Batreiie
The Business of Innovation
Environmental Technology
Verification Program
Materials Management
and Remediation Center
Generic Protocol
for Verification of
In Situ
Chemical Oxidation
EW ET
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GENERIC
VERIFICATION PROTOCOL
for
In Situ
Chemical Oxidation
Version 1.0
August 30, 2012
Prepared by
Battelle
505 King Avenue
Columbus, OH 43201-2693
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Al TABLE OF CONTENTS
Section
Generic Verification Protocol In Situ Chemical Oxidation
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Al Table of Contents 1
A2 List of Acronyms and Abbreviations 4
A3 Distribution List* 5
A4 Verification Test Organization 6
A4.1 Battelle 6
A4.2 Vendor(s) 10
A4.4 Test Facilities 10
A4.5 Verification Test Stakeholders 11
A5 Background 11
A5.1 Technology Need 11
A5.2 Technology Description 12
A6 Verification Test Description and Schedule 13
A6.1 Verification Test Description 13
A6.2 Proposed Testing Schedule 14
A6.3 Testing Facilities 15
A7 Quality Objectives and Criteria for Measurement Data 16
A8 Special Training/Certification 16
A9 Documentation and Records 16
MEASUREMENT AND DATA ACQUISITION 18
Bl Experimental Design 18
Bl.l Lab Testing 22
B1.1.1 Soil, Groundwater, Subsurface Materials, Oxidant Characterization 22
Bl.l.2 Technology Specific Oxidant Demand and Soil pH Buffering Tests 23
Bl.l.3 Measuring Residual Oxidant 24
Bl.1.4 Soil pH Buffer Capacity 26
Bl.l.5 Macrocosm Tests 27
B1.2 Field Testing 28
B1.3 Operational Parameters 29
B1.4 Operational and Sustainability Factors 30
B1.5 Statistical Evaluation 30
Bl.5.1 Percent Reduction 30
Bl.5.2 Degradation Ratio 31
Bl.5.3 Persistence 31
Bl.5.4 Technology Specific Oxidant Demand 31
B1.6 Reporting 32
B2 Sampling Method Requirements 32
B3 Sample Handling and Custody Requirements 33
B4 Analytical Method Requirements 33
B5 Quality Control Requirements 34
B6 Instrument/Equipment Testing, Inspection, and Maintenance 35
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B7 Instrument Calibration and Frequency 35
B8 Inspection/Acceptance of Supplies and Consumables 36
B9 Non-Direct Measurements 36
BIO Data Management 37
ASSESSMENT AND OVERSIGHT 39
Cl Assessments and Response Actions 39
Cl.l Technical Systems Audits 39
C1.2 Data Quality Audits 40
C1.3 QA/QC Reporting 40
C2 Reports to Management 41
DATA VALIDATION AND USABILITY 43
Dl Data Review, Verification, and Validation Requirements 43
D2 Verification and Validation Methods 43
D3 Reconciliation with User Requirements 44
REFERENCES 45
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Page
Figures
Figure 1. Organizational Chart 7
Tables
Table 1. Estimated Verification Testing Schedule 15
Table 2. Summary of Test Data Quality Indicators and Testing Frequency 21
Table 3. Macrocosm Sample Matrix 28
Table 4. HACK DR5000 Tests, Method, and Range 34
Table 5. Soil, Groundwater, and Subsurface Material Analytical Tests 34
Table 6. Maintenance and Calibration of Equipment 35
Table 7. Summary of Data Recording Process 37
Table 8. Summary of Quality Assessment and Control Reports 42
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A2 LIST OF ACRONYMS AND ABBREVIATIONS
ADQ audit of data quality
ASME American Society of Mechanical Engineers
ASTM American Society for Testing and Materials
AWS American Welding Society
BTEX benzene, toluene, ethylbenzene, and xylene
COA certificates of analysis
COC contaminants of concern
EPA U.S. Environmental Protection Agency
ETV Environmental Technology Verification
HDPE high density polyethylene
ISCO in situ chemical oxidation
LRB laboratory record book
meq milliequivalents
MGP/PAH manufactured gas plants with PAH contamination
MMR Materials Management and Remediation
MNA monitored natural attenuation
MTBE methyl tertiary-butyl ether
NOD natural oxidant demand
ORP oxidation reduction potential
PAH polycyclic aromatic hydrocarbons
PCB polychlorinated biphenyl
PPE personal protective equipment
QA quality assurance
QAPP Quality Assurance Project Plan
QM Quality Manager
QC quality control
QMP Quality Management Plan
RMO Records Management Office
ROI radius of influence
SRM standard reference material
TOC total organic carbon
TSA technical systems audit
VOA volatile organic analysis
VTC Verification Test Coordinator
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A3 DISTRIBUTION LIST*
U.S. Environmental Protection Agency (EPA)
EPA Materials Management and Remediation (MMR) Center Project Officer
EPA MMR Center Quality Manager (QM)
Battelle
Battelle MMR Center Manager
Battelle Verification Test Coordinator (VTC)
Battelle MMR Center QM
Battelle Technical Staff
* Once vendors agree to participate in a verification test in this technology category, this generic
protocol will be modified to be specific for the technology(ies) to be verified and then reviewed,
finalized, and distributed to the following:
Vendor(s)
Peer Reviewers, at least one EPA (possibly from Office of Solid Waste and Emergency
Response) reviewer and one non-EPA reviewer
Reference Laboratory, if applicable
Test Collaborators (e.g., field site manager), if applicable
The U.S. Environmental Protection Agency, through its Office of Research and Development, funded and managed,
or partially funded and collaborated in, the research described herein. It has been subjected to the Agency's peer
and administrative review. Any opinions expressed in this report are those of the author(s) and do not necessarily
reflect the views of the Agency, therefore, no official endorsement should be inferred. Any mention of trade names
or commercial products does not constitute endorsement or recommendation for use.
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A4 VERIFICATION TEST ORGANIZATION
This protocol provides generic procedures for implementing a verification test for the
performance of in situ chemical oxidation (ISCO), focused specifically to expand the application
of ISCO at manufactured gas plants with polyaromatic hydrocarbon (PAH) contamination
(MGP/PAH) and at active gas station sites. This protocol will be used to develop a Quality
Assurance Project Plan (QAPP) for verification of ISCO. Verification tests will be performed by
Battelle, which managed the ETV MMR Center through a cooperative agreement with EPA.
The scope of the MMR Center covered verification of materials management technologies, and
technologies to remediate contaminated land and groundwater.
Quality assurance (QA) oversight will be provided by the Battelle QM and by the EPA QM at
their discretion. Based on the procedures outlined in this document, it is anticipated that
verifications performed based on this generic protocol will be EPA Category III verification
tests. The final determination will be made by the EPA QM once the generic protocol is
modified to be specific to the technology(ies) being verified. The organization chart in Figure 1
identifies the responsibilities of the organizations and individuals associated with these
verification tests. Roles and responsibilities are defined further below.
A4.1 Battelle
Battelle's VTC. Battelle's VTC will have overall responsibility for ensuring that the technical,
schedule, and cost goals established for the verification tests are met. Specifically, the VTC will:
• Assemble a team of qualified technical staff to conduct the verification tests,
• Hold a kick-off meeting approximately one week prior to the start of the verification
tests to review the critical logistical, technical, and administrative aspects of the
verification tests and confirm responsibility for each aspect of the verification test,
• Direct the team (e.g., Battelle testing staff and vendor) in performing the verification
tests in accordance with the QAPP,
• Ensure that all quality procedures specified in the QAPP and in the MMR Center
Quality Management Plan1 (QMP) are followed,
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Battelle
Duality
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Rottalla
Figure 1. Organizational Chart
Maintain real-time communication with the Battelle Manager, Battelle QM,, and on
any potential or actual deviations from the QAPP,
Prepare the draft and final QAPP, verification report, and verification statements,
Provide test data, including data from the first day of testing, to the Battelle Manager,
Battelle MMR Center QM,
Conduct a technical review of all test data. Designate an appropriate Battelle
technical staff member to review data generated by the VTC,
Revise the draft QAPP, verification report, and verification statements in response to
reviewers' comments,
Document and prepare any deviations to the QAPP that may occur during testing,
Address any comments from reviewers regarding testing or the deviations,
Respond to any issues raised in assessment reports and audits, including instituting
corrective action as necessary,
Serve as the primary point of contact for vendor(s) representative(s),
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• Coordinate distribution of the final QAPP, verification report(s), and statement(s),
and
• Establish a budget for the verification tests and manage staff to ensure the budget is
not exceeded.
Battelle's Manager. Battelle's manager will:
• Review the draft and final QAPP,
• Review the draft and final verification report and verification statements,
• Ensure that necessary Battelle resources, including staff and facilities, are committed
to the verification tests,
• Ensure that confidentiality of sensitive vendor information is maintained,
• Ensure that testing staff respond to QAPP deviations and any issues raised in
assessment reports, audits, or from test staff observations, and that any necessary
corrective actions have been implemented,
• Facilitate a stop work order if Battelle QA staff discovers adverse findings that will
compromise data quality or test results.
Battelle Testing Staff. Battelle testing staff will support the VTC in conducting these
verification tests. Battelle testing staff will:
• Assist in planning for the tests, and making arrangements for the receipt of and
training on the ISCO chemicals and application procedure,
• Attend the verification test kick-off meeting, as requested,
• Assist vendor staff as needed during ISCO chemicals receipt and application,
• Participate in training provided by the vendor(s), as requested,
• Conduct verification testing following all aspects of the ETV MMR Center QMP as
well as this QAPP,
• Record qualitative observations about the maintenance and operation during the ISCO
application,
• Ensure that the data from the ISCO application are immediately reviewed for quality,
and after the first day of testing and thereafter on at least a weekly basis, compiled,
recorded, and transmitted to the VTC,
• Notify the VTC of any QAPP deviations and institute corrective action as necessary,
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• Support the VTC in the preparation of the QAPP, report, and verification statements,
as necessary, and
• Support the VTC in responding to any issues raised in assessment reports and audits
related to technical performance, statistics, or data reduction as needed.
Battelle's Quality Manager. The Battelle QM or a designated QA Officer will:
• Review the draft and final QAPP,
• Attend the verification test kick-off meeting and lead the discussion of the QA
elements of the kick-off meeting checklist,
• Prior to the start of verification testing, verify the presence of applicable training
records, including any vendor training on test equipment,
• Prepare audit checklists,
• Conduct a technical systems audit at least once near the beginning of each
verification test,
• Conduct audits to verify data quality,
• Prepare and distribute an audit report for each audit,
• Verify that audit responses for each audit finding and observation are appropriate and
that corrective action has been implemented effectively,
• Communicate to the VTC and/or technical staff the need for immediate corrective
action if an audit identifies QAPP deviations or practices that threaten data quality,
• Provide a summary of the Q A/quality control (QC) activities and results for the
verification reports,
• Review the draft and final verification report and verification statements,
• Maintain real-time communication with the VTC on QA activities, audit results, and
concerns,
• Recommend a stop work order if audits indicate that data quality or safety is being
compromised,
• Work with the VTC and Battelle's Manager to resolve data quality concerns and
disputes,
• Delegate QA activities to other Battelle quality staff as needed to meet project
schedules, and
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• Review and approve QAPP amendments, deviations and audit reports.
A4.2 Vendor(s)
The vendor's responsibilities are as follows:
• Review and provide comments on the draft QAPP,
• Approve the final QAPP prior to test initiation,
• Provide the ISCO chemical to be tested for evaluation during the verification tests,
• Provide all equipment/supplies/reagents/consumables needed to test the ISCO
chemical for the duration of the verification tests,
• Supply a representative to train Battelle staff in the application of the ISCO chemical
and provide written consent for Battelle staff to test the ISCO chemical,
• Provide written instructions for routine calibration, operation, and maintenance of the
ISCO chemical, and
• Review and provide comments on the draft verification report and statement for their
oxidant.
A4.3 Test Facilities
Portions of this verification test will be conducted in the laboratory and in the field. The roles of
specific site managers participating in this verification test are as follows:
• Allow laboratory and field access to vendor(s)and Battelle during the scheduled
verification test including set-up and tear-down operations,
• Define site health and safety requirements to Battelle and vendor staff who may visit
during the testing,
• Provide adequate working space during verification test,
• Provide access to adequate water flow, and
• Provide sufficient power for the simultaneous operation of all test equipment.
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A4.4 Verification Test Stakeholders
The final QAPP, and the verification report and verification statement based on testing described
in the final QAPP, will be reviewed by experts in the application of ISCO. The responsibilities
of verification test stakeholders include:
• Participate in technical panel discussions (when available) and/or review an outline of
the verification tests to provide input to the test design,
• Review and provide input to the QAPP, and
• Review and provide input to the verification report and verification statements.
The names and affiliations of the verification test stakeholders will be listed in the final QAPP.
A5 BACKGROUND
A5.1 Technology Need
The ETV Program's MMR Center was scoped to verify the performance of materials
management technologies, and technologies to remediate contaminated land and groundwater.
Stakeholder committees of buyers and users of such technologies recommend technology
categories, and technologies within those categories, as priorities for testing. A technology
category recommended for testing is the application of ISCO.
ISCO involves the injection of chemical oxidants into groundwater and/or soil to rapidly
transform contaminants to nontoxic byproducts (e.g., carbon dioxide). Chemical oxidation can
be deployed under a variety of applications, in either the unsaturated or saturated zones. Many
environmental contaminants react at moderately high rates with these oxidants. ISCO can be
utilized for remediation of a wide variety of contaminants, including chlorinated solvents,
benzene, toluene, ethylbenzene, and xylenes (BTEX), methyl tertiary-butyl ether (MTBE), 1,4-
dioxane, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs).
ISCO can transform contaminants into less toxic compounds and be cost competitive in
comparison with other remediation technologies (pump and treat, monitored natural attenuation
[MNA], etc.)3.
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The technology tested under this plan is the application of chemical oxidants that can transform
undesirable chemical species into species that are harmless or non-objectionable. The testing can
focus on any oxidants available for ISCO (e.g., permanganate [MnO/f], hydrogen peroxide
[IHbCh], persulfate [S2Og2~], and ozone [63]). In addition, catalysts and chelating agents used in
conjunction with the oxidants will be tested. Hydrogen peroxide and sodium persulfate have
been catalyzed with ferrous iron and citric acid. Another potential activator for sodium
persulfate is the addition of sodium hydroxide. Site-specific conditions and parameters, in
conjunction with oxidant-specific characteristics, must be carefully considered to determine
which oxidant is most appropriate for deployment in the field3.
In order to expand the application of ISCO at manufactured gas plants with PAH contamination
(MGP/PAH) and at active gas station sites, this new application must gain acceptance. This
acceptance is based on the performance of the vendor's ISCO chemical against a set of
performance parameters. This protocol describes generic testing procedures to evaluate the
performance of ISCO that would be submitted by a vendor for testing.
A5.2 Technology Description
This section describes the specific ISCO chemicals identified for testing. This section will be
updated for the QAPP based on the participating oxidants. What follows is an example of what
might be included in this section; the text should be accompanied by figures, as appropriate,
that illustrate the principles of technology operation.
Chemical oxidation is a process in which the oxidation state of a substance is increased. ISCO
involves the introduction of a chemical oxidant into the subsurface to transform groundwater or
soil contaminants into compounds with lower toxicity. Radical intermediates formed using some
oxidants (H2O2, S2Og2", Os) are largely responsible for various contaminant transformations.
They react very quickly and persist for very short periods of time. The persistence of the oxidant
in the subsurface is important since this affects the contact time for advective and diffusive
transport and ultimately the delivery of oxidant to targeted zones in the subsurface. Activators
can be added to catalyze the formation of oxidant radicals. Persulfate can be combined with
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chelated metal complexes, and alkaline to catalyze the formation of sulfate radicals, a more
powerful oxidant3.
A6 VERIFICATION TEST DESCRIPTION AND SCHEDULE
A draft and final QAPP derived from this generic protocol will provide a plan for generating
performance data for ISCO application. The data generated are intended to provide
organizations and users interested in ISCO performance with information on the tested ISCO
chemical in comparison to a set of performance parameters.
The overall objective of the verification test is to test the application of ISCO at sites to oxidize
contaminants. Before field implementation, laboratory tests will determine the ISCO field
parameters using site soil and groundwater. The specific field parameters will be selected based
on performance characteristics from the lab tests. The verification test is designed to address and
quantify these performance characteristics.
A6.1 Verification Test Description
ISCO testing will consist of laboratory tests and injection of oxidant at a contaminated site. The
lab tests will use site soil and groundwater to determine the site-specific ISCO parameters such
as the oxidant, catalyst, chelating agent, oxidant concentrations, and activator concentrations.
The main contaminants of concern (COC) for the testing are expected to be organic
contaminants, such as, BTEX, chlorinated volatile organic compounds (CVOCs), and petroleum
hydrocarbons.
Lab testing will involve soil and groundwater characterization, ignitability tests for oxidants
when combined with combustible materials (e.g. gasoline), exposure of subsurface materials to
oxidants, natural oxidant demand (NOD), soil pH buffering tests, and macrocosm tests.
Field testing will involve applying the oxidant to the subsurface at a contaminated site, collecting
soil-gas samples in the vadose zone before and after oxidant injection (to determine volatilization
versus destruction), analyzing groundwater for COC and residual oxidant at specific time points.
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The performance factors include a focus on safety for lab tests to determine the effect of
exposure of oxidants on subsurface materials, and to determine if and/or how readily oxidants
will ignite when exposed to combustible materials In the field, safety concerns will be addressed
by soil-gas sampling to determine if contaminant vaporization is occurring, metals will be
analyzed before and after oxidant injection to understand the scope of metals mobilization, and
the temperature will be measured to determine if there is a rapid temperature increase as a result
of oxidant addition.
Additional performance factors include: the percent reduction of the contaminant in NAPL
sorbed and aqueous phases, the radius of influence (ROI) of the oxidant in the subsurface, the
degradation ratio (mass oxidant required to remove a certain mass of contaminant), the
persistence of the oxidant in the subsurface after injection, and operational parameters. After the
lab and field testing, operational parameters, such as, the required personal protective equipment
(PPE), the ease of oxidant injection, the cost, size of equipment used, the length of the injection
period, the time until completion of the remediation, and the need for further reinjection will be
evaluated and documented.
ISCO will be verified for the following performance parameters (attributes):
• Safety,
• Percent Reduction/ Need for additional injection
• Technology Specific Oxidant Demand,
• Distribution of Oxidant/ROI,
• Degradation Ratio,
• Persistence, and
• Operational Parameters (required PPE, ease of injection, cost, size of equipment,
length of injection period, remediation time),
A6.2 Proposed Testing Schedule
Table 1 shows an estimated schedule of testing and data analysis/reporting activities to be
conducted in a verification test designed using this generic protocol. Data from the verification
testing should be immediately checked by the testing staff. For each oxidant, data should be
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compiled, recorded, and transmitted to the VTC on the first day of testing and on a weekly basis
thereafter so that any data quality issues can be rapidly identified. The VTC should post the first
day of testing data for QA review within five days of test initiation and the remaining data every
two weeks thereafter. Unaudited data should include the disclaimer "has not been reviewed by
Battelle QM."
Table 1. Estimated Verification Testing Schedule
Task
Finalize QAPP
Test Preparation
Lab Testing at Battelle
Testing at Field Site
Draft report
Final report
Technical Systems Audits
Audit of Data Quality
Month 1
Month 2
X (lab)
X (lab)
Month 3
Month 4
X (field)
X (field)
Month 5
Month 6
A6.3 Testing Facilities
The ISCO lab testing will be conducted at Battelle's Columbus, OH laboratories. Field testing
will occur at a contaminated site. Battelle treatability laboratories are equipped with the
necessary labware (glassware, electrodes, Tumbler, spectrophotometer, etc.) to conduct the ISCO
experiments. Laboratory studies will determine the site specific parameters (NOD, pH buffering
capacity, degradation ratio, oxidant type, oxidant concentration, chelating agent, catalyst, and
oxidant persistence). Field locations will be found with soils that have a broad spectrum of
characteristics including but not limited to COCs, mineralogy, and geochemical attributes, in
order to expand the understanding of soil chemistry/ISCO interactions. Ideal site conditions
where ISCO can be applied include, but are not limited to, the following: sites with
sandy/porous permeable soils, sites with shallow groundwater aquifers, sites that cannot be
remediated by traditional mechanical methods, sites located away from any drinking water zones
or aquifers, and sites located away from any underground utilities.
The vendor must train Battelle staff in the handling and application of their ISCO chemical. It is
anticipated that the same staff will be involved in the laboratory and field testing.
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A7 QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA
The objective of these verification tests is to verify the performance of ISCO chemicals against
vendor recommended parameters. The verification tests will also rely upon operator
observations to assess other performance characteristics of the ISCO chemicals including data
completeness, ease of use, and maintenance requirements.
Quantitative performance parameters for vendor ISCO chemical performance are discussed in
Section B. Additionally, the verification tests rely in part on observations of the Battelle testing
staff for assessment of the performance of the ISCO chemical. The requirements for these
observations are described in the discussion of documentation requirements and data review,
verification, and validation requirements for these verification tests.
The Battelle QM or designee will perform a technical systems audit (TSA) of laboratory testing
activities to augment these QA/QC requirements. A TSA will be performed at Battelle during
lab testing and at one participating site during field testing and will occur within the first week of
each testing phase.
A8 SPECIAL TRAINING/CERTIFICATION
Documentation of training related to ISCO chemical testing, safety of handling ISCO chemical,
data analysis, and reporting is maintained for all Battelle technical staff in training files at their
respective locations. The Battelle QM may verify the presence of appropriate training records
prior to the start of testing. The vendors will be required to train technical staff from Battelle and
each participating utility prior to the start of testing. Battelle will document this training with a
consent form, signed by the vendor, which states which staff has been trained to use the vendor's
ISCO chemical. In the event that other staff members are required to use the ISCO application,
they will be trained by the Battelle staff that was trained by the vendors. Battelle technical staff
supporting these verification tests has a minimum of a Bachelor's degree in a scientific field or
equivalent work experience.
A9 DOCUMENTATION AND RECORDS
The documents for these verification tests will include the final QAPP, vendor instructions,
reference methods, the verification report, verification statement, and audit reports. The project
records will include certificates of analysis (COA), chain-of-custody forms, laboratory record
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books (LRBs), data collection forms, electronic files (both raw data and spreadsheets), and QA
audit files. The final QAPP should include the forms to be used for lab and field data collection.
All of these documents and records will be maintained at the laboratory, with the participating
field sites, or in the VTC's office during the tests. At the conclusion of testing, all raw data and
test records will be provided to the VTC. All test records will be transferred to permanent
storage at Battelle's Records Management Office (RMO) at the conclusion of the verification
tests. Electronic documents and records will also be uploaded to a SharePoint site designated for
these tests and will be provided upon request. All Battelle LRBs are stored indefinitely by
Battelle's RMO; other project-related data are stored for 10 years. Section BIO further details
the data recording practices and responsibilities.
All data generated during the conduct of this project will be recorded directly, promptly, and
legibly in ink. All data entries will be dated on the date of entry and signed or initialed by the
person entering the data. Any changes in entries will be made so as not to obscure the original
entry, will be dated and signed or initialed at the time of the change and shall indicate the reason
for the change. Project-specific data forms will be developed prior to testing to ensure that all
critical information is documented in real time. The draft forms will be provided to the Battelle
QM for review prior to use so that appropriate changes, if any, can be made.
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SECTION B
MEASUREMENT AND DATA ACQUISITION
Bl EXPERIMENTAL DESIGN
The verification tests described in this generic protocol address verification of ISCO by
evaluating the following performance factors:
• Safety,
• Percent Reduction / Need for Reinj ection
• Technology Specific Oxidant Demand,
• Distribution of Oxidant/ROI,
• Degradation Ratio,
• Persistence, and
• Operational Parameters (PPE, ease of injection, cost, size of equipment, length of
injection period, remediation time.
Before field testing, lab studies will be conducted to:
(1) Characterize the soil and groundwater from the site. Soil characterization will include:
metals, physical properties (e.g., bulk density, particle size distribution, fractional organic
carbon [FOC], and percent moisture), and COCs. Groundwater characterization will
include: metals, alkalinity, anions (chloride, sulfate, sulfide, and nitrate), and field
parameters (pH, oxidation reduction potential [ORP], and conductivity, and temperature).
(2) Determine the NOD. Finding the NOD will give an understanding of the interaction
between the organic matter in the soil and the oxidant. The NOD must be found before
conducting macrocosm studies with oxidant, soil and groundwater, as the NOD will be
taken into account when choosing oxidant concentrations.
(3) Determine the soil pH buffering capacity. The pH buffer capacity test will determine the
soil's ability to resist a change in pH upon the addition of alkaline or acidic solutions.
Knowing the soil pH buffering capacity will be essential for proper dosing during testing
with alkaline activated sodium persulfate.
(4) Expose oxidant to subsurface materials (e.g., ductile iron, carbon steel, concrete, etc.)
typically found at field sites. Subsurface material physical properties (yield strength,
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tensile strength, elongation, and hardness) will be measured before and after oxidant
application to determine the affect of the oxidant on the subsurface materials. Testing
exposure of oxidant to the subsurface material is a safety performance parameter of the
verification test.
(5) The ISCO chemicals will also be tested for ignitability. This safety parameter will
determine how readily the oxidant will ignite when applied to combustible materials, e.g.
gasoline.
(6) Prepare macrocosm tests to determine the oxidant, catalyst, chelating agents, and dosages
to not only successfully degrade organic contaminants, but to also not weaken the
subsurface materials at a field site.
(7) Calculate the percent reduction in contaminant concentration, in soil and/or groundwater
after the addition of oxidant at a number of time points.
(8) Calculate the degradation ratio, the mass of oxidant that is required for removal of a
certain amount of contaminant. The field oxidant dosage will be based on the results from
the laboratory study.
The following tests will be conducted in the field:
(1) Determine the persistence of oxidant in the subsurface. Persistence is the rate at which
the oxidant reacts with the organic matter and contaminants along with in situ field
parameters. This would be determined in the field by measuring oxidant concentration
over time in the monitoring wells.
(2) Measure the soil-gas concentration in the vadose zone before and after the injection of the
oxidant to determine if the contaminant is vaporized during injection of the oxidant. The
concentration of metals will also be measured in the groundwater before and after oxidant
application. There is a possibility of increased metals mobility due to the change in
geochemical conditions in the soil after ISCO application. The temperature in the
subsurface will also be measured in the field to ensure that the oxidant does not rapidly
increase subsurface temperatures. Measuring the soil-gas concentration, metals in the
groundwater, and temperature in the subsurface are field safety performance parameters.
(3) As a performance parameter, the percent reduction of contaminant will be used from the
lab tests to determine the field test parameters (type of oxidant, activator, and dosage).
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Determining the percent reduction from field samples will not only show how well the
oxidant in interacting with the contaminant but will also be used as a comparison with the
lab results. Comparing the percent reduction from the field to the lab will demonstrate
how well the lab macrocosm tests simulate field conditions.
(4) Measure the ROI of the oxidant. The ROI is the ability of the oxidant to travel through
the subsurface both horizontally and vertically. In the field, the residual oxidant
concentration will be measured from monitoring wells after injection, unless direct push
measurements are suitable by coring, hydropunch samples or electrical conductivity.
Higher resolution of vertical distribution is not always achievable through monitoring
well data alone.
Table 2 presents a summary of the tests to be performed. The verification test will be conducted
during an approximate 6 month timeframe.
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Table 2. Summary of Test Data Quality Indicators and Testing Frequency
Phase
Lab
Lab
Lab
Field
Performance
Parameter
Safety
Technology
Specific
Oxidant
Demand
Pprppnt
n c? i oc? 1 1 1
Reduction,
Degradation
Ratio,
Persistence
Percent
Reduction
Degradation
Ratio,
Persistence,
ROI
Objective
Before field
implementation at
site, determine if the
oxidant will weaken
subsurface
materials.
Conduct ignitability
tests for the oxidants
Determine the
oxidant demand
from organic matter
in site specific soil
Macrocosm tests
using site soil and
ground water will
determine the
appropriate oxidant,
dose, and catalyst
before field
implementation.
Apply oxidant to the
field at
concentrations
determined from the
lab tests to oxidize
organic
contaminants to less
toxic compounds
Comparison
Based On
Vendor
recommended
criteria
Vendor
recommended
criteria
Vendor
recommended
criteria
Vpnrlor
V C?l IU\_/I
recommended
pritpria
\sl lid ICI
Testing
Frequency
Each oxidant
exposed to 2
subsurface
materials at a
high and low
concentration
Ignitability test
with
combustible
material on
each oxidant
Each oxidant at
3
concentrations,
residual oxidant
tested after 0
hr, 1 hr, 4 hr, 8
hr, 24 hr, daily
thereafter up to
168 hours.
Two
concentrations
of each oxidant
Samples will be
measured for
residual
oxidant, COC,
PH,
temperature
Soil and
groundwater
samples will be
analyzed for
residual
oxidant, COC,
PH,
temperature
Number of
Data
Points
TBD
TBD
TBD
TBD
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Phase
Field
Performance
Parameter
Safety
Objective
Collect soil gas
samples from the
vadose zone to
determine if
contaminant
vaporization is
occurring, collect
metals samples in
the groundwaterto
determine the scope
of metals
mobilization due to
ISCO application
Comparison
Based On
Vendor
recommended
criteria
Testing
Frequency
Soil-gas
samples
collected
before and
after injection,
metal samples
will be collected
before and
after injection
Number of
Data
Points
TBD
Bl.l Lab Testing
This section describes the specifics of the various laboratory tests. These tests will be critical
before oxidant injection in the field. Lab testing will involve characterization of the soil and
groundwater, ignitability tests for oxidants, and exposure of subsurface materials to oxidants. In
addition, the soil oxidant demand, and buffering capacity will be measured. Extensive
macrocosm tests will determine the oxidant, catalyst, chelating agent, and dosages based on the
performance parameters.
B1.1.1 Soil, Groundwater, Subsurface Materials, Oxidant Characterization
Soil grab samples will be characterized for particle size, bulk density, COC, Foe, and percent
moisture. Soil samples may have to be shipped to outside laboratories for analysis.
Groundwater parameters such as alkalinity, total iron, sulfate, sulfide, and nitrate will be
analyzed at Battelle. These aquifer parameters can be measured using a HACK DR5000 UV-Vis
Spectrophotometer. Metals and COCs will also be analyzed in groundwater. The pH, ORP, and
temperature will be measured onsite with a Horiba U22 water quality monitoring system during
groundwater sample collection.
Ignitability tests will be conducted on oxidants and combinations of oxidant with catalysts with
combustible material to determine how readily the oxidant will ignite. Each oxidant will be
tested at typical field concentrations for ignitability.
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The physical properties of typical subsurface materials found at field sites such as tensile
strength, and hardness will be found. Each oxidant will be exposed to two subsurface materials
(e.g., ductile iron, carbon steel, concrete etc.) at a high and low concentration for the tests. The
subsurface materials and oxidants will be placed in 2 L high density polyethylene (HDPE)
containers and tumbled on a Rotary Agitator (Associated Designs Co.) at 30 rpm for 48 hours.
After 48 hours, the physical properties of the materials will tested and compared to the baseline
condition using the appropriate American Society for Testing and Materials (ASTM), American
Welding Society (AWS), and American Society of Mechanical Engineers (ASME) methods.
Bl.1.2 Technology Specific Oxidant Demand and SoilpH Buffering Tests
The NOD test is an estimation of the consumption of an oxidant due to reactions by organic and
reduced species in the soil and groundwater that are unrelated to the breakdown of the COC.
Soils rich in organic matter have a high oxidant demand and, therefore, determining the NOD is
critical in finding the required chemical dosage. The NOD test procedure has the following
steps:
(1) Determine the NOD at three concentrations for each oxidant. Choose a maximum
oxidant dose. The other two concentrations are found at half and one-tenth of the
maximum dose. Sodium persulfate concentrations can range from 20 to 200 g/L in the
field.
(2) Air dry soil overnight. Remove stones, twigs, and other debris from the soil. Measure
the particle density of the dry soil. In a 40 mL volatile organic analysis vial volatile
organic analysis (VOA) add dry soil at a 1:1 v/v solids to solution ratio. Use amber
VOAs with a Teflon® lined septa cap.
(3) Add oxidant solutions to soil in each VOA. If activators are being tested with oxidants
then solutions should be prepared with activators at potential field test conditions.
Prepare all solutions using site groundwater. The VOAs should be filled leaving minimal
headspace. Shake the VOA vigorously to mix the contents.
(4) After allowing the soil to settle, measure the residual oxidant in the water layer as a time
zero sample (the protocol for measuring residual oxidant is listed below). Remove the
sample volume needed for the oxidant measurement with a syringe through the septa.
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(5) Tumble the VOAs at 30 rpm. Measure the residual oxidant after 1 hr, 4 hr, and 8 hr.
Measure the oxidant every 24 hours after the time zero sample up to 168 hours, or until
there is a minimal change in oxidant (5 to 10%). Venting the sample may be required if
soil is rich in organic matter and organic contaminants. Samples should be vented by
piercing the septa with a high gauge needle (thin diameter) before sample collection.
Note the there is an ASTM method for permanganate.
Note that it is not possible to do a NOD with peroxide since it reacts too quickly.
Note for activated persulfate the NOD test should be done with the activator as well.
The oxidant depletion rate can be estimated over the range of tested doses by plotting the
depletion rate versus initial oxidant dose.
Bl.1.3 Measuring Residual Oxidant
The concentration of residual oxidant will be determined using iodometric titration. Oxidant
samples will be titrated with sodium thiosulfate. The concentration of oxidant can be determined
by the stoichiometric relationship between thiosulfate and the oxidant. Residual oxidant can be
found by the following steps:
• Add 50 mL of de-ionized water into a 125 mL Erlenmeyer flask.
• Add 2 g of potassium iodide into the flask.
Hydrogen Peroxide:
(1) Add 10 mL 25% (by weight) sulfuric acid into flask.
(2) Add a few drops of ammonium molybdate (3% by weight).
(3) Using a micropipette add 0.1 to 0.25 mL of oxidant sample solution into the flask and mix.
(4) Place flask on a stir plate. Add a stir bar and titrate with 0.1 N sodium thiosulfate (0.01 N
should be used for lower concentration solutions) while continuously stirring.
(5) When sample is straw yellow (very light yellow), add several drops of starch solution (2% by
weight) until dark blue/purple.
(6) Add drops of thiosulfate until clear. Record final volume and use volume to estimate
oxidant concentration. Note that the reaction is reversible, as oxygen from air partitions back
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into solution, it will return to blue/purple color again. Do not continue titrating once the solution
is clear. Use the following equation to determine the percentage of EbCh in the sample.
0.1 mole thiosulfate 1 mole E202
% H202 = x ml 0.1 N Thiosulfate *
1000 mL Thiosulfate solution 2 mole Thiosulfate
34gH202 1
* * * 100
1 mole H202 y g solution added
Permanganate:
(1) Add 10 mL 25% sulfuric acid into flask.
(2) Added volume of sample solution depends upon expected concentration of
permanganate:
-0.25 mL oxidant solution for 10 g/L to 20 g/L permanganate
-0.5 mL oxidant solution for 5 g/L to 10 g/L permanganate
-1.0 mL oxidant solution for 0.5 g/L to 5 g/L permanganate (less than 1 g/L use
colorimetric method).
(3) Titrate with 0.01 N sodium thiosulfate while continuously stirring on a stir plate.
(4) When sample is straw yellow (very light yellow), add several drops of starch solution
(2% by weight) until dark blue/purple.
(5) Add drops of thiosulfate until clear. Record final volume and use volume to estimate
oxidant concentration.
g
x-Potassium Permanganate
L
0.01 mole thiosulfate
= y ml 0.0IN Thiosulfate *
1000 ml Thiosulfate solution
1 mole Permanganate 158 g Potassium Permanganate
5 mole Thiosulfate 1 mole Potassium permanganate
1 1000 ml
y ml solution added 1 L
Persulfate
(1) Add to 2 g sodium bicarbonate into flask.
(2) Add 10 mL 25% sulfuric acid. Sulfuric acid should be added slowly as bicarbonate will
bubble over if added too quickly.
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(3) Add 0.25 mL of oxidant solution (volume can vary depending on concentration) and mix.
(4) Cover flask (parafilm or stopper) and let stand in dark for a minimum of 15 minutes.
Test duration with control as persulfate reaction can be very slow.
(5) Titrate with 0.01 N sodium thiosulfate (use 0.1 N for higher concentration solutions)
while continuously stirring on a stir plate.
(6) When sample is straw yellow (very light yellow), add several drops of starch solution
(2% by weight) until dark blue/purple.
(7) Add drops of thiosulfate until clear. Record final volume and use volume to estimate
oxidant concentration.
x g/L Sodium Persulfate
0.01 mole thiosulfate
= y ml 0.0IN Thiosulfate *
1000 mL Thiosulfate solution
1 mole persulfate 238 g Persulfate 1 1000 ml
# * * *
2 mole Thiosulfate 1 mole Persulfate y ml solution added 1 L
Bl.1.4 SoilpHBuffer Capacity
The soil pH buffer capacity test will determine the soil's ability to resist a change in pH upon the
addition of alkaline or acidic solutions. The results of the pH buffering test will be used during
the alkaline activated sodium persulfate macrocosm tests. The test procedure has the following
steps:
(1) Weigh approximately 500 g of wet soil in a glass tray and air dry.
(2) After drying the soil, use a pestle to break up the larger clumps of soil. Remove the
stones, twigs, and roots.
(3) Calibrate the pH meter at pH 4, 7, and 10. The percent calibration should be above 96%.
(4) Prepare a stock solution of sodium hydroxide in de-ionized water (18.2 M Q-cm
resistivity). Verify the concentration by determining the density of the solution at room
temperature and finding the corresponding concentration in the CRC Handbook of
Chemistry and Physics.
(5) Prepare 50 mL of the following NaOH solutions 0, 0.001, 0.005, 0.01, 0.02, 0.04, 0.06,
and 0.08 M by diluting the NaOH stock. Prepare the solutions in a 50 mL volumetric
flasks using de-ionized water.
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(6) Add ten-grams of dried soil into a wide-mouth 125 mL HDPE bottle. Add twenty-five
milliliters of NaOH solution into the bottle using a 25-mL disposable pipette.
(7) Shake the eight bottles well by inverting them before placing them on an orbital shaker.
Set the orbital shaker at 100 rpm, and shake for one-hour.
(8) After one- hour, remove the bottles from the shaker and allow the contents to settle for 20
minutes.
(9) After settling, measure the pH in the water layer. The pH buffering capacity will be
determined from the slope of the graph of the milliequivalents (meq) NaOH added/1 OOg
soil versus the soil pH. The pH buffering capacity has units of meq NaOH/lOOg soil *
pH.
(lO)For persulfate pH needs to stay above 10.5 for about 30 days; therefore, the buffering test
needs to be long enough to demonstrate the persistence.
Bl.1.5 Macrocosm Tests
The objective of the macrocosm tests is to determine the parameters necessary to the design the
field-scale treatment test. Specific objectives include:
(1) Determine concentrations of ISCO amendments (i.e., oxidant, catalyst, dosages)
necessary to oxidize elevated concentrations of organic contaminants in soil.
(2) Determine persistence for ISCO, which will help to assess treatment time in situ.
Measure the concentration of ISCO amendments at different time points.
(3) Evaluate the percent reduction in contaminant concentration in macrocosms at a number
of time intervals.
(4) Evaluate the degradation ratio, the mass of oxidant needed to remove a certain mass of
contaminant.
The macrocosms will be prepared with soil and groundwater in a ratio that is representative of
conditions expected in the field. Macrocosms will be prepared in 250 mL amber bottles, with
Teflon® lined screw caps. The bottles will be filled with sufficient volume to analyze a number
of parameters. An example sample matrix is shown in Table 3. The concentrations of oxidant
for the test will be chosen from typical field concentrations at ISCO sites. The NOD will be
taken into account when selecting the oxidant concentrations. The results of the pH buffering
test will be used when preparing alkaline activated oxidant macrocosms. Two activators,
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including iron sulfate and sodium hydroxide (NaOH), will be tested. Sodium citrate also will be
used in several of the macrocosms in order to chelate the iron sulfate as well as to facilitate
solubilization of iron naturally present in the soil. Aqueous samples will be withdrawn from the
sacrificial macrocosm bottles for oxidant, metals, COC, pH, ORP, nitrate, sulfate, sulfide, and
chloride analysis. The anions will be found using a HACK DR5000, which requires a small
sample volume for each measurement. Samples will be collected at time zero (baseline) and at
other time points that will be defined in the QAPP for the verification test.
Table 3. Macrocosm Sample Matrix
Potential
Oxidant
Types:
Catalyst &
Chelant:
Oxidant
Dose
Oxidant:
Fe(ll):Citric
Acid:NaOH
Molar Ratio
Liquid to
Solid Ratio
Sampling
Frequency
Catalyzed
Hydrogen
Peroxide
Fe(ll)
pnn
g/kg
(as
H202)
100:
1
TBD
TBD
Fe(ll) +
Citric
Acid
200
g/kg (as
H202)
100: 1
:2
TBD
TBD
Catalyzed Sodium
Persulfate
Fe(ll)
100
g/L
as
Na2S2
08
100:
1
TBD
TBD
Fe(ll) +
Citric
Acid
100 g/L
as
Na2S2Os
100 :1:1
TBD
TBD
NaOH
100
g/L as
Na2S2
08
(b)
TBD
TBD
Potassium
Permanganate
NA
1.0 g/kg as
MnO4~
NA
TBD
TBD
Ozone
NA
TBD
NA
TBD
TBD
Analysis
Oxidant,
COC, pH,
ORP,
nitrate,
sulfate,
sulfide,
chloride
(a) The oxidant dose varies based on a number of factors including but not limited to initial
concentration of the COC, site geology, and NOD.
(b) Alkaline molar ratio to be determined from soil pH buffering test.
B1.2 Field Testing
Parameters Measured Contaminant concentration will be measured in performance monitoring
wells within and outside of the radius of influence of the injection points. Parameters that will be
measured in include ORP, DO, pH, alkalinity and conductivity. Soil-gas samples to measure
contaminant vapors in the vadose zone will be collected using the procedure in Section B2.
Samples will be collected in the vadose zone before and after the injection of the oxidant to
determine if the contaminant is vaporized during injection of the oxidant. The concentration of
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metals will also be measured in the groundwater before and after oxidant application. Samples
will be collected from groundwater wells and analyzed for the eight Resource Conservation and
Recovery Act metals. The temperature in the subsurface will also be measured in the field to
ensure that the oxidant does not rapidly increase subsurface temperatures.
Injection and Monitoring Wells. For an ISCO pilot study a minimum of four injection wells is
recommended with monitoring wells placed between the injection wells. A minimum of three
injections wells should be installed. Depending on the expected radius of influence the
monitoring wells should be placed at different distances from the injection wells to determine the
distribution of the oxidant during the pilot study.
Monitoring Frequency. Baseline monitoring should be conducted in all monitoring wells prior to
injection of the oxidant to fully understand site conditions. If possible baseline sampling over
time should be conducted to evaluate natural contaminant concentration changes. Sampling
frequently after injection is required to determine the distribution of the oxidant. Initially
sampling can be conducted every two weeks or once per month with sampling frequency
decreasing as time after injection increases.
B1.3 Operational Parameters
Field operational parameters include:
(1) Determining the required amount of PPE during testing. In the field, PPE will be selected
based on the potential hazard of contaminant vaporizing during injection of oxidant, and
the hazards of working with concentrated caustic solutions and oxidants. At a minimum
field personnel should be equipped with eye protection (goggles and face shield), a hard
hat, respiratory protection (dust mask and acid gas cartridges) steel toed boots, gloves
(nitrile or neoprene), and clothing protection (long sleeves, pants, a Tyvek® suit should be
considered).
(2) Cost factors include: mobilization, well installation, labor for oxidant injection, labor for
sample collection (soil-gas, COC, oxidant, etc.), materials, equipment rental, travel,
sample analysis, and subcontractor costs. The cost will be directly related to the size of
the treatment area.
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(3) Understanding the ease of oxidant injection, the length of the injection period, equipment
size and compatibility with oxidants, and the injection duration time.
(4) Oxidant re-injection may be required, if COC concentrations are high, significant mass
sorbed to soil, or if there is incomplete contact (actual contact or residence time) of
oxidant with the contaminant in the subsurface. There may be regions in the treatment
target area where the oxidant will not reach due to site geometry or partitioning of the
contaminant mass. Pilot tests are often limited by budget and involve just one injection.
During the pilot test it should be determined whether subsequent injections will be
required in the entire treatment area or in the hot spots.
B1.4 Operational and Sustainability Factors
Operational and sustainability factors such as waste generated, maintenance needs, calibration
frequency, data output, consumables used, power requirements, hazardous components, ease of
use, repair requirements, and sample throughput will be evaluated based on operator
observations. Battelle testing staff and testing staff from any participating field sites will
document observations in a LRB or data sheets. Examples of information to be recorded include
the oxidant injection volume, oxidant concentration, oxidant solution flow rate, injection
pressure, and geochemical measurements (nitrate, chloride, sulfate, iron, alkalinity, etc.).
B1.5 Statistical Evaluation
The statistical methods and calculations used for evaluation of the quantitative performance
parameters are described in the following sections.
Bl.5.1 Percent Reduction
For lab and field testing, the percent reduction of the COC will be determined from soil and/or
groundwater samples at different time points (that will be determined during QAPP
development) after the addition of the oxidant. Percent reduction will be determined for the
contaminant of concern by subtracting the contaminant concentration from the matrix at a time
point after oxidant addition from the initial contaminant concentration and dividing by the initial
concentration (Equation 1).
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r-. r-i T • inn I Inital ContaTtilnat Concentration—Contaminant Concentration after Oxidant Addition! /i \
Percent Reduction = 100 (1)
Inital Contaminat Concentration v '
Bl.5.2 Degradation Ratio
The degradation ratio will be evaluated from soil and/or groundwater samples from the lab and
field tests. The degradation ratio will be calculated by finding the mass of oxidant required to
remove a certain amount of contaminant at a particular time after oxidant addition. The
degradation ratios from the lab tests will be another performance parameter used to identify the
field test parameters. Furthermore, determining the degradation ratio in the field will serve as an
indicator of how well the oxidant is transforming the contaminant into less toxic compounds.
The degradation ratio will be calculated using Equation 2:
r. j *• n *• Mass of Oxidant
Degradation Ratio = (2)
" Mass of Contaminant Degraded by Oxidant Addition
Bl.5.3 Persistence
The persistence is the rate at which the oxidant reacts with the organic matter and contaminants
along with in situ field parameters. The persistence will be measured from macrocosm samples
during the lab tests in the field. Determining how long the oxidant persists in the subsurface will
be accomplished by measuring the residual oxidant in groundwater monitoring wells at time
intervals (that will be determined during QAPP development) after initial oxidant addition during
the field study.
Bl.5.4 Technology Specific Oxidant Demand
Laboratory tests will determine the natural oxidant demand for the site soil. The NOD will be
determined for each tested oxidant and combination of oxidant with activators. The results of the
NOD test will help determine the concentration of oxidant to apply in the field. The NOD will
be found at a number of time intervals by dividing the residual oxidant remaining by the mass of
soil. The reaction of the oxidant with the NOD is a second order reaction and there for dependent
on oxidant concentration. The units of the NOD are mg oxidant/kg soil. The oxidant demand
will be found by using Equation 3:
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Natural Oxidant Demand =
Volume of Solution (Initial Oxidant Concentration-Residual Oxidant Concentration)
(3)
Masso/5oi(
B1.6 Reporting
The statistical comparisons described above will be conducted separately for the ISCO chemical,
and information on the operational performance will be compiled and reported. At least one
verification report will be prepared for each ISCO chemical. The verification report will present
the test procedures and test data, as well as the results of the statistical evaluation of those data.
Operational aspects of the technologies will be recorded by testing staff during and immediately
following testing and will be summarized in the verification report. For example, descriptions of
the data acquisition procedures, consumables used, repairs and maintenance needed, and the
nature of any problems will be presented in the report. The verification report will briefly
describe the ETV program, the MMR Center, and the procedures used in verification testing.
The results of the verification tests regarding ISCO chemical performance will be stated
quantitatively. The draft verification report will be reviewed by the vendor and peer reviewers.
The resulting review comments will be addressed in a subsequent revision of the report, and the
peer review comments and responses will be tabulated to document the peer review process. The
reporting and review process will be conducted according to the requirements of the ETV/MMR
Center QMP, in as much as they do not require inclusion of EPA.1
B2 SAMPLING METHOD REQUIREMENTS
Soil and groundwater will be shipped to Battelle labs in sufficient quantities to conduct the lab
testing. Soil samples should be collected in areas with the highest contamination. Groundwater
samples should be collected from wells in the screen interval of the water table where
contaminants are expected to be found. Groundwater should be collected from wells after
purging with a peristaltic pump or bailer. Samples should be shipped in 5 gallon buckets and in
oversize containers to ensure no leaking or spilling or the contents.
Upon receipt of the soil material, subsurface materials, and groundwater, samples will be
characterized at laboratory facilities in Battelle; however, some analysis may have to be
conducted in labs outside Battelle. Those samples will be shipped in coolers to the respective
labs for analysis.
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The soil-gas concentration will be measured in vadose zone during and after oxidant injection.
Soil-gas sampling will be collected from soil-gas monitoring points. They are generally installed
at three or more depths and in at least three locations. A monitoring point consists of three nylon
tubes extending from the ground surface to a screened depth. The screen is surrounded by a sand
pack. A bentonite seal at least 2 feet thick is placed above and below the sand pack to ensure
that pressure and soil-gas samples are collected discretely at that depth. The nylon tubing may
be connected with quick-connect couplings. Soil-gas samples are collected by attaching a tubing
from the quick-connect to a vacuum pump. A desiccator will be attached to the tubing before the
vacuum pump to remove any moisture. A 1-L Tedlar® bag will be attached after the pump to
store the gas sample. Before sample collection, the monitoring point will be purged with the
pump to remove approximately 1 to 2 L of soil-gas. The soil-gas samples can be analyzed in the
field for total petroleum hydrocarbon, carbon dioxide, and oxygen using a gas analyzer or the
Tedlar® bags can be shipped to a laboratory for analysis. Hand-driven gas probes (1-inch
diameter, stainless steel) can be used primarily at sites with relatively shallow water tables or
where soils are penetrable to a depth of within 5-feet of the water table.
B3 SAMPLE HANDLING AND CUSTODY REQUIREMENTS
Each sample bottle will be affixed with a pre-printed label consisting of sample identification,
date and time of sample collection, collector's name, sample destination, analysis required, and
preservative (as appropriate). In addition, all sampling- and shipping-related materials, such as,
chain-of-custody forms, and prepaid/addressed FedEx air bills will be included. Samples will be
packed carefully with wet ice in double zip-lock bags.
B4 ANALYTICAL METHOD REQUIREMENTS
Site groundwater parameters (chloride, total iron, sulfate, not needed?, and total alkalinity) will
be analyzed at Battelle using a HACK DR 5000 UV-Vis Spectrophotometer. Testing using the
Hach will follow the methods supplied by the manufacturer. The necessary reagents and powder
pillows will be purchased from the manufacturer. Tests will require a small amount of sample
volume. Samples may have to be filtered with a 0.45 jim syringe filter if the groundwater
contains excessive particulate matter. The test methods, and analytical range are listed in Table
4.
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Soil, groundwater, oxidant, and subsurface material analytical tests (e.g., particle size
distribution, bulk density, percent moisture, metals, ignitability, tensile strength, and COC) will
be determined following the appropriate EPA or ASTM method by outside laboratories
(Table 5). In accordance with the method, Battelle will collect the samples in the appropriate
container, add the recommended preservative, and ship the sample (if required) to the laboratory
within the hold time for analysis.
Table 4. HACH DR5000 Tests, Method, and Range
Parameters
Chloride
Total Iron
Sulfate
Sulfide
Nitrate
Total Alkalinity
Method
Hach8113
Hach 8008
Hach 8051
Hach 81 31
Hach 8039
Hach 10239
Range
0.1 -25 mg/L Cl-
0.02-3 mg/L
2-70 mg/L
5-800 |jg/L
0.3-30 mg/L
25-400 mg/L
CaCOs
Unit
mg/L
mg/L
mg/L
ljg/L
mg/L as NOs-N
mg/L as CaCOs
Table 5. Soil, Groundwater, and Subsurface Material Analytical Tests
Parameters
Particle Size Distribution
Bulk Density
Percent Moisture
Total Metals
Volatile Organic Compounds
Ignitability
Tensile Strength
Hardness
Method
ASTM D 422
ASTM C29
ASTM D 22 16
EPA SW6020
EPA 8260/5035
U.S. EPA Method
1010
ASTMA615A370
ASTM A370
Laboratory
TBD
B5 QUALITY CONTROL REQUIREMENTS
QC procedures will follow the requirements described in this protocol, the final QAPP, the ETV
QMP2, and any specified requirements for analysis. All standard values and equipment
calibrations for these technologies will be documented in the study records. Potential QC
samples include: method blanks, analytical duplicates, sample duplicates, and standard reference
materials (SRM).
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B6 INSTRUMENT/ EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE
Battelle staff will operate and maintain the necessary instruments. Maintenance and calibration
information of equipment related to ISCO testing are included in Table 6.
B7 INSTRUMENT CALIBRATION AND FREQUENCY
Field measurements, such as pH, ORP, conductivity, and temperature will be measured using a
Horiba U22 probe. The probe will be calibrated in the field daily before taking measurements.
The probe will be calibrated by placing it in a standard solution that simultaneously calibrates the
instrument for all the measuring parameters.
A Thermo Scientific pH and ORP probe will be used for the measurements in lab macrocosm
samples. Prior to the measurements, the pH probes will be calibrated. A three-point calibration
will be done on the pH probe at a pH of 4, 7, and 10. The calibration will be deemed successful
is the calibration slope is 96% or higher. The accuracy of the ORP probe will be checked with
quinhydrone solutions.
Table 6. Maintenance and Calibration of Equipment
Test
100-1, 000 ul
Pipette for
NOD, pH
Buffering
Capacity,
Macrocosm
Tests
Horiba U-22
probe (pH,
ORP,
dissolved
oxygen,
conductivity)
Thermo
Scientific pH
probe
HACH
DR5000
Bench-top
Analytical
Balance
Method of
Assessment
Type of
Calibration:
17025; Method:
ISO type A 1x5
ml, accuracy will
also be checked
gravimetrically
Standard Solution
Buffering Solution
Self diagnostic
test; standard
solutions
Accuracy
checked with
weights
bracketing the
target weight
Frequency
Calibrated
every 6
months,
accuracy
checked prior
to use
Daily prior to
use
Daily prior to
use
Daily prior to
use
Daily prior to
use
Acceptance Criteria
Within uncertainty
measurement for pipette (ul)
96% > calibration slope
96% > calibration slope
±5% of standard solution
±0.1% of stated value
Corrective
Action
Recalibrate or
replace
Recalibrate;
repeat
measurements if
calibration not
met after tests
Recalibrate;
repeat
measurements if
calibration not
met after tests
re-start
instrument
re-zero
instrument, and
repeat
measurement
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The HACK DR5000 performs a series of diagnostic tests each time the instrument is powered up
to ensure operation of major system components. This procedure, which takes approximately
two minutes, checks the system, lamp, filter adjustment, wavelength calibration and voltage. In
addition, standards can be purchased from the vendor, to check the accuracy of the particular
test.
A 100 to 1,000 jiL micropipette will be used to prepare solutions for the soil pH buffering tests
and the NOD tests. The micropipettes are calibrated at Battelle Instrument Labs every six-
months by trained technicians. Furthermore, the accuracy of the micropipettes will be checked
gravimetrically before use by drawing a particular volume of water at room temperature by the
micropipette and ejecting it into a weighing dish on an analytical balance.
Bench-top analytical balances are calibrated at Battelle Instrument Labs every six months by
trained technicians. The accuracy of the bench-top balance will be checked before use with four
weights that bracket the target amount to be measured (two weights below the target and two
above).
If the calibration/accuracy checks for any instrument or equipment described above indicates an
error in excess of 10%, the instrument will be recalibrated, when feasible, or replaced.
B8 INSPECTION/ACCEPTANCE OF SUPPLIES AND CONSUMABLES
Upon receipt of any supplies or consumables used for testing, Battelle will visually inspect and
ensure that the materials received are those that were ordered and that there are no visual signs of
damage that could compromise the suitability of the materials. If damaged or inappropriate
goods are received they will be returned or disposed of and arrangements will be made to receive
replacement materials. COA or other documentation provided with all reagents and standards
will be checked to ensure suitability for these verification tests. Unsuitable materials will be
returned or disposed of and arrangements for the receipt of replacement materials will be made.
B9 NON-DIRECT MEASUREMENTS
Non-direct measurements will not be used during these verification tests.
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BIO DATA MANAGEMENT
Various types of data will be acquired and recorded electronically or manually by Battelle staff
during these verification tests. All manually-recorded data, such as solution preparation records
and results from supporting analyses will be recorded. Table 7 summarizes the types of data to
be recorded. All maintenance activities, repairs, calibrations, and operator observations relevant
to the application of the ISCO chemical will be documented by Battelle staff in an LRB or on
data sheets. Report formats will include all necessary data to allow traceability from the raw
data to final results.
Table 7. Summary of Data Recording Process
Data to Be Recorded
Dates and details of
test events
ISCO chemical
operator/analyst, data
collection and analysis
dates, sample volume
and/or time, sample
description
ISCO chemical and
reference test
calibration information,
reagent and test
solution information,
Where
Recorded
ETV LRBs or
data forms
ETV LRBs or
electronically
ETV LRBs or
electronically
How Often
Recorded
Start/end of
test event
When
performed
When
performed
By Whom
Battelle staff
Staff from
participating
field sites
Battelle staff
Staff from
participating
field sites
Battelle staff
Staff from
participating
field sites
Disposition of Data
Used to
organize/check test
results; manually
incorporated in data
spreadsheets as
necessary
Incorporated in
verification report as
necessary
Incorporated in
verification report as
necessary
Records received by or generated by any Battelle staff during testing will be reviewed by a
Battelle staff member within five days of receipt or generation, respectively, before the records
are used to calculate, evaluate, or report verification results. If a Battelle staff member generated
the record, this review will be performed by a Battelle technical staff member involved in the
verification test, but not the staff member who originally received or generated the record. The
review will be documented by the person performing the review by adding his/her initials and
date to the hard copy of the record being reviewed. Some of the checks that will be performed
include:
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• QC samples and calibration standards were analyzed according to the QAPP and
the acceptance criteria were met. Corrective action for exceedances was taken,
• 100% hand-entered and/or manually calculated data were checked for accuracy,
• Calculations performed by software are verified at a frequency sufficient to ensure
that the formulas are correct, appropriate, and consistent,
• For each cut and paste function, the first and last data value was verified vs. the
source data,
• Data are reported in the units specified in the QAPP, and
• Results of QC samples are reported.
Calculations to be checked include any statistical and concentration calculations described in the
QAPP. A dedicated shared folder within the Battelle network will be established for all project
records.
Battelle will provide ISCO chemical test data (including records, data sheets, and notebook
records) from the first day of testing within five days of generation to EPA for simultaneous
review. Thereafter, the data will be provided to EPA every two weeks. The goal of this data
delivery schedule is prompt identification and resolution of any data collection or recording
issues. These data will be labeled as preliminary and may not have had a QA review before their
release.
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SECTION C
ASSESSMENT AND OVERSIGHT
Cl ASSESSMENTS AND RESPONSE ACTIONS
Every effort will be made in these verification tests to anticipate and resolve potential problems
before the quality of performance is compromised. One of the major objectives of the QAPP is
to establish mechanisms necessary to ensure this. Internal quality control measures described in
the final QAPP, which is peer reviewed by a panel of outside experts, implemented by the
technical staff and monitored by the VTC, will give information on data quality on a day-to-day
basis. The responsibility for interpreting the results of these checks and resolving any potential
problems resides with the VTC, who will contact the Battelle QM, if any deviations from the
QAPP are observed. The VTC will describe the deviation in a deviation form. Technical staff
has the responsibility to identify problems that could affect data quality or the ability to use the
data. Any problems that are identified will be reported to the VTC. Technical staff and the VTC
will work with the Battelle QM to resolve any issues. Action will be taken by the VTC and
Battelle testing staff to identify and appropriately address the issue, and minimize losses and
correct data, where possible. Independent of any EPA QA activities, Battelle will be responsible
for ensuring that the following audits are conducted as part of these verification tests.
Cl.l Technical Systems Audits
The Battelle QM or designee will perform a TSA at Battelle during lab testing and at one
participating field site during ISCO field application. The purpose of these audits is to ensure
that the verification tests are being performed in accordance with the MMR Center QMP1 and
the QAPP. The Battelle QM will compare actual test procedures to those specified or referenced
in this plan, and review data acquisition and handling procedures. The Battelle QM or designee
will prepare a project-specific checklist based on the QAPP requirements to guide the TSA,
which will include a review of the test location and general testing conditions; observe the
testing activities; and review test documentation. The Battelle QM will also check data
acquisition procedures, and confer with testing staff. The Battelle QM will prepare an initial
TSA report and will submit the report to VTC within 10 business days after completion of the
audit. At EPA's discretion, EPA QA staff may also conduct an independent on-site TSA during
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the verification tests. The ISA findings will be communicated to technical staff at the time of the
audit and documented in the ISA reports.
C1.2 Data Quality Audits
As an EPA QA Category III test, the Battelle QM, or designee, will audit at least 10% of the
sample results data acquired in the verification tests and 100% of the calibration and QC data
versus the QAPP requirements. Two audits of data quality (ADQs) will be conducted for this
project: Data collected on the first day of testing for the ISCO chemical will be audited within
10 business days of receipt and assessed using a project-specific checklist. The remaining data
will be audited at the conclusion of testing and will be completed within 10 business days of
receipt of all test data. During these audits, the Battelle QM, or designee, will trace the data from
initial acquisition (as received from the vendor's technology), through reduction and statistical
comparisons, to final reporting. All calculations performed on the data undergoing the ADQ will
be checked. Data must undergo a 100% validation and verification by technical staff (i.e., VTC
or designee) before it is assessed as part of the ADQ. All QC data and all calculations performed
on the data undergoing the audit will be checked by the Battelle QM or designee. Results of
each ADQ will be documented using the checklist and reported to the VTC. A final ADQ that
assesses overall data quality, including accuracy and completeness of the technical report, will be
prepared as a narrative and distributed to the VTC within 10 business days of completion of the
audit.
C1.3 QA/QC Reporting
Each assessment and audit will be documented in accordance with Section 3.3.4 of the MMR
Center QMP.l Assessment reports will include the following:
• Identification of findings and observations,
• Recommendations for resolving problems,
• Response to adverse findings or potential problems,
• Confirmation that solutions have been implemented and are effective, and
• Citation of any noteworthy practices that may be of use to others.
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C2 REPORTS TO MANAGEMENT
During the laboratory and field evaluation, any QAPP deviations will be reported immediately to
EPA. The Battelle QM and/or VTC, during the course of any assessment or audit, will identify
to the technical staff performing experimental activities any immediate corrective action that
should be taken. A summary of the required assessments and audits, including a listing of
responsibilities and reporting timeframes, is included in Table 8. If serious quality problems
exist, the Battelle QM will notify the Battelle Manager, who is authorized to stop work. Once
the assessment reports have been prepared, the VTC will ensure that a response is provided for
each adverse finding or potential problem and will implement any necessary follow-up corrective
action. The Battelle QM will ensure that follow-up corrective action has been taken.
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Table 8. Summary of Quality Assessment and Control Reports1
Assessment
ISCO chemical
lab Testing ISA
(within the first
week of testing)
ISCO chemical
field Testing ISA
(within the first
week of testing)
ADQ (Day 1
data)
for ISCO
chemical
ADQ (Remaining
data and
verification
report)
Prepared By
Battelle
Battelle
Battelle
Battelle
Report Submission
Timeframe
10 business days after ISA is
complete2
ISA response is due to QM
within 10 business days
ISA responses will be verified
by the QM and provided to
EPA within 20 business days
10 business days after ISA is
complete2
ISA response is due to QM
within 10 business days
ISA responses will be verified
by the QM and provided to
EPA within 20 business days
ADQ will be completed within
10 business days after receipt
of first data set
ADQ will be completed within
10 business days after
completion of the verification
report review
Submitted To
EPA ETV MMR Center
EPA ETV MMR Center
EPA ETV MMR Center
EPA ETV MMR Center
1 Any QA checklists prepared to guide audits will be provided with the audit report.
2 A separate TSA report will be prepared for each technology; the report submission timeframe is the
same for each.
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SECTION D
DATA VALIDATION AND USABILITY
Dl DATA REVIEW, VERIFICATION, AND VALIDATION REQUIREMENTS
The key data review and data verification requirements for these tests are stated in Section BIO
of this protocol. In general, the data review requirements specify that data generated during
these tests will be reviewed by a Battelle technical staff member within five days of generation
of the data. The reviewer will be familiar with the technical aspects of the verification test but
will not be the person who generated the data. This process will serve both as the data review
and the data verification, and will ensure that the data have been recorded, transmitted and
processed properly. Furthermore, this process will ensure that the ISCO application and testing
data were collected under appropriate testing.
D2 VERIFICATION AND VALIDATION METHODS
Data verification is conducted as part of the data review as described in Section BIO of this
protocol. A visual inspection of handwritten data will be conducted to ensure that all entries
were properly recorded or transcribed, and that any erroneous entries were properly noted (i.e.,
single line through the entry, with an error code, such as "wn" for wrong number, and the initials
of the recorder and date of entry). Electronic data from the ISCO chemical, if applicable, and
any other analytical equipment used during the test will be inspected to ensure proper transfer
from the data logging system. All calculations used to transform the data will be reviewed to
ensure the accuracy and the appropriateness of the calculations. Calculations performed
manually will be reviewed and repeated using a handheld calculator or commercial software
(e.g., Excel). Calculations performed using standard commercial office software (e.g., Excel)
will be reviewed by inspection of the equations used for the calculations and verification of
selected calculations by handheld calculator. Calculations performed using specialized
commercial software (i.e., for analytical instrumentation) will be reviewed by inspection and,
when feasible, verified by handheld calculator, or standard commercial office software.
To ensure that the data generated from these tests meet the goals of the tests, a number of data
validation procedures will be performed. Sections B and C of this protocol provide a description
of the validation safeguards employed for these verification tests. Data validation efforts include
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the completion of QC activities, and the performance of two ISA audits as described in Section
C. The data from these tests will be evaluated relative to the measurement quality objectives
described in Sections A and B of this protocol. Data failing to meet these criteria will be flagged
in the data set and not used for evaluation of the ISCO chemical, unless these deviations are
accompanied by descriptions of their potential impacts on the data quality.
An ADQ will be conducted by the Battelle QM to ensure that data review, verification, and
validation procedures were completed, and to assure the overall quality of the data.
D3 RECONCILIATION WITH USER REQUIREMENTS
This purpose of these verification tests is to verify the performance of ISCO testing in the lab
and field tests. To meet the requirements of the user community, input on the tests described in
the final QAPP will be provided by external experts. Additional performance data regarding
operational characteristics of the evaluated ISCO application will be collected by verification test
personnel. To meet the requirements of the user community, these data will include thorough
documentation of the performance of the technologies during the verification tests. The data
review, verification, and validation procedures described above will assure that data meeting
these requirements are accurately presented in the verification reports generated from this test,
and will assure that data not meeting these requirements will be appropriately flagged and
discussed in the verification reports.
This protocol and the resulting ETV verification report will be reviewed by the vendor, EPA, and
expert peer reviewers. The reviews of the QAPP will help to improve the design of the
verification tests and the resulting report such that they better meet the needs of potential users of
these technologies.
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SECTION E
REFERENCES
1. Battelle. 2009. Quality Management Plan for the ETV Materials Management and
Remediation Center, Version 4.0, U.S. EPA Environmental Technology Verification
Program, prepared by Battelle, Columbus, Ohio, February.
2. U.S. EPA. 2008. Environmental Technology Verification Program Quality Management
Plan, EPA Report No: 600/R-08/009 EPA/600/R-03/021, U.S. Environmental Protection
Agency, Cincinnati, Ohio, January.
3. U.S. EPA. 2006. In-Situ Chemical Oxidation, EPA Report No: EPA/600/R-06/072, U.S.
Environmental Protection Agency, August.
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