0.5 (ppm-C)
1.8; 4.5 (ppm-C)
12.5; 25 (ppb)
12.5; 25 (ppb)
25; 50 (ppb)
25; 50 (ppb)
25; 50 (ppb)
field
So/vent
H20
H?O
H2O, H* (acid)
H20, H* (acid)
H20
H,0/poiy
(ethylene glycol)
H20/poly'
(ethylene glycol)
Methanol"
Methanol
S(oc*t solution lor
spike of split samples
Concentration ol
components
10.000; 25,000 (ppm)
25,000; 50,000 (ppm)
5,000; 10,000 (ppm)
10,000; 25,000 (ppm)
200; 500 (ppm-C)
1 ,800; 4,500 (ppm-C)
12.5; 25.0 (ppm)
12.5; 25.0 (ppm)
25; 50 (ppm)
25; 50 (ppm)
25; 50 (ppm)
Field spike
volume
(50 uL)
( 1 mL)
( 1 mL)
( 1 mL)
(40 ML)
(500 nl)
(40 ML)
( 1 mL)
( 1 mL)
25; 50 (ppb)
Methanol
25; 50 (ppm)
( 1 mL)
-------
STEP
Samples, from Storage
Field Blanks and Standards
\
Subsampling
Procedural Standards
I
Analytical Separation
Analysis
Reference Standards
I
Calculations
Results
SOURCES OF ERROR
"Aged" samples; loss of analytes;
contamination
Sample aging/contamination in lab; cross-
contamination; mishandling/labeling
"Aged" standards; analyst error
Matrix interferences; inappropriate/
invalid methodology; instrumental
malfunction/analyst error
Matrix interference; inappropriate/
invalid methodology; instrumental
malfunction/analyst error
"Aged" standards
Transcription/machine errors; sample loss in
tracking system; improper extrapolation/
interpolation; over-reporting/
under-reporting errors
Figure 1.2. Steps in water sample analysis and sources of error
STEP
In-Situ Condition
t
Establishing a Sampling Point
I
Field Measurements
t
Sample Collection
Sample Delivery/Transfer
I
Field Blanks, Standards
I
Field Determinations
Preservation/Storage
Transportation
SOURCES OF ERROR
Improper well construction/placement;
inappropriate materials selection
Instrument malfunction; operator error
Sampling mechanism bias; operator error
Sampling mechanism bias; sample exposure,
degassing, oxygenation; field conditions
Operator error; matrix interferences
Instrument malfunction; operator error;
field conditions
Matrix interferences;
handling/labeling errors
Delay; sample loss
Figure 1.1. Steps in ground-water sampling and sources of error
-------
CASE STUDY - WOOD PRESERVING SITE (Franks et al., 1985)
• CREOSOTING FACILITY OPERATED BETWEEN 1902 AND
1981
• SURFICIAL SAND/GRAVEL AQUIFER - PENSACOLA BAY
• PRIMARY CONTAMINANTS
PHENOLS 0.00 to 116 mg/L
ORG. N COMPOUNDS 0.00 to 88 mg/L
PAH's 0.00 to 19 mg/L
(naphthalene, indene)
CH« 0.0 to 14 mg/L
• BOTH UPPER WATER TABLE ZONE AND DEEPER
CONFINED ZONE AFFECTED TO DEPTHS OF 25 M
EXPLANATION
ALTITUDE Of WATER
TAILE. CONTOUR
INTERVAL I FOOT.
DATUU II IE* LEVEL.
-------
CASE STUDY - WOOD PRESERVING SITE
• 1983 monitoring results, from up to 45 sampling points,
emphasized shallow water table aquifer contamination (at levels In
excess of 1 mg/L)
• "Affected'Volume: Naphthalene 4.1 x 10s mj
Phenols 3.5 x 10* mj
CH4 7J x 105 m1
• Other 'plume' effects: pH -5.4
TDS-350
Dissolved Oxygen -0
• H,S, NH,, Fe, DOC variable
CASE STUDY - WOOD PRESERVING SITE
• 1985 monitoring results, from up to 75 sampling points disclosed
extensive contamination of the lower confined zone as well.
• On-site analyses Identified organic nitrogen compounds and much
more 'rapid* migration of naphthalene and CH4 than predicted.
• The 'affected volume' of water table aquifer contamination
Increased by 49% (naphthalene), 66% (phenols) and 100% (CHJ
over previous levels.
• Nearly 1.4 x 10* m1 of contaminated material and H2O
-------
WATER TABLE ZONE
NAPHTHALENE
WATER TABLE ZONE
TOTAL PHENOLS
M 1-10
-------
MONTTDRTKG .. CASF CTT mv
WISCONSIN -DNR
• 25 LANDFILLS (19 MUNICIPAL, 6 INDUSTRIAL)
- EXTENT OF VOC CONTAMINATION
- OCCURRENCE OF INDIVIDUAL VOC'S
AND CONTAMINATION
°F ^ORGANIC PARAMETERS
AS CONTAMINANT INDICATORS
- PRACTICES IN OTHER STATES
WDNR STUDY
CONDITIONS
1 •UPGRADIENT WELL, A NUMBER OF DOWNGRADIENT
WELLS AT EACH SITE
-90% OF THE WELLS AT WATER TABLE WITH 10 TO 15'
SCREENS
-10% SEALED BELOW THE WATER TABLE
•
-95% OF THE WELLS WITHIN ISO' DISTANCE FROM LANDFILL
CELLS
PROTOCOL
. BAILER SAMPLING AFTER PURGING 4 WELL VOLUMES
• FOUR VOC SAMPLES FROM EACH BAILER
. EXPANDED ANALYTES (COD, CT, tl\ ALK, HARDNESS)
• CAREFUL, CONSISTENT PROCEDURES
-------
WDNR STUDY
RESULTS
• -2.5 WELLS/LANDFILL ON THE AVERAGE
• 15/19 SITES HAD CONTAMINATED GROUND WATER
• 32/79 SAMPLES HAD DETECTABLE VOC'S
• DCA, DCE, VCM. BZ, PER, TCE, TOC MAJOR
CONTAMINANTS
• RELIABLE SAMPLES COULD BE TAKEN AT LEVEL OF
-1/ig/L
• NAP, FREONS, ACETONE, DIMETHYLSULFIDE COMMONLY
OBSERVED
• INORGANIC CONSTITUENTS COINCIDE WITH VOC
DETECTS IN 41% OF SAMPLES
WDNRSTUDY
RESULTS
MOST LIKELY CONTAMINATED SITUATION
• MUNICIPAL, UNLINED, NO CONTAMINANT OR
LEACHATE COLLECTION IN COARSE OR "MIXED"
SURFICIAL RATHER THAN FINE DEPOSITS (NO
CORRELATION WITH AGE OF FILL, DEPTH, DEPTH
TO BEDROCK OR BEDROCK TYPE)
OTHER STATES? (MORE THAN 3,000 LANDFILLS)
• -2/3 REQUIRE SOME SAMPLING
(-25% ON A ROUTINE BASIS)
-1/3 HAVE BEEN SAMPLED FOR VOC'S
FEW REQUIRE MORE THAN ANNUAL FREQUENCY
-------
FIGURE 8. VOC MONITORING STRATEGIES NATIONWIDE (BY STATES).
CASE-BY-CASE R§] ROUTINED MIXED• NO SAMPLING
-------
CASE STUDY NO. 1
Dominant VOC Distribution at
Well Locations
LEGEND
Unique Well Types
« 1,1,2-Trichloroethane
• Trichloroethylene
• Trlchloromethane
a Dichloromethane
Tetrachloroethytene
Tetrachloromethane
• 1,2-Transdlchloroethene
o No Organlcs
WMI CASE STUDY 1984
• LARGE LANDFILL, EVAPORATION/ACID NEUTRALIZATION
PONDS SITE
• FORTY-FOUR WELLS OVER AREA OF 3.6 X 10s M*
• REASONABLY CONTROLLED SAMPLING/ANALYSIS
PROTOCOLS
• ARE YOG'S GOOD TRACERS, CONTAMINATION
INDICATORS
-------
WMI CASE STUDY
RESULTS
-20% OF "UPGRADIENT WELLS CONTAMINATED
(TCA, TCE)
-50% OF "DOWNGRADIENT" WELLS CONTAMINATED
(TCA, TCE, CLF, PER, DCE)
-30% OF "DOWNGRADIENT", OFFSITE WELLS
CONTAMINATED (TCA, TCE)
ISOLATED DETECTS FOR NONVOLATILES (PHENOLS)
VOCS REASONABLE TRACERS FOR 'DETECTION*
(RARELY ONE OR TWO COMPOUNDS)
WMI CASE STUDY
'REMEDIATION' MEASURES
• LOWER GROUND-WATER MOUND
• POND DRAINAGE, SLUDGE REMOVAL, BACKFILLED
AND CLAY COVERED
'REMEDIATION* SUCCESS
• VOCS NOT MEASURABLY REDUCED
(MOST CONCENTRATIONS >1000 PPB VOC'S)
• Cr REDUCED SOMEWHAT NEAR ACID PONDS
• IMPROPERLY PLUGGED EXPLORATORY BOREHOLES
A LIABILITY
-------
DETECTION LIMITS (ASTM Recommendations)
THREE TREATMENTS
• HEAVILY CENSORED #1
• NEGATIVELY CENSORED #2
• ACTUAL RESULTS #3
DETECTION LIMITS (ASTM) - EXAMPLE
HEAVY
<3/ig
<3
<3
4
3
<3
<3
<3
<3
<3
NEGATIVE
2/ig
0
0
4
3
0
1
0
0
2
UNCENSORED
2Mg
-2
-1
4
3
-3
1
-1
0
2
DETECTION LIMITS (ASTM) - EXAMPLE
fl Average - 3.5 pg
(ARE CONSTITUENTS PRESENT OR NOT?)
f2 Average - 1.2 pg
95Z Confidence 0.14 to 2.26 pg
(CONTAMINATED!)
#3 Average — 0.5 pg
951 Confidence -1.13 to 2.13 pg
(DATA EQUIVOCAL!)
• PRUDENT TO REPORT LESS THAN ZERO VALUES AS TRACE
-------
PART 3
OA/OC EVALUATION
American Chemical Society, 1980. "Guidelines for Data Acquisition and Data Quality
Evaluation." ACS Committees on Environmental Improvement and Environmental Analytical
Chemistry. Analytical Chemistry, 52, 2242-2249.
American Society for Testing and Materials, 1987. Intralaboratory Quality Control Procedures
and a Discussion on Reporting Low-Level Data. ASTM D4210-83, Vol. 11.01, p. 9-18. ASTM,
Philadelphia, PA.
Campbell, J. A. and W. R. Mabey, 1985. A systematic approach for evaluating the quality of
ground water nonitoring data. Ground Water Monit. Review, Fall 1985, pp. 58-62.
Einerson, J. H. and P. C. Pei, 1988. A comparison of laboratory performances. Environ. Sti.
and Techno!., 22, 10, 1121-1125.
Kirchmer, C. J., 1983. Quality control in water analyses. Environmental Science and Techn. 17,
4, 174A-181A.
DATA REPORTING
Gilliom, R. J., R. M. Hirsch and E. J. Gilroy, 1984. Effect of censoring trace-level water-quality
data on trend detection capability. Environ. Sci. and Techn. !£, 7, 530-535.
McBean, E. A. and F. A. Rivers, 1984. Alternatives for handling detection limit data in impact
assessments. Ground Water Monit. Review, Spring 1984, 42-44.
Porter, P. S., R. C. Ward, and H. F. Bell, 1988. The Detection Limit. Environ. Sci. & Technol.
22, 8, 856-873.
Winefordner, J. D. and G. L. Long, 1983. Limit of detection - A closer look at the IUPAC
definition. Analyt. Chem. 5_5_, 7, 712A-724A.
-------
SESSION III
Characterization of Subsurface Physiochemical Processes
Dr. Carl D. Palmer
Dr. Carl D. Palmer is an assistant professor in the Department of Environmental Science and Engineering
at the Oregon Graduate Center. He received his Ph.D. in Hydrogeology in 1983 from the Department of
Earth Science at the University of Waterloo, Waterloo, Ontario. Dr. Palmer's research activities has
involved modeling of aqueous geochemical systems, the use of tracer tests, heat transport in the subsurface,
ground-water monitoring, and modeling. He is currently developing innovative methods for enhancing
remedial activity at hazardous waste sites, studying geochemical controls on the transport and fate of
chromium, developing methods for aquifer characterization, and addressing groundwater monitoring issues.
Dr. Palmer was a speaker at the U.S. EPA workshop on the "Transport and Fate of Contaminants in the
Subsurface" that was held in each of the EPA regions during 1987/88. He is coauthor of five chapters in
an EPA document of the same title. Dr. Palmer is editor and author of a book entitled. The Chemistry
of Groundwater that is to be published next year by Lewis Publishers.
I. INTRODUCTION/OVERVIEW
II. ORGANIC CONTAMINANTS
A. Processes
1. Abiotic degradation
2. Biotic degradation
3. Dissolution
4. Sorption of neutral, nonpolar, hydrophobic compounds
a. Isotherms
b. Definition of Kp
c. Role of Soil Organic Carbon
d. Linear Retardation
B. Method for Determining Kp
1. Correlation Equations
a. K,,,. versus solubility
b. K,,,. versus octanol/water partition coefficient
c. Organic Carbon
2. Batch Tests
a. General Methodology
b. Soil Preparation
c. Non-settling Particles
3. Column Tests
4. Field Data
5. Comparison
C. Other Considerations
1. Nonlinear Isotherms
2. lonization
3. Cosolvent Effects
4. Kinetics
-------
CHARACTERIZATION OF SUBSURFACE
PHYSICOCHEMICAL PROCESSES
ORGANIC
CONTAMINANTS
CHEMICAL PROCESSES AFFECTING
ORGANIC CONTAMINANTS
• ABIOTIC DEGRADATION
• BIOTIC DEGRADATION
• DISSOLUTION
• SORPTION
• IONIZATION
DNAPL SPILL
TRANSPORT OF REACTIVE SOLUTES
DNAPL SOURCE
uuu
After Feenstra and Cherry,
19BB.
9X?
Dispersive
Term
ax
Advectlve
Term
9C
at -
Chenge In
Mess per
Unit Him
+ RXN
Reaction
Term
-------
SORPTION ISOTHERMS
• LANGMUIR
• FREUNDLICH
• LINEAR
LANGMUIR ISOTHERM
AQUEOUS CONCENTRATION
FREUNDLICH ISOTHERM
= KCa
SOLUTION CONCENTRATION
1200
800
£ W
8§
Q 3,
in —
CD
400
1,1,1-THICHLOROBTHANE
1,1A2-TErRACHLOROCTHANE
1.2-DICHLOROETHANE
0 400 tOO 1200 1600 2000 2400
AQUEOUS CONCENTRATION (ug/L)
-------
iaoo
eoo
ADSORPTION ISOTHERMS FOR
NONPOLAR ORGANICS
ARE LINEAR IF
C < 10"6M
OR
C < 0.5 * SOLUBILITY
m
0.0 .005 .010 .018 .020 .025
FRACTION ORGANIC CARBON
After Karickhoff, 1981.
PARTITION COEFFICIENT
CONCENTRATION ON SOIL
CONCENTRATION IN WATER
= SLOPE OF ISOTHERM
Kp= focKoc
Kp = Soil Partition Coefficient
f « fraction of organic carbon
In the soil
KQC= Partition Coefficient between
aqueous phase and some
some hypothetical, pure organic
carbon
-------
SORPTION OF ORGANICS
SORPTION OF NONPOLAR,
HYDROPHOBIC COMPOUNDS IS
PRIMARILY BY PARTITIONING TO
ORGANIC MATTER IN THE SOIL
TRANSPORT WITH LINEAR RETARDATION
- V
8C
9x
= R
Dispersive
Term
Advectlve
Term
9C
at
Change In
Mass per
Unit Time
LINEAR RETARDATION
R = 1 + Kppb/n
Kp= Partition Coefficient
Pb= Dry Bulk Density of Medium
n = Porosity of Medium
METHODS FOR OBTAINING Kp
• CORRELATION EQUATIONS
• BATCH TESTS
• COLUMN TESTS
• FIELD DATA
-------
O)
O 2
1
0
log Koc - -0.55 log 8 + 3.64
(S In mg/L)
Ktnagi tnd Boring, IBtO
•3-2-1 01 234667
log S (mg/L)
D«U from Kiriekhoff. 1BI1.
012346678
Log Kow
REGRESSION EQUATIONS
Log Koe = -0-55 Log S + 3.64
LogK= 0.544 Log Kow+ 1.377
ORGANIC CARBON
Kp - focKoc
WET COMBUSTION
DRY COMBUSTION
-------
ORGANIC CARBON
WET COMBUSTION
Oxidation of Soil Carbon
by Dlchromate:
2Cr2O*" + 3C°
3CO2+ 8H2O
WET COMBUSTION METHODS
WALKLEY-BLACK
Dlchromate oxidation without external heat
MODIFIED MEBIUS PROCEDURE
Dlchromate oxidation with external heat
WET COMBUSTION
PROBLEMS
Reduction of Cr(VI) by Fe(ll) and Chloride
Oxidation of Cr(lll) by Mn02
Incomplete Oxidation of Carbon
(Walkley-Black)
ORGANIC CARBON
DRY COMBUSTION
HEAT
6H
-------
ORGANIC CARBON
DRY COMBUSTION
• Drive off Carbonates with Acid
• Pass Oxygen over Sample at
600° to 1000° C
• Measure CO2 Generated
ORGANIC CARBON / DRY COMBUSTION
QUANTITATION OF CO2
• Gravimetric Determination of CO2
on Absorbent (e.g. Ascarlte)
• Catalytic Conversion of CO^ to
Methane and Measurement with
Flame lonlzatlon Detector
BATCH TESTS
SOLUTION WITH SOIL WITH SHAKE AND
CONTAMINANT ORGANIC EQUILIBRATE
MATTER
BATCH TESTS
SAMPLE AND
MEASURE
CONTAMINANT
CONCENTRATION
IN SOLUTION
= VW(C0 - C)/M.
-------
BATCH TESTS
SOIL PREPARATION
• Dry Soil
• Sieve (<2 mm)
• Estimate Kp
DESORPTION OF HEXACHLOROBENZENE
1 | 1 • • • • • •—
O
UJ
CQ 0.8
oc
8 o.e
Z
O 0.4
I,
OC
u.
0
0
10
20
30
40
TIME (DAYS)
BATCH TESTS
NEED ESTIMATE OF Kp
• If Kpls large and too much soil added
then concentration In solution cannot
be accurately determined
• If Kpls small and too little soil added
then concentration on the solid cannot
be accurately determined
Z 1x10*
I 3x10*
" 1x10 •
§ 3x1°4
O 1x1°4
3x10*
1x10*
^,-1x10*
V-3X104
After Pankow, 1984.
0.1 U BJ 1J U U 10J
CONCENTRATION OF
NONSETTUNQ PARTICLES (mg/L)
-------
-WATER IN
WATER PLUS
COMPOUND
¥
WATER PLUS
COUPOUNO OUT
MON-BQSBINQ
A A
vi va
VOLUME -^-
RETARDATION FACTORS
FIELD METHODS
i BREAKTHROUGH CURVES
' SPATIAL DISTRIBUTION
1
0.8
0.6
0.4
0.2
0.0
STANFORD/WATERLOO
TRACER TEST
CHLORIDE
CARBON TETRACHLORIDE
TETRACHLOROETHYLENE .
200 400
TIME (DAYS)
COMPARISON OF METHODS
FOR RETARDATION FACTORS
SOLUTE
CTET
BROMO
T.CE
OCB
HCB
OFFICE
ESTIMATED
1.3
1.2
1.3
2.3
2.3
LAB
BATCH
1.9
2.0
3.6
6.9
5.4
FIELD
TEMPORAL
2.7
1.7
3.3
2.7
4.0
SPATIAL
2.1
2.2
4.3
6.2
6.5
After MacKay et al.. 1936.
AtUr Curtll (t •!. (19M)
-------
SORPTION OF TCE ON GLACIAL TILL
McKay and Trudell (1988)
Myrand et al. (1989)
Johnson etal. (1989)
1234
LOG AQUEOUS CONCENTRATION (PPB)
COSOLVENTS
1000
100
G.
* 10
0.1
ANTHRACENE
.ifter :."kedi-(Uzza, ec al., 1935
CLO 0.1 u en tu u
FRACTION CO-SOLVENT
(MTTHANOL)
IONIZATION
Cl
ADVECTION-DISPERSION
EQUATION
WITH FIRST-ORDER DECAY
.,90 9C 9C
D —- -v — = — -KG
9x 9t
-------
CHARACTERIZATION OF SUBSURFACE
PHYSICOCHEMICAL PROCESSES
CHARACTERIZATION OF SUBSURFACE PHYSICOCHEMICAL PROCESSES
II. VOLATILIZATION
A. Four Phase System
B. Gas Phase Concentration
C. Processes
D. Theory of Vapor Phase Diffusion
1. Transport Equation
2. Tortuosity
3. Retardation
E. Methods for Obtaining Vapor "Diffusion Coefficients
F. Examples of Vapor Transport
G. Additional Factors
1. Cultural Features
2. Temperature
H. Summary
VOLATILIZATION AND
VAPOR TRANSPORT
A
• RESIDUAL-PRODUCT
D VAPOR
• DISSOLVED
-------
FREE-PRODUCT
RESIDUAL-PRODUCT
VAPOR
DISSOLVED
FOUR PHASE SYSTEM
(AfUrSchwllli,19B8)
WATER
I 1 NAPL CHI AIR
VOLATILIZATION
pk= xkpk
Pk = partial pressure of
component k In soil
air
Xk = mole fraction of kth
component In NAPL
P° = vapor pressure of
pure component
EQUATION OF STATE
FOR AN IDEAL GAS
n/V = P/(RT)
n = Number of Moles
V = Volume of Gas
P = Partial Pressure
R = Gas Constant
T = Temperature (kelvlns)
FACTORS AFFECTINQ
SUBSURFACE VAPOR CONCENTRATIONS
• DIFFUSION
• ADVECTION
• DENSITY
• CULTURAL FEATURES
• PARTITIONING TO SOIL
• PARTITIONING TO PORE WATER
• THERMAL EFFECTS
• DEGRADATION REACTIONS
• GROUND WATER CONCENTRATIONS
• WATERLEVEL FLUCTUATIONS
• RECHARGE
PARTIALLY SATURATED
POROUS MEDIA
-------
DIFFUSION
FICKS SECOND LAW:
2
3 G
at
AIR PHASE TORTUOSITY
MILLINGTON-QUIRK
(MILLINGTON, 1959)
2.333
7>
w)
0 0.1 DJt 0.1 0.4 0.6 0.8
VAPOR PHASE
RETARDATION FACTOR
R = 1
VAPOR DIFFUSION
WITH LINEAR RETARDATION
A
9t
*°
1
K
1
20
T0
T
AA
D 82G
8x
BENZENE
OLUENE HEXANE
0 0_2 0.4 0.8 OJi 1
HENRY'S CONSTANT (dimensionleas)
PARTITIONING INTO PARTITIONING INTO
BOIL ORGANIC MATTER RESIDUAL SOIL WATER
-------
10% WATER CONTENT, 1% SOC
TOTAL POROSfTY = 0.35
0.04 0.06 0.12 0.16 0.2 0.24
WATER CONTENT
1000 2000 1000 4000
TIME (MIN)
From Johnson ec al., 1987.
a 4 • • 10
PORE VOLUMES
12
VAPOR DIFFUSION
IS IMPORTANT WHEN
THE HENRY'S CONSTANT IS LARGE
THE SOIL WATER CONTENT IS LOW
METHODS FOR OBTAINING
VAPOR DIFFUSION COEFFICIENTS
• ESTIMATION METHOD
• COLUMN TESTS
• FIELD DATA
2 4 6 8 10 12 14 16
PORE VOLUMES
-------
Sample Line to QC
Nitrogen + organic* In
Nitrogen + organic* out
After Johnson ec •!., 1987
VAPOR DIFFUSION COEFFICIENTS
EFFECT OF MOLECULAR WEIGHT
! /D2 =
VAPOR DIFFUSION COEFFICIENTS
EFFECT OF TEMPERATURE
(Hamaker, 1972)
, /Da = (T2 / T,)
m
m
11.5 (THEORETICAL)
11.75-2.0 (EXPERIMENTAL)
OREGON GRADUATE CENTER
LARGE EXPERIMENTAL
AQUIFER PROGRAM
OGC/LEAP
Richard L. Johnson
Director
ADVECTIVE FLOW
i ATMOSPHERIC PUMPING
i WATER-LEVEL FLUCTUATIONS
i GRAVITY-DRIVEN FLOW
i VAPOR EXTRACTION WELLS
FACTORS CONTROLLING
GRAVITY-DRIVEN FLOW
• PERMEABILITY
• VAPOR PRESSURE
• MOLECULAR WEIGHT
• DIFFUSION COEFFICIENT
• RETARDATION
• WATER CONTENT
• SOURCE SIZE
• SURFACE COVER
-------
VAPOR TRANSPORT
VAPOR VAPOR
MONITORING MONITORINQ
WELL'A' WELL'S'
CONCENTRATION
VAPOR TRANSPORT
VAPOR
MONITORING
IMPERMEABLE WELL'S"
BOUNDARY
CONCENTRATION
TOTAL HYDROCARBONS
1000
TIME (DAYS)
2000
Ol
E
E
UJ
CC 60
100
80
CC
Q.
20
TCE VAPOR PRESSURE AS A
FUNCTION OF TEMPERATURE
4 8 12 18 20 24
TEMPERATURE (°C)
28
I
OJ
0.4-
0.3-
=
HENRYS CONSTANT FOR TCE AS
A FUNCTION OF TEMPERATURE
12 16 20 24 28
TEMPERATURE (°C)
§ 3.5
i25
< 2
I"
OC 1
Q 0.5
> 0
VAPOR RETARDATION FACTOR FOR TCE
AS A FUNCTION OF TEMPERATURE
12 16 20 24 28 32
TEMPERATURE (°C)
36
-------
FACTORS AFFECTING DIFFUSION
a MOLECULAR SIZE
D TEMPERATURE
D HENRY'S GAS CONSTANT
D GRAIN SIZE
D AIR-FILLED POROSITY
D WATER-FILLED POROSITY
n SOIL CARBON CONTENT
ENVIRONMENTAL EFFECTS
D THE BACKFILL
D THE TANKS
D BACKFILL/SOIL INTERFACE
D PIPES AND CONDUITS
D TRENCHES, ETC.
D WATER LEVEL
D ATMOSPHERIC PUMPING
D INFILTRATION
u
o
2
1.6
1.2
OJ
cc 0.4
i
C7
TOTAL
HYDROCARBON
VAPOR
C4
20 40 60 60
PERCENT VOLATILIZED
100
-------
CHARACTERIZATION OF SUBSURFACE
PHYSICOCHEMICAL PROCESSES
III. INORGANIC CONTAMINANTS
A. Processes
1. Speciation
2. Oxidation/Reduction
3. Dissolution/Precipitation
4. Adsorption/surface chemistry
a. Oxide-water interface
b. Adsorption of ions onto oxide surfaces
c. Surface complexation models
d. Comparison and validity of models
B. Chemical Models
1. Mass balance
2. Speciation
3. Mass Transfer
C. Organic/Inorganic Interactions
D. Example: Chromium
INORGANIC
CONTAMINANTS
13 PRIORITY METALS
SILVER
ARSENIC
BARIUM
CADMIUM
CHROMIUM
NICKEL
MERCURY
LEAD
SELENIUM
THALLIUM
ANTIMONY
COPPER
ZINC
-------
PRIMARY HAZARDOUS
SUBSTANCES DETECTED
«ODI
MUNIC
AIIMTDI
CMCINOOINIC
CXOJON
WkWIUTUJ
INOftUKICI
UMNO VUtm
01 ui
OMAMC*/VDC>
uaaurnvi
tuioai
TCI
TBUMNI
3«
After Palacr ec al., 1988.
OTHER IMPORTANT METALS
• IRON
• MANGANESE
• ALUMINUM
CHEM-DYNE HAZARDOUS WASTE SITE
HAMILTON, OH
AIR STRIPPING OF VOLATILE ORQANICS
REMEDIATION BROUGHT TO A HALT
WHEN AIR STRIPPER BECOMES
CLOGGED WITH IRON PRECIPITATES
INORGANIC CONTAMINANTS
PROCESSES
• SPECIATION
• OXIDATION/REDUCTION
• DlSSOLUTION/PRECIPfTATlON
• ADSORPTION/ION EXCHANGE
Ziy
INORGANIC CONTAMINANTS
SPECIATION
Cd2tCdCr, CdCg
CdCli,CdOH+
Zn2+, ZnCr, ZnSOj
Cu2+, CuCOj, CuOH+
INORGANIC CONTAMINANTS
SPECIATION
Hg2++
[Hgci+]
8 [Hg2+][cr]
-------
After Moore and Ramamoorthy,
(1984).
OXIDATION/REDUCTION
REDOX CAN GREATLY AFFECT
CONTAMINANT TRANSPORT
REDOX REACTIONS ARE OFTEN
MIC ROB I ALLY MEDIATED
REDOX CONDITIONS ARE NOT EASILY
PREDICTED
ION EXCHANGE
2NaX
K = [CaX][Na*]
" [NaX]2[Ca2*
ISOTHERMS
OXIDATION/REDUCTION
HCrOI+3Fe2++7H
3Fe3++ Cr3++ 4HP
DISSOLUTION/PRECIPITATION
2+
Ba
-------
METAL CATION BINDING TO OXIDE SURFACES
•pH EDGE"
100
»
20
F9 (III)
Cd
12345 8788
PH
After Schindler et al., 1976.
pH EDGES
Q100
20
0
Q100
E
20
CATIONS
ANIONS .
pH
After Dzombak, 1986.
S 100
CD
5 60
u.
O 40
I-
U 20
Mw tenlunln end Uckto (1112)
0.7 M
0.5 M
0.2 M
NO
Cl
SO,
30g/LSIO,
5x10-7MCd
I - 0.7 M
8 B
pH
H HH HN HH H
B
H H H M
10
&*
L +OH
After Schindler, 1981.
-------
iP~* £XS*~
II
V:1 *V^
M
SURFACE COMPLEXATION MODELS
XOH
XOM++ H+ ; K1
XOH + L'— XL + OH' ;K
SURFACE COMPLEXATION MODELS
K =
K =
[XOM+][Hf]
- - —
[XOH][M2+]
P(L][OH-]
exp
2 [XOH][L-]
OH
)/RT}
SURFACE
COMPLEXATION MODELS
• TWO-LAYER MODELS
• STERN-LAYER MODELS
TWO-LAYER MODEL
GOOD FOR:
• ANION ADSORPTION
• CATION ADSORPTION AT LOW
ADSORBATE CONCENTRATION
HIGH CATION
CONCENTRATION
MULTIPLE SITE MODELS
SURFACE PRECIPITATION MODELS
TRIPLE-LAYER MODELS
-------
(«ckj> K>urna«)
NATURAL POROUS MEDIUM
COMPUTATIONAL TOOLS
• MASS BALANCE
• CHEMICAL SPECIATION
• MASS TRANSFER
• MULTICOMPONENT TRANSPORT
ACTIVTIY OF Cd109ON MINERALS
UNFIUCTIONATU IAND
QUAin? (NO COATWOI)
FELDIPAH (NO OQATMOC)
MAVYUMEIULI
QTZ + niD » OXH3EI
HLD + CALCITI
CAMONATI OIUUNS
_ j 62 DM* from
-i Full«r§ndDivl»(1«87)
] 65
HH 4B
j 02
] 110
j 330
i . i . . i - i . i — . — i — —
MASS BALANCE
Wl
| » 100 1iO »0 •» «0 »• «»
ACTIVITY (CPS/g)
•L
|
1
=
1A WE
_
A.1- D<" — *^/AD\
T D <-==i> (AH;
A + C<=> (AC)
D ^^ D
ua ug
LIB
T
COMPUTATIONAL
TOOLS
• BALANCE
• WATEQ4F
• PHREEQE
• SOLMNEQ88
• MINTEQ
• EQ6
DATA REQUIREMENTS
FOR COMPUTATIONAL TOOLS
• FIELD
- Temperature
- Alkalinity/Acidity
- Redox Conditions
LABORATORY
- 'Complete* Analysis
QROUNDWATER
FLAW
-------
MOOiaRADATION
coNiuumoN of csmiiN
COHIUUPTION Of OHOAMC HATTm
NATURAL HFO
HIQM ADiOWTlDK CAWkCfTY
ACtOfUID UfTAt ION!
~T
OIUOUHION OF HFO
OEtoHpnoM or NATUHAL MFTALJ
REDUCED iORfTTVl CAf ACtTY
COUPETTnOM FOM AOSOHFTK1N VTCf
ORGANIC/INORGANIC
INTERACTIONS
• INDIRECT
- REDOX CONDITIONS
- pH CHANGES
• DIRECT
- CHELATION
- COMPETITION FOR
- OXIDATION/REDUCTION
CHARACTERIZATION OF SUBSURFACE PHYSICOCHEMICAL PROCESSES
IV FACILITATED TRANSPORT
A. Mechanisms
B. Particle Transport
1. Types of particles
2. Particle removal mechanisms
3. Mechanisms controlling the transport of microorganisms
(^. Suspect environments
D. Examples
E. Importance to Transport of Organic Contaminants
-------
CHARACTERIZATION OF SUBSURFACE
PHYSICOCHEMICAL PROCESSES
FACILITATED
TRANSPORT
FACILITATED TRANSPORT
• COSOLVENT EFFECTS
• PARTICLE TRANSPORT
- ORGANIC
- INORGANIC
- BIOLOGICAL
FILTRATION MECHANISMS
SURFACE
FILTRATION
•TRAINING
PHYSICAL-
CHEMICAL
o'-'o'-'o^'o1-
gbgogogo
TYPES OF PARTICLES
• BACTERIA
• VIRUSES
• NATURAL ORGANIC MATTER
• INORGANIC PRECIPITATES
• ASBESTOS FIBERS
•CLAY
MECHANISMS CONTROLLING THE
TRANSPORT OF MICROORGANISMS
• STRAINING
• ADSORPTION
• SEDIMENTATION
• INTERCEPTION
• DIFFUSION
• CHEMOTAXIS
• DEATH
• GROWTH
FACILITATED TRANSPORT
SUSPECT ENVIRONMENTS
• HIGH CONCENTRATIONS OF
- ORGANIC CARBON
- DISSOLVED SOLIDS
- SUSPENDED SOLIDS
• HIGH FLOW RATES
• ABRUPT TRANSITIONS IN pH
• ABRUPT TRANSITIONS IN
REOOX CONDITIONS
• SUPERSATURATION WITH
MINERAL PHASES
-------
METHODS FOR PARTICLE DETECTION
• FILTRATION
- Membrane Filters
- Ultraflltratlon
• MICROSCOPY
• ELECTROPHORESIS
• LIGHT SCATTERING
SIZE- 104 nm •
SIZE- 102nm •
MWDMCCTiaM
PARTICLE FORMATION IN OTIS AFB PLUME
WHEN IS PARTICLE TRANSPORT
OF ORGANICS IMPORTANT?
EXAMPLE:
Massof NSP = 10mg/L
n f
oe
1000 pb
-6
MS=2X10
WHEN IS PARTICLE TRANSPORT
OF ORGANICS IMPORTANT?
EXAMPLE:
Massof NSP = 10 mg/L
*oc =0.1
THEREFORE:
IMPORTANT IF
Kow> 10 6
aoeim Q u M • > m Q DOIOLVIO
-------
PRIORITY POLLUTANTS WITH
K VALUES GREATER THAN 10 6
oc
DDE
DDT
Aroclor 1260
hexachlorobenzene
Dioctyl phthalate
PAHs
TCDD
Toxaphene
FACILITATED TRANSPORT
AND REMEDIATION
• PLUGGING OF INJECTION WELLS
• EASY REMOVAL FROM SUBSURFACE
• AGGREGATION IN THE SUBSURFACE
REFERENCES
CHA&ACTgRIZATIOH OF SUBSURFACE PHTSICOCHZHICAL PROCESSES
C«rl D.
ORGANIC CONTAXIHANTS:
Anderson, M.A., 1988. 'Dissolution of Tetrachloroethylene into Ground Water."
Ph.D. Dissertation, Oregon Graduate Center, Beaverton, OR.
Anderson, M.A., J.F. Pankou, and R.L. Johnson, 1987. "The Dissolution of
Residual Dense Non-aqueous Phase Liquid (DNAPL) from a Saturated Porous Medium."
IN: Proceedings. Petroleum Hydrocarbons and Organic Chemicals in Groundvater.
National Water Well Association and the Amnerican Petroleua Institute, Houston,
TX, 1987, pp. 409-428.
Baehr, A.L., 1987. "Selective Transport of Hydrocarbons in the Unsaturated Zone
Due to Aqueous and Vapor Phase Partitioning," Water Resources Research. Vol.
23, pp. 418-452.
Barker, J.F., G.C. Patrick, and D. Major, 1987. "Natural Attenuation of Aromatic
Hydrocarbons in a Shallow Sand Aquifer." Ground Water Monitoring Review. Winter
1987, pp. 64-71.
Chiou, C.T. , T.D. Shoup, andP.E. Porter, 1985. "Mechanistic Roles of Soil Humus
and Minerals in the Sorptlon of Nonlonic Organic Compounds from Aqueous and
Organic Solutions." Organic Geochemistry. Vol. a, pp. 9-14.
Chiou, C.T., D.W. Schmedding, and M. Manes, 1982. "Partitioning of Organic
Compounds on Octanol-Water Systems." Environmental Science and Technology. Vol.
16, pp. 4-10.
Chiou, C.T., L.J. Peters, and V.H. Freed, 1979. "A Physical Concept of Soil-
Water Equililbria for Nonionic Organic Compounds." Science. Vol. 206, pp. 831-
832.
Chiou, C.T., P.E. Porter, and D.W. Schmedding, 1983. "Partition Equilibria of
Nonionic Organic Compounds Between Soil Organic Matter and Water." Environmental
Science and Technology. Vol 17, pp. 227-231.
Coates, J.T. and A.W. Elzerman, 1986. "Desorption Kinetics for Selected PCB
Congeners from River Sediment." Journal cf Contaminant Hydrology. Vol. 1, pp.
191-210.
Curtis, G.P., P.V. Roberts, and M. Reinhard, 1986. 'A Natural Gradient
Experiment on Solute Transport in a Sand Aquifer, 4. Sorptlon of Organic Solutes
and its Influence on Mobility." Water Resources Research, Vol. 22, pp. 2059-
2067.
Fu, J.K. and R.G. Luthy, 1976«. "Aromatic Compound Solubility in Solvent/Water
Mixtures." J_. Environ, fing^., Vol. 112, pp. 328-345.
-------
Fu. J.K. and R.G. Luthy, 1976b. -Effect of Organic Solvent on Sorption of
Aromatic Solutes onto Soils." J^ Environ. Eng. . Vol. 112, pp. 346-366.
Johnson, R.L., S. Brillante, L. Isabelle, J. Houck, and J. Pankov, 1985.
•Migration of Chlorophenolic Compounds at the Chemical Waste Disposal Site at
Alkali Lake, OR - 2. Contaminant Distributions, Transport, and Retardation.*
Croundwater. Vol. 23, pp. 652-666,
Johnson. R.L., C.D. Palmer, andU. Fish, 1989. "Subsurface Chemical Processes."
IN: Transport ajad £&££ o_£ CgnrM^nflnc? in the Subsurface. To b« published by
USEPA, Sept, 19B9.
Johnson, R.L., C.D. Palmer, and U. Fi»h 1989. "Subsurface Chenical Processes:
Field Examples." IN: Transport and Fate af Contaminants in £h£ Subsurface. To
be published by USEPA, Sept, 1989.
Karickhoff, S.U. and K.R. Morris, 1985. "Sorption Dynamics of Hydrophobic
Pollutants in Sediment Suspensions." Environ. Toxlcol. Gifim^., Vol. 4. pp. 469-
479.
Karickhoff, S.U., D.S. Brovn and T.A. Scott, 1979. "Sorption of Hydrophobic
Pollutants on Natural Sediments." Water Research. Vol. 13, pp. 241-248.
Karickhoff, S.W., 1984. "Organic Pollutant Sorption in Aquatic Systems." J_ojirjial
fil Hydraulic Engineering. Vol. 110, pp. 707-735.
Karickhoff, S.U., 1981. "Semi-Empirical Estimation of Sorption of Hydrophobic
Pollutants on Natural Sediments and Soils." Chemosphere. Vol. 10, pp. 833-846.
Kenaga, E.E. and C.A.I. Goring, 1980. &SJU Special Technical Publication 231-
ASTM, Washington, D.C.
Mabey. W.R. et al., 1982. "Aquatic Fate Procesa Data for Organic Priority
Pollutants." Chapter 4, EPA/440/4-81-014, Office of Water Regulations and
Standards, U.S. Environmental Protection Agency, Washington, D.C.
Mackay, D.M, D.L. Freyberg, P.V. Roberts, and J.A. Cherry, 1986. A Natural
Gradient Experiment on Solute Transport in t Sand Aquifer, 1. Approach and
Overview of Plume Movement." Water Resources Research. Vol. 22, pp. 2017-2029.
McKay, L.D., and M.R. Trudell, 1987. "Sorpclon of Trlchloroethylene in Clayey
Soils at the Tricll Waste Disposal Sit* near Sarnia, Ontario. Unpublished
Report, University of Waterloo Institute for Ground Water Research.
Myrand D. et al. , 1989. "Diffusion of Volatile Organic Compounds In Natural Clay
Deposits." Journal of Contaminant Hydrology.
Nkedi-Klzza, P., P.S.C. Rao, and A.G. Hornsby, 1985. "Influence of Organic
Cosolvents on Sorption of Hydrophobic Organic Chemicals by Soils." Environmental
Science and Technology. Vol. 19, pp. 975-979.
Palmer, C.D. and R.L. Johnson, 1989. "Physical Processes Controlling the
Transport and Fate of Contaminants in the Aqueous Phase." IN: Transport iDd Fate
Si Contaminants in the Subsurface. To be published by USEPA, Sept. 1989.
Palmer, C.D. and R.L. Johnson, 1989. "Physical Processes Controlling the
Transport of Non-Aqueous Phase Liquids In the Subsurface." IN: Transport and
Fate si Contaminants in the Subsurface. To be published by USEPA, Sept, 1989.
Palmer, C.D. and R.L. Johnson, 1989. "Determination of Physical Transport
Parameters." IN: Transport and Fata o_f C,Pntajlnants in the Subsurface . To be
published by USEPA, Sept, 1989.
Pankov, J.P., 1984. "Groundwater Contamination by Organic Compounds : Principles
of Contaminant Migration and Determination. • Notes from Short Course, Feb. 7
and 8, 1984.
Roberts, P.V., M.N. Golz, and D.M. HacKay, 1986. "A Natural Gradient Experiment
on Solute Transport In a Sand Aquifer: 3. Retardation Estimates and Mass Balances
for Organic Solutes." Water Resources Research. Vol 22, pp. 2047-2058.
Schellenberg, K.C., C. Leuenberger, andR.P. Schwarzenbach, 1984. "Sorptlon of
Chlorinated Phenols by Natural Sediments and Aquifer Materials." Environmental
Science ajjd Technology. Vol. 18, pp. 1360-1367.
Schnitzer, M. , 1982. "Organic Matter Characterization." IN: Methods c£ Sail
Analysts. Part i ^ Chemclal and Microbiological Properties. 2nd Edition, A.L.
Page, R.H. Miller and D.R. Keeney, Editors, Number 9 (Part 2) in the Series
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-------
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SESSION IV
Characterization of Subsurface Degradation Processes
Dr. J. Michael Henson
Dr. Henson joined RMT's staff in February 1988. He directs biological remediation investigations and is
responsible for identifying the potential for biological degradation of solid and hazardous wastes. Just prior
to joining RMT, he was a research microbiologist with the U.S. EPA's Robert S. Kerr Environmental
Research Laboratory where he conducted research on the microbiological transformation of pollutants in
subsurface environments. Specific research activities were directed at metabolism of pollutants by enhancing
the growth and activity of aerobic and anaerobic bacteria. Remediation projects included sites that were
contaminated with fuel hydrocarbons and halogenated hydrocarbons.
Other research projects Mike has directed include quantitation of bacterial lipids in environmental samples
to assess the status of the microbial community within those environments. Some of these environments
include bioreactors enhanced to degrade pollutants, methane-producing digesters, and undisturbed soils.
He has utilized Fourier transform-infrared spectroscopy to analyze bacterial polymers and bacterial biofilms
involved in microbially-facilitated corrosion in the marine environment.
He earned his Ph.D. in 1983 from the University of Florida where he investigated the role that fatty-acid
intermediates played in the anaerobic conversion of biomass to methane. These studies were augmented
by studying the effects that various supplements had on anaerobic conversion processes. Dr. Henson also
participated in the design and construction of various anaerobic digestions systems. At Clemson University,
he earned a MS while performing research to determine the potential for microbial degradation of
petroleum products in the marine environment. The effects of the results of microbial degradations
processes might have on the marine environment were also investigated.
I. INTRODUCTION TO SESSION
A. Objectives
B. Relationship of abiotic and microbiological transformations
II. ABIOTIC TRANSFORMATIONS
A. Introductions
B. Abiotic reactions that organic chemicals may undergo
1. Hydrolysis
2. Substitution
3. Elimination
4. Oxidation
5. Reduction
C. Rates of abiotic reactions
D. Examples of compounds susceptible to abiotic reactions
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KNOWLEDGE of:
(1) transport processes and
(2) non-biological or h'"'"?'"' reactions
that a contaminant may undergo in the subsurface
will provide an understanding of the fate of that
contaminant.
This knowledge should guide site investigation remediation
efforts.
ABIOTIC VS BIOTIC TRANSFORMATIONS
Abiotic transformations are much slower than
biotic transformations (generally)
Abiotic transformations receive little attention
as a potential remediation mechanism
Abiotic transformations may not provide a
permanent treatment technology
OBJECTIVES
Discuss abiotic and biotic degradation
processes
Provide information for site evaluation
related to biological remediation
Build the foundation for Biorestoration
discussion topic
ABIOTIC TRANSFORMATIONS
Definitions:
1) "not biotic" - Webster's Ninth New Collegiate
Dictionary
2) "those reactions that do not involve (a) metabolically
active organisms, (b) extracellular enzymes, or
(c) metabolic intermediates such as NADH. NADPH.
flavins, flavoproteins. hemoprotein. iron porphyrins.
chlorophyll, cytochromes, and glutathiones" -
Dragun, 1988
-------
EXAMPLES OF HYDROLYSIS HALF LIVES
ABIOTIC REACTIONS - ORGANIC CHEMICALS
• Hydrolysis
• Substitution
• Elimination
• Oxidation
• Reduction
YDROLYSIS
• A chemical reaction In which an organic chemical
reacts with either water or a hydroxide Ion.
R - X + H,O »R-OH » H' + X"
R - X + OH ~fl-OH + X
• Nucleophlllc displacement reaction
Sn 1 - requires two separate reactions
Sn2 - one-step reaction
• First order with respect to concentration of organic
chemical
Compound
Atrazine
Chloroethane
Chloromethane
Dichloromethane
Malathion
Parathion
Methyl Parathion
Tetrachloromethane
Trichloromethane
Half-Life (in H,0. pH = 7)
2.5h
38d
339d
704y
8.Id (pH = 6.0)
17d (pH = 6.0)
10.9d (pH = 6.0)
700y (1 ppm)
7y (1000 ppm)
3500y
ORGANIC CHEMICALS NOT SUSCEPTIBLE TO HYDROLYSIS
Aldehydes
Alkanes, Alkenes, Alkynes
Aliphatic amides
Amines
Carboxy groups
Nitro-groups
ORGANIC CHEMICALS SUSCEPTIBLE
TO HYDROLYSIS
• Alkyl halides
• Chlorinated amides
• Carbamates
• Esters
• Epoxides
• Sulfones
• Phosphonk - and Phosporic - acid esters
EFFECTS OF SOILS ON HYDROLYSIS
Soil can have great affect on hydrolysis half-lives
pH at soil particle surfaces
presence of metals
sorption
soil water content
soil type
O.693
-------
SUBSTITUTION
Hydrolysis is a Snl or Sn2 nucleophilic
substitution reaction
HS or RS will react with alkyl halides
Results in sulfur-containing intermediates
ELIMINATION
• Involves the loss of two leaving groups
ABIOTIC DEGRADATION OF 1.1.1-TRICHLOROETHANE
[Cline, et al. 1988]
1.1-Dichloroethylene Elimination pathway
1.1.1-TCA
Acetic Acid
Substitution pathway
s25% 1,1-DCE. .75% Acetic Acid
May produce more 1.1-DCE in southern aquifers
1,1-DCE more soluble
Forms a double (or triple) bond
R - CH - CH, > R - CH = CH,
I I
X, X,
OXIDATION/REDUCTION
• Coupled reactions
Reaction mechanisms: El, two-step process
E2. one-step process
Examples: 1,2-dibromoethane
1.2-dibromoprobane
Oxidation is the net loss of electrons
Reduction is the net gain of electrons
Can be very complex in soil systems
with multiple redox couples
• Rates; First-order
-------
CHARACTERIZATION OF SUBSURFACE DEGRADATION PROCESSES
III. MICROBIOLOGICAL TRANSFORMATIONS
A. Introduction
1. Principles of microbial ecology
2. Degradation vs mineralization
3. Environmental factors controlling bioremediation
4. MicrobiaJ adaptation/acclimation
B. Metabolic diversity of microbes and possibilities for biological remediation
1. Oxygen respiration
2. Denitrification
3. Sulfate respiration
4. Nitrate respiration
5. Fermentation
6. Iron respiration
7. Carbonate respiration
C. Rates of biodegradation
D. Classes of compounds amenable to bioremediation
1. Hydrocarbon fuels
2. Creosote wastes
3. Phenols and halogenated phenols
4. Halogenated aliphatic hydrocarbons
5. Halogenated aromatic compounds
6. Polychlorinated biphenyls
7. Pesticides
8. Other organic compounds
IV EVALUATION OF A SITE FOR BIOLOGICAL REMEDIATION
A. Collection of samples for microbiological analysis
1. Collection of soil/aquifer samples
2. Preservation and holding of samples
B. Enumeration of microorganisms present
1. Necesssity for enumeration
2. Viable/Plate counts
3. Acridine orange direct counts
4. Most Probable Number counts
5. Other techniques
C. Evaluation of biodegradation potential
1. Presence of substrates toxic to microorganisms
2. Establishing proper controls
3. Microcosm evaluation
V. SUMMARY
A. Abiotic degradation
B. Biotic degradation
-------
BIOREMEDIATION
MINERALIZATION
Utilization of microbial processes in a controlled
environment to remove a variety of compounds from
a location where they are unwanted.
Conversion of organic chemicals to CO, [CHJ, water,
and inorganic minerals.
1,2-dichlorophenol > CO, + H,O + Cl + Biomass
BIODEGRADATION
BIOREMEDIATION
Requires integrated approaches from several disciplines:
• Microbiology
• Hydrogeology
• Engineering
Biological transformation of an organic chemical to
another form, without regard to extent.
MICROBIAL ECOLOGY OF SUBSURFACE
• 1 x 10° to 1 x 10* microbes/gm soil
(lower in pristine environments)
• >90% of microbes attached to solids
• metabolically active
• metabolically versatile
• oxic and anoxic conditions
POTENTIALLY LIMITING ENVIRONMENTAL FACTORS
• pH
• salinity - osmotic pressure
• available water
• temperature
• hydrogeologic conditions
-------
ADAPTION/ACCLIMATION
An observed increase in the rate of biodegradation
after some period of exposure of the microbial community
to a chemical.
TIME
ADAPTATION TIME
MICROBIAL ADAPTATION
• When adaptation occurs, the rate of-removal if not
governed by an intrinsic property of the microbes.
but Is governed by the physical processes controlling
the availability of nutrients - principally oxygen.
• Allows for mathematical models
NON-GROWTH METABOLISM
Gratuitous metabolism:
enzyme has low substitute specificity
Ex: methane mono-oxygenase
Cometabolism or Co-oxidation:
a substance that can not be used for growth is transformed
in the presence of a growth substitute
Ex: some PAH's
AEROBIC METABOLISM
RESPIRATION
• Oxygen is the terminal electron acceptor
• Water is the product
• Energy is released, which is partially captured
DEGRADATION
• Oxygen is a co-substrate
Mono-oxygenase
CH, + O2 > CHSOH -t- H3O
Di-oxygenase
-------
ANAEROBIC METABOLISM
Anaerobic respiration:
Anaerobic fermentation:
NITRATE RESPIRATION
terminal electron acceptor is an
inorganic compound such as nitrate,
sulfate, nitrate, carbonate
terminal electron acceptor is an
organic compound such as pyruvic
acid to lactic acid or acetaldehyde to
ethanol
Ammonia is the product
Occurs under reducing conditions
Energy transfer much less than oxygen
DENITRIFICATION
CARBONATE RESPIRATION
Nitrate is electron acceptor
N, is product of nitrate metabolism
Facultative organisms are involved
Wide variety of biochemistry
Energetics similar to oxygen
Methane is the product
Highly specialized group of bacteria - methanogens
Occurs under highly reducing conditions
Energy transfer much less than oxygen
SULFATE RESPIRATION
Hydrogen sulfate is produced
Occurs under reducing conditions
Energy transfer much less than oxygen
Area of much research
Some compounds are amenable to degradation under
sulfate-reducing conditions
IRON RESPIRATION
Fe1* is electron acceptor
Fe1* is the product
Area of research - learn from environment
Energetics similar to oxygen
-------
BIOLOGICAL REACTION KINETICS
FERMENTATION
Organic compound Is electron acceptor
Products wary: alcohols, organic acids.
Occurs under reducing conditions
Energy transfer much less than oxygen
Primarily carbohydrates; role in mixed consortia
First order with respect to concentration of
organic chemical.
MAJOR CLASSES OF GASOLINE COMPONENTS
Hydrocarbon
Class
Alkanes
Cycloalkane
Aromatic
Monod kinetics (hyperbolic) may apply with higher
concentrations where degradation rate becomes
Independent of concentration.
Conroe,
Texas
16.8
47.1
19.5
Colinga,
California
18.0
555
10.2
Jennings,
Louisiana
24.5
38.4
15.6
SEQUENCE FOR CONSUMPTION
OF ELECTRON ACCEPTORS
• Second order rate expression Is derived from
Monod equation. Dependent on concentration
of organic chemical and mlcroblal blomass.
«- 0
O EC
I*
I!
4—H,S
NOr-NH,
Glu-^EtOH CO,-*-CH4
RELATIVE EASE OF BIODEGRADATION;
i.e.. COMPOUNDS APPROPRIATE FOR CONSIDERATION
• Hydrocarbons: fuels, BTEX, PNA's
lower molecular weight.
normal paraffins
• Organics in general; THF, MEK, IPA, EG.
Phenols, Chlorinated Phenols, other
alcohols, esters, aldelydes
• N-, S-, O- containing organic*
• Creosote; PNA's and PCP
• Halogenated compounds; not always straight
forward, may require other biological
reactions - Co-Metabolism.
Key considerations: solubility .and
-------
CREOSOTE
• By-product from the production of coke from coal.
i.e., it is a coal tar
• Complex mixture of organic compounds with over
200 compounds identified
• Composition varies with the source of coal,
equipment, and process
• Primarily composed of neutral fraction
• Most common wood preservative
PENTACHLOROPHENOL(PCP)
• Dissolved in No. 2 Fuel Oil as carrier
• Technical grade PCP is about 85 to 90 % pure PCP
tetrachlorophenol
chlorinated phenoxyphenols
chlorinated dibenzofurans
chlorinated dibenzodioxins
• Kow = 1760
• Solubility = 14 mg/L (20 C)
• Protonated form insoluble, pKa = 4.7 - 4.8
COMPOSITION OF CREOSOTE
Naphthalene
Acenaphthalene
Fluorene
Phenanthrene
Aqueous
Solubility (jjg/l) Log Kow Koc
31,700
3.930
1.980
1.290
4.33
4.18
3.37 1,300
DEGRADABILITY
• PCP
4.46 23,000
moderately persistent
half-life 30 to 60 day range
acclimated population
aerobic and anaerobic conditions
mineralized - partial products are possible
Creosote complex mixture of PAH's
half-life increases with molecular weight
PAH's with 3 rings or less quicker
Co-metabolism may be important
Aerobic [anoxic - denitrification, less
known about other anoxic processes]
Fluoranthene
260
5.33
Pyrene
135
5.32 84,000
(62,700)
-------
HALOGENATED ALIPHATIC COMPOUNDS
Anaerobic Conditions
PCE
k,
TCE
DCE
VC
C02
METHANE MONO-OXYGENASE
CH, + 0, > CH,OH (used by bacteria)
Also reacts with many other hydrocarbons
to produce alcohols
Reacts with ethylene to produce epoxtde
TCE degradation by methane addition -
Wilson and Wilson. 1985
(From Benson ££ al., 198!
-------
PCB DEGRADATION
Anaerobic conditions
Reductive dechlorination; i.e., chlorines are replaced by
H's
Reduces toxicity
Enhances aerobic degradability
Soils previously exposed to PCB's showed activity.
Added 700 ppm Arochlor 1242
Time 0 - 1% mono-chlorinated biphenyls
Time 16 wks.- 76% mono-chlorinated biphenyls. Penta
chlorinated biphenyls gone.
- Most activity took place within first 4
weeks.
BASIC PREMISES OF BIODEGRADATION AS
THEY RELATE TO BIOREMEDIATION
• Provides carbon and energy requirements
• Take advantage of carbon cycle
• Environmental factors may be determinate
• Biodegradation can occur in many environments
• Utilize enzymes evolved to degrade biogenic compounds to
degrade man-made compounds
Aerobic conditions
lower chlorinated compounds more susceptible
treatment evaluations should
perform mass balance
GC/MS to detect preferential
degradation
GENERAL CONCLUSIONS
Soil conditions very important.
Bioavailability of PCB'c very important, hydrophobe
compound.
Previous exposure results in adapted bacteria.
Not the cure yet, but new organisms, tricks, and OEM's
may make cost effective quickly.
Anaerobic pretreatment followed by aerobic treatment.
INFORMATION REQUIREMENTS FOR REMEDIAL DESIGN
• Thorough assessment of site
cite history
geology
hydrology
• Regulatory requirements
• Thorough assessment of microbiology
presence of requisite microorganisms
assessment of toxicity to microorganisms
nutrient requirements to enhance degradation
compatibility of geochemistry with enhancement
REQUISITE MICROORGANISMS
• Detected in many samples of subsurface materials
• Do not assume ubiquity, however
• Must be able to metabolize compounds of concern
• Examine for toxicity
-------
EVALUATION PHASE
METHODS FOR MICROBIAL ENUMERATION
Toxicity
Limiting nutrients or electron acceptor
Analogue addition
Numbers of microbes present
GROWTH CONDITIONS
Microorganisms require carbon, nitrogen,
phosphorous, and other inorganics
Also require a Terminal Electron Acceptor
oxygen, nitrate, (denitrification)
sulfate, nitrate (nitrate reduction),
carbonate, organics (fermentation)
Naturally-occurring microorganisms
IORATORY EVALUATIONS
• Based of collection of lubiurface core materials
• Number of heterotrophic and specific
compound-degrading bacteria present
• Disappearance of parent compound
• Nutrient mixture that best supports removal
nitrogen, phosphorous, potassium, other nutrient*
geochemistry may support without additions
• Electron acceptor evaluation and consumption
• GC/MS of daughter products
• Determination of removal rates and final enumeration
PURPOSE: To ensure system is not toxic; requisite
organisms are present; show subsequent
increase. Not to predict activity or rates
Plate Counts:
Standard microbiological technique:
habitat-simulating
• Most Probable Number (MPN):
Statistical counting technique in
liquid medium
• Acridine Orange Direct Count (AODC):
Stain microorganisms - count
via microscopy. Not a viable count
Cell components:
Fatty acids
Total Lipid Phosphate
DNA
CRITICAL EVALUATION OF BIORESTORATION CLAIMS
• Reduction in Substrate Concentration - Mass Balances
• Increase in Biomass/Activity
• Production of Catabolites
• Consumption of Terminal Electron Acceptors
• Adaptation/Acclimation Phenomena
• Biodegradation Kinetics
• All factors relative to appropriate abiotic controls
-------
SUMMARY
Abiotic
Biotic
Rates not as fast as microbiological
transformation rates
In subsurface, observe abiotic
transformations
Explains some constituents that were
not originally present
Diversity of metabolic activities
resulting in many possible remediation
schemes
Explains the presence of some constituents
Explains alteration of ecosystem
Provides potential technology for
site remediation if applied correctly
in appropriate environments
REFERENCES for J. M. Henson, Characterization of Subsurface
Degradation Processes
Atlas, R. H. 1984. Petroleum Microbiology. Macmlllan Publishing Company,
New York.
Oaenn, C. S. 1988. Environmental Biotechnology. Plenum Preas, New York.
Dragon, J. 1988. The Soil Chemistry of Hazardous Waste. Hazardous Materials
Control Research Institute, Silver Spring, MD.
Gibson, D. T. 1984. Hlcroblal Degradation of Organic Compounds. Marcel
Dekker, Inc., New York.
Parr, J. F., P. B. Marsh, and J. M. Kla. 1983. Land Treatment of Hazardous
Wastes. Noyes Data Corporation, Park Ridge, NJ.
Loehr, R. C. and J. F. Malina, Jr.' 1986. Land Treatment: A Hazardous Waste
Management Alternative. Center for Research in Water Resources. The
University of Texas at Austin, Austin, TX.
Vogel, T. M., C. S. Crlddle, and P. L. McCarty. 1987. Transformations of
halogenated aliphatic compounds. Environ. Scl. Technol. 21:722-736.
Tiedje, J. M., S. A. Boyd, and B. Z. Fathepure. 1987. Anaerobic degradation
of chlorinated aromatic hydrocarbons. Dev. Indust. Microbiol. 27:117-
127.
Nyer, E. K. and G. J. Skladany. 1989. Relating the physical and chemical
properties of petroleum hydrocarbons to soil and aquifer remediation.
Ground Water Monitoring Review. 9:54-60.
Henson, J. M., M. V. Yates, and J. W. Cochran. 1989. Metabolism of
chlorinated methanes, ethanes, and ethylenes by a mixed bacterial
culture growing on methane. J. Indust. Hlcrobiol. 4:29-35.
Wilson, J. T. and C. H. Ward. 1987. Opportunities for bloreclanation of
aquifers contaminated with petroleum hydrocarbons. Dev. Indust.
Nicrobiol. 27:109-116.
Wilson, J. T., L. E. L»ach. M. Henson, and J. N. Jones. 1986. In situ
biorestoratlon as a ground water remediation technique. Ground Water
Monitoring Review 6:56-64.
Lee, M. D., J. M. Thomas, R. C. Borden, F. B. Bedient, J. T. Wilson, C. H.
Ward. 1988. Blorestoration of aquifers contaminated with organic
compounds. CRC Critical Reviews in Environmental Control 18:29-89.
Schwarzenbach, R. P., W. Giger, C. Schaffner, and 0. Warner. 1985.
Groundwater contamination of volatile halogenated alkanes: Abiotic
formation of volatile sulfer compounds under anaerobic conditions.
Environ. Sci. Technol. 19:322-327.
Cooper, W. J., H. Mehran, D. J. Riuiech, and J. A. Jones. 1987. Abiotic
transformation of halogenated organics. 1. Elimination reaction of
1,1,2,2-tetrachloroethane and formation of 1,1,2-trlchloroethene.
Environ. Scl. Technol. 21:1112-1114.
Cllne, P. V., J. J. Delflno, T. Potter, 1988. Degradation and advection of
1,1,1-trichloroethane in the saturated zone containing residual solvent.
Proc. Superfund '88, Washington, DC. Hazardous Materials Control
Research Institute, Silver Spring, MD.
Thomas, J. M. and C. H. Ward. 1989. In situ biorestoratlon of organic
contaminants in the subsurface. Environ. Sci. Technol. 23:760-766.
-------
SESSION V
Applications and Limitations of In-Situ Soils Remediation
Dr. Ronald C. Sims
Dr. Sims has advanced degrees in environmental microbiology (University of North Carolina at Chapel Hill,
School of Public Health) and environmental engineering (Washington State University) at the M.S. level,
and has Ph.D. minors in toxicology, soil science and mathematics in addition to his Ph.D. major in biological
engineering (North Carolina State University). After receiving his Ph.D. degree, Dr. Sims joined the faculty
of the Division of Environmental Engineering at Utah State University, Logan, Utah, in 1982. Dr. Sims
served as principal investigator foe the U.S. EPA project to develop guidance concerning in-situ treatment
technologies applicable to contaminated surface soils (Review of In-Place Treatment Techniques for
Contaminated Surface Soils, 1984).
In addition to his academic position at Utah State University, Dr. Sims has also worked for the University
of North Carolina at Chapel Hill, North Carolina, as Director of the International Program in
Environmental Aspects of Industrial Development, for Mobay Chemical Corporation, Charleston, South
Carolina, as Environmental Control Laboratory Supervisor, and as an environmental engineer for Research
Triangle Institute (RTI), Research Triangle Park, North Carolina. Dr. Sims spent the 1989-1990 academic
year on sabbatical leave with the U.S. Environmental Protection Agency's Robert S. Kerr Environmental
Research Laboratory, Ada, Oklahoma, where he assisted EPA in the area of subsurface bioremediation
investigations.
-------
APPLICATIONS & LIMITATION OF IN-SITU SOILS REMEDIATION -
SOIL VACUUM EXTRACTION
Ronald C. Sims, Professor and Head, Environmental Engineering Division
Utah State University, Logan, Utah
I. DESCRIPTION OF PROCESS
A. Characterization
1. Site characterization requirements
a. location
b. permeability
2. Waste/soil information requirements
a. volatility
b. water solubility
c. partitioning into oil
d. soil texture
e. soil organic carbon
f. soil moisture
B. Components and operating characteristics
1. Components
2. Operating characteristics
3. Passive systems
4. Active systems
5. Soil gas monitoring probes
II. APPLICATIONS OF SOIL VACUUM EXTRACTION
A. Approach
1. Timing
2. Iterative design
3. Target treatment level
4. Treatment train
B. Removal of volatile light non-aqueous phase liquids
C. Control of explosive vapors or harmful gases
D. Removal of non-volatile organic chemicals in soil
III. LIMITATIONS OF SOIL VACUUM EXTRACTION
A. Contaminants
B. Site/soil factors
1. Location
2. Permeability
-------
SOIL REMEDIATION
Soil Vacuum Extraction
Bioreclamation
Contaminant Immobilization
Contaminant Mobilization
APPROACH
Description of Process
Applications
Limitations
-------
SESSION 5: RONALD C. SIMS
DRAFT
Summary Matrix of Treatment Technologies
Wastes amenable
Technology to treatment Statua
Potential
Ease of level of
application treatment
Reliability
Soil Flushing
Immobilization
Sorption (heavy metals)
Agri. products
Activated carbon
Tetren
Sorption (organics)
Soil mositure
Agri products
Activated carbon
Ion exchange
day
Synthetic resins
Zeolites
Precipitation
Sutfides
Carbonates, phosphates
and hydroxides
Degradation
Oxidation
Soil catalyzed reactions
Oxidizing agents
Reduction
Organics
Chromium
Selenium
Sodium
Polymerization
Biodegradation
Soil moisture
Soil oxygen • aerobic
Soil oxygen • anaerobic
SoilpH
Nutrients
Soluble organics
and inorganics
Heavy metals
Heavy metals
Heavy metals
Organics, nonvolatile,
Kd<10
Organics
Organics, low
water solubility
Cat ionic components
Certain cationic and
anionic compounds
Heavy metals
Heavy metals
Heavy metals
Aliphatic organics,
other organics
Various organics
Chlorinated organics,
unsaturated aromatics,
aliphatics
Hexavalent chromium
Hexavalent selenium
PCS, dioxin, halo-
genated compounds
Aliphatics, aromatics,
oxygenated organic
compounds
Organics
Organics
Halogenated organics
Organics
Organics
Laboratory
Pilot scale
Field
Conceptual
Laboratory
Easy • difficult
Variable Good
Easy • difficult
Easy • difficult
Easy - difficult
High Retreatment required
Unknown Unknown
High Unknown
Conceptual Easy • difficult
High
Retreatment required
Laboratory
Bald
Laboratory
Laboratory
Easy • difficult
Easy • difficult
Easy • difficult
Easy - difficult
High Retreatment required
Low • high Unknown
High
Variable
Good
Unknown
Conceptual Easy • difficult Unknown Unknown
Conceptual
Laboratory
Difficult
Easy • difficult
High
Unknown
Fair
Retreatment required
Limited field Easy • difficult Variable
Limited field Moderate - difficult High
Limited field Easy • difficult
Limited field
Limited field
Conceptual
Easy • difficult
Easy • difficult
Moderate
High
High
High
High
Good
Good
Retreatment required
Retreatment required
Retreatment required
Good
Expt field Moderate • difficult Variable Unknown
Reid Easy • difficult Low • high
Field Easy • difficult Low • high
Conceptual Moderate • difficult Low • high
Field Easy • difficult High
Field Easy • difficult High
Retreatment required
Retreatment required
Retreatment required
Retreatment required
Retreatment required
(continued)
-------
SESSION 5: RONALD C. SIMS
DRAFT
(continued)
Wast a a amenable
Potantlal
Eaaa of laval of
Technology
Nonspecific organic
amendments
Analog enrichment tor
cometabolism
Exogenous acclimated or
mutant micro-organisms
Cell-free enzymes
Photolysis
Proton donors
Enhance volatilization
to treatment
Organics, arsenite
wastes
Some organic* with
analogs
Various organic*
Organics
Some organics. includ-
ing TCDO. Kepone.
PCS
Specific organics
Statua
Laboratory
Laboratory
Field
Laboratory
Field
Laboratory
application
Easy • difficult
Easy - difficult
Easy • difficult
Difficult
Easy • difficult
Easy • difficult
treatment
Low* high
Low *high
High
High
High
High
Reliability
Retreatment required
Unknown
Retreatment required
Unknown
Unknown
Good
Reduction of Volatile
Material*
Soil vapor extract
Soil coolii
ing
Volatile organic* and
inorganic*
Volatile organic*
Field
Easy • difficult
Expt., Difficult
limited field
Low* Good
medium
Low • Relreaiment required
medium
Adapted from EPA 1934.
PEI Associates, Inc. and University of Cincinnati. 1989 Handbook on In Situ Treatment of
Hazardous Waste. Draft. U.S. Environmental Protection Agency, Office of Research and
Development, Risk Reduction Research Laboratory, Cincinnati, Ohio.
Sims, R.C., et al. 1986. Contaminated Surface Soils In-PIace Treatment Techniques. Noyes
Publications, Park Ridge, NJ
Sims, R.C., D.L Sorensen, J.L Sims, J.E. McLean, R.H. Man mood, and R.R. Dupont. 1984.
Review of In-PIace Treatment Techniques for Contaminated Surface Soils. Volumes 1 and 2.
EPA-540/2-84-003a,b. U.S. Environmental Protection Agency, Hazardous Waste Engineering
Research Laboratory, Cincinnati, Ohio.
-------
- Detoxification
&&*.
^jfjjotc
fj-^Absorpti
and
Chemical \ J Exudation
Decomposition
Groundwater
CHAmCI(iil7lllO«
101110>11C
cssur
CSVP
sstc
ci
Oil
c«
Ctiir»cleriiitUi>
Ck.r.cKrii.tio. .r ,.
$itc/i«il iitiiilttivc
Conslilutxt «lltnu«tion requirej
-------
' COALS OF W SITU TREATMENT '
PROTECTION OF PUDUC HEALTH AND ENVIRONMENT
TftfATMF-KT OF WASTE CONSTITUENTS TO AN ACCEPTABLE LEVEL
t
1 SOIL SYSTEM 1
DEGRADATION
DEToxrn CATION
IMMOBILIZATION
Fat* of Huaidoui ConunHnanU in Soil
CHARACTERIZATION
-------
INTERPHASE TRANSFER
POTENTIAL
Partitioning Information
Ko - partitioning of constituent between water and oil phase
Kd - partitioning of constituent between water and soil phase
Kh - partitioning of constituent between water and air phate
DEGRADATION
Biotic
Abiotic
VOLATILIZATION
Tw*m Sottmnl
IHIufM faff. Off
-------
VOLATILIZATION
Naphthalene - 30% loss from soil
1-Methylnaphthalene - 20% loss from soil
ABOTC DEGRADATION
Naphthalene
12% loss from sol
1-Methylnaphthalene - 12% loss from soil
Anthracene
Phenanthrene
9% loss from soil
17% loss from soil
Park el al. Environmental Toxicology and Chemistry. 1990. Vol. 9(2).
BIOLOGICAL DEGRADATION
Hall-hie ol a PAH Compound:
t.
0.693
k
Where
t „ - half-life ol PAH compound in soil (time)
k « first-order rate constant (lime1) for
microoial degradation
RETARDATION or IMMOBILIZATION
R = Vw/Vp
R = Retardation
Vw = velocity of water
Vp = velocity of pollutant
IMMOBILIZATION
R.I + H*L
9
p - soil bulk density
Kf • partition coefficient
0 • volumetric moisture content
-------
SOIL-BASED WASTE CHARACTERIZATION
Chemical
Class
Acid
Base
Polar Ncuuai
Nonpoiai Neutral
inorganic
Soil Sorption
Parameters
Freundlch Sorption
Constants (K.Nj
Sorption Dated on
Organic Content (K_)
Octanol water partition
Coellicieni (K_)
Soil Degradation
Parameters
Hail-iiie (!„)
Rate Constant
Relative bio-
flegradabiliiy
Chemical
Properties
MoiecularWeigni
Melting po
-------
'MOBILITY AND DEGRADATION INDEX (MDi)
MDI -
T - lime required lor chemical to travel through a
critical depth
i,,2 . chemical hall-lite in soil or lime required lor
chemical to be degraded to one-hall ol the
original concentration
2 -
*///
a
2
o>
o
0-
Vd« 0.004 in/hr (0.01 cm/hr)
de> 2»l(60em)
-2 -t-
-------
MATHEMATICAL MODELS
SOIL VACUUM EXTRACTION
Characterization
Components
Ratio* o( Concentration of Pesticides Between Water/Soil snd Air/Soil at
15 cm After 81 Days (Ranked In Order from Greatest Potential tor Leaching and
Volatilization to Least Potential)
Pesticide
d)
Disulfoton
Phorate
Melhylpaialhion
Toxaphene
Endosullan
Paralhioa
Heplachlor
Aldnn
Leaching potential
(concentration in soil
water/concentration
in soil)
(2)
330
23
4.8
0.5
O.I2
0.06
0.06
0.0009
Pesticide
(3)
Toxaphene
Disulfolon
Phorate
Heplachlor
Endosulfan
Aldnn
Methylparalhion
Paralhion
Volatilization
polenbal
(concentration in soil
air/concentrauon in
soil)
(4)
7.4
3.6 X IQ-
5.2 X IQ-
5.5 x ID"
4.0 x |Q-
2.0 X I0~
1.2 x 10"
1.6 x 10'
McLean et al. 1988. Evaluation of Mobility of Pesticides in Soil Using
U.S. EPA Methodology. Journal of Environmental Engineering. Vo. 114(3):
689-703.
INFORMATION
Performance Standards
3-D Contamination
Vapor Monitoring Probes
Pathways of Vacuum Propagation
-------
•noil
1011
lull !»»« !-•
tauiru
fi
<5*5>
»i»a»i lout
0
-o
Kiuociiion
-------
Vinyl Chlorld**
l,l-dieMerothy1««* (1,1-OCE)*
«itJ»y1«it EWorld**
Hydrofl»n Cycnid* (p(C*«9)
D1ch1oro«thy1«n«
fftthyl Ethyl K*ton«
VAPQ8 PBjSjjUjES Of SOME CQHHQW.Y aETECTgO COMPQUMOS EXCEgPIMfi 10.0 mm Ho
Vapor Prtg»ur« IH JM «* 20aC
2660
1000
591
362.4
360 (7°C)
200
130
150.5
100
96
9S.2
90
61
57'.9
42
30
28.4
26.75
25
19
14.3
11.8
11.6
C4rfaon T*tr»cft lurid* (€014}*
1,2-Oiehloroithi.n**
(TCE)*
B1 s ( ch 1 sreawthy 1 ) ithtr
Tol utn*
2-Chloro«thyl vinyl tthtr
l,3-dietjlorprop«n«
(1,1,2-TCA)
Chlorob«nz«n«
* Known or tu*p«ettd c*rc1nofl«n
VAPOR PRESSURES Of SOME COHHOHLY DETECTED CaMPOtfflOS LESS THAU 10.0 m H£
Coaoound Vagor Pr»ssur« (am Hal »t 20*C
Ethylfa«nz«n«
Tr1»thyl«a1n«
o-xyl M*
1,1,2,2-T«tr*cJ>l or«th*n«
Styrtn*
2-Chloroph*nol
4-H1troph«riol
1,3-01ch1orob»rztn«
l,4-Q1chlarob«nz*n«
1,2*01chlorob«nztn«
2,4,6-Tr1ch1oroph«nol
2-N1troph«nol
B1s(2chloro1sopropyl)«th«
81t(2-chloro«thyl}«th*r
Phtnol
l,2,4-Tr1chlorob«nz«n«
Htx»chloro«th»n«
Htxtchlorobutad1*n*
N1trob*nztn*
2,4-01chlorophtnol
7
7
6.6
5
4.5
2.2
2.2
2.2
i.a
i.s
i.o
i.o
0.85
0.71
0.53
0.42
0.4
0.15
0.15
0.12
-------
*•*. PVC P«rtoc««j Cooox : :
(Conanjoui) /\l : |
\n«i
V
Uonuing
Prate
-------
30 -
2S .
20 •
IS •
10 •
5 •
\
\\
- *7
Extrapolated curv«
ti snort oiiunc«»
tram •unction pip*
150 elm extraction flow
pritaurt drop curv*
10 20 30
40 SO 60 70 80 90
DltUnci Irom utrtctlon point
100 10S
GROUND ELEVATION
1/8 POLYETHYLENE RISER TUBE
4-6" DIAMETER OF BOREHOLE
GROUT
2" DIAMETER PVC VENT PIPE
BENTONITE SEAL
PVC THREADED CAP
SAND PACK
2* DIAMETER-0.020 INCH SLOTTED PVC
Schematic of Gas Monitoring Well
-------
Aerobic Biodegradation
The following seven (7) slides have been provided by Dr. Robert Hinchee. Bale Lie Columbus
Laboratories, Columbus. Ohio.
Hydrocarbon
+
Oxygen
+ Nutrients
Bjomass
CO2 + H2 O (Respiration)
-------
Aerobic Biodegradation - Respiration
C6H6+ 7V202
6 CO2+3 H2O
3.1 Ib 0/lb C6H
6"6
CfiH
6"14
6 C02+ 7 H20
3.5,lb 0,/lb C6H14
OXYGEN SUPPLY
Water
Air Saturated
Pure Oxygen Saturated
500 mg/ 1 Hydrogen Peroxide
Air
s
Oxygen Supply
to Carrier/lb Oxygen
100.000
25.000
5.000
4
! >
Monitoring Point Y In-Situ Respiration Test
December 19, 1988
X Oxygen, k =-.00059/mln
O Carbon Dioxide
1000
2000 3000
Time (minutes)
4000 4500
-------
With Nutrients
110
25% Field Capacity
50% Field Capacity
75% Field Capacity
A Sterile Control
| Standard Deviation
O
15 20
Time (Days)
Cumulative Hydrogen Removal
Hill AFB Soil Venting Site
January
Date*
February
-------
APPLICATIONS & LIMITATIONS OF IN-SITU SOILS REMEDIATION -
BIORECLAMATION
Ronald C. Sims, Professor and Head, Environmental Engineering Division
Utah State University, Logan, Utah
DESCRIPTION OF THE PROCESS
A. Bioreclamation systems
1. Information requirements
2. Approaches
B. Characterization
1. Waste/site/soil characterization
2. Determination of containment requirements
3. Enhancement of microbial processes
APPLICATION OF BIORECLAMATION
A. Waste types
1. Non-halogenated chemicals
2. Halogenated chemicals
B. Treatability studies
1. Environmental factors
2. Rate and extent evaluation
3. Detoxification evaluation
C. Full-scale sites
1. Wood-preserving waste contamination
2. Petroleum waste contamination
3. Pesticide contamination
4. PCB contamination
LIMITATIONS OF BIORECLAMATION
A. Site-specific aspects
1. Unsuitable site/waste characteristics
2. Time required for clean-up
3. Level of clean-up attainable
4. Cost of clean-up
B. Additional factors
1. Production of biochemical by-products or intermediates
2. Mixtures of metals and organic chemicals
3. Microorganism seeding
-------
BIORECLAMATION
Characterization
Containment
Microbial Activity Enhancement
^v
JC
lophtho
**^>
T
^
COOH
CH,
"^l P^^V^T-'H (^^V^^f0**
J — * 1 I J — ^L i J — *
*r ViX^X*^ Vx^v>^
«fli l,2-dihydrx»y- 1,2 -dihydroiy-
1,2-dihydro- naphlholent
naphlhaltn*
a OH
*
OH
CII'CI*" ^ ^^COOH*^ *""*»»^
/
f^O ^ muconolactont
y/
•NCO-
' /3-o«oadipol«
)N. COOH
J ^* CH2
*^ CH* * K"EBS <
COOH CYCLE
-* A *
ocilic acid succinic ocid / 1 \
v^
S \ ^
^J fCOOH^ t^VOH , 5°°^
11 3
OH Salicylaldthyde Pyruvic oc
I
a OH
COOH
^ f "^T-OH Salicylic acid
\ COOH
CHO. o*-hydro«ym\iconic temioldehydt
)\.CH3
HCOOH < *CHOH 2-<»o-
CH 4-hydroiy-
C«0 valeric ocid
COOH
A
CHj CHj
— CHO C=0
COOH
acttaldehyde pyruvic ocid
J
\^ ^/
PROPOSED/ACTIVE BIOREMEOIATION SITES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
«
• • •
Site Name
L.A. CUrk & Sons
American Creosote
Brown Wood Preserving
Crosby
Wi Imington
Burlington Northern
North Cavil cade Street
Old Inger
Brio Refining
Joplin
Baxter/Union Pacific
Burlington Northern
Libby
ARCO
Koppers Company
J.H. Baxter
Wood Preserving
Coal Gasification
Reai on
3
4
4
4
4
5
6
6
6
7
8
8
8
8
9
9
Contaminant
•
..
2
•
...
Metabolism of naphthalene by soil bacteria (DEAN-RAYMOND and BARTHA 1975, GIBSON 1976
and GIBSON 1968).
-------
POLYNUCLEAR AROMATICS
ACENAPrtTHYLENE
ANTHRACENE
BENZlolANTHRACENE
DIBENZU.h) ANTHRACENE
BENZlolPYRENE
BENZO16) FLUORANTHENE
BENZOW FLUORANTHENE
e
1
1000
800 H
400 H
200 H
Synth, mix
Oil r*(. wul*
CTMWMWUM
Number of ring*
ENHANCEMENT OF
MICROBIAL ACTIVITY
SOIL/SITE ASSIMILATIVE CAPACITY (SSAC)
Twhniquas
(1) Soil incorporation or muting
(2) Aeration ol m« toil
(3) Addition ol nutrients
(4) Addition ol microtxal carbon and
•nargy sources
(5) Water addition (irrigation)
(6) Drainage
(7) Runon and Runoff Control*
(6) pH adju«un«nt
INDENOl 1.2,3-edlPYRENE
Polynuclear aromatic hydrocarbon compounds
-------
Nunn clay loam
• ZKOiUGraM*
4*Oil*GlMM
30
60 90 120 ISO
TllylE( t
tS*Co«
13
26
87
139
43
*
-------
WAYS TO MAXIMIZE
AVAILABLE SOIL OXYGEN
• Prevent Water Saturation
• Presence of Sand, Loam (Not Hvy Clay)
• Moderate Tilling
• Avoid Compaction
• Controlled Waste Loading
EFFECT OF SOIL MOISTURE ON
PAH DEGRADATION
Moisture Half-Life (Days)
(Field Capacity) Anthracene Phenanthrene Fluoranmene
20-40
60-80
43
37
61
54
559
231
EFFECT OF MANURE AND pH AMENDMENTS ON PAH DEGRADATION
IN A COMPLEX WASTEINCORPORATED INTO SOIL
PAH Compound
Half-Life In Wa*te:Soil Mixture (Days)
Without Amendments With Amendments
Acenaphthylene 78
Anthracene 28
Phenanthrene 69
Fluoranthene 104
Benz(a)antrhaeene 123
Benz(a)pyrene 91
Dibenz(a.h)anthracene 179
14
17
23
29
52
69
70
Aprill.W. et al. 1989. Assessing Detoxification and Degradation of
Wood Preserving and Petroleum Wastes in Contaminated Soils. Waste
Management & Research (In Press).
-------
TEMPERATURE EFFECT ON DEGFtADATION RATE
Hall-Lile (days)*
Compound IOC 20 C
Fkxxm 60 47
(40-71) (42-iJ)
Prt»wufv*n* 200 <60
(160-240)
(320-770) (190-420)
Ppm 1 1900
(11004100)
t*Au(ft)pyt
<60
200
(1702*0)
210
(ISO )70)
220
(1*04*0)
' £*;ol!£'S^r^U~.««.
Coover, M.P., and R.C. Sims. 1987. The Effect of Temperature on
Polycyclic Aromatic Hydrocarbon Persistence in an Unacclimated
Agricultural Soil. Haz. Waste & Haz. Mat. Vo. 4(1):69-82.
(ȣ>
0
14
28
(14C) 7.1 2-DIMETHYLBENZ(a)ANTHRACENE
TRANSFORMATION PRODUCTS IN
A SANDY LOAM SOIL
"C o MCK kacbon (X)
a** t • acl >»^«« wut
Compot^o Prooucu
62 (69) 4 (6) 12 (13) 0 (0)
26 43 ig o
ZO (60) 53 (II) 17 (IG) 0 (0)
AND
Taui
78 (88)
as
90 (87)
-o.«~, .«».» «.«*« ^^.n.v.,
Park, K.S., et al. 1988. Biological Transformation and Detoxification
of 7,12-Dimethylbenz(a)anthracene in Soil Systems. J. Wat. Pollut.
Control Fed. Vol. 60(10)-.1822-1825.
-------
SESSION5: RONALD C.SIMS
FIELD STUDY SITE PROFILE
-------
SESSION 5: RONALD C. SIMS
FIELD RESULTS FOR SOIL SAMPLES
Compound
AVG SO CV (•/.)
Naphthalene 166 66 37
Ac«napruh«o» 729 276 36
Ph*nanttv«ne 76 28 36
B«nz(a)
anWacvn* 66 42 49
•nltvawn* 52 36 69
91 days UiO/9)
AVG SO CV(%)
3 1.6 61
1 1.8 157
2.6 0.6 23
2 0.6 36
NO
C, . InMl Set GonoMWMui
PERFORMANCE EVALUATION-- MONITORING
• Soil Cores
• Soil-Pore Liquid
• Ground Water
• Runofl Water
• Air
-------
MAW fALAMCf
100 ,, . , I 50
ng loil/pltti
ZOO
250
COSTS
SfiflCfi Current Dollars
• Laboratory Treatability Study - 50.000-100,000
• Pilot Scale Study -• 150.000-200,000
• Full Scale Study - 400,000 +
-------
APPUCATION AND LIMITATIONS OF IN-SITU SOILS REMEDIATION -
CONTAMINANT IMMOBILIZATION
Ronald C. Sims, Professor and Head, Environmental Engineering Division
Utah State University, Logan, Utah
I. DESCRIPTION OF PROCESS
A, Characterization
1. Sorption
2. Ion exchange
3. Precipitation
B. Site characteristics
1. Waste properties
2. Soil properties
3. Climate
11. APPLICATIONS OF IMMOBILIZATION
A Sorption
1. Control of soil moisture
2. Addition of agricultural byproducts
3. Addition of activated carbon
4. Chelation
B. Ion exchange
1. Addition of clays
2. Addition of synthetic resins
3. Addition of zeolites
C. Precipitation
1. Precipitation as sulfides
2. Precipitation as carbonates, phosphates, and hydroxides
III. LIMITATIONS OF IMMOBILIZATION
A. Characteristics limiting processes
1. Site factors
2. Soil factors
3. Waste factors
B. Potential reversibility of reactions
1. Environmental factors
2. Chemical factors
3. Microbiological factors
-------
CONTAMINANT IMMOBILIZATION
Sorptlon
Ion Exchange
Precipitation
SGAPTION
S-KCN
S - Amount ol constituent sorted per unit dry
weight ol soil
K, N - Constants
C - Solution phase equilibrium concentration
90
8 BO
CO
70
60
SO
• a • 2ov.
A e • 10%
• e • 60%
eo%
10 20
DISTRIBUTION COEFFICIENT, Kd
IMMOBIUZATION TECHNIQUES
REVIEW OF IN-PLACE TREATMENT TECHNIQUES FOR
CONTAMINATED SURFACE SOILS. 1984
EPA-540/2-84-003a,b. Vols. 1 and 2.
R.S. Sims, O.L Soreneen, J.L. Sim*, J.E. McLean,
R.H. Mahmood, and R.R. Dupont.
IMMOBIUZATION TECHNIQUES
HANDBOOK ON IN SITU TREATMENT OF HAZARDOUS
WASTES. 1989. DRAFT. U.S. EPA (PEI Associates,
Inc. and Univ. ol Cincinnati). To Be Published
Fall, 1989.
EQUILIBRIUM SOLUTION CONCENTRATION
mtq/l
Typical adsorption Isotherm for imt«H «nd soil.
-------
•MOBILIZATION TECHNIQUES
Sorption
Soil moisture control
Agricultural product
Activated carbon
IMMOBILIZATION TECHNOJES
ton Exchange
Uetai + Clay-Calcium — Calcium + Clay-Metal
IMMOBILIZATION TECHMQOES
I ton Exchange
Clay
Synthetic Resins
Zeolite*
MMOBUJZATION TECHNQUES
Precipitation
Sulfides
Hydroxides
Carbonates
IMMOBILIZATION OF METALS
pH Effect
As pH decreases, the number ot negatively
charged sites decreases due to competition
from H« and AM tons
IMMOBILIZATION Of METALS
Iron and Manganese Oxides
Play a prinicple role In metal retention in soil
Below pH 6 oxides dissolve releasing sorbed metal
tons Into solution
-------
CHROMIUM
ARSENIC
+1.0
+0.5
in 0.0
-0.5
Dragun, J. 1988. The Soil Chemistry ol Hazardous Materials.
Hazardous Materials Control Research Institute. Sirv er Spring,
+1.0
+0.5
Eh 0.0
-0.5
Oragun, J. 1988. The Soil Chemistry of Hazardous Materials.
Hazardous Materials Control Research Institute, Sllv «r Spring,
MO
SELENIUM
+1.0
+0.5
Eh 0.0
-0.5
MO
10
Dragun, J. 1988. The Soil Chemistry ol Hazardous Materials.
Hazardous Materials Control Research Institute, Sirv er Spring.
MO
-------
APPLICATIONS & LIMITATION OF IN-SITU SOILS REMEDIATION - CONTAMINANT MOBILIZATION
(SOILS FLUSHING)
Ronald C. Sims, Professor and Head, Environmental Engineering Division
Utah State University, Logan, Utah
I. DESCRIPTION OF THE PROCESS
A. Types of flushing solutions
1. Aqueous solutions
2. Petroluem recovery solutions
B. Properties of bulk fluids that hinder soil flushing
1. Low water solubility
2. High interfacial tension
3. High mobility ratio
II. APPLICATIONS OF SOILS FLUSHING
A. Treatment train concept
1. Product removal
2. In situ soil flushing
3. In situ bioredamation of residual contamination
B. Applications for bulk fluids
1. Surfactants
2. Alkaline/polymer flooding
IB. LIMITATIONS OF SOILS FLUSHING
A. Potential impact on soils and the environment
1. Soil permeability
2. Toxicity to aquatic organisms
B. Limitations of methods for bulk liquids
1. Aqueous solutions
2. Petroleum recovery methods
C. Treatment of fluids withdrawn from subsurface
1. Adverse effects on reuse
2. Above-ground treatment processes required
-------
CONTAMINANT MOBILIZATION • SOIL FLUSHING
Water
Acidic Solutions
Basic Solutions
Surfactants
Chalation Solutions
•'^"SS
Sims, et al. 19B4. Review of In-Place Treatment
Techniques for Surface Contaminated Soils. EPA-540/2-
84-003a,b. Vols. 1 and 2.
BULK FLUIDS
Low Water Solubility
High Intertatial Tension
Poor Relative Permeability
RELATIVE PERMEABILITY
M . (Kd/Ud) / [Ko/Uo]
M . Mobility Ratio
Kd - Fluid Permeability
Ko . Oil Permeability
Ud - Viscosity of Fluid
Uo - Viscosity of Oil
APPLICATIONS FOR BULK SOLUTIONS
In-Silu Solvent Flushing
Hot Water or Steam
Carbon Dioxide
Surfactants
Alkaline Solutions
Polymer Solutions
£ «H
a—•« **ik»c«M J-0.27C d'-0.»»OI
a—-a •••»(•) nitn fi.jic°-"i('-o.»»7i
O—-o IM»* U,Z
20
T
>0 40
CONCENTRATION (mg/l)
FNA «d«orpcion i»oth«rm in •«ch«Qol and Ada, Oklaho
•oil.
-------
REFERENCES: SESSION 5
Omenn, C.S. 1987. Environmental Biotechnology - Reducing Risks from
Environmental Chenlcals through Biotechnology- Proceedings of
Conference held July 19-23 it the University of Washington. Seattle,
Hashlngton. Plenum Press, New York. ISBN 0-306-42984-5. 505pp.
Engineering Foundation. 19B8. Biotechnology Applied to Hazardous
Hastes. Conference held 1n Longboat Key. Florida. October 31 -
November 4.
Hazardous Materials Control Research Institute (HMCRI). 1988. Us*
of Genetically Altered or Adapted Organisms In the Treatment of
Hazardous Hastes. Conference held 1n Hashington. D.C.. November 30 -
December 2.
U.S. EPA. 1986. Haste-Soil Treatabtnty Studies for Four Complex
Industrial Hastes. Methodologies and Results. Volumes 1 and 2. •
EPA-600/6-86-003 a.b. October. EPA. Robert S. Kerr Environmental
Research Laboratory. Ada. OK.
Sims. R.C.. J.I. Slot, O.K. Sorensen. J.E. McLean. R.3. Mahmood. and
J.J. Jurlnafc. 1986. Contaminated Surface Soils In-Plac* Treatment
Techniques. Noyes Publications, Park Ridge. New Jersey. 536pp.
Woodward, R.E. 1988. B1oremed1at1on Feasibility Studies for
Hazardous Haste. Pollution Engineering 20(7): 102-103.
U.S. EPA. 1966. Permit Guidance Manual for Hazardous Hast* Land
Treatment Demonstrations. Office of Solid Hast*. Washington. D.C.
EPA-530/SH-86-032. February.
Martin. J.P.. R.C. S1os. and J.E. Matthews. 1986. Review and
Evaluation of Current Design and Management Practices for Land
Treatment Units Receiving Petroleum Hastes. Hazardous Hastes and
Hazardous Materials. 3(3):261-280.
U.S. EPA. 1981. A Survey of Existing Hazardous Hast* Land Treatment
Facilities In the United States. U.S. EPA, Contract No. 68-03-2943.
S1ms, R.C. 1986. Loading Rates and Frequencies for Land Treatnent
Systems. In: Land Treatment: A Hazardous Haste Management
Alternative (R.C. Loehr and J.F. Hallna. Eds. Hater Resources
Symposium Number Thirteen. Center for Research 1n Hater Resources.
College of Engineering, The University of Texas at Austin.
Loehr. R.C.. J.H. Martin, and E.F. Neuhauser. 1983. Disposal Of
Oily Hastes by Land Treatment. Report to 38th Annual Purdue
industrial Haste Conference, Purdue University. Hest Lafayett*.
Indiana, Kay.
Sims. R.C, and LM.R. Overcash. 1983. Fate of Polynuclear Aromatic
Compounds (PNAs) 1n Soil-Plant Systems. Residue Reviews. 88:1-68.
K.H. Brown and L.E. Duel. 1982. An Evaluation of Subsurface
Conditions at Refinery Landfarm Sites. Prepared for the American
Petroleua Institute and the U.S. EPA. Grant No. CR-807868.
U.S. EPA. 1988. Treatment Potential for 56 EPA Listed Hazardous
Chemicals In Soil. Robert S. Kerr Environmental Research Laboratory,
Ada, OK. EPA/600/6-88-001.
Mahmood. R.J.. and R.C. S1ms. 1986. Mobility of Organic* In Land
Treatment Systems. Journal of Environmental Engineering
112(2):236-245.
Overcash, M.R.. K.H. Brown, and G.B. Evans. 1987. Hazardous Haste
Land Treatment: A Technology and Regulatory Assessment. Prepared
for the U.S. Department of Energy by Argonne National Laboratory,
September 22.
U.S. EPA. 1983. Hazardous Haste Land Treatment. Revised Edition.
SH-874. Office of Solid Haste and Emergency Response. U.S. EPA.
Hashington. D.C.
ZH rides. T. 1983. Btodecontaut nation of Spill Sites. Pollution
Engineering. 15(115:25-27.
-------
APPLICATIONS & LIMITATION OF AQUIFER RESTORATION-PRODUCT REMOVAL
Ronald C. Sims, Professor and Head, Environmental Engineering Division
Utah State University, Logan, Utah
I. DESCRIPTION OF THE PROCESS
A Characterization of product
1. Location
2. Distribution
B. Product pumping systems
1. Light NAPLs
a. dual-pump systems
b. floating-filter pumps
c. collector trenches
d. surface oil/water separators
2. Dense NAPLs
a. single wells
b. subsurface drainlines
II. APPLICATIONS OF PRODUCT REMOVAL
A Site characteristics
1. Location
2. Distribution
B. Product pumping systems
1. Light NAPLs
a. dual-pumping systems
b. floating-filter pumps
c. collector trenches
d. surface oil/water separators
2. Dense NAPLs
a. single wells
b. subsurface drainlines
III. LIMITATIONS OF PRODUCT REMOVAL
A Site characteristics
1. Three dimensional distribution
2. Complex geological structure
B. NAPL contamination of clean areas
1. LNAPL residual saturation
2. DNAPL residual saturation
-------
AQUIFER RESTORATION
Product Removal
Pump and Treat
Biorestoration
PRODUCT REMOVAL
Product Characterization
Product Location
Pumping Systems
Non-Aqueous Phase Liquid (NAPL)
light Non-Aqueous Phase Liquid (LNAPL)
Oil
Pentachlorophenol
Dense Non-Aqueous Phase Uquti (DNAPL)
Creosote
Methylene Chloride
Wil.r T«bl«
-------
Wiur Tiblt
WATW TACLI DCPMMIOII
OIL SUMACt (f P«AI*Um (WTOD)
OHOUHO tUMFACt
Spigot tor Product Rtmonl
(Claud Dunng Opruan)
Spigot tar Tank Dnvw* ar tor
.Pump Cooing Waw
OHOUNO SUWACC
-------
_ i
S
I •
3
W
*,
I
t.
til in
HHCtnr of font iPACt on. HTUKMCD
• f (KHIABIIITT TO OK.
• KHU(*IIII1T TO HIO
FIGURE 1
PERMEABILITY VERSUS % OIL SATURATION
CUMULATIVE WATER PRODUCTION V*. TIMI
miHAJIT OU. MCOVUT PUH* TUT
Session 6: Ronald C. Sims
II
fl
I ,J
I ,.
If ,J
1-
p,
3 !
• 11 ii »
TOU tWCI TUT (TAftTU (CAT*)
CUMUUkTTVE OIL PRODUCTION VS. TIME
MIMAJir OIL HfCOVtUT run* TtIT
ii i* a
TUU UlCt TUT (TAHTVD (DAT!)
FIGURE 4
CUMULATIVE OIL
AND WATER PRODUCTION
-------
APPUCATIONS & LIMITATIONS OF AQUIFER RESTOFIATION-PUMP AND TREAT
Ronald C. Sims, Professor and Head, Environmental Engineering Division
Utah State University, Logan, Utah
DESCRIPTION OF THE PROCESS
A Characterization of pumping systems
1. Extraction wells
2. Extraction and injection wells
B. Characterization of treatment systems
1. Physical processes
2. Biological processes
3. Chemical processes
APPUCATIONS OF PUMP AND TREAT TECHNOLOGY
A Applications of pumping systems
1. Site characteristics
2. Waste location and pumping system
a. wellpoint systems and suction wells
b. deep wells and ejector wells
3. Pulsed pumping
4. Well repositioning
B. Application of treatment systems
1. Gasoline and volatile organics
2. Non-volatile organics
3. Inorganics
LIMITATIONS OF PUMP AND TREAT TECHNOLOGY
A Transport processes in the subsurface
1. Diffusion
2. Hydrodynamic isolation
3. Sorption-desorption
4. Liquid-liquid partitioning
B. Geologically complex aquifers
-------
PUMP AND TREAT
Pumping Systems
Treatment Systems
CONTROL OF
HYDROLOGY ON THE
RATE OF REMEDIATION
Seepage Velocity a Hydraulic Permeability « Hydraulic Gradient
Hydraulic permeability is an intrinsic property ol the
subsurface. II is difficult or impossible lo improve il. but
it is easily degraded.
The hydraulic gradient is controlled by the amount ol
water available lor pumping, and by the difference in
elevation between the source area and the land surface.
HYDRAULIC CONTAINMENT
The migration of a plume away Irom its source area can often be
prevented by capturing (he plume with a purge well. The well
musl pump hard enough to overcome regional Mow in the aquiler.
The How Irom purge wells that is necessary to capture a plume
depends on the hydraulic permeability of the aquiler, the regional
hydraulic gradient, and the sue ol the source area.
HYDRAULIC CONTAINMENT OF
SUBSURFACE REMEDIATION
Hydraulic containment of a source area can be achieved if more
water is eitracted than Injected. If water is recircuiated through
the source area, a portion of the extracted water can be discharged
to a sewer ol surface drainage, resulting in a net extraction of
water across the entire system.
-------
Underground
Tank To Treatment
Static Piezometric Surface
Domestic
Well
„ •.*,.•
'r:::::;:::. impermeable Bedrock '^::;^;:::
••.«..».••••••.•••••••"••"••-••••"••••••••
Cro««-Seotlon«l View
Upper Confining Bad
Lower Confining Bed
/ / / / / V V i / ) ) I
Flow Lines
Equipotential Lines
Domestic
Well
Extraction Well* with
Radius of Influence*
Plan View
0 injection
p^
HPM well cluster
BHtractlon well
-------
AQUIFERS AND
NATURAL CONFINING LAYERS
Frequently, geological structures that readily yield water are
layered above or between geological materials thai do not readily
transmit water. These non-lransmlstlv* layers can act as
natural containment lor subsurface Dioremediaiion Don't
assume trie bed rocK is a confining layer; it is ollen fractured.
LIFE-CYCLE DESIGN
Time Effect on Concentrations
Capital Costs
Operator Expenses
Nyer, E.K. 1985. Groundwater Treatment Technology.
Van Nostrand Reinhold Co., New York
BACKHOEKEYS TRENCH
INTO BEDROCK
BACKFILL
SLOUGHS
FORWARD
LEACHATE
z
o
cc
I
o
o
WELL AT BEGINNING
OF PLUME
WELL AT END
OF PLUME
-------
( 10" UCaCII I
LEACHING COLUMN CONFIGURATION
O
i
LU
o
o
o
ON
RESIDUAL
CONTAMINATION
\
— TIME
CCNCtNTBMION
TOIUENF ELUl IOfJ FROM A
CONTAMINAICD lRAVLfif)C
CITY CORE
POBC VtX.Lf«S
-------
— TIME
MODERATE
FAST
MODERATE
-------
APPLICATION & LIMITATIONS OF AQUIFER RESTORATION - BIORESTORATION
Ronald C. Sims, Professor and Head, Environmental Engineering Division
Utah State University, Logan, Utah
I. DESCRIPTION OF THE PROCESS
A Characterization
1. Pump and treat aqueous phase
2. In situ treat residual contamination
B. Phases of in-situ aquifer biorestoration
1. Site investigation and characterization
2. Determination of containment requirements
3. Performance of treatability studies
4. Bioremediation design, implementation, monitoring
II. APPLICATIONS OF BIORESTORATION
A. Types of environments
1. Dissolved phase
2. Sorbed phase
3. Residual saturation
B. Biorestoration systems
1. Subsurface injection of nutrients and electron acceptor
a. wells
b. injection galleries
2. Pulsed pumping of nutrients and electron acceptor
3. Hydraulic containment of biorestoration
4. Physical containment of biorestoration
III. LIMITATION OF BIORESTORATION
A. Biological factors limiting biorestoration
1. Waste type resistant to biodegradation
2. Microorganism population
3. Toxicity
4. Biochemical by-products
B. Environmental factors limiting biorestoration
1. Low-permeability of aquifer
2. Problems with adequate containment
3. Costs for bioremediation
4. Time requirements
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AQUIFER BIORESTORATION
Pump and Treat Aqueous Phase
In Situ Treatment of Residual Saturation
PRIMARY EMPHASIS IN
SUBSURFACE REMEDIATION
Hazardous wastes mat occur as a discrete oily-phase act as
source areas lor plumes ol contamination in ground water. They
also contaminate the soil air with hazardous fumes. The primary
emphasis in subsurface bioremediation has been the source
*r»>*. Subsurface bioremediahon of the plumes is often
technically feasible, but il is usually easier to pump them out and
treat them on the surface.
IDENTIFY THE MOST
CONTAMINATED FLOW PATH
Some regions ol the source area will clean up faster than others
One How path will be the last to clean up. if m,s flow path can
be identified, then us propen.es can be used to determine how
much e.lort .s required to remed.alt the entire source area and
how long it will lake.
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•1"
•fl
- ..
-* -«
CHARACTERIZATION OF THE
MOST CONTAMINATED
INTERVAL
Time required to
clean fnost
contaminated
How path
Length of path
through source
area
Concentration ol
X contaminant along
How path
a
Seepage velocity along the
most contaminated How pain
II the supply ol mineral nutrients is adequate, the rate Of
bioremediation is the rale ol supply ol electron acceptor. As a
result, the rate ol remediation is directly proportional to the
concentration ol electron acceptor in the injected water, and
directly proportional to the (low velocity ol water through the
source area.
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PROBLEMS WITH WELLS
AS MONITORING TOOLS
Treatment can occur In the well Itself. The waler in me well
may not be representative ol the water m the aquiler.
A conventional monitoring well produces a composited waler
sample. Waler Irom the most contaminated How path is diluted
by water Irom many other How paths that are less contaminated.
A waler sample Irom a well tells nothing about the amount ol
hazardous material that is absorbed to aquifer solids or it
trapped as an oily phase.
HOW TO PLUG UP AN INJECTION WELL
Add oxygen or hydrogen peroxide to water with
-> get Fe (OH),
Add oxygen or hydrogen peroxide to water with
Mg/l ol organics
-> get biofouling
Add phosphate to aquifer with Ca (Mg) CO, matrix
•> Ca (Mg) FO4
Nutrients c
In-line c
Oxygen Source
In-situ 4
Aeration
Soil Flushing
3>
^<
Injection"
Well
Groundwater
Leactiat e Plume'//////
Aeration
Well Bank
Simplified View of
Bioreclamation of
Soil and Groundwater
Aeration Zone
Direction of Groundwater Flow *—N
Extraction Well
^'l'**^.^^^^
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V / 52R /
\ ' '
N / /
SMITH
/ a j HANGAR
TANKS/--,/£ /TV^AOMIN
GORE
BUILDING
FAILED FLANGE
51 Y
ORIGINAL SOURCE
SCALE
50m
CO-DISTRIBUTION OF CONTAMINATION
AND HYDRAULIC PERMEABILITY IN AN
AQUIFER CONTAMINATED BY A FUEL SPILL
Depth Interval
(Im D6IOW ku(l4CV)
fwrvAl CorM Of
Sat toed uues 0.4,
and the bulk density is 2.0 kg/dm'.
Each kilogram ol aquifer contains 0.2 liter ol water, and
each liter ol pore water is exposed to 37,500 mg ol luel
hydrocarbons.
The oxygen demand ol the hydrocarbons is 128.000 mg
O, per liter pore water.
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FORMULATION OF
NUTRIENT MIX
• Usually determined empirically
» No! related to C.N.P.S ratios
» Use higM concentrations to project significant
concentrations into the aquifer
• Should formulations be related to O.N.P.S
ratios?
PROPERTIES OF
MOLECULAR OXYGEN
ADVANTAGES
• Low toxicity lo acclimated organisms
* Supports removal ol many organic compounds
• Inexpensive
DISADVANTAGES
* Low solubility in water
• Will precipitate iron hydroxide
lfLt»«tlON IN INJfCTIOH
|CT Aiovf USL WCLIS\
S\
ao~" »n-«o 10-0 •!>-•> •o-'1
ZONI OF '4
CONT ANIMATION
WtTC* TA11U
HOKI2ONTAL SCALE m MCICHS
PROPERTIES or
HYDROGEN PEROXIDE
ADVANTAGES
« Miscible in water
* Supports bioremediation of many organic compounds
* Chemicnlly oxidizes many organic and inorganic
contaminants
» Removes biolouling
DISADVANTAGES
* Tone al concentrations much above 500 mg/liler
» Will precipitate iron hydroxide
* Relatively expensive
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COST COMPARISON
OF ELECTRON ACCEPTORS
Electron Acceptors
Sodium Nitrate
Liquid O«ygcn
Hydrogen Peronde
Bulk Electrons Real Cost
Cost Accepted tp»rmoietoi
(p«f kg) (moltl / kg) eltcifont
•ceoplM)
S0.66 58.8 $1.12
$146 125.0 $1.17
$1.54 58.8 $2.62
MONITOR THE OPERATION
OF THE SYSTEM AS WELL
AS ITS PERFORMANCE
• Delivery ol mineral nutrients
• Delivery ol electron acceptor
• Position in the water table
• Effectiveness ol containment
ADVANTAGES OF
PULSING AMENDMENTS
II more tfion one amendment is required to promote subsurface
bioremedialion. they can be injected in alternating pulses. This
prevent* undue production ol blomass near me injection
system, oh.cn would otherwise plug the system.
High concentrations ot hydrogen peroxide (> 100.000 mg/liler)
can remove bloloullng and restore the efficiency in injection
wells or injection galleries.
Pulses ol hydrogen peroxide at high concentration can sterilize
the aquiler and destroy calalase activity, preventing premature
decomposition ol the peroxide.
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Session 6: Ronald C. Sims
o
E
c
o
o
T3
O
to
1/5
•• «»• IM !•• tm
Julian Date
60-1
JO-
Pilot Scale Biodegradation Project
Dissolved Oxygen Levels Vt. Time
w*n »eo-»OB-4
O O n n no O O
160 210
Jvllan Dalt Of
2«0 310
40-
60
Pilot Scale Biodegradation Project
Dissolved Oxygen Levels Vs. Time
wtii teO'Soe-3
1*0 21O 260
JuMtn Dal* Of Sampl*
310
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Session 6: Ronald C. Sims
60-i
d
Pilot Scale Biodegradation Project
Dissolved O«yoco Levels Vs. Time
w.ll .UO-10B-2
60
1*0 210 2«0
JuHtn Otlt 01 S«mpl«
I f i rivQ i i | I'i'i
310
W«ll » B 0-31-2
PERFORMANCE OF BIORESTORATION NEAR BO 31
Parameter
(mg/Kg aquifer)
Total Fuel Hydrocarbon
Toluene
nj » a Xylene
0 • Xylene
Benzene
Before Just Before
8/87 8/68
6.500 1.220'
544 37
58 <1
42 8.4
0.3 0.6
After
10/88
8.400
<0.3
<0.3
<0.3
<0.3
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Session 6: Ronald C. Sims
STOICIIIOMETRY OF AEROBIC BIORESTORATION
Oyr;cn featured
Estimated based on:
Total Fuel Hydrocarbons
BTX only (8/87)
BTX only (3/88)
Aciually required
BD31-? GO 500-2
nig Oj / liier pore water--
62.2)2 90,000
8.710 12.000
2.364 3.420
2.989 2.952
HOW OFTEN SHOULD A
MONITORING WELL BE SAMPLED?
The frequency ol sampling should be related to the lime eipected
lor significant changes lo occur along the most contnmm.itcd How
path.
IMPORTANT CONSIDERATIONS
• Time required lor water to move Irom injection wells to the
monitoring wells
* Seasonal variations in water-table elevation or hydraulic
gradient.
• Changes in me concentration ol electron acceptor.
• Cost ol monitoring compared to dny-lo-day cost ol
operntion.
FACTORS CONTROLLING THE
RATE AND EXTENT OF
BIOREMEDIATION AT FIELD SCALE
* Rale ol supply ol essential nulnenls, usually the
electron acceptor
* Spatial variability in How velocity
* Seclusion ol the waste Irom the microorganisms
-------
Rates and eitent ol treatment al held scale should be
estimated with a comprehensive mathematical model
that incorporates
• biological reaction rales
* stoichiomelry ol waste transformation
« mass-transport considerations
» spatial variability in treatment efficiency
COSTS ASSOCIATED WITH
SUBSURFACE REMEDIATION
SUE CHAR ACT eniZAT ION
Wells. Soil Gas Survey. Coring and Core Analysis.
Geological Section, Aquiler Tests. Tracer Tests
flf A(f DIAL DESIGN
Treatabiiity Tests. Mathematical Modeling
SYSTEM DESIGN
Permits. Negotiating trade-offs between cost and timo
required
MORE COSTS
ASSOCIATED WITH
SUBSURFACE REMEDIATION
SYSTEM INSTALLATION
Wells, infiltration galleries, pumps, pipelines, tanks,
control devices, treatment systems
MATERIALS AND OPERATING EXPENSES
Waier. electron acceptor, fertilizer, inoculanl.
maintenance, power, sewer charges
MONITORING
Monitoring wells and pumps, cores and their analysis
SITE SECURITY AND OPERATIONAL OVERSIGHT
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REFERENCES: SESSION 6
Goldstein, P.M., L.M. Mallory, and M. Alexander. 1985. Reasons for possible
failure of inoculation to enhance biodegradation. Applied and
Environmental Microbiology 50:977.
Lee, M.D., Thomas, J.M., Borden, R.C., Bedient, P.B., Wilson, J.T., and Ward,
C.H. 1988. Biorestoration of aquifers contaminated with organic
compounds. CRC Critical Reviews in Environmental Control. 18(1):29-89.
Nyer, E.K. 1985. Groundwater Treatment Technology. Van Nostrand Reinhold
Company, Inc. ISBN: 0-442-26706-1. 188 pp.
Wilson, J.T., and D.H. Kampbell. 1989. Challenges to the practical
application of biotechnology for the biodegradation of chemicals in ground
water. Preprint Extended Abstract, American Chemical Society, Division
of Environmental Chemistry, April 9-14, Dallas, Texas.
Wilson, J.T., I.E. Leach, M. Henson, and J.N. Jones. .1986. In situ
biorestoration as ground water remediation technique. Ground Water
Monitoring Review, pp. 56-64 (Fall).
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