EPA/540/R-93/501
August 1993
TECHNOLOGY EVALUATION REPORT
PEROX-PURE™ CHEMICAL OXIDATION TECHNOLOGY
RISK REDUCTION ENGINEERING LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
TECHNICAL REPORT DATA
!Please read Instructions on the reverse before completir
1. REPORT NO. 2.
EPA/540/R-93/501
3. R
4. title ano subtitle
Technology Evaluation Report
Peroxidation Systems, Inc.
Perox-Pure Chemical Oxidation Technology
S. REPORT OATS
Auaust 1993
8. PERFORMING ORGANIZATION cooe
7. AUTHOR(S)
Dr. Kirankumar Topudurti, e.t. a.l.
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME ANO AOORESS
PRC Environmental Management Inc.
233 N. Michigan Ave.
Chicago, IL 60601
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-C0-0047
12. SPONSORING AGENCY NAME ANO AOORESS
Risk Reduction Engineering Laboratory
Office of Research & Development
U.S. Environmental Protection Agency
Cincinnati OH 4RPfift
13. TYPE OF REPORT ANO PERIOO COVEREO
Project Report
14. SPONSORING AGENCY COOE
EpA/600/14
is. supplementary notes
Norma M. Lewis - Project Officer, 513/569-7665
is.abstract This report evaluates the perox-pure chemical oxidation technology's ability
to remove volatilejDrganic compounds (VOC) and other organic contaminants present in
liquid wastes. Th^ report also presents economic data from the Superfund Innovative
Technology Evaluation (SITE) demonstration and three case studies.
The perox-pure chemical oxidation technology was developed by Peroxidation System;
Inc. (PSI), to destroy dissolved organic contaminants in water. The technology uses
ultraviolet (UV) radiation and hydrogen peroxide to oxidize organic compounds present
in water at parts per million levels or less. This treatment technology produces no
air emissions and generates no sludge or spent media that require further processing,
handling, or disposal/ Ideally, the end products are water, carbon dioxide,
halides (for example, chloride), and in some cases, organic acids. The technology
uses medium-pressure, mercury-vapor lamps to generate UV radiation. The principal
oxidants in the system, hydroxyl radicals, are produced by direct photolysis of
hydrogen peroxide at UV wavelengths.
;The perox-pure chemical oxidation technology was demonstrated under the SITE
Program at Lawrence Livermore National Laboratory Site 300 in Tracy, CA. Over a 3-weec
period in September 1992,. about 40,000 gallons of VOC contaminated ground water was
treated in the perox-pure system. For the SITE demonstration, the perox-pure system
achieved trichloroethene (TCE) and tetrachloroethene (PCE) removal efficiencies of
QDOut J J • i ft J j . i pei tent, respectively.
17. KBY V*OROS ANO OOCUMENT ANALYSIS
a. DESCRIPTORS
b. I06NTI F 1ERS/OPEN CNOEO TERMS
c. COSati Field/Croup
SITE, Water, Chemical Oxidation
Groundwater
Photolysis
"s. eiSVSiowiTION STATEMENT
Release to Public
19. SECURITY CL^Sj tieport)
unclassified
21. NO. OF PAGES
111
20. SECURITY CLASS 1 This page)
unclassified
22. PRICE
EPA form 2220-1 (*.». 4.!
-------
Notice
The information in this document has been prepared for the U.S. Environmental Protection
Agency's (EPA) Superfund Innovative Technology Evaluation (SITE) program under Contract
No. 68-C0-0047. This document has been subjected to the EPA's peer and administrative reviews
and approved for publication as an EPA document. Mention of trade names or commercial products
does not constitute an endorsement or recommendation for use.
ii
-------
Foreword
The Superfund Innovative Technology Evaluation (SITE) program was authorized in the 1986
Superfund Amendments and Reauthorization Act (SARA). The program is a joint effort between
EPA's Office of Research and Development (ORD) and Office of Solid Waste and Emergency
Response (OSWER). The purpose of the program is to assist the development of innovative hazardous
waste treatment technologies, especially those that offer permanent remedies for contamination
commonly found at Superfund and other hazardous waste sites. The SITE program evaluates new
treatment methods through technology demonstrations designed to provide engineering and cost data
for selected technologies.
A field demonstration was conducted under the SITE program to evaluate the perox-pure""
chemical oxidation technology's ability to treat groundwater contaminated with volatile organic
compounds. The technology demonstration took place at the Lawrence Livermore National
Laboratory in Tracy, California. The purpose of the demonstration was to obtain information on the
performance and cost of the technology and to assess its use at this and other uncontrolled hazardous
waste sites. Documentation consists of two reports: (1) this Technology Evaluation Report, which
describes field activities and laboratory results, and (2) an Applications Analysis Report, which
interprets the data and discusses the potential applicability of the technology.
Copies of this report can be purchased from the National Technical Information Service,
Ravensworth Building, Springfield, Virginia 22161, (703) 487-4600. Reference copies will be
available at EPA libraries in the Hazardous Waste Collection.
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
HI
-------
Abstract
This report evaluates the perox-purem chemical oxidation technology's ability to remove
primarily volatile organic compounds (VOC) from groundwater at the Lawrence Livermore National
Laboratory (LLNL), Site 300 in Tracy, California. The perox-pure"" chemical oxidation technology
was developed by Peroxidation Systems, Inc., to destroy dissolved organic contaminants in water. The
technology uses ultraviolet (UV) radiation and hydrogen peroxide to oxidize organic compounds
present in water at parts per million levels or less. This treatment technology produces no air
emissions and generates no sludge or spent media that require further processing, handling, or
disposal. Ideally, the end products are water, carbon dioxide, halides (for example, chloride), and,
in some cases, organic acids. The technology uses medium-pressure, mercury-vapor lamps to generate
UV radiation. The principal oxidants in the system, hydroxy! radicals, are produced by direct
photolysis of hydrogen peroxide at UV wavelengths.
The perox-pure"" chemical oxidation technology was demonstrated under the Superfund
Innovative Technology Evaluation (SITE) program at LLNL Site 300 in Tracy, California. Over a 3-
week period in September 1992, about 40,000 gallons of VOC-contaminated groundwater was treated
in the perox-pure"* system. The technology demonstration had the following primary objectives: (1)
determine the ability of the perox-pure1* system to remove VOCs from groundwater at the LLNL site
under different operating conditions, (2) determine whether treated groundwater met applicable
disposal requirements at the 95 percent confidence level, and (3) gather information necessary to
estimate treatment costs, including process chemical dosages and utility requirements. The secondary
objective for the technology demonstration was to obtain information on the presence and types of
by-products formed during the treatment.
For the SITE demonstration, the perox-pure'" system achieved trichloroethene (TCE) and
tetrachloroethene (PCE) removal efficiencies of about 99.7 and 97.1 percent, respectively. The system
also achieved chloroform; 1,1-dichloroethane (DCA); and 1,1,1 -trichloroethane (TCA) removal
efficiencies of 93.1, 98.3, and 81.8 percent, respectively. In general, the perox-pure"" system
produced an effluent that contained (1) TCE, PCE, and DCA below detection limits, and
(2) chloroform and TCA slightly above detection limits. The treatment system effluent met California
drinking water action levels and federal drinking water maximum contaminant levels for TCE, PCE,
chloroform, DCA, and TCA at the 95 percent confidence level.
IV
-------
TABLE OF CONTENTS
Section Page
Notice ii
Foreword iii
Abstract iv
Table of Contents v
Abbreviations, Acronyms, and Symbols x
Conversion Factors xii
Acknowledgements xiii
1 EXECUTIVE SUMMARY 1
INTRODUCTION 1
OVERVIEW OF THE SITE DEMONSTRATION 2
RESULTS FROM THE SITE DEMONSTRATION 4
2 INTRODUCTION 6
OVERVIEW OF THE SITE PROGRAM 6
Technology Selection 7
Site Selection 8
TECHNOLOGY AND DEMONSTRATION SITE SELECTION 9
DEMONSTRATION OBJECTIVES 10
EVALUATION CRITERIA AND REGULATORY CONSIDERATIONS 10
PROJECT ORGANIZATION 11
TECHNICAL OPERATIONS 13
3 DESCRIPTION OF TECHNOLOGY 14
PROCESS DESCRIPTION 14
TREATMENT SYSTEM EQUIPMENT 15
FACTORS AFFECTING THE perox-pure~ TECHNOLOGY 18
Influent Characteristics 18
Operating Parameters 19
Maintenance Requirements 20
TREATMENT SYSTEM SUPPORT EQUIPMENT AND FACILITIES 21
UTILITY REQUIREMENTS 22
v
-------
TABLE OF CONTENTS
(Continued)
Section Page
4 DESCRIPTION OF DEMONSTRATION SITE 23
SITE CHARACTERISTICS 23
SITE CONTAMINATION 25
5 DEMONSTRATION PROCEDURES 26
TESTING PROGRAM 26
FIELD ACTIVITIES 31
Site Preparation and Mobilization 31
Site Demobilization and Waste Disposal 33
SAMPLING PROCEDURES AND FIELD MEASUREMENTS 34
Liquid Sampling Procedures 42
Field Measurements 42
Field Sampling Quality Assurance Procedures 43
ANALYTICAL PROCEDURES 46
Analytical Methods 47
Data Reduction, Validation, and Reporting 47
Analytical Quality Assurance 48
DEVIATIONS FROM THE DEMONSTRATION PLAN 53
System Operation 53
Sample Collection 54
Field Measurement 55
Analytical Procedures 55
TECHNICAL SYSTEMS REVIEW 55
COMMUNITY RELATIONS AND TECHNOLOGY TRANSFER 56
6 PERFORMANCE DATA AND EVALUATION 58
CRITICAL PARAMETERS 58
NONCRITICAL PARAMETERS 59
SUMMARY OF RESULTS 59
Summary of the Results for Critical Parameters 59
Summary of Results for Noncritical Parameters 69
CONCLUSIONS 74
FIELD OPERATIONAL AND EQUIPMENT PROBLEMS 75
vi
-------
TABLE OF CONTENTS
(Continued)
Section Page
7 COST OF DEMONSTRATION 77
EPA SITE CONTRACTOR COSTS 77
Phase I: Planning 77
Phase II: Demonstration 78
DEVELOPER COSTS 78
8 CONCLUSIONS AND RECOMMENDATIONS 79
CONCLUSIONS 79
RECOMMENDATIONS 80
Appendix
A ANALYTICAL DATA FOR REPRODUCIBILITY RUNS
Vll
-------
LIST OF TABLES
Table Page
1 LIST OF FEDERAL AND STATE ARARS FOR THE perox-pure™ CHEMICAL
OXIDATION DEMONSTRATION AT THE LLNL SITE 12
2 TARGET LEVELS FOR VOCs IN EFFLUENT SAMPLES 28
3 EXPERIMENTAL MATRIX FOR perox-pure" SYSTEM 30
4 OUTLINE OF SAMPLE COLLECTION AND FIELD MEASUREMENT
PROGRAM 36
5 ANALYTICAL METHODS AND QA OBJECTIVES FOR CRITICAL
PARAMETERS 40
6 ANALYTICAL METHODS AND QA OBJECTIVES FOR NONCRITICAL
PARAMETERS 41
7 SAMPLE CONTAINERIZATION, PRESERVATION, AND HOLDING TIMES 44
8 SURROGATE AND MS/MSD SPIKING COMPOUNDS ACCEPTANCE
CRITERIA 49
v 1 u
-------
LIST OF FIGURES
Figure Paee
1 perox-pure-CHEMICAL OXIDATION TREATMENT SYSTEM 16
2 LLNL SITE LOCATION 24
3 perox-pure" CHEMICAL OXIDATION TREATMENT SYSTEM SAMPLING
AND MEASUREMENT LOCATIONS 35
4 COMPARISON OF VOC CONCENTRATIONS AT DIFFERENT INFLUENT pH
LEVELS 61
5 COMPARISON OF VOC CONCENTRATIONS AT DIFFERENT HYDROGEN
PEROXIDE LEVELS 62
6 COMPARISON OF VOC CONCENTRATIONS AT DIFFERENT FLOW RATES
AND HYDROGEN PEROXIDE LEVELS 63
7 COMPARISON OF VOC CONCENTRATIONS IN SPIKED AND UNSPIKED
GROUNDWATER 66
8 VOC REMOVAL EFFICIENCIES IN REPRODUCIBILITY RUNS 67
9 COMPARISON OF 95 PERCENT UCLS FOR EFFLUENT VOC
CONCENTRATIONS WITH TARGET LEVELS IN REPRODUCIBILITY RUNS ... 68
10 VOC REMOVAL EFFICIENCIES IN QUARTZ TUBE CLEANER RUNS 70
11 CARBON CONCENTRATIONS IN REPRODUCIBILITY RUNS 72
IX
-------
Abbreviations, Acronyms, and Symbols
AAR
Applications Analysis Report
AOX
Adsorbable organic halide
ARAR
Applicable or relevant and appropriate requirement
°C
Degree Celsius
CaC03
Calcium carbonate
CDEP
Department of Environmental Protection, State of Connecticut
CERCLA
Comprehensive Environmental Response, Compensation, and Liability Act
CFR
Code of Federal Regulations
COC
Chain of custody
DCA
1,1 -dichloroethane
1,1-DCE
1,1 -dichloroethene
1,2-DCE
1,2-dichloroethene
EPA
U.S. Environmental Protection Agency
ESBL
Engineering-Science Berkeley Laboratory
FS
Feasibility study
°F
Degree Fahrenheit
GC
Gas chromatography
gpd
Gallons per day
gpm
Gallons per minute
GSA
General Services Area
GTC
General Testing Corporation
h2o2
Hydrogen peroxide
hv
Ultraviolet radiation
ICP
Inductively coupled plasma
kW
Kilowatt
kWh
Kilowatt-hour
L
Liquid
LLNL
Lawrence Livermore National Laboratory
Lpm
Liters per minute
MCL
Maximum contaminant level
M 8/L
Micrograms per liter
mg/L
Milligrams per liter
mL
Milliliter
mL/min
Milliliters per minute
#imho/cm
Micromhos per centimeter
MS/MSD
Matrix spike/matrix spike duplicate
N
Normal (equivalents/liter) solution
NA
Not applicable
ND
Not detected
NTU
Nephelometric Turbidity Unit
OH-
Hydroxyl radical
ORD
Office of Research and Development
OSWER
Office of Solid Waste and Emergency Response
P
Polyethylene
%
Percent
PCE
Tetrachloroethene
POC
Purgeable organic carbon
ppm
Parts per million
X
-------
PRC
PSI
QAPP
QA/QC
RI
RCRA
RPD
RREL
SARA
S/SD
SDWA
SITE
SVOC
TC
TCA
TCE
TER
TIC
TOC
TOX
TRL
TSR
UCL
UV
VOA
VOC
Abbreviations, Acronyms, and Symbols (Continued)
PRC Environmental Management, Inc.
Peroxidation Systems, Inc.
Quality Assurance Project Plan
Quality assurance/quality control
Remedial investigation
Resource Conservation and Recovery Act
Relative percent difference
Risk Reduction Engineering Laboratory
Superfund Amendments and Reauthorization Act
Sample/sample duplicate
Safe Drinking Water Act
Superfund Innovative Technology Evaluation
Semivolatile organic compound
Total carbon
1,1,1-trichloroethane
Trichloroethene
Technology Evaluation Report
Tentatively identified compound
Total organic carbon
Total organic halide
Target reporting limit
Technical systems review
Upper confidence limit
Ultraviolet
Volatile organic analysis
Volatile organic compound
XI
-------
Conversion Factors
To Convert From To
Length:
inch
foot
mile
centimeter
meter
kilometer
Area:
square foot
acre
square meter
square meter
Volume:
gallon
cubic foot
liter
cubic meter
Mass:
pound
kilogram
Energy:
kilowatt-hour
megajoule
Power:
kilowatt
horsepower
Temperature:
("Fahrenheit - 32) "Celsius
Multiply By
2.54
0.305
1.61
0.0929
4,047
3.78
0.0283
0.454
3.60
1.34
0.556
XII
-------
Acknowledgements
This report was prepared under the direction and coordination of Ms. Norma Lewis,
U.S. Environmental Protection Agency (EPA) Superfund Innovative Technology Evaluation Project
Manager and Emerging Technology Section Chief in the Risk Reduction Engineering Laboratory
(RREL), Cincinnati, Ohio. Contributors and reviewers for this report were Messrs. Ron Turner,
Carl Chen, and John Ireland of EPA RREL, Cincinnati, Ohio; Mr. Chris Giggy of Peroxidation
Systems, Inc., Tucson, Arizona; Ms. Lida Tan of EPA Region IX, San Francisco, California; Mr. Kai
Steffens of PROBIOTEC, Duren, Germany; Dr. Shyam Shukla of Lawrence Livermore National
Laboratory (LLNL), Livermore, California; and Mr. Geoffrey Germann of Engineering-Science, Inc.,
Fairfax, Virginia. EPA RREL's quality assurance team also reviewed this report under the direction
of Ms. Ann Kern.
This report was prepared for EPA's SITE program by Mr. Patrick Wooliever, Dr. Kirankumar
Topudurti, and Mr. Behzad Behtash of PRC Environmental Management, Inc. (PRC). Special
acknowledgement is given to Mr. John Greci of LLNL for his invaluable support during the
demonstration, and to Ms. Deodre Knodell, Ms. Carol Adams, and Mr. Tobin Yager of PRC for their
editorial, graphic, and production assistance during the preparation of this report.
xiii
-------
SECTION 1
EXECUTIVE SUMMARY
INTRODUCTION
The perox-pure*" chemical oxidation technology, developed by Peroxidation Systems, Inc.
(PSI), was evaluated under the U.S. Environmental Protection Agency (EPA) Superfund
Innovative Technology Evaluation (SITE) program. The perox-pure™ technology demonstration
was conducted at Lawrence Livermore National Laboratory (LLNL), Site 300 in Tracy, California,
over a 3-week period in September 1992.
The perox-pure"" chemical oxidation technology is designed to destroy dissolved organic
contaminants in water. The technology uses ultraviolet (UV) radiation and hydrogen peroxide to
oxidize organic compounds present in water at parts per million (ppm) levels or less. This
treatment technology produces no air emissions and generates no sludge or spent media that
require further processing, handling, or disposal. Ideally, end products are water, carbon dioxide,
halides (for example, chloride), and in some cases, organic acids. The technology uses medium-
pressure, mercury-vapor lamps to generate UV radiation. The principal oxidants in the system,
hydroxyl radicals, are produced by direct photolysis of hydrogen peroxide at UV wavelengths.
The perox-pure"" chemical oxidation treatment system (Model SSB-30) used for the SITE
technology demonstration was assembled from the following portable, skid-mounted components:
a chemical oxidation unit, a hydrogen peroxide feed module, an acid feed module, a base feed
module, a UV lamp drive, and a control panel. The oxidation unit consists of six reactors in series
with one 5-kilowatt (kW) UV lamp in each reactor; the unit has a total volume of 15 gallons. The
UV lamp is mounted inside a UV-transmissive quartz tube in the center of each reactor so that
water flows through the space between the reactor walls and the quartz tube. Circular wipers
mounted on the quartz tubes periodically remove any solids that have accumulated on the tubes.
The perox-pure"" system requires little attention during operation and can be operated and
monitored remotely, if needed. Remotely monitored systems can be connected to devices that
automatically dial a telephone to notify responsible parties at remote locations of alarm conditions.
Remotely operated and monitored systems are hard-wired into centrally located control panels or
computers through programmable logic controllers.
1
-------
The technology demonstration had the following primary objectives: (1) determine the
ability of the perox-pure" system to remove volatile organic compounds (VOC) from groundwater
at the LLNL site under different operating conditions, (2) determine whether treated groundwater
met applicable disposal requirements at the 95 percent confidence level, and (3) gather
information necessary to estimate treatment costs, including process chemical dosages and utility
requirements. The secondary objective for the technology demonstration was to obtain
information on the presence and types of by-products formed during treatment.
This report presents information from the SITE demonstration that will be useful for
implementing the perox-pure™ chemical oxidation technology at Superfund and Resource
Conservation and Recovery Act hazardous waste sites. Section 2 presents an overview of the SITE
program; discusses the perox-pure"" technology and demonstration site selection; and presents the
demonstration objectives, the evaluation criteria and regulatory considerations, the project
organization, and technical operations. Section 3 describes the perox-pure" system, discusses the
factors affecting the perox-pure" system's performance, and outlines the support equipment and
facilities and utility requirements. Section 4 describes the site selected for the technology
demonstration. Section 5 describes the demonstration procedures, which include the testing
program, field activities, sampling procedures and field measurements, analytical procedures,
deviations from the demonstration plan, technical systems review, and community relations and
technology transfer. Section 6 discusses the critical and noncritical parameters for the technology
demonstration, summarizes the analytical data for those parameters, evaluates the perox-pure"
system's performance, and describes field operational and equipment problems. Section 7 presents
EPA's and the developer's costs for the technology demonstration. Section 8 presents conclusions
and recommendations. References are provided at the end of this report.
OVERVIEW OF THE SITE DEMONSTRATION
Groundwater from a shallow aquifer at the LLNL site was selected as the waste stream for
evaluating the perox-pure" chemical oxidation system. About 40,000 gallons of groundwater
contaminated with VOCs was treated during the demonstration. The principal groundwater
contaminants were trichloroethene (TCE) and tetrachloroethene (PCE), which were present at
concentrations of about 1,000 and 100 micrograms per liter 0tg/L), respectively. Groundwater
was pumped from two wells into a 7,500-gallon bladder tank to minimize any variability in
influent characteristics. In addition, cartridge filters were used to remove suspended solids
2
-------
greater than 3 micrometers in size from the groundwater before it entered the tank. Treated
groundwater was stored in two 20,000-gallon steel tanks before being discharged.
The technology demonstration was conducted in three phases. Phase 1 consisted of eight
runs of raw groundwater, Phase 2 consisted of four runs of spiked groundwater, and Phase 3
consisted of two runs of spiked groundwater to evaluate the effectiveness of quartz tube cleaning.
These phases are described below.
During Phase 1, the principal operating parameters for the perox-pure™ system, hydrogen
peroxide dose, influent pH, and flow rate (which determines the hydraulic retention time), were
varied to observe treatment system performance under different operating conditions. Preferred
operating conditions, those under which the concentrations of effluent VOCs would be reduced to
below target levels for spiked groundwater used in Phases 2 and 3, were then determined for the
system.
Phase 2 involved spiked groundwater and reproducibility tests. Groundwater was spiked
with about 200 to 300 jig/L each of chloroform; 1,1-dichloroethane (DCA); and 1,1,1-
trichloroethane (TCA). These compounds were chosen because they are difficult to oxidize and
because they were not present in the groundwater at high concentrations. This phase was also
designed to evaluate the reproducibility of treatment system performance at the preferred
operating conditions determined in Phase 1.
During Phase 3, the effectiveness of the quartz tube wipers was evaluated during two runs
using scaled and clean quartz tubes.
During the demonstration, samples were collected at several locations, including the
treatment system influent; effluent from Reactors 1, 2, and 3; and the treatment system effluent.
Samples were analyzed for VOCs, semivolatile organic compounds, total organic carbon (TOC),
total carbon (TC), purgeable organic carbon (POC), total organic halides (TOX), adsorbable
organic halides (AOX), metals, pH, alkalinity, turbidity, temperature, specific conductance,
hydrogen peroxide residual, and hardness. In addition, samples of influent to Reactor 1 and
treatment system effluent were collected and analyzed for acute toxicity to freshwater organisms.
The hydrogen peroxide, acid, and base solutions were also sampled and analyzed to verify
concentrations.
3
-------
Strict quality assurance and quality control procedures were followed to produce well
documented sampling and analytical data of known quality. To accomplish this goal, a detailed
and comprehensive quality assurance project plan (QAPP) was developed before the
demonstration. During the demonstration, field sampling and measurement activities, field
laboratory analytical activities, and off-site laboratory analytical activities for critical parameters
were audited. In general, all sampling and analytical activities conformed with the procedures
described in the QAPP. Only one minor issue was noted during the audits. The issue was
regarding nonavailability of calibration data for a factory calibrated wattmeter. The SITE team
resolved this issue by recalibrating the wattmeter at the end of demonstration and providing the
calibration data to EPA's quality assurance manager.
RESULTS FROM THE SITE DEMONSTRATION
For the spiked groundwater, PSI determined the following preferred operating conditions:
(1) influent hydrogen peroxide level of 40 milligrams per liter (mg/L); (2) hydrogen peroxide level
of 25 mg/L in the influent to Reactors 2 through 6; (3) an influent pH of 5.0; and (4) a flow rate
of 10 gallons per minute (gpm). At these conditions, the effluent TCE, PCE, and DCA levels
were generally below detection limit (5 iig/L) and effluent chloroform and TCA levels ranged
from 15 to 30 fig/L. The average removal efficiencies for TCE, PCE, chloroform, DCA, and
TCA were about 99.7, 97.1, 93.1, 98.3, and 81.8 percent, respectively.
For the unspiked groundwater, the effluent TCE and PCE levels were generally below
detection limit (1 ng/L) with corresponding removal efficiencies of about 99.9 and 99.7 percent.
The effluent TCA levels ranged from 1.4 to 6.7 ^g/L with corresponding removal efficiencies
ranging from 35 to 84 percent.
The perox-pure™ system effluent met California drinking water action levels and federal
drinking water maximum contaminant levels (MCL) for TCE, PCE, chloroform, DCA, and TCA
at the 95 percent confidence level.
The quartz tube wipers were effective in keeping the tubes clean and appeared to reduce
the adverse effect scaling has on contaminant removal efficiencies.
Bioassay tests showed that the perox-purem system effluent was acutely toxic to freshwater
organisms, although the influent was not toxic. Comparison of effluent toxicity data with that of
4
-------
hydrogen peroxide residual in the effluent (10.5 mg/L) indicated that the effluent toxicity may be
due to hydrogen peroxide residual rather than perox-pure™ treatment by-products. Additional
studies are needed to draw any conclusion on the effluent toxicity.
TOX removal efficiencies ranged from 93 to 99 percent. AOX removal efficiencies
ranged from 95 to 99 percent.
For spiked groundwater, during reproducibility runs, the system achieved average removal
efficiencies of 38 percent and about 93 percent for TOC and POC, respectively.
The temperature of groundwater increased at a rate of 12 °F per minute of UV exposure
in the perox-purem system. Since the oxidation unit is exposed to the surrounding environment,
the temperature increase may vary depending upon the ambient temperature or other atmospheric
conditions.
5
-------
SECTION 2
INTRODUCTION
This section provides information about SITE program; discusses the perox-pure™
technology; summarizes the technology and demonstration site selection; and describes the
demonstration objectives, evaluation criteria and regulatory considerations, project organization,
and technical operations.
OVERVIEW OF THE SITE PROGRAM
The Superfund Amendments and Reauthorization Act of 1986 (SARA) (Section 209(b))
amends Title III of the Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA) of 1980 by adding Section 311. Section 311 directs the U.S. Environmental Protection
Agency (EPA) to establish an "Alternative or Innovative Treatment Technology Research and
Demonstration Program." In response to the SARA directive, EPA established a formal program
to accelerate the development, demonstration, and use of new or innovative treatment
technologies. This program is called the SITE program.
The overall goal of the SITE program is to "carry out a program of research, evaluation,
testing, development, and demonstration of alternative or innovative treatment technologies...
which may be utilized in response actions to achieve more permanent protection of human health
and welfare and the environment." Specifically, the program's goal is to maximize the use of
alternatives to land disposal in cleaning up Superfund sites by encouraging the development and
demonstration of new, innovative treatment and monitoring technologies. The SITE program
categorizes alternative technologies by their development status, as follows:
• Available alternative technologies that have been fully proven and are
available for commercial or private use
• Innovative alternative technologies that have been fully developed but lack
complete cost or performance information
• Emerging alternative technologies that are in an early stage of development
involving laboratory or pilot testing
One of the most important components of the SITE program is the Demonstration
program, through which EPA evaluates field- or pilot-scale technologies that can be scaled up for
6
-------
commercial use. The Demonstration program is the primary focus of the SITE program because
the innovative alternative technologies evaluated are close to being available for remediation of
Superfund sites. The main objective of the Demonstration program is to develop performance,
engineering, and cost information for innovative technologies. With this information, potential
users can make informed decisions on whether to use these technologies to remediate hazardous
waste sites. Specifically, potential users can use this information to compare the technology's
effectiveness and cost to other alternatives and make sound judgments regarding the technology's
applicability to a specific site.
The results of the demonstration identify possible limitations of the technology, the
potential need for pre- and post-processing of wastes, the types of wastes and media to which the
process can be applied, the potential operating problems, and the approximate capital and
operating costs. The demonstrations also permit evaluation of long-term risks. Demonstrations
usually occur at Superfund sites or under conditions that duplicate or closely simulate actual
wastes and conditions found at Superfund sites to ensure the reliability of the information
collected and acceptability of the data by users.
Developers are responsible for demonstrating their innovative systems at selected sites and
are expected to pay the costs to transport equipment to the site, operate the equipment on site
during the demonstration, and remove the equipment from the site. EPA is responsible for
project planning, sampling and analysis, data quality assurance and quality control, report
preparation, and information dissemination.
Two important elements of the Demonstration program include (1) technology selection
and (2) site selection. These two elements are discussed below.
Technology Selection
Technologies are accepted into the program through an annual solicitation published in the
Commerce Business Daily and trade journals. In response to the solicitations, technology
developers submit proposals to EPA addressing the following selection criteria:
• Technology Factors. Description of the technology and its history;
identification of effective operating range; materials handling capabilities;
application to hazardous waste site cleanup; mobility of equipment; capital
and operating costs; advantages over existing comparable technologies;
7
-------
previous performance data; and identification of health, safety, and
environmental problems.
• Capability of the Developer. Development of other technologies;
completion of field tests; experience, credentials, and availability of key
personnel; and capability to commercialize and market the technology.
• Approach to Testing. Operations plan; materials and equipment; range of
testing; health and safety plan; monitoring plan; quality assurance plan;
assignment of responsibilities; backup treatment system plan; and
regulatory compliance plan.
Site Selection
Once EPA has evaluated the technology proposals and notified the developers of their
acceptance into the SITE program, the demonstration site selection process begins. Potential SITE
demonstration locations include federal and state Superfund removal and remedial sites, sites from
other federal agencies, and developers' facilities. The criteria used to screen and select candidate
demonstration sites include the following:
• Compatibility of waste with the technology
• Volume of waste
• Variability of waste
• Availability of data characterizing the waste
• Accessibility of waste
• Applicability of the technology to site cleanup goals
• Availability of required utilities (such as power sources, water sources, and
sewers)
• Support of community, state and local governments, and potentially
responsible parties
The staff of EPA's Office of Research and Development (ORD) and Office of Solid Waste
and Emergency Response (OSWER) evaluate the technology proposals and, with the assistance of
EPA regional offices, match the technologies to appropriate sites. OSWER and ORD establish the
criteria for the selection of each demonstration site. Candidate demonstration sites are selected
8
-------
cooperatively by OSWER, ORD, EPA regional offices, and the states. The final demonstration
site is selected in close cooperation with the technology developer.
Each site is evaluated based on considerations and preferences provided by the developer
and on four principal program goals. These goals are as follows:
• Production of the most useful information on each technology's capabilities
• Expeditious implementation
• Production of information relevant to the specific site cleanup goals
• Involvement of EPA regions and states in the SITE program
TECHNOLOGY AND DEMONSTRATION SITE SELECTION
In April 1991, EPA learned that PSI was contracted by LLNL to perform pilot-scale
studies as part of remediation activities at the LLNL site. At that time, EPA and PSI discussed
the possibility of PSI participating in the SITE program to demonstrate how the perox-pure""
chemical oxidation technology could be used to treat contaminated groundwater at Site 300 of
LLNL in Tracy, California. EPA subsequently accepted the perox-purem technology into the
SITE Demonstration program. Through a cooperative effort between EPA ORD, EPA Region IX,
LLNL, and PSI, the perox-pure™ technology was demonstrated at LLNL Site 300 under the SITE
program. The demonstration took place over a 3-week period in September 1992. During the
demonstration, about 40,000 gallons of groundwater contaminated with VOCs was treated in the
perox-purem system.
The perox-purem technology can be applied at Superfund and other hazardous waste sites
where groundwater or other liquid wastes are contaminated with organic compounds. The
technology has been used to treat landfill leachate, groundwater, and industrial wastewater, all
containing a variety of organic contaminants, including chlorinated solvents, pesticides,
polynuclear aromatic hydrocarbons, and petroleum hydrocarbons. In some applications, where the
contaminant concentration was higher than about 500 mg/L for the perox pure" system to handle
alone, the system was combined with other treatment technologies.
9
-------
DEMONSTRATION OBJECTIVES
In addition to meeting the general objectives of the SITE program, the perox-pure""
technology demonstration had three primary objectives and one secondary objective. The primary
objectives of the technology demonstration were as follows:
• Assess the technology's ability to destroy VOCs from groundwater at the LLNL
site under different operating conditions
• Determine whether the treated water meets applicable disposal requirements at the
95 percent confidence level
• Obtain information required to estimate the operating costs for the treatment
system, such as electrical power consumption and chemical doses
The secondary objective for the technology demonstration was to obtain preliminary
information on the presence and types of by-products formed during treatment.
EVALUATION CRITERIA AND REGULATORY CONSIDERATIONS
EPA used the following technical criteria to evaluate the effectiveness of the perox-pure"
technology in treating groundwater containing VOCs.
• Removal efficiencies achieved for VOCs present in groundwater at the LLNL site
and those that were added to the groundwater
• Compliance of the treated groundwater with federal drinking water MCLs and
California state drinking water action levels at the 95 percent confident level
The groundwater at the LLNL site contained primarily TCE and PCE which can be oxidized
easily. To enhance the applicability of SITE demonstration data, the groundwater was spiked in
line with three VOCs that are difficult to oxidize (chloroform, DCA, and TCA).
For purposes of SITE demonstrations, EPA follows procedures regarding on- and off-site
remedial actions taken under CERCLA. According to OSWER, application for and receipt of
permits is not required for on-site response actions performed under CERCLA authority.
Although the normal permitting processes are not required for demonstrations, CERCLA removal
and remedial activities must comply with applicable or relevant and appropriate requirements
10
-------
(ARAR) of federal and state environmental and public health laws. Table 1 summarizes the
ARARs identified for this project.
PROJECT ORGANIZATION
Participants in the SITE demonstration included the EPA Risk Reduction Engineering
Laboratory (RREL), PSI, EPA Region IX, LLNL, the German Federal Ministry of Research and
Technology, and the PRC Environmental Management, Inc. (PRC), SITE team.
To demonstrate the perox-pure"" chemical oxidation technology at the LLNL site, a
cooperative agreement was signed between the EPA RREL and PSI. PSI was responsible for the
treatment system delivery, setup, operation, and demobilization.
The EPA SITE project manager had the overall responsibility for overseeing, reviewing,
and approving the project quality assurance activities during the demonstration. The PRC SITE
team, including Engineering-Science, Inc., Versar, Inc., General Testing Corporation, Sound
Analytical Services, and James Reed & Associates, provided sampling, analytical, and other
technical support to EPA RREL. PRC was responsible for the overall direction of the PRC SITE
team, including the activities of the subcontractors and coordination with the EPA RREL, EPA
Region IX, LLNL, PSI, and the German Federal Ministry of Research and Technology.
EPA Region IX and LLNL assisted the SITE program by providing access to the
demonstration site, coordinating community relations activities, ensuring all applicable state and
local regulations were met, and coordinating with RREL for the disposal of waste generated
during the demonstration.
Under a U.S.-German bilateral program, the German Federal Ministry of Research and
Technology reviewed the demonstration plan and requested additional analyses. The EPA SITE
project manager arranged for the additional analyses and supported the U.S.-German bilateral
program activities.
11
-------
TABLE 1
LIST OF FEDERAL AND STATE ARARS FOR THE perox-pure~
CHEMICAL OXIDATION DEMONSTRATION AT THE LLNL SITE
Demonstration
Program Activity
ARAR
Description
Basis
Response
Waste extraction
RCRA 40 CFR
Part 262 or State
equivalent
Standards that apply to
generators of hazardous
waste
The groundwater is
extracted for treatment
Provide appropriate
containment for all waste
storage tanks as advised
by EPA Region IX.
Storage prior to
processing
RCRA 40 CFR
Part 264 or State
equivalent
Standards that apply to
the storage or treatment of
hazardous wastes in tanks
The waste is stored in a
tank prior to processing
Tank integrity will be
monitored and maintained
to prevent leakage or
failure; the tank will be
decontaminated when
processing is complete.
Waste processing
RCRA 40 CFR
Part 264 or State
equivalent
Standards that apply to
the storage or treatment of
hazardous wastes in tanks
The treatment process
occurs in a tank
Tank integrity will be
monitored and maintained
to prevent leakage or
failure; the tank will be
decontaminated when
processing is complete.
Waste
characterization
RCRA 40 CFR
Part 261
Standards that apply to
waste characteristics
Need to determine if
treated material is
RCRA hazardous waste
Testing will be performed
prior to disposal.
Storage after
processing
RCRA 40 CFR
Part 264 or State
equivalent
Standards that apply to
the storage of hazardous
wastes in containers
The treated waste will be
placed in tanks prior to a
decision on their final
dispositions
The containers will be
maintained in good
condition; the container
storage area will be
constructed to control
runon and runoff of
precipitation.
Transportation
for off-site
disposal
RCRA 40 CFR
Part 262
Manifest requirements and
packaging and labeling
requirements prior to
transporting
If found hazardous,
wastes generated during
the demonstration must
be manifested and
managed as a hazardous
waste
If found hazardous, obtain
an ID number from EPA.
40 CFR Part 263
Transportation standards
If found hazardous,
wastes generated during
the demonstration must
be transported as a
hazardous waste
If found hazardous, use a
transporter that is licensed
by EPA to transport the
wastes off-site for
disposal.
Off-Site disposal
40 CFR Part 264
and Part 268, or
state equivalent
Requirements for the off-
site disposal of hazardous
wastes
If found hazardous,
wastes generated during
the demonstration must
be disposed of as
hazardous wastes. If
disposed of in land-
based units, the waste
must comply with land
disposal restrictions.
If found hazardous,
dispose of the wastes at a
RCRA-permitted
hazardous waste facility.
12
-------
TECHNICAL OPERATIONS
Initially, background information on the technology was obtained from the developer and
from literature. Subsequently, a demonstration plan was prepared that discussed the perox-pure""
chemical oxidation technology and the planned demonstration procedures. The demonstration
procedures included preparing a schedule for the project; obtaining information on the site and its
contamination; characterizing the groundwater at the site; mobilizing equipment and materials to
the site, collecting groundwater for demonstration; developing a matrix of test runs to evaluate the
technology; and identifying the appropriate sampling and analytical procedures to be followed
during the demonstration (PRC, 1992).
13
-------
SECTION 3
DESCRIPTION OF TECHNOLOGY
This section provides an overview of the perox-pure" chemical oxidation technology,
perox-pure"" treatment system equipment, and factors affecting the technology and briefly
describes the treatment system support equipment and utility requirements. Detailed information
on applications of this technology is presented in the Applications Analysis Report for the perox-
pure" technology, prepared under the SITE program (EPA, 1993).
PROCESS DESCRIPTION
The perox-pure1" chemical oxidation technology was developed -by PSI to destroy dissolved
organic contaminants in water. The technology uses UV radiation and hydrogen peroxide to
oxidize organic compounds present in water at ppm levels or less. In broad terms, oxidation is a
chemical change in which electrons are lost by an atom or a group of atoms. Oxidation is always
accompanied by reduction, a chemical change in which electrons are gained by an atom or group
of atoms. The atom or group of atoms that has lost electrons has been oxidized, and the atom or
group of atoms that has gained electrons has been reduced. The reduced atom or group of atoms
is called an oxidant. Oxidation and reduction always occur simultaneously; the total number of
electrons lost in the oxidation must equal the number of electrons gained in the reduction. In the
perox-pure*" technology, organic contaminants in water are oxidized by hydroxyl radicals,
powerful oxidants produced by UV radiation and hydrogen peroxide. Subsequently, the organic
contaminants are broken down into carbon dioxide, water, halides, and in some cases, organic
acids.
A variety of organic contaminants can be effectively oxidized by the combined use of
(1) UV radiation and hydrogen peroxide, (2) UV radiation and ozone, or (3) ozone and hydrogen
peroxide. The principal oxidants in the perox-pure"- system, hydroxyl radicals, are produced by
direct UV photolysis of the hydrogen peroxide added to contaminated water. The perox-pure"
system generates UV radiation by using medium-pressure, mercury-vapor lamps.
In principle, the most direct way to generate hydroxyl radicals (OH*) is to cleave hydrogen
peroxide (H202) through photolysis. The photolysis of hydrogen peroxide occurs when UV
radiation (hu) is applied, as shown in the following reaction:
14
-------
H202 * Av « 2 OH'
(1)
Thus, photolysis of hydrogen peroxide results in a quantum yield of two hydroxyl radicals
formed per quantum of radiation absorbed. This ratio of hydroxyl radicals generated from the
photolysis of hydrogen peroxide is high. Unfortunately, at 253.7 nanometers, the dominant
emission wavelength of low-pressure UV lamps, the absorptivity (or molar extinction coefficient)
of hydrogen peroxide is only 19.6 liters per mole-centimeter. This absorptivity is relatively low
for a primary absorber in a photochemical process. Because of the low absorptivity value for
hydrogen peroxide, a high concentration of residual hydrogen peroxide must be present in the
treatment medium to generate a sufficient concentration of hydroxyl radicals. According to PSI,
the perox-pure*" system overcomes this limitation by using medium-pressure UV lamps.
The hydroxyl radicals formed by photolysis react rapidly with organic compounds, with
rate constants on the order of 108 to 1010 liters per mole-second; they also have a relatively low
selectivity in their reactions (Glaze and others, 1987). However, naturally occurring water
components, such as carbonate ion, bicarbonate ion, and some oxidizable species, act as free
radical scavengers that consume hydroxyl radicals. Free radical scavengers are compounds that
consume any species possessing at least one unpaired electron. In addition to naturally occurring
scavengers, excess hydrogen peroxide can itself act as a free radical scavenger, decreasing the
hydroxyl radical concentration. Reactions with hydroxyl radicals are not the only removal
pathway possible in the perox-pure" system; direct photolysis by UV radiation of organic
compounds also provides a removal pathway for contaminants. With these factors affecting the
reaction, the proportion of oxidants required for optimum removal is difficult to predetermine.
Instead, the proportion for optimum removal must be determined experimentally for each waste.
TREATMENT SYSTEM EQUIPMENT
The perox-pure" chemical oxidation systems typically consist of the following portable,
skid-mounted components: a chemical oxidation unit, a hydrogen peroxide feed module, a UV
lamp drive, and a control panel unit. In addition to these main system components, other
equipment is used to address site-specific conditions or requirements, including contaminated
water characteristics and effluent discharge limits. For example. Figure 1 presents a schematic
diagram of the main and ancillary components of the perox-pure" chemical oxidation system used
for the SITE demonstration (Model SSB-3G).
15
-------
GROUNDWATER FROM
W—875—08 AND W-7-0
ra-ep-
SODIUM
HYDROXIDE
EXTRACTION WELL
~~TO DISPOSAL
UV LAMP
HYDROGEN
PEROXIDE
SPUTTER -
CARTRIDGE
FILTERS
SULFURIC
ACID
HYDROGEN
PEROXIDE
REACTOR
OXIDATION UNIT
STATIC
MIXER
STATIC
MIXER
BLADDER
TANK
SPIKING
SOLUTION
Figure 1. perox-pure™ Chemical Oxidation Treatment System
-------
For the SITE demonstration, skid-mounted acid feed module and base feed module were
used to adjust the pH of the influent and effluent, respectively. PSI provided the acid (sulfuric
acid) and base (sodium hydroxide) solutions in drums. Two cartridge filters arranged in parallel,
capable of screening suspended silt larger than 3 micrometers, were used to remove particles from
the groundwater, which was primarily contaminated with VOCs including TCE and PCE. A
spiking solution feed module was used to spike effluent from cartridge filters with chloroform,
DCA, and TCA for certain demonstration runs. A 7,500-gaIlon bladder tank was used (1) as an
equalization tank and (2) as a holding tank to perform a few demonstration runs at flow rates
greater than the groundwater well yield. The bladder tank was useful in minimizing the
volatilization of contaminants. To ensure a relatively homogeneous process water, static mixers
were used after chemicals were added at upstream locations in the treatment system.
The SSB-30 model consists of six reaction chambers, or reactors, with one UV lamp in
each reactor. Each UV lamp has a power rating of 5 kW, for a total system rating of 30 kW. The
UV lamps are mounted inside UV-transmissive quartz tubes at the center of the reactors, so that
water flows through the space between the reactor wall and the quartz tube. Circular wipers are
mounted on the quartz tubes housing the UV lamps. The wipers periodically remove any
suspended particles that have coated the quartz tubes. In a coating environment, coating
diminishes the effectiveness of the system by blocking some of the UV radiation.
Contaminated water is pumped to the treatment system and enters the oxidation unit
through a section of pipe containing a temperature gauge, a flow meter, an influent sampling port,
and hydrogen peroxide and sulfuric acid addition points. Hydrogen peroxide is added to the
contaminated water before it enters the first reactor; however, a splitter can be used to add
hydrogen peroxide at the inlet of each lamp section to allow for different doses into each reactor.
Inside the oxidation unit, the contaminated water follows a serpentine path that parallels each of
the six UV lamps. The water passes each lamp individually, allowing lamps to be turned on or off
as needed. Sample ports are located after each reactor. Inside the oxidation unit, photolysis of
hydrogen peroxide by UV radiation results in the formation of hydroxyl radicals; these free
radicals react rapidly with oxidizable compounds, such as organic contaminants.
Treated water exits the oxidation unit through an effluent pipe equipped with a
temperature gauge and sample port. The hydrogen peroxide dose is usually set so that the
concentration of the residual hydrogen peroxide in the treated water is less than 5 mg/L. Sodium
17
-------
hydroxide is then added to adjust the treated groundwater pH so that the effluent meets the pH
discharge requirement.
The control panel on the perox-pure"" system monitors water flow rate, total flow through
the system, UV lamp current in each reactor, and alarm conditions for the perox-pure"
equipment. Hydrogen peroxide and acid injection are activated by switches on the control panel
and are monitored with flow meters.
FACTORS AFFECTING THE perox-pure- TECHNOLOGY
Several factors influence the effectiveness of the perox-pure1" chemical oxidation
technology. These factors can be grouped into three categories: (1) influent characteristics,
(2) operating parameters, and (3) maintenance requirements. Each of these is discussed below.
Influent Characteristics
The perox-pure"* chemical oxidation technology is capable of treating water containing a
variety of organic contaminants, including VOCs, semivolatile organic compounds (SVOC),
pesticides, polynuclear aromatic hydrocarbons, polychlorinated biphenyls, and petroleum
hydrocarbons. Under a given set of operating conditions, contaminant removal efficiencies
depend on the chemical structure of the contaminants. Removal efficiencies are high for organic
contaminants with double bonds (such as TCE, PCE, and vinyl chloride) and aromatic compounds
(such as phenol, toluene, benzene, and xylene), because these compounds are easy to oxidize.
Organic contaminants without double bonds (such as TCA and chloroform) are not easily oxidized
and are more difficult to remove.
Contaminant concentration also affects treatment system effectiveness. The perox-pure""
system is most effective in treating water with contaminant concentrations less than about
500 mg/L. If contaminant concentrations are greater than 500 mg/L, the perox-pure"* system may
be used in combination with other treatment technologies, such as air stripping. For highly
contaminated water, the perox-pure"* system can also be operated in a "flow-through with recycle"
mode, in which part of the effluent is recycled through the oxidation unit to improve overall
removal efficiency.
18
-------
The perox-pure~ system uses a chemical oxidation process to destroy organic
contaminants; therefore, other species in the influent that consume oxidants present an additional
load for the system. These species are called scavengers. A scavenger may be described as any
species in water other than the target contaminants that consumes oxidants. Common scavengers
include anions such as bicarbonate, carbonate, sulfide, nitrite, bromide, and cyanide. Metals
present in reduced states, such as trivalent chromium, ferrous iron, manganous ion, and several
others, are also likely to be oxidized. In addition to acting as scavengers, these reduced metals can
cause additional concerns under alkaline pH conditions. For example, trivalent chromium can be
oxidized to hexavalent chromium, which is more toxic. Ferrous iron and manganous ion are
converted to less soluble forms, which precipitate in the reactor, creating suspended solids that
can build up on the quartz tubes housing the U V lamps. Natural organic compounds, such as
humic acid (often measured as TOC), are also potential scavengers in this treatment technology.
Other influent characteristics of concern include suspended solids, oil, and grease. These
constituents can build up on the quartz tubes housing the UV lamps, resulting in reduced UV
transmission and decreased treatment efficiency.
Operating Parameters
Operating parameters are those parameters that can be varied during the treatment process
to achieve desired removal efficiencies. The principal operating parameters for the perox-pure™
system are hydrogen peroxide dose, influent pH, and flow rate.
Hydrogen peroxide dose is selected based on treatment unit configuration, contaminated
water chemistry, and contaminant oxidation rates. Under ideal conditions, hydrogen peroxide is
photolyzed to hydroxyl radicals, which are the principal oxidants in the system. Direct photolysis
of each hydrogen peroxide molecule yields two hydroxyl radicals. The molar extinction
coefficient of hydrogen peroxide at 253,7 nanometers, the dominant emission wavelength of low-
pressure UV lamps, is only 19.6 liters per mole-centimeter, which is low for a primary absorber in
a photochemical process (Glaze and others, 1987). Therefore, although the yield of hydroxyl
radicals from hydrogen peroxide photolysis is relatively high, the low molar extinction coefficient
requires that a relatively high concentration of hydrogen peroxide exist in the water. However,
because excess hydrogen peroxide is also a hydroxyl radical scavenger, hydrogen peroxide levels
that are too high could decrease treatment efficiency. According to PSI, the perox-pure" system
overcomes these limitations by using medium pressure UV lamps.
19
-------
The perox-pure" system is equipped with a hydrogen peroxide splitter that allows the
operator to inject hydrogen peroxide to the oxidation unit influent and directly at an individual
reactor. The distribution of the total hydrogen peroxide dose is an important operating parameter,
because the hydroxyl radical has a short lifetime. If the total hydrogen peroxide dose is delivered
to the influent, depending on other operating conditions, the resulting hydroxyl radical
concentration in the last reactor may be zero. Consequently, removal efficiency in the last reactor
would decrease significantly. Distributing part of the hydrogen peroxide dose directly to the
reactors guarantees that hydroxyl radicals are present throughout the oxidation unit.
Influent pH controls the equilibrium among carbonic acid, bicarbonate, and carbonate.
This equilibrium is important to treatment efficiency because carbonate and bicarbonate ions are
hydroxyl radical scavengers. If the influent carbonate and bicarbonate concentration is greater
than about 400 mg/L as calcium carbonate, the pH should be lowered to between 4 and 6 to
improve the treatment efficiency. At low pH, the carbonate equilibrium is shifted to carbonic
acid, which is not a scavenger.
Flow rate through the treatment system determines the hydraulic retention time. In
general, increasing the hydraulic retention time improves treatment efficiency by increasing the
time available for contaminant destruction. Theoretically, at a certain point, the reaction proceeds
toward equilibrium, and increasing the hydraulic retention time no longer significantly increases
removal efficiency. PSI notes that it did not observe such a phenomenon in the range of hydraulic
retention times provided by the perox-pure" system.
Maintenance Requirements
The maintenance requirements for the perox-pure" system summarized below are based on
discussions with PSI, during and after the SITE demonstration. Regular maintenance by trained
personnel is essential for the successful operation of the perox-pure" system.
The only major system component that requires regular maintenance is the UV lamp
assembly. Regular UV lamp assembly maintenance includes periodically cleaning the quartz tubes
housing the UV lamps. Eventually, the lamps may need to be replaced. The frequency at which
the quartz tubes should be cleaned depends on the type and concentration of suspended solids
present in the influent or formed during treatment. Cleaning frequency may range from once
every month to once every 3 months. UV lamp assemblies can be removed from the oxidation
20
-------
unit to provide access to the quartz tubes, which can then be cleaned manually. The quartz tubes
can also be cleaned automatically during operation with wipers. Automatic tube cleaning is a
standard feature on most PSI treatment units. The quartz tube wipers require replacement once
every 3 to 6 months depending upon the cleaning cycle frequency.
Maintenance requirements for the medium-pressure, mercury-vapor, broad-band UV
lamps used in the perox-pure™ system are similar to those for conventional, low-pressure UV
lamps. The life of low-pressure UV lamps normally cited by most manufacturers is 7,500 hours,
based on a use cycle of 8 hours. The use cycle represents the length of time the UV lamp is
operated between shutdowns. Decreasing the use cycle or increasing the frequency at which a UV
lamp is turned on and off can lead to early lamp failure.
A number of factors contribute to UV lamp aging. These factors include plating of
mercury to the interior lamp walls, a process called blackening, and solarization of the lamp
enclosure material, which reduces its transmissibility. These factors cause steady deterioration in
lamp output at the effective wavelength (253.7 nanometers) and decrease output at the end of a
lamp's life by 40 to 60 percent. This reduction in lamp output requires more frequent
replacement of the UV lamps. According to PSI, no significant decline in UV lamp output occurs
until after about 3,000 hours of operation. Therefore, PSI recommends replacing the UV lamps
after 3,000 hours. PSI guarantees the UV lamps in the perox-pure"" unit for 3,000 hours when
they are turned on and off no more than two or three times a day.
The only other part of the UV lamp assembly requiring periodic maintenance is the gasket
between the UV lamp and the reactor. This gasket, which is used to maintain a water-tight seal
on each reactor, is generally replaced once a year.
Other components of the perox-pure" system, such as valves, flow meters, piping,
hydrogen peroxide feed module, acid feed module, and base feed module, should be checked for
leaks once a month. In addition, the influent, hydrogen peroxide, acid, and base feed pumps
should be checked once a month for proper operation and maintenance. Feed pump heads are
usually replaced annually. PSI offers a full-service program to its customers that covers all
regular maintenance and replacement parts for the system.
21
-------
TREATMENT SYSTEM SUPPORT EQUIPMENT AND FACILITIES
Typically, support equipment and facilities are needed depending on the site logistics,
required operating procedures, and equipment limitations. The major support equipment and
facilities used during the SITE demonstration of the perox-pure™ system included a cartridge
filtration system to remove suspended solids from groundwater, storage tanks for untreated and
treated groundwater, an acid feed module for untreated groundwater, a base feed module for
treated groundwater, an office and laboratory trailer, and pumps.
A more detailed discussion of the specific support equipment and facilities used during the
field demonstration is given in Section 5.
UTILITY REQUIREMENTS
Utilities required for the perox-pure*" chemical oxidation technology demonstration
included water, electricity, and telephone service. LLNL provided most of the support required
to arrange utilities for the demonstration.
Water was required for equipment and personnel decontamination, for field laboratory use,
and for drinking. During operation of the demonstration unit, personnel and equipment
decontamination required about 10 gallons per day (gpd) of potable water. About 5 gpd of
distilled, deionized water was needed for field laboratory use, and about 5 to 10 gpd were needed
for drinking water.
Electricity was needed for the perox-purem system, the office trailer, and the laboratory
equipment. The perox-pure"" system required 480-volt, 3-phase electrical service. Additional
electrical power (110-volt, single-phase) was needed for operating the pumps, the mixing device
in the spiking solution feed system, the office trailer lights, and the on-site laboratory and office
equipment.
Telephone service was required for ordering equipment, parts, reagents, and other
chemical supplies; scheduling deliveries; and making emergency communications.
22
-------
SECTION 4
DESCRIPTION OF DEMONSTRATION SITE
The perox-pure" technology demonstration was conducted at the LLNL Site 300 in Tracy,
California. This section describes the LLNL site characteristics and summarizes the site
contamination results.
SITE CHARACTERISTICS
LLNL is a 640-acre research facility about 45 miles east of San Francisco and 3 miles east
of Livermore, California (see Figure 2). Development of the site began in 1942, when it was used
as a U.S. Navy aviation training base. Subsequent activities at LLNL varied considerably under
the management of several government agencies, including the Atomic Energy Commission, the
Energy Research and Development Agency, and the U.S. Department of Energy, which is the
present owner. Various hazardous materials, including VOCs, metals, and tritium were used and
released at the site.
The demonstration was conducted at Site 300, which is operated by LLNL but is separate
from the LLNL main campus (see Figure 2). Site 300 occupies 11 square miles in the Altamont
Hills about 15 miles southeast of Livermore and 8.5 miles southwest of Tracy, California. LLNL
established Site 300 as a high-explosives test area in 1955. Site 300 operations include (1)
hydrodynamic testing; (2) charged particle-beam research; (3) physical, environmental, and
dynamic testing; and (4) high-explosive formulation and fabrication.
EPA chose a specific area of Site 300 for the technology demonstration. This area is called
the General Services Area (GSA). The GSA occupies about 80 acres in the southeastern corner of
Site 300. Various administrative, medical, engineering, and maintenance operations are conducted
in buildings located in the GSA. Before 1982, several GSA facilities used dry wells to dispose of
waste rinse, process, and wash waters. Wastes from these facilities might have included
photolaboratory rinse water; water- and oil-based paint waste; automotive shop waste containing
degreasing solvents; and acid dip rinse water. Between 1983 and 1984, the dry wells were
investigated and closed. After the dry well closure, wastewater from these activities was shipped
off site for treatment and disposal. Other wastes are currently stored on site in a permitted
23
-------
Sacramento
Stockton
LLNL-
Paclflc Ocaan
Figure 2. LLNL Site Location
Source: LLNL, 1990
24
-------
hazardous waste storage area. The suspected sources of groundwater contamination in the GSA
are the dry wells, accidental releases and leaks during facility operations, and leaking underground
fuel storage tanks.
LLNL's Environmental Restoration Division submitted a remedial investigation (RI) report
and a feasibility study (FS) report to EPA Region IX in May and December 1990, respectively.
The FS report outlined a treatment system for contaminated groundwater from the central GSA.
The system will be designed to treat both vapor and groundwater obtained from extraction wells
in the area. Groundwater will be collected both on and off site for remediation. Currently,
several treatment alternatives are being evaluated at the site.
SITE CONTAMINATION
Dry wells, accidental releases and leaks during facility operations, and leaking
underground fuel storage tanks are suspected sources of groundwater contamination in the central
GSA. Based on the RI report (LLNL, 1990), the shallow aquifer at the site was selected as the
candidate waste stream for the technology demonstration.
In May 1992, LLNL performed an 8-hour drawdown pump test using existing
groundwater extraction wells. The groundwater was sampled throughout the test and analyzed for
VOCs, SVOCs, metals, and a variety of other parameters, such as pH and alkalinity. Samples for
VOC and SVOC analyses were collected after approximately 1, 3, 6, and 8 hours elapsed pumping
time. These analyses showed that (1) only five VOCs were present above detection limits, (2)
SVOCs were not present above detection limits, and (3) all five VOCs detected showed gradual
decreases in concentration over the 8-hour test duration. At the end of 8 hours, TCE; PCE;
1,1-dichloroethene (1,1-DCE); 1,2-dichloroethene (1,2-DCE); and TCA were present at
1,200 fig/L; 95 /xg/L; 7.1 >*g/L; 8.7 ng/L; and 7.5 jtg/L, respectively.
The following parameters were also measured in the groundwater samples collected after
6 hours of pumping: (1) pH was 7.8; (2) alkalinity was 300 mg/L as calcium carbonate; (3) the
concentration of total dissolved solids was 930 mg/L; (4) the concentration of iron was 10 ng/L,
and (5) the concentration of manganese was 20 ng/L.
25
-------
SECTION 5
DEMONSTRATION PROCEDURES
Procedures for the perox-purew chemical oxidation system demonstration were developed
to evaluate the system's effectiveness in treating groundwater contaminated with VOCs from
Site 300 at LLNL. A demonstration plan was prepared that detailed the proposed sampling,
analytical, quality assurance, quality control, and health and safety procedures for the
demonstration (PRC, 1992). This section summarizes the actual demonstration procedures,
including the testing program, field activities, sampling procedures and field measurements,
analytical procedures, deviations from the demonstration plan, technical systems review, and
community relations and technology transfer activities.
TESTING PROGRAM
The demonstration was conducted in the GSA at Site 300 in Tracy, California, over a 3-
week period in September 1992. The demonstration was divided into three stages: (1) site
preparation; (2) technology demonstration; and (3) site demobilization. During the demonstration,
the perox-pure1" system (Model SSB-30) treated about 40,000 gallons of groundwater
contaminated with VOCs. Principal groundwater contaminants included TCE and PCE, which
were present at concentrations of about 1,000 and 100 /ig/L, respectively. Other VOCs, such as
chloroform, 1,1-DCA, 1,1-DCE, 1,2-DCE, and TCA, were present at average concentrations
below 15 ng/L. Groundwater was pumped from two wells into a 7,500-gallon bladder tank to
minimize any variability in influent characteristics. In addition, cartridge filters were used to
remove suspended solids greater than 3 micrometers in size from the groundwater before it
entered the bladder tank. Treated groundwater was stored in two 20,000-gallon steel tanks before
being discharged.
Both primary and secondary objectives were identified for the technology demonstration.
Primary objectives were critical for the technology evaluation, while secondary objectives
provided useful, but noncritical information. The primary objectives for the demonstration were
as follows:
• Determine the VOC removal efficiencies in the treatment system under
different operating conditions
26
-------
• Determine whether the treated groundwater met the applicable discharge
standards at the 95 percent confidence level
• Gather the information necessary to estimate treatment costs, including
chemical doses and utility requirements
The first objective was met by calculating the percent contaminant removal efficiencies
using Equation 2:
CRE = MCI " MCE x 100 (2)
MCI
where
CRE = percent contaminant removal efficiency
MCI = mean contaminant concentration in the influent
MCE = mean contaminant concentration in the effluent
To determine whether the concentration of selected contaminants in the treated water met
the applicable target levels (see Table 2), PRC performed a one-tailed Student's t-test, assuming
that the data were normally distributed. The upper confidence limit (UCL) for the mean
contaminant concentration in the treated water was calculated at the 95 percent confidence level
using Equation 3:
UCL = x * — (3)
y/i
where
x = sample mean contaminant concentration
t = Student's t-test statistic value at a specified confidence level
s = sample standard deviation
n = sample size (number of replicates)
Information such as chemical doses and power consumption was recorded during the
demonstration to estimate costs. Additional information, such as operating and maintenance costs
for the technology, was provided by the developer and operating facilities.
27
-------
TABLE 2
TARGET LEVELS FOR VOCs IN EFFLUENT SAMPLES
voc
Target Level
(W/L)
Chloroform
100
DCA
5
1,1-DCE
6
1,2-DCE
6
TCA
200
TCE
5
PCE
5
28
-------
The secondary objective for the demonstration was to obtain information on the presence
and types of by-products formed during treatment. This objective was accomplished by analyzing
the treated water for VOCs and SVOCs using gas chromatography and mass spectrometry
(GC/MS) methods and by performing bioassays to evaluate whether the treated groundwater
contained by-products harmful to fresh water organisms.
The technology demonstration was conducted in three phases (see Table 3), Phase 1
consisted of eight runs using raw groundwater, Phase 2 consisted of four runs using spiked
groundwater, and Phase 3 consisted of two runs using spiked groundwater to test the effect of
quartz tube cleaning. These phases are described below.
The principal operating parameters for the perox-pure"" system include hydrogen peroxide
dose, influent pH, and flow rate, which determines the hydraulic retention time. These
parameters were varied during Phase 1 to observe treatment system performance under different
operating conditions. For Phase 1 runs, the initial operating conditions were based on
groundwater characterization performed by LLNL in May 1992 (see Section 4) and PSI's
professional judgment and experience. In Runs 1, 2, and 3 the influent pH was varied while the
other parameters were held constant to determine preferred operating conditions. The preferred
operating conditions were those under which the concentration of effluent VOCs would be
reduced to below target levels (see Table 2) during Phase 2 spiked groundwater runs. After the
preferred value for pH was determined, that value was held constant, while the other parameters
were varied. Preferred operating conditions for each parameter were determined based on quick
turnaround analytical data for three selected indicator VOCs: TCE, PCE, and TCA, Even though
TCE and PCE are easily oxidized, they were chosen because they were present in relatively high
concentrations. TCA was chosen because it is relatively difficult to oxidize, although it was
present at a low concentration. Based on quick turnaround analytical data, PSI selected Run 3
operating conditions as the preferred operating conditions for spiked groundwater.
Phase 2 involved spiked groundwater and reproducibility tests. Groundwater was spiked
with sufficient chloroform, DCA, and TCA so that the spiked groundwater contained about
200 txg/L of each of these VOCs. These compounds were chosen because they are relatively
difficult to oxidize and because they were not initially present in the groundwater at high
concentrations. Phase 2 increased the applicability of the demonstration data to other sites that
may be contaminated with VOCs that are difficult to oxidize. Phase 2 was also designed to
evaluate the reproducibility of the perox-pure™ system's performance at the preferred operating
29
-------
TABLE 3
EXPERIMENTAL MATRIX FOR perox-pure™ SYSTEM
Run
Number
Influent
pH
Hydrogen Peroxide at
Influent to Reactor 1
(mg/L)
Hydrogen Peroxide
at Influent to
Reactors 2 to 6
(mg/L)
Flow Rate
(gpm)
Phase 1 (Raw Groundwater Runs)
J
8.0
40
25
10
2
6.5
40
25
10
3
5.0
40
25
10
4
5.0
70
50
10
5
5.0
30
15
10
6
5.0
240
Hydrogen Peroxide
was added at Influent
to Reactor 1 only
10
7
5.0
240
40
8
5.0
60
40
Phase 2 (Spiked Groundwater and Reproducibility Runs)
9
5.0
70
50
10
10
5.0
40
25
10
11
5.0
40
25
10
12
5.0
40
25
10
Phase 3 (Quartz Tube Cleaner Runs)
13
5.0
40
25
10
14
5.0
40
25
10
Notes:
mg/L = milligrams per liter
gpm = gallons per minute
30
-------
conditions determined in Phase 1. Specifically, Runs 10, 11, and 12 were performed at Run 3
conditions to evaluate the reproducibility of the perox-pure™ system's performance.
During Phase 3, the effectiveness of the quartz tube wipers was evaluated by performing
two runs using spiked groundwater at the preferred operating conditions. The quartz tubes used
in Phase 3 were obtained from a hazardous waste site where the water hardness and iron content
caused scaling on the tubes, PSI obtained two sets of quartz tubes for Phase 3. One set of quartz
tubes was relatively clean, because the wipers were routinely used to minimize scaling. The other
set of tubes had significant scaling because wipers were not used. Because PSI was able to obtain
only two tubes of each type (scaled and clean), only two reactors were used during Phase 3.
Specifically, Run 13 was performed using scaled quartz tubes, while Run 14 was performed using
clean quartz tubes. In both runs, only two UV lamps were operating.
FIELD ACTIVITIES
After the GSA location was selected, support services, facilities, and equipment were
procured and installed. EPA arranged utility connections, ordered and rented equipment, and
supervised and directed subcontractors. Field activities associated with site preparation and
mobilization, and site demobilization and waste disposal are described below.
Site Preparation and Mobilization
Approximately 10,000 square feet of the site was used for the perox-pure" chemical
oxidation system and support equipment and facilities. This equipment included treated and
untreated water storage tanks, nonhazardous and potentially hazardous waste storage containers,
an office and field laboratory trailer, and a parking area. A temporary canopy covering
approximately one-fourth of the demonstration area was erected to provide shelter for the perox-
pure" system and personnel during the technology demonstration. Site preparation and
mobilization included setting up major support equipment, on-site support services, and utilities.
These activities are discussed below.
Maior Support Equipment
Support equipment for the perox-pure™ system demonstration included a cartridge
filtration system to remove suspended solids from groundwater, storage tanks for untreated and
31
-------
treated groundwater, an acid feed module for untreated groundwater, a base feed module for
treated groundwater, a spiking solution feed system, a static mixer, two 55-gallon drums for
collecting equipment wash down and decontamination rinse water, a dumpster, a forklift with
operator, pumps, sampling equipment, health and safety equipment, and vehicles. Specific items
included the following:
• One cartridge filtration system containing two filters upstream of the
treatment unit; the filters were capable of removing suspended solids
greater than 3 micrometers in size from groundwater
• One 55-gallon closed-top, polyethylene drum containing spiking solution
equipped with a floating lid and a mixing device; during the demonstration,
a spiking solution containing chloroform, DCA, and TCA was added in line
to the groundwater to evaluate the perox-pure"" system's ability to treat
compounds that are difficult to oxidize
• One static mixer to mix the spiking solution and groundwater before the
mixture entered the untreated groundwater storage tank
• One 7,500-gallon bladder tank used to store untreated groundwater and
minimize VOC losses during storage and as an equalization and storage tank
during the technology demonstration
• One pump for transferring contaminated water from the bladder tank to
the perox-pure"" system and one pump for adding spiking solution in line
to the groundwater
• One sulfuric acid feed module to adjust the pH of the influent to the
perox-pure"" system; PSI provided the module, which consisted of a
55-gallon acid feed drum, two pumps, and flow measuring devices
• One sodium hydroxide feed module provided by PSI consisting of a
55-gallon base feed drum, two pumps, and flow measuring devices to
adjust the pH of the effluent from the perox-pure"" system
• Several large garbage cans to store nonhazardous wastes before disposal
• A number of 55-gallon drums to contain used disposable field sampling and
analytical equipment, used disposable health and safety gear, and field
laboratory wastes before disposal
• A forklift with operator for setting up equipment and for moving drummed
wastes
• Sampling equipment for aqueous media and process chemical solutions
• Analytical equipment for measuring field parameters at the demonstration
site
32
-------
• Two 20,000-gallon steel tanks to store treated groundwater before analysis
and disposal
• Health and safety related equipment, such as a first-aid kit, protective
coveralls, latex or similar gloves, nitrile gloves, steel-toe boots and
disposable overboots, safety glasses, and a hard hat
• Vehicles to transport personnel and supplies to and from the site
On-Site Support Services
One portion of the field trailer (12 by 44 feet) was used for on-site laboratory analyses,
the rest of the trailer served as an office for field personnel and provided shelter and storage for
small equipment and supplies. Two toilets were available near the demonstration area.
Utilities
Utilities required for the demonstration included water, electricity, and telephone service.
LLNL provided most of the support required to arrange utilities for the demonstration. Water was
required for equipment and personnel decontamination, for field laboratory use, and for drinking.
During operation of the demonstration unit, personnel and equipment decontamination required
about 10 gpd of potable water. About 5 gpd of distilled, deionized water was needed for field
laboratory use, and about 5 to 10 gpd were needed for drinking water.
Electricity was needed for the perox-pure"* system, the office trailer, and the laboratory
equipment. The perox-pure"" system required 480-volt, 3-phase electrical service. Additional
electrical power (110-volt, single-phase) was needed for operating the pumps, the mixing device
in the spiking solution feed system, the office trailer lights, and the on-site laboratory and office
equipment.
Telephone service was required mainly for ordering equipment, parts, reagents, and other
chemical supplies; scheduling deliveries; and making emergency communications.
Site Demobilization and Waste Disposal
After the demonstration was completed and on-site equipment was disassembled and
decontaminated, equipment and site demobilization activities began. Equipment demobilization
33
-------
included loading the skid-mounted units on a flat-bed trailer and transporting them off site,
returning rented support equipment, and disconnecting utilities.
Decontamination was necessary for the perox-pure" unit, the storage tanks, and field
sampling and analytical equipment. Demonstration equipment was either cleaned with potable
water or steam, as required. LLNL tested and disposed of the treated water collected during the
demonstration in accordance with applicable discharge permits. LLNL also handled all hazardous
wastes through their Hazardous Waste Management Program. Regular garbage service at LLNL
collected all nonhazardous wastes generated during the demonstration.
SAMPLING PROCEDURES AND FIELD MEASUREMENTS
Samples were collected and measurements were taken during the demonstration to evaluate
the effectiveness of the perox-purem chemical oxidation system. Figure 3 shows sampling and
measurements locations and Table 4 outlines the sample collection and field measurement program
for the technology demonstration. Tables 5 and 6 give quality assurance (QA) objectives for
critical and noncritical parameters, respectively. During the demonstration, TOX and AOX were
added to the analyte list as requested by the German Federal Ministry of Research and
Technology, under a U.S.-German bilateral technology transfer program. Additionally, GC/MS
analyses for VOCs and SVOCs were done in all test runs instead of only in Runs 10, 11, and 12, as
requested by the German Federal Ministry of Research and Technology.
The following parameters were considered critical for evaluating the perox-pure""
technology: (1) VOCs, hydrogen peroxide, base, and acid concentrations; and (2) flow rate and
pH. 'VOCs were measured by both GC and GC/MS methods. Only GC measurement of VOCs
listed in Table 2 was considered critical, because GC data was planned for quantitative use (for
example, to evaluate the primary objectives) while GC/MS data was planned for qualitative use
(for example, to evaluate the secondary objective). This section describes liquid sampling
procedures, field measurements, and associated QA procedures as implemented during the
demonstration. Deviations from the demonstration plan are discussed later in this section.
34
-------
GROUNDWATER FROM
W—875—08 AND W-7--0
S3
W6
SODIUM
HYDROXIDE
EXTRACTION WELL
$9
~¦TO DISPOSAL
S7
/-UV LAMP
Ml
HYDROGEN
PEROXIDE
SPLITTER -
CARTRIDGE
FILTERS
SULFURIC W51
ACID 1
S3
HYDROGEN
PEROXIDE
SA
REACTOR
S2
S4
M3
OXIDATION UNIT
STATIC
MIXER
STATIC
MIXER
BLADDER
TANK
M2
SPIKING
SOLUTION
• SAMPLING LOCATION
O MEASUREMENT LOCATION
Figure 3. perox-pure™ Chemical Oxidation Treatment System Sampling and Measurement Locations
-------
TABLE 4
OUTLINE OF SAMPLE COLLECTION AND FIELD MEASUREMENT PROGRAM
Location*
Run
No.
Analytical
Parameter
Number of Field and Field QC Samples/Measurements
Field Generated
Lab QC Samples
Total No.
of Samples'1
(Measurements*)
Number of
Samples
(Measurements)
per run
Total Number of
Field
Samples
(Measurements)
Field QC
Total %
of Field +
Field qc
Samples'*
No. of
MS/MSD
Sample
Sets' .
No, of
S/SD
Sample
Sets" '•
No. of
Field
Blanks*
No. of
Trip
Blanks'*
Peed Line to Equaluation
Tank (Ml)
9-14
Flow Rate
(»)
(18)
NA
NA
(18)
NA
NA
(18)
Spike Solution Feed Tank
(M2)
9-14
Flow Rate
(3)
(18)
NA
NA
(18)
NA
NA
(18)
Feed Line from the
Equaliration Tank (SI,
M3)
1-14
VOCs (GC Analysis)
4
56
0
0
66
S
0
62
VOCs (GC/MS Analysis)
1
14
0
0
14
1
0
16
SVOCs
1
14
0
0
14
1
0
16
PH
2
28
NA
NA
28
NA
2
32
Alkalinity
2
28
NA
NA
28
2
0
32
Hardness
2
28
NA
NA
28
2
0
32
Flow Rate
(3)
(42)
NA
NA
(42)
NA
NA
(42)
Temperature
1
14
NA
NA
14
NA
1
16
TOX
I
14
0
0
14
1
0
16
*, 7, 9,
and IS
AOX
1
4
0
0
4
1
0
6
10-12
TC
1
3
0
0
3
1
0
5
TOC
1
S
0
0
3
1
0
5
POC
1
3
0
0
3
1
0
S
Metals
1
3
0
0
3
1
0
S
Hydrogen Peroxide
Feed Tank (S2, M4)
1-14
Hydrogen Peroxide
1
14
NA
NA
14
NA
1
16
Flow Rate
(3)
(42)
NA
NA
(42)
NA
NA
(42)
-------
TABLE 4
OUTLINE OF SAMPLE COLLECTION AND FIELD MEASUREMENT PROGRAM (Continued)
Location4
Run
No.
Analytical
Parameter
Number of Field and Field QC Samples/Measurements
Field Generated
Lab QC Samples
Total No.
of Samples'1
(Measurements*)
Number of
Sample!
(Measurements)
per run
Total Number of
Field
Samples
(Measurements)
Field QC
TotaJ No,
of Field +
Field QC
Sample*''
No. of
MS/MSD
Sample
SeUc
No. of
S/SD
Sample
Sets"
No. of
Field
Blanks'1
No. of
Trip
Blanks'1
Sulfuric Acid Feed Tank
(S3, M5)
1-14
Acid
1
14
NA
NA
14
NA
1
16
Flow Rate
(3)
(42)
NA
NA
(42)
NA
NA
(42)
Influent Line to Reactor 1
(S4)
1-14
pH
2
28
NA
NA
28
NA
2
32
Alkalinity
2
28
NA
NA
28
2
0
32
Hardness
2
28
NA
NA
28
2
0
32
10-12
Specific Conductance
1
3
NA
NA
3
0
1
6
Turbidity
1
3
NA
NA
3
0
1
S
Bioassay: C. dubia
1
3
NA
NA
3
NA
NA
3
Bioassay: P. promelas
1
3
NA
NA
3
NA
NA
3
Effluent from Reactor I
(SS)
1-14
VOCs (GC Analysis)
4
56
0
0
66
3
0
62
Effluent from Reactor 2
(SA)
12-14
VOCs (GC Analysis)
4
12
1
1
14
1
0
16
VOCs (GS/MS Analysis)
1
3
0
0
3
0
0
3
SVOCs
1
3
0
0
3
0
0
3
Hydrogen Peroxide
1
3
NA
NA
3
NA
1
6
PH
2
6
NA
NA
6
NA
1
8
Temperature
1
3
NA
NA
3
NA
1
5
Alkalinity
2
6
NA
NA
6
1
0
8
Hardness
2
6
NA
NA
6
1
0
8
TOX
1
3
2
0
5
1
0
7
13
AOX
1
1
1
0
1
0
0
2
-------
TABLE 4
OUTLINE OF SAMPLE COLLECTION AND FIELD MEASUREMENT PROGRAM (Continued)
Location8
Run
No.
Analytical
Parameter
Number of Field and Field QC Samples/Measurements
Field Generated
Lab QC Samples
Total No.
of Samples1'
(Measurement**)
Number of
Samples
(Measurements)
per run
Total Number of
Field
Samples
(Measurements)
Field QC
Total No.
of Field +
Field QC
Samples'1
No . of
MS/MSD
Sample
Setsc
No. of
S/SD
Sample
Sets'
No, of
Field
Blanks1'
No, of
Trip
Blanks1'
Effluent from Reactor S
(S6)
1-12
VOC« (GC Analysis)
4
48
0
0
48
3
0
64
Effluent from the
Treatment System (ST)
1-12
VOCs (GC Analysis)
4
48
12
8
68
4
0
76
VOCs (GC/MS Analysis)
1
12
12
3
27
2
0
31
SVOCs
1
12
12
0
24
2
0
28
Hydrogen Peroxide
1
12
NA
NA
12
NA
1
14
pH
2
24
NA
NA
24
NA
2
28
TOX
1
12
12
2
26
2
0
30
4, 7,
and 9
AOX
1
3
3
2
8
1
0
10
10-12
TC
1
3
0
0
3
1
0
5
TOC
1
3
0
0
3
1
0
6
POC
1
3
0
0
3
1
0
E
Metals
1
3
0
0
3
1
0
S
Specific Conductance
1
3
NA
NA
3
0
1
6
Turbidity
1
3
NA
NA
3
0
1
5
Bioassay: C. dubia
1
3
NA
NA
3
NA
NA
3
Bioassay: P. promelas
1
3
NA
NA
3
NA
NA
3
Sodium Hydroxide
Feed Tank (S8, M6)
1-14
Base
1
14
NA
NA
14
NA
1
16
Flow Rate
(3)
(42)
NA
NA
(42)
NA
NA
(42)
Discharge Line (S9)
1-14
PH
2
28
NA
NA
28
NA
2
32
Watt Hour Meter
1-14
Electricity Consumption
(1)
(14)
NA
NA
(")
NA
NA
(14)
-------
TABLE 4
OUTLINE OF SAMPLE COLLECTION AND FIELD MEASUREMENT PROGRAM (Continued)
Notes:
MS/MSD Matrix spike/matrix spike duplicate
NA Not applicable
QC Quality control
S/SD Sample/sample duplicate
' The numbers in the parentheses refer to sample or measurement locations identified in Figure 3.
b Field blanks were collected once every run. Trip blanks were collected once every day (shipment).
c MS/MSD and S/SD samples were obtained through the collection of a triple volume/container of sample. MS/MSD and S/SD
samples were counted as two when calculating the total number of samples.
d The total number of samples includes samples collected for analysis (I) at the laboratory and (2) in the field.
e No samples were collected for measurements. The measurements were made directly at the sampling location.
-------
TABLE 5
ANALYTICAL METHODS AND QA OBJECTIVES FOR CRITICAL PARAMETERS
Parameter
Method Ref.a
Unit
TRLb
Precision*
Accuracy11
VOCs
Chloroform
SW-846 8010
Mg/L
1.0
± 30%
50 - 150%
DCA
SW-846 8010
Mi/L
1.0
± 30%
50 - 150%
1,1-DCE
SW-846 8010
iig/L
1.0
± 30%
50 - 150%
1,2-DCE
SW-846 8010
Mg/L
1.0
± 30%
50 - 150%
TCA
SW-846 8010
Mg/L
1.0
± 30%
50 - 150%
TCE
SW-846 8010
Mg/L
1.0
± 30%
50 - 150%
PCE
SW-846 8010
M g/L
1.0
± 30%
50 - 150%
pH
MCAWW 150.1
pH unit
NA
± 0.2e
+ 0.04f
Acid
Note g
N
0.01
± 10%
± 10%h
Hydrogen Peroxide
Boltz and Howell,
1979
mg/L
1
± 10%
± 10%h
Base
Note i
N
0.01
± 10%
± 10%
Flow Rate
Note j
Lpm
0.1
± 10%
NA
Notes:
NA = Not applicable
N = Normal (equivalents/liter) solution
Lpm = Liters per minute
SW-846: EPA (1986); MCAWW: EPA (1983)
b Target Reporting Limits (TRL) for effluent (treated) samples. Influent samples with
elevated concentrations of VOCs will have higher detection limits
c Precision as RPD unless stated otherwise
d Accuracy as percent recovery unless stated otherwise
e For pH, precision is expressed in pH units as range
f For pH, accuracy is expressed in pH units as bias
g Titration with a standardized base solution (for example, 0,1 N NaOH)
h For acid, base, and hydrogen peroxide measurements, accuracy is expressed as percent bias
from true value of a QC check standard
1 Titration with a standardized acid solution (for example, 0.1 N H2S04)
1 Flow rate was measured using the equipment available on the treatment system. The
equipment was calibrated manually with a graduated container and a stop watch
40
-------
TABLE 6
ANALYTICAL METHODS AND QA OBJECTIVES FOR NONCRITICAL PARAMETERS
Parameter
Method Ref.8
Unit
TRLb
Precision*
Accuracy4
VOCs (GC, noncritical)
SW-846 8010
M g/L
Ł 10
± 30%
50 - 150%
VOCs (GC/MS)
SW-846 8240
M8/L
Ł 50
See Table 8
See Table 8
SVOCs8 (GC/MS)
SW-846 8270
n g/L
«Ł 25
See Table 8
See Table 8
Metalsf
SW-846 6010
Mg/L
100
± 25%
75 - 125%
TC and TOC
SM 5310C
Mg/L
100
± 25%
75 - 125%
POC
SM 5310B
Mi/L
100
± 25%
75 - 125%
Bioassay
EPA/600/4/85-013
% Sample
NA
NA
NA
Turbidity
MCAWW 180.1
NTU
0.1
± 20%
± 10%
Alkalinity
MCAWW 310.1
mg/L as CaC03
10
± 10%
± 10%
Hardness
MCAWW 130.2
mg/L as CaC03
10
± 25%
75 - 125%
Temperature
MCAWW 170.1
°C
5
± 0.5
± 1
TOX
SW-846 9020
Mg/L
< 5
± 30%
50 - 135%
AOX
DIN 38409 H14«
Mg/L
<; 10
± 30%
50 - 135%
Specific Conductance
SW-846 9050
^mho/cm
10
± 10%
± 10%
Electricity Consumption
Noneh
kilowatt hour
0.1
NA
NA
Notes:
jimho/cm = Micromhos per centimeter
NA = Not applicable
NTU = Nephelometric Turbidity Unit
* SW-846: EPA (1986); SM: APHA el ah (1989); MCAWW; EPA (1983)
b TRL for effluent (treated) samples. Influent samples with elevated concentrations of
VOCs will have higher detection limits
c Precision estimated as relative percent difference for all applicable parameters except for
temperature; for temperature precision is estimated as range
d Accuracy estimated as percent recovery for all applicable parameters except for turbidity,
specific conductance, and temperature; for turbidity and specific conductance accuracy
expressed as percent error; for temperature, accuracy expressed as bias
e SVOCs: bases, neutrals, and acids
f Iron and manganese
s Kai Steffens (1993)
h Electricity consumption was measured as described in the watt hour meter manual
41
-------
Liquid Sampling Procedures
Samples of untreated and treated groundwater were collected at locations SI, S4, S5, SA,
S6, S7, and S9 from sample taps located in the process flow (see Figure 3). Sample ports were
opened briefly prior to collecting samples to allow any stagnant water in the line to clear. Samples
of process chemicals (sampling locations S2, S3, and S8 in Figure 3) were collected from storage
containers through a sample port on the container, or from a pipet used to draw a sample from the
container. The time interval between collecting the first and last replicate sample sets during runs
varied from 45 to J 80 minutes.
Because VOC samples were preserved by adding ascorbic acid (reducing agent added to
stop the oxidation of VOCs) and hydrochloric acid, samples were first collected into a 250-
milliliter (mL) bottle containing ascorbic acid in a manner to minimize or eliminate head space.
Starch iodide paper was used in the field to determine the amount of reducing agent needed. The
sample was gently shaken, allowed to sit for 5 minutes, and then transferred to a 40-mL volatile
organic analysis (VOA) vial containing hydrochloric acid. Samples were transferred to the VOA
vials without introducing any air bubbles. TC, TOC, and POC samples were collected in the same
manner as VOC samples using sulfuric acid instead of hydrochloric acid for preservation. TOX
and AOX samples were preserved using ascorbic acid and sulfuric acid. SVOC samples were
preserved using sodium thiosulfate (reducing agent).
For metals, SVOCs, turbidity, and hardness samples, about 10 percent of the container was
left unfilled to prevent breakage in case the sample was accidentally frozen before analysis.
Minimal headspace was left in alkalinity, TOX, AOX, and bioassay sample containers.
Acid, base, hydrogen peroxide, pH, specific conductance, and temperature samples were
collected into a plastic beaker and analyzed on site immediately. The plastic beakers were rinsed
with distilled water prior to the collection of each sample.
Field Measurements
Parameters measured in the field included groundwater flow rate to and from the
equalization tank, flow rates of the spiking solution, hydrogen peroxide, sulfuric acid, and sodium
hydroxide, and electrical power consumption. Groundwater flow rates were measured using
factory calibrated and field confirmed in-flow paddle wheel meters. Process chemical and spiking
42
-------
solution flow rates were measured using pulse pumps with variable speed and piston volume
settings. All flow meters were calibrated by direct measurement of diverted flow into graduated
containers. Electrical power was measured with a factory calibrated watt meter wired into the site
electrical supply.
Field Sampling Quality Assurance Procedures
This section describes procedures followed during the technology demonstration to
maintain sample integrity and quality, including procedures related to sample containerization,
preservation and holding times, chain of custody (COC), trip blanks, and field blanks.
Sample Containerization. Preservation, and Holding Times
Sample containerization, preservation, and holding times followed are given in Table 7.
All samples for critical parameters arrived at the appropriate laboratory intact, properly cooled,
and appropriately preserved. GC analysis of four VOC samples (a replicate from location S6
during Run 8, a replicate from location SI and a trip blank during Run 10, and a replicate from
location S7 during Run 12) was performed 1 day after the designated holding time. Data for the
investigative samples was within 20 percent of the corresponding replicates. The trip blank
analyzed after the holding time had characteristics similar to other trip blanks collected during the
demonstration. All reported detections or reporting limits for these samples were qualified as
estimated. Three influent samples (Location S4 in Runs 10, 11, and 12) and one effluent sample
(Location S7 in Run 10) for bioassay exceeded the holding time by 36 hours due to delay caused
by overnight shipping service (Federal Express). Based on the groundwater characteristics, this
delay should not have significant impact on data quality.
One influent sample each from Runs 12 and 13 collected for SVOC analysis, arrived at the
off-site laboratory in broken containers and therefore, were not analyzed. Because SVOCs are
noncritical parameters for this demonstration, only one sample was collected at each location and
no additional samples were available. Because Runs 9 through 14 should have the same influent
characteristics, average influent characteristics from Runs 9 through 11 and Run 14 were used to
substitute for missing data. Reanalysis of four matrix spike/matrix spike duplicate (MS/MSD)
samples due to low surrogate recovery in SVOC samples occurred after the holding time expired;
43
-------
TABLE 7
SAMPLE CONTAINERIZATION, PRESERVATION, AND HOLDING TIMES
Parameter
Media
Minimum
Sample
Volume1,2
(mL)
Container
Preservative
Holding Time
Bioassay: C. dubia,
P. promelas
L
4,000
P
Cool, 4°C
36 hours
Metal* (ICP)
L
1,000
P,G
HNOj to pH<2, Cool 4'C
6 months
SVOCs (GC/MS
Analysis)
L
2 # 1,000
G
NajSjOj, Cool 4°C
7 days to extraction,
40 day* to analysis
TC, TOC, and POC
L
8 @s 40
VOA
Na~S203, Cool 4*C, H2S04
to pH<2
14 days
Turbidity
L
250
P,G
Cool, 4*C
48 hours
VOCs (GC Analysis)
L
3 <58 40
VOA
Ascorbic Acid, Cool 4°C
HC1 to pH<2
14 days
VOCs (GC/MS Analysis)
L
3 $ 40
VOA
Ascorbic Acid, Cool 4°C
HC1 to pH<2
14 days
Acid
L
250
P,G
None
Analysed
Immediately in Field
Alkalinity
L
500
P,G
Cool 4*C
14 days
Base
L
250
P,G
None
Analyzed
Immediately in Field
Hardness
L
250
P,G
HNOj to pH<2
6 months
Hydrogen Peroxide
L
40
G
None
Analysed
Immediately in Field
PH
L
100
P,G
None
Analysed
Immediately in Field
Specific Conductance
L
100
P,G
None
Analysed
Immediately in Field
Temperature
L
100
P,G
None
Analysed
Immediately in Field
AOX
L
250
G
Ascorbic Acid, Cool 4°C
H2S04 to pH<2
7 days
TOX
L
250
G
Ascorbic Acid, Cool 40C
H;S04 to pH<2
7 days
Notes:
Minimum sample volume applies to all samples, including field QC samples.
2 For samples selected for MS/MSD or S/SD analyses, triple containers/volume were
required. With the exception of VOC samples, MS/MSD and duplicate samples were taken
from the same container, whenever practical.
G = Amber glass and Teflon'Mined cap
ICP = Inductively coupled plasma
L = Liquid
P = Polyethylene
44
-------
nevertheless, QA objectives for precision and accuracy for these samples were met during
reanalysis.
Chain-of-Custodv
Each sample container was labeled with a unique sample identification number. The label
identified the sampling location, date, time of collection, and analyses to be performed. Samples
that were analyzed on site were delivered to the field laboratory trailer immediately. Project
number, project name, sampler's name, station number, date, time, sampling location, number of
containers, and analytical parameters were included on all COC forms. Samples were placed in ice
chests, packed with ice, and shipped to the various off-site laboratories. COC forms were
packaged inside each ice chest, and a custody seal was affixed across the openings of each ice
chest to prevent sample tampering. Except for one field blank, all samples arrived at the
appropriate laboratory with complete documentation, in the proper container, and with custody
seals intact. The field blank for VOCs by GC analysis in Run 6 was not analyzed due to an error
in the COC form. This error appeared to have little impact on data quality because no problems
were noted with VOC samples collected during Run 6.
Field Blanks
Field blanks were collected to assess the potential for contamination of the sample during
sample collection from dust or other sources at the demonstration site. Field blanks were collected
for VOC, SVOC, TOX, and AOX analyses. A sample bottle was filled with organic-free water
and left open near the treatment system during the sample collection period. When sampling was
complete, the sample bottle was closed and shipped to the laboratory with the rest of the samples.
A separate bottle was set up for each analysis. Field blanks were collected at a frequency of one
per run.
During Runs 7 and 9, there was trace level contamination of field blanks with critical
VOCs and as a result, data from Run 7 (at locations S5 and S6 for chloroform), and Run 9 (at
location S7 for TCA) were qualified as nondetected due to probable field contamination.
45
-------
Trio Blanks
Trip blanks were prepared for VOCs, TOX, and AOX to determine whether contamination
was introduced through sampling containers or as a result of exposure during shipment. The PRC
SITE team used thoroughly cleaned sample containers prepared and certified by vendors to be free
of contamination. Engineering-Science Berkeley Laboratory (ESBL) prepared trip blanks in the
laboratory by filling sample containers with analyte-free water. The trip blanks were shipped
with sampling equipment and bottles and were handled in the same way as regular samples. Trip
blanks were collected and analyzed at a frequency of one per cooler of VOC samples per
shipment. No trip blanks were found to be contaminated.
ANALYTICAL PROCEDURES
This section describes the analytical methods and procedures used for data reduction,
validation, and reporting during the technology demonstration. In addition, analytical QA is
discussed. Generally, the samples were successfully analyzed as required by the QAPP. Except
for the aromatic VOC results for one replicate sample in Run 9 at Location S5, no data were
qualified as unusable during the validation process [for this demonstration, aromatic VOCs are
noncritical analytes]. Some samples required dilution due to matrix interferences or levels of
target analytes above the calibration range. The target reporting limits (TRL) for samples affected
were adjusted to reflect the dilutions. Unless specifically noted, samples collected for the U.S.-
German bilateral technology transfer program met QA objectives.
Other data quality issues discussed below include laboratory blank contamination and
calibration outliers. At least one laboratory blank in each run except Runs 13 and 14 contained
noncritical VOCs. All reported detections of these noncritical VOCs in these blanks were
qualified as not detected due to probable laboratory contamination, and results were raised to the
reporting limit. Also, for all runs some calibration outliers were reported for calibration runs
associated with noncritical VOCs. All reported detections or reporting limits for the affected
analytes were qualified as estimated. Both of these conditions are considered minor and neither
had significantly affected the data quality.
46
-------
Analytical Methods
Tables 5 and 6 include the analytical and measurement methods used for the technology
demonstration. In selecting the appropriate analytical methods for the demonstration, the PRC
SITE team evaluated the specific analytes of interest, the sample matrix, and the minimum
detection limits required all within the context of the demonstration objectives. All parameters
were analyzed according to the methods described in the demonstration plan, with the exception
of some samples collected in the reproducibility runs. During the GC analysis of VOC samples,
one of three GCs at ESBL needed repair. Because ESBL was uncertain about the time required
for repairing the GC, to avoid holding time violations, all influent samples (Location SI) in Runs
9 through 12 and one replicate sample at Location S5 in Run 9 were analyzed for VOCs using
GC/MS instead of GC as described in the demonstration plan. Accuracy and precision data for
samples analyzed by GC/MS were better than for those analyzed by GC. A comparison of average
influent VOC concentrations in Runs 9 through 12 with those in Runs 13 and 14 showed no trend
to conclude that use of GC/MS instead of GC affected data quality. A similar observation was
made when Run 9, Location S5 data for replicate samples were compared.
The AOX sample analysis did not strictly follow the German Method DIN 38409 H14.
The method requires pyrolysis temperature to be set at 950 °C. However, General Testing
Corporation (GTC) performed this analysis at 800 °C, the recommended temperature for TOX
analysis by SW 846 Method 9020. During an EPA audit of GTC's analytical procedures, the
auditor recommended that some samples be analyzed at both 800 °C and 950 °C to evaluate the
temperature impact on data quality. However, operation of the instrument at 950 °C caused
undue stress on the pyrolysis tube and damaged the tube only after a few firings. For this reason,
GTC could successfully analyze only one sample at both temperatures. AOX levels at 950 °C and
800 °C were 0.60 and 0.71 mg/L, respectively. Based on this limited data, no conclusion could be
drawn on the impact of lower temperature on data quality.
Data Reduction, Validation, and Reporting
Laboratory data reduction, validation, and reporting procedures used in this technology
demonstration are described in the demonstration plan. Equations presented in the demonstration
plan for calculating compound or parameter concentrations were followed. Data validation and
reporting procedures for QA data did not deviate from those proposed in the demonstration plan.
47
-------
As recommended by the EPA RREL QA
this section instead of raw QA data. A summary
the preferred operating condition runs (Runs 10,
manager, a discussion of QA data is included in
of data for investigative samples collected during
11, and 12) is included in Appendix A,
Analytical Quality Assurance
Analytical QA is the process of ensuring and confirming data reliability. This process
includes establishing data quality objectives for the project and developing data quality indicators
(quantitative or qualitative measures of precision, accuracy, completeness, representativeness, and
comparability) that can be used to determine whether the data met the project's QA objectives.
Precision and Accuracy
Precision and accuracy goals depend on the types of samples and analyses performed for
critical parameters and on the ultimate use of analytical data. Precision and accuracy objectives
for critical and noncritical parameters are given in Tables 5 and 6, respectively. Additional
surrogate and MS/MSD spiking compound acceptance criteria are given in Table 8. Precision and
accuracy QA objectives stated in the demonstration plan were met for all critical parameters
analyzed or measured in the field.
Precision for critical VOCs was estimated as the relative percent difference (RPD) between
the analytical results of the MS and MSD samples. The spiking solution contained all critical
VOCs and vinyl chloride, as requested by the German Federal Ministry of Research and
Technology. The RPD between the spiked analyte levels measured in the MS sample and MSD
sample was calculated using Equation 4:
RPD = 1 MS-MSD | x 10Q
0.5 (MS *MSD)
For measurements of acid, base, and hydrogen peroxide concentrations, precision was
estimated as RPD between a sample/sample duplicate (S/SD) pair. An analogous equation to
Equation 4 was used for S/SD, where S replaces MS and SD replaces MSD.
48
-------
TABLE 8
SURROGATE AND MS/MSD SPIKING COMPOUNDS ACCEPTANCE CRITERIA
Method
Surrogate Compound
Percent Recovery
8270-BN
Nitrobenzene-d5
35-114
2-Fluorobiphenyl
43-116
p-Terphenyl-dl4
33-141
8270-A
Phenol-d5
10-110
2-Fluorophenol
21-110
2,4,6-Tribromophenol
10-123
8240
Toluene-d8
88-110
4-Bromofluorobenzene
86-115
1,2-Dichloroethane-d4
76-150
8010
Bromochloromethane
50-150
Chlorofluorobenzene
50-150
Method
Matrix Spike Compound
Percent
Recovery
RPD
8270-BN
1,2,4-Trichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
n-Nitroso-di-n-propylamine
1,4-Dichlorobenzene
39-98
46-118
24-96
26-127
41-116
36-97
28
31
38
31
38
28
8270-A
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methylphenol
4-Nitrophenol
9-103
12-110
27-123
23-97
10-80
50
42
40
42
50
8240
1,1-Dichloroethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
Vinyl chloride
61-145
71-120
75-130
76-125
76-125
50-150
14
14
13
13
11
25
8010
1,2-Dichloroethane
1.1-Dichloroethene
1.2-Dichloroethene
1,1,1 -T richloroethane
Trichloroethene
Tetrachloroethene
Chloroform
See Table 5
See Table 5
49
-------
Precision for pH was estimated as a range by analyzing duplicate aliquots -
- an S/SD pair.
D(pH) = \pH1 - PH21
(5)
where
D(pH)
pHj and pH2
range for pH
observed values for duplicate aliquots of a sample
Precision was estimated as RPD at each flow rate required during the demonstration by
performing duplicate measurements.
RPD results for GC analysis of VOCs ranged from 0 to 29 percent compared to the QA
objective of less than or equal to 30 percent. RPD results for GC/MS analysis of VOCs ranged
from 0 to 9 percent (the QA objective was less than or equal to 11 to 25 percent depending on the
spike compound). RPD values for both TOX and AOX analyses was determined using MS and
MSD data. The RPD was determined to be 28 percent (the QA objective was less than or equal to
The range of RPD for the process chemical concentrations were as follows: 0 to 2.3
percent for acid analyses (the QA objective was less than or equal to 10 percent), 0 to 6 percent
for base analyses (the QA objective was less than or equal to 10 percent), and 0.8 to 8.5 percent
for hydrogen peroxide analyses (the QA objective was less than or equal to 10 percent).
The range of RPD for precision for pH analysis was 0.01 to 0.012 compared to the QA
objective of less than or equal to 0.2. The QA objective of less than or equal to 10 percent for
precision for flow rates was easily met.
Accuracy for VOCs was estimated from MS samples by calculating the percent recovery of
laboratory MS samples using Equation 6:
30 percent).
50
-------
(C, - C)
%R = x 100
C,
(6)
where
%R - percent recovery
Cj « measured concentration in spiked sample aliquot
C0 = measured concentration in unspiked sample aliquot
C, = actual concentration of spike added
For pH, accuracy was estimated as bias, reported in pH units, from the true value using
Equation 7:
B = pHm - pH, P)
where
B = bias
pHm = measured pH of standard reference material
pH, = actual pH of standard reference material
Similarly, accuracy for acid, base, and hydrogen peroxide concentration measurements was
estimated as percent bias using QC check samples prepared by ESBL.
Percent recovery results for GC analysis of VOCs ranged from 54 to 143 percent compared
to the QA objective of 50 to 150 percent. Percent recovery results for GC/MS analysis of VOCs
ranged from 75 to 99 percent, which met the QA objective listed in Table 8.
The percent bias for the pH analyses ranged from 0,00 to 0.04 compared to the QA
objective of 0.04, Percent bias for process chemical concentrations was as follows: 100 to 104
percent for acid analyses (the QA objective was 90 to 110 percent); 98 to 102 percent for base
analyses (the QA objective was 90 to 110 percent); and 92 to 104 percent for hydrogen peroxide
analyses (the QA objective was 90 to 110 percent).
51
-------
Accuracy for TOX and AOX analyses was measured as percent recovery in the MS sample.
The percent recovery for the samples ranged from 82 to 106 percent (the QA objective was 50 to
135 percent).
Completeness
Completeness is an assessment of the amount of valid data obtained from a measurement
system compared to the amount of data expected to achieve a particular statistical level of
confidence. The percent completeness is calculated by dividing the number of samples with
acceptable data by the total number of samples planned to be collected. The result is then
multiplied by 100. Greater than 95 percent of completeness was achieved for the demonstration
samples. The QA objective for degree of completeness was 90 percent and was met during the
demonstration.
For all parameters, critical or noncritical, analyzed either in the field or at an off-site
laboratory, all but one sample had usable results. Only results for analysis of aromatic VOCs, a
noncritical parameter, on a replicate taken from location S5 (effluent from Reactor 1) during
Run 9 were unusable due to poor surrogate recovery. Two samples collected for SVOC analysis, a
noncritical parameter, were not analyzed because they arrived at the laboratory in broken
containers.
Assuming that the lower temperature for AOX analysis had little impact on data quality,
all results from samples analyzed for TOX and for AOX under the U.S.-German bilateral
technology transfer program are considered usable.
Representativeness
For this project, representativeness involves sample size, sample volume, sampling times,
and sampling locations. The QA goal was to obtain a statistically adequate number of samples that
represented the various waste streams at the time samples were collected. The volume of sample
collected depends on the analytical method chosen, allowing for QC sample analyses and
reanalysis, if needed. A sufficient number of samples were collected to analyze all of the
parameters required; therefore, the QA objective for representativeness was met.
52
-------
Comparability
All parameters were measured using standard methods listed in Tables 5 and 6. Therefore,
the demonstration data are considered comparable to any other perox-pure™ system's performance
data generated using standard methods.
Target Reporting Limits
The TRLs for critical and noncritical parameters are provided in Tables 5 and 6,
respectively. TRLs were set based on the project requirements and the analytical laboratory's
experience in analyzing groundwater samples and effluents similar to those of the perox-pure"
system. Except for those cases noted below, TRL QA objectives for all parameters were met.
As expected, most influent samples required dilution to quantitate levels of critical VOCs
above the calibration range or due to matrix interference. In addition, some effluent samples
from Runs 9 through 14 required dilution because spiking compound levels were above the
calibration range. Any TRLs affected were adjusted to reflect these dilutions. TRLs for all
undiluted sample analyses met the QA objectives.
DEVIATIONS FROM THE DEMONSTRATION PLAN
Due to unforeseen site conditions or necessary procedural changes, the PRC SITE team
deviated from procedures described in the demonstration plan in a few cases. The PRC SITE
team discussed these deviations with the EPA project manager and implemented the resolutions
after the EPA project manager approved them. These deviations can be classified as follows:
system operation, sample collection, field measurement, and analytical procedures. This section
describes all deviations of each type that occurred during the technology demonstration, any
related effect, and corrective actions taken.
System Operation
The following system operation deviations occurred during the technology demonstration:
• Based on the 8-hour drawdown test performed in May 1992, LLNL
estimated that during the demonstration, contaminated groundwater could
53
-------
be extracted from Wells W-7-0 and W-875-08 at approximately 9 gpm and
3 gpm, respectively. The demonstration tests were designed assuming that
the combined stream would be the influent to the perox-pure"" system.
However, based on observations made in early September 1992, LLNL
informed the PRC SITE team that the wells might not provide the
estimated yield throughout the demonstration. The PRC SITE team
resolved this issue by reducing the extraction rates from both wells in the
same proportion, so that the influent characteristics would be
approximately the same as those estimated before the demonstration. The
SITE team extracted groundwater from Wells W-7-O and W-875-08 at 6
gpm and 2 gpm, respectively. This approach did not affect the
demonstration schedule or the technology evaluation.
• Flow rates through the perox-pure™ system for Runs 7 and 8 were planned
to be 50 gpm. Because PSl's acid feed pump could not transfer enough acid
to the process flow to maintain influent pH at approximately 5, the system
flow rate was reduced to 40 gpm. This deviation did not alter the selection
of preferred conditions from Phase 1 of the technology evaluation despite
the increased hydraulic retention time resulting from the change in flow
rate because only Runs 1 through 6 were evaluated to select the preferred
operating conditions, as stated in the demonstration plan.
• PSI requested that one of its operating facilities ship three scaled (coated)
and three clean (uncoated) quartz tubes to perform Phase 3 test runs.
However, of the six quartz tubes, one tube was broken in transit. PSI did
not have enough time to replace the broken tube. Therefore, Phase 3 tests
(Runs 13 and 14) were performed using only two instead of three UV
lamps. As a result, perox-pure™1 system's performance with coated tubes
and uncoated tubes was compared based on the removals achieved in two
reactors, instead of those achieved in three reactors.
• The approach for calibrating the meter measuring the system flow rate at
location SI was changed. Instead of calibrating the flow meter only at the
beginning and end of the demonstration at three flow rates covering the
expected flow rates, calibrations were performed before each run at the
specified flow rate for that run. This approach provided continuous check
on the flow rate measurement during the demonstration.
• The demonstration plan called for emptying all but 10 to 50 gallons of
contaminated water from the bladder tank between Phases 1 and 2. The
tank was emptied to the extent possible, but contained approximately 250
gallons after the completion of Phase 1. The PRC SITE team compensated
for this by allowing for this dilution in the spiking solution flow rate.
Based on the influent concentrations of the spiking compounds, this
deviation had no effect on the technology evaluation.
54
-------
Sample Collection
• Samples for TOX and AOX analyses were added to the analyte list as
requested by German Federal Ministry of Research and Technology, under
a U.S.-German bilateral technology transfer program.
Field Measurement
• In addition to the measurement parameters listed in the demonstration plan,
the PRC SITE Team also monitored the flow rates of the supply wells, W-
7-0 and W-875-0, to confirm that the proportional contribution of the
wells remained constant.
• Because the solubility of the spiking compounds in water was less than
anticipated, the spiking solution was prepared in two batches instead of one
batch as stated in the demonstration plan. This deviation resulted in a
slight dilution of the spiking solution and was compensated for by
increasing the spiking solution flow rate. This deviation had no effect on
the technology evaluation.
Analytical Procedures
Because of capacity limitations, GC/MS analyses of VOCs and SVOCs were
performed by Versar laboratory instead of ESBL. This change in analytical
laboratory had no effect on the technology evaluation.
• To avoid holding time violations, ESBL analyzed some influent samples by
GC/MS instead of GC as described in the demonstration plan. Accuracy
and precision data for samples analyzed by GC/MS were better than for
those analyzed by GC.
GC/MS analyses of VOCs and SVOCs was originally planned only for
reproducibility runs. Based on the request of the German Federal Ministry
of Research and Technology, one sample each from the influent and
effluent matrices was analyzed for VOCs and SVOCs by GC/MS in all runs.
TECHNICAL SYSTEMS REVIEW
During the demonstration, EPA directed that two technical systems reviews (TSR) be
conducted to audit the sampling and analytical procedures. One TSR focused on field sampling
and analytical activities, and the other focused on the off-site laboratory analyses.
55
-------
The TSR for field-related activities was conducted on September 17, 1992. The TSR
covered project organization and QA management, process measurements, sampling procedures,
and on-site laboratory measurements. Overall, all aspects of the technology evaluation were
considered well organized and competently implemented. EPA noted one minor issue regarding
the calibration data for the wattmeter used to measure power consumption of the perox-pure*"
system. While not considered a critical parameter, power consumption was considered important
since this measurement was required to address utility costs incurred during the treatment process.
The wattmeter was factory calibrated by General Electric Corporation before shipment to LLNL
site. However, because of the cost associated with receiving the data ($950), the EPA project
manager and PRC SITE team did not request the data. Based on the TSR recommendation, the
wattmeter was recalibrated after the demonstration and the data were sent to the EPA project
manager. The data showed that the QA objectives specified in the demonstration plan were met.
A TSR for VOC analysis by GC at ESBL was conducted on September 24, 1992. No
concerns were noted for any portion of the laboratory operation including QA management and
analytical methods. One suggestion given by the auditor was that ESBL establish retention time
windows as soon as possible, instead of after the completion of quick turnaround analyses. ESBL
immediately established the retention time windows as suggested by the auditor.
COMMUNITY RELATIONS AND TECHNOLOGY TRANSFER
The public had several opportunities to participate in the SITE demonstration activities.
The technology demonstration was first announced in a fact sheet distributed in July 1992 to
community members and government officials identified in the LLNL's Community Relations
Plan for Site 300. The fact sheet discussed the SITE program, the technology, the proposed
demonstration location, and the objectives of the demonstration. A 30-day comment period for
questions or concerns about the demonstration was offered to the public. The public comment
period was held from July 8 to August 7, 1992. EPA did not receive any responses during the
public comment period.
Invitations to a formal Visitors' Day were distributed to approximately 150 individuals,
including federal, state, and local officials and agencies; environmental and business professionals;
nearby universities with environmental engineering departments; media representatives; interested
community groups; and nearby residents. The Visitors' Day was conducted on September 23,
1992. All Visitors' Day participants received information about the SITE program, the
56
-------
perox-pure™ chemical oxidation technology, LLNL Site 300, and the criteria and approach used to
evaluate the technology.
A total of 17 people attended the Visitors' Day, The session included presentations by an
LLNL representative, the EPA SITE project manager, the technology developer, and the EPA
support contractor for the demonstration. Following the presentations, the group went to the
demonstration area to view the perox-pure™ system while it was in operation. Of the 17
attendees, seven were federal, state, or local officials; five were environmental professionals or
businessmen; four were media representatives; and one was a local resident.
The field demonstration and Visitors' Day program were videotaped to produce a
comprehensive videotape of all major field activities.
57
-------
SECTION 6
PERFORMANCE DATA AND EVALUATION
The perox-pure" chemical oxidation technology demonstration had the following
objectives: (1) assess the technology's abilities to destroy VOC in groundwater at the LLNL site
under different operating conditions; (2) determine whether the treated water met applicable
disposal requirements; and (3) obtain information required to estimate the operating costs for the
treatment system, such as electrical power consumption and chemical doses. A secondary
objective of the demonstration was to obtain preliminary information on the presence and types of
by-products formed during treatment.
The technology demonstration was conducted in three phases as described in detail in
Section 5. Phase 1 consisted of eight runs, Phase 2 consisted of four runs, and Phase 3 consisted
of two runs. Unaltered groundwater was used during Phase I, and spiked groundwater was used
during Phases 2 and 3. The principal operating parameters for the perox-pure*" system, hydrogen
peroxide dose, influent pH, and flow rate, were varied during Phase I test runs to observe the
system's performance under different operating conditions. Phase 2 consisted of reproducibility
test runs using groundwater spiked with known concentrations of contaminants. Phase 3 evaluated
the effectiveness of the quartz tube wipers by performing two runs using scaled and clean quartz
tubes.
• In each test run, various critical and noncritical parameters were measured at specific
sampling or measurement locations (as described in Section 5) to evaluate the system's
performance. This section presents and discusses the performance data collected during the
perox-pure" SITE demonstration. In addition, field operational problems encountered during the
demonstration are discussed.
CRITICAL PARAMETERS
The critical parameters for this technology demonstration include specific VOC
concentrations, acid, base, and hydrogen peroxide concentrations, pH, and flow rate. Table 5 in
Section 5 identifies the critical parameters and presents the QA objectives for each parameter.
VOCs were measured by both GC and GC/MS methods. GC measurement of VOCs was used to
determine the removal efficiencies of critical VOCs and to verify compliance with disposal
requirements. The hydrogen peroxide concentration and the pH and flow rate measurements were
58
-------
considered critical since they are principal parameters for the perox-purem technology and are
required to establish the operating conditions in each test run. Acid and base concentrations were
atso considered critical because the cost of these chemical additives will be included in the
treatment costs.
NONCRITICAL PARAMETERS
Table 6 in Section 5 lists the noncritical parameters for this technology demonstration and
presents the QA objectives for each parameter. Noncritical parameters include noncritical VOCs
and SVOCs, metals, TC, TOC, POC, bioassay, turbidity, alkalinity, hardness, temperature,
specific conductance, TOX, AOX, and electricity consumption.
SUMMARY OF RESULTS
This section summarizes the results of both critical and noncritical parameters for the
perox-pure* chemical oxidation system demonstration, as well as the technology's effectiveness in
treating groundwater contaminated with VOCs. Data are presented in graphic or tabular form.
For samples with analyte concentrations at nondetectable levels, one-half the detection limit was
used as the estimated concentration. However, if more than one replicable sample had
concentrations at nondetectable levels, using one-half the detection limit as the estimated
concentration for all replicable samples with nondetectable levels of contaminants will
significantly reduce the standard deviation of the mean and will affect the statistical inferences
made. For this reason, 0.5, 0.4, 0.6, and 0.4 times the detection limit were used as estimated
concentrations for the first, second, third, and fourth replicate samples, respectively. Throughout
this section, the terms "Reactor 6 effluent," "perox-pure™ system effluent," and "effluent" are used
synonymously.
Summary of the Results for Critical Parameters
Results for the critical parameters are presented below for each phase of the
demonstration.
59
-------
Phase 1 Results
In Phase 1 (Runs 1 through 8), only three VOCs were detected in the influent to and
effluent from the perox-pure™ system. In general, TCE and PCE were detected only in the
influent. TCA could not be measured in the influent because it was present at concentrations two
orders of magnitude lower than the average TCE concentration and was diluted out during the
analysis. However, TCA concentration could be measured in effluent samples because no dilution
was required. In general, TCA was detected in the effluent from the perox-pure™ system.
Figures 4 through 6 present Phase 1 VOC concentration data for TCE and PCE. TCA
concentrations are not shown in these figures because TCA concentrations in the influent could
not be measured.
Figure 4 presents TCE and PCE concentrations in the influent to the treatment system and
effluent from Reactors 1, 3, and 6 for Runs 1, 2, and 3. Concentrations are expressed as a
function of influent pH. In all three runs, the effluent TCE and PCE concentrations were well
below the target concentration of 5 /xg/L and below the detection limit of 1 ng/L. Figure 4 shows
that the perox-pure™ system performed best in Run 1, when the influent pH was 8 (the
unadjusted pH of the groundwater). In this run, the Reactor 1 effluent had lower concentrations
of TCE and PCE than in Runs 2 and 3, and it had the same concentrations of TCE and PCE as the
Reactor 6 effluent in Runs 2 and 3. However, Reactor 6 effluent TCA concentration was lowest
in Run 3 at 1.4 ixg/L (Reactor 6 effluent TCA concentrations in Runs 1 and 2 were 6.7 and 3.1
/tg/L, respectively). Because TCA is difficult to oxidize, PSI selected Run 3 as the preferred
operating condition, with an influent pH of 5.0.
Figure 5 presents a comparison of VOC concentrations in Runs 3, 4, and 5 as a function of
hydrogen peroxide levels. Although the effluent TCE and PCE concentrations were the same in
all runs, the data also show that Reactor 1 effluent TCE and PCE concentrations were the lowest
in Run 4 (the highest hydrogen peroxide level) and in Run 5 (the lowest hydrogen peroxide level).
Reasons for higher concentrations of TCE and PCE in the Reactor 1 effluent at intermediate
hydrogen peroxide levels cannot be determined from this data. The Reactor 6 effluent TCA
concentrations in Runs 3, 4, and 5 were 1.4, 1.8, and 2.1 ng/L, respectively. No definite trend
can be identified based on TCE, PCE, and TCA data in Runs 3, 4, and 5.
60
-------
0.!
TCE
PCE
VOC Concentration, |ig/L
10 100 1,000
10,000
i ! ( ! in1 i i i i i m i i r r 11: ' • ' nnr
I l iiiiii
1,300
iwiio.5
SB**;
OS 1 ;
i
i so
111:11 IlilillllljO.S j
:0.5 Run 1
mmmmm
g||gg||o.5 | Influent pH ~ 8.0
Cm
Influent
Reactor I
Reactor 3
Reactor 6
s
TCE
PCE
0,000
Run 2
Influent pH
0.1
10
TCE
PCE
11*1111
1I1S8
'
100 1,000 10,000
1——i—i—n—r-
uoo
Run 3
Influent
5.0
Figure 4. Comparison of VOC Concentrations at Different Influent pH Levels
(Hydrogen Peroxide Level at Reactor I = 40 mg/L; Hydrogen Peroxide Level at Reactors
2 through 6 = 25 mg/L; Flow Rate = 10 gpm)
61
-------
VOC Concentration, jig/L
1,000 10,000
TCE
PCE
? T Till!
flTTi
Run 3
(Hydrogen Peroxide Level
at Reactor I = 40 mgIL;
at Reactors 2 through 6 = 25 mgIL)
Influent
Reactor I
Reactor 3
Reactor 6
0.1
10
100
10,000
980
o.s,
p.s
10.5
tce
o.s
Run 4
I (Hydrogen Peroxide Level
at Reactor I = 70 mgIL; \
at Reactors 2 through 6 = 50 mgIL)
PCE
'0.5
0.5
Hill
o.i
TCE
PCE
10
100
,000 10,000
I—I VI
RunS
(Hydrogen Peroxide Level
at Reactor I - 30 mg/L;
at Reactors 2 through 6=15 mg/L)
Figure 5. Comparison of VOC Concentrations at Different Hydrogen Peroxide
Levels (Influent pH = 5.0; Flow Rate = 10 gpm)
62
-------
0.1
VOC Concentration, \iglL
1 10 100 1,000 10,000
TCE
/¦
Run 4
PCE
0.5
(Hydrogen Peroxide Level
0.5'
at Reactor 1 = 70 mg/L;
0.5
at Reactors 2 through 6 = 50 mg/L;
Flow Rote = 10 gpm)
Influent
Reactor 1
Reactor 3
Reactor 6
1,000 10,000
TCE
PCE
rm
^i=0.5
*0.5
= 0.5
120
Run 6
(Hydrogen Peroxide Level
at Reactor I = 240 mg/L,
Flow Rate = IQgpm)
0.1
10
100
1,000 10,000
1,100
TCE
—
[¦miio.5
'-tvs
PCE
1,000 10,000
TCE
Run 7
(Hydrogen Peroxide Level
at Reactor I = 240 mg/L,
Flow Rate = 40 gpm)
3§0.5
Run 8
(Hydrogen Peroxide Level
at Reactor I = 60 mg/L;
Flow Rate = 40 gpm)
PCE
Figure 6. Comparison of VOC Concentrations at Different Flow Rates and
Hydrogen Peroxide Levels (Influent pH = 5.0)
63
-------
Figure 6 presents TCE and PCE concentrations at different flow rates and hydrogen
peroxide levels. Runs 4 and 6 were performed at a flow rate of 10 gpm. Runs 7 and 8 were
performed at a flow rate of 40 gpm. In Runs 4 and 6, identical total amounts of hydrogen
peroxide were added to the contaminated groundwater. However, in Run 4, hydrogen peroxide
was added at multiple points in the system using the splitter, while in Run 6, all hydrogen
peroxide was added at the influent to the system. Based on a comparison of TCE and PCE
concentrations in Runs 4 and 6, the effect of adding hydrogen peroxide at multiple points in the
perox-pure™ system cannot be evaluated, because in both runs, TCE and PCE concentrations in
the effluent were below the detection limit of 1.0 However, effluent TCA concentrations in
Runs 4 and 6 were 1.8 and 3.0 ng/L, respectively. Based on the decreased concentrations of the
less easily oxidized TCA with splitter use, adding hydrogen peroxide at multiple points in the
perox-pure™1 system appears to enhance the system's performance.
A comparison of Runs 6 and 7 shows that both TCE and PCE concentrations in Reactor 1
effluent were higher in Run 7 than in Run 6. Similarly, the effluent TCA concentration in Run 7
(3.9 Mg/L) was higher than in Run 6 (3.0 Mg/L). These observations are consistent with the
operating conditions, because contaminated groundwater had a much longer UV exposure time in
Run 6 than in Run 7. UV exposure times were 1.5 and 0.4 minutes in Runs 6 and 7, respectively.
A comparison of TCE and PCE concentrations in Runs 7 and 8 shows that both TCE and
PCE concentrations in Reactor 1 effluent were higher in Run 7 than in Run 8. Effluent TCA
concentrations were about the same in both runs (3.9 and 4.0 ng/L in Runs 7 and 8, respectively).
The higher Reactor 1 effluent TCE concentration in Run 7 may be attributed to higher influent
TCE concentrations in that run. Reactor 1 effluent TCE concentrations correspond to 99.5 and
greater than 99.9 percent TCE removal in Runs 7 and 8, respectively. Similarly, the Reactor 1
effluent PCE concentrations correspond to 92.9 and greater than 99.2 percent PCE removal in
Runs 7 and 8, respectively. These data indicate that higher doses of hydrogen peroxide may have
scavenged hydroxy! radicals or excess hydrogen peroxide reduced UV transmittance through
water, resulting in lower removal efficiencies for Run 7 than those for Run 8.
Based on quick turnaround analyses performed during Runs 1 through 6, PSI selected
Run 3 operating conditions as preferred for spiked groundwater. As a result. Runs 10 through 14
were performed using Run 3 operating conditions.
64
-------
Phase 2 Results
Phase 2 (Runs 9 through 12) results for VOC removal in the perox-pure"* system are
presented in Figures 7 through 9. Figure 7 presents a comparison of the system's performance in
treating spiked groundwater (Run 9) and unspiked groundwater (Run 4). Figure 7 shows that
TCE and PCE concentrations in treated groundwater were higher in Run 9 (spiked groundwater)
than in Run 4 (unspiked groundwater). These data suggest that spiking compounds (chloroform,
DCA, and TCA) affected the perox-pure'" system's performance in removing TCE and PCE,
perhaps because of the additional oxidant demand. However, treated groundwater TCE and PCE
concentrations plotted in Figure 7 are estimated concentrations. Because the detection limit for
TCE and PCE in Run 9 was 5 ^g/L and in Run 4 was 1 jug/L, and because TCE and PCE were
present at nondetectabie levels in treated groundwater in both runs, the estimated concentrations
in Run 9 are higher than in Run 4. Therefore, the data are inconclusive with regard to the effect
of spiking compounds on the removal of TCE and PCE.
During the reproducibility runs (Runs 10, 11, and 12), the effluent TCE, PCE, and DCA
levels were generally below detection limit (5 ^g/L) and effluent chloroform and TCA levels
ranged from 15 to 30 ng/L. VOC removal efficiencies in reproducibility runs are plotted in
Figure 8. Figure 8 shows that for TCE and PCE, which are relatively easily oxidized, most of the
removal occurred in Reactor 1, leaving only trace quantities of TCE and PCE to be removed in
the rest of the perox-purem system. However, for chloroform, DCA, and TCA, which are more
difficult to oxidize, considerable removal occurred beyond Reactor I. During the three
reproducibility runs, average removal efficiencies for TCE, PCE, chloroform, DCA, and TCA
after Reactor 1 were 99.5, 95.9, 41.3, 67.0, and 17.4 percent, respectively. Effluent samples
showed overall removal efficiencies for TCE, PCE, chloroform, DCA, and TCA were 99.7, 97.1,
93.1, 98.3, and 81.8 percent, respectively. The overall removal efficiencies of the perox-pure"
system were reproducible for all VOCs. However, for certain compounds, the removal
efficiencies after Reactor i were quite variable (for example, chloroform removal efficiencies
ranged from 27.4 to 56.3 percent). This variability may be associated with sampling and analytical
precision.
Figure 9 compares the 95 percent UCL of effluent VOC concentrations with target levels
in reproducibility runs. For this project, the target level for a given VOC was set at the most
stringent limit in cases where the VOC has multiple regulatory limits. For all VOCs but
65
-------
VOC Concentration, jig/L
1 10
1,000
Chloroform
150
DCA
Phase 2 — Run 9
Spiked
Influent
Reactor 1
iJf Reactor 3
Reactor 6
0.1 1 10 100 1,000
Phase I — Run 4
Unspiked
Figure 7. Comparison of VOC Concentrations in Spiked and Unspiked Groundwater
(Influent pH = 5.0; Hydrogen Peroxide Level at Reactor 1 = 70 mg/L; Hydrogen Peroxide Level at
Reactors 2 through 6 = 50 mg/L; Flow Rate =10 gpm)
66
-------
Reactor I
Reactor 3
Reactor 6
v_
TCE
PCE
Chloroform
Run 10
DCA
TCA
TCE
PCE Chloroform DCA
Run II
TCA
TCE
PCE Chloroform
Run 12
DCA
TCA
Figure 8. VOC Removal Efficiencies in Reproducibility Runs
(Influent pH = 5.0; Hydrogen Peroxide Level at Reactor I = 40 mg/L; Hydrogen
Peroxide Level at Reactors 2 through 6 = 25 mg/L; Flow Rate = 10 gpm)
67
-------
1,000 r
o
do
SO
a.
_r
u
3
S?
m
o»
100
10
Target Level
TL = 5
3.2
3.1-
TL = 200
TL = 100
15
13
33.
TL = 5
4.9
3-2 '3.1
TCE
PCE
Chloroform
DCA
32
18
34
TCA
Run
10
Run
11
Run
12
Figure 9. Comparison of 95 Percent UCLs for Effluent VOC Concentrations with Target Levels in
Reproducibility Runs (Influent pH = 5.0; Hydrogen Peroxide Level at Reactor 1 = 40 mg/L; Hydrogen Peroxide Level at
Reactors 2 through 6 = 25 mg/L; Flow Rate = 10 gpm)
-------
chloroform, the most stringent limit is the California drinking water action level. For chloroform,
the most stringent limit is the MCL specified in the Safe Drinking Water Act (SDWA). Figure 9
shows that the perox-pure™ system effluent met the target levels at the 95 percent confidence
level in all three reproducibility runs, indicating that the system performance was reproducible.
Phase 3 Results
Figure 10 presents VOC concentrations in Runs 12, 13, and 14, conducted to evaluate
quartz tube cleaning. In Run 12, quartz tubes from the previous demonstration runs were used.
In Run 13, scaled quartz tubes were used. These tubes had been exposed to an environment that
encouraged scaling and had not been maintained with cleaners or wipers. In Run 14, quartz tubes
that had been maintained by cleaners or wipers were used.
A comparison of removal efficiencies for TCE in Reactors 1 and 2 shows that TCE
removal efficiencies were about the same in all runs. PCE removal efficiencies were about 3
percent less in Run 13 than that in Runs 12 or 14. Removal efficiencies for chloroform, DCA,
and TCA were uniformly lower in Run 13 than in Run 14, indicating that periodic cleaning of
quartz tubes by wipers is required to maintain the perox-pure'" system's performance. Without
such cleaning, removal efficiencies in the system will likely decrease in an aqueous environment
that would cause scaling of quartz tubes. For example, after Reactor 2, chloroform removal
efficiency in Run 13 was 53.4 percent, compared to 61.3 percent in Run 14. Because the quartz
tubes used in Run 12 had little coating, removal efficiencies in Run 12 were expected to be higher
than those in Run 13. However, the demonstration did not confirm this for all VOCs. For
example, Run 12 TCA removal efficiencies were less than Run 13 TCA removal efficiencies;
reasons for this inconsistency cannot be identified from the data.
Summary of Results for Noncritical Parameters
The technology demonstration also evaluated analytical results of several noncritical
parameters. These results are summarized below.
GC/MS analysis of influent and effluent samples for VOCs indicated that new target
compounds or tentatively identified compounds (TIC) were not formed during the treatment.
69
-------
iM
TCE
PCE
Reactor I
Reactor 2
_/
Chloroform
Run 12
DCA
TCA
TCE
PCE
Chloroform
Run 13
DCA
TCA
TCE
PCE
Chloroform
Run 14
DCA
TCA
Figure 10. VOC Removal Efficiencies in Quartz Tube Cleaner Runs
(Influent pH = 5.0; Hydrogen Peroxide Level at Reactor I = 40 mg/L; Hydrogen Peroxide
Level at Reactors 2 through 6 = 25 mg/L; Flow Rate = 10 gpm)
70
-------
GC/MS analysis of influent and effluent samples for SVOCs showed that target SVOCs
were not present at detectable levels. However, several unknwon TICs were present in both the
influent and effluent samples.
Average influent TOX and AOX concentrations were 800 ng/L and 730 ^g/L,
respectively. The perox-pure™ system achieved TOX removal efficiencies that ranged from 93 to
99 percent and AOX removal efficiencies that ranged from 95 to 99 percent.
The TC, TOC, and POC concentrations in influent and effluent samples in Runs 10, 11,
and 12 are presented in Figure 11. Average TC concentrations in the influent and effluent were
75 mg/L and 55 mg/L, respectively. The decrease in TC concentration in the perox-purem system
may be attributable to the loss of dissolved carbon dioxide as a result of the turbulent movement
of contaminated groundwater in the perox-pure™ system.
Figure 11 shows an average decrease in TOC concentrations of about 40 percent during
treatment. The decrease corresponds to the amount of organic carbon that was converted to
inorganic carbon during treatment, suggesting that about 40 percent of the organic carbon was
completely oxidized to carbon dioxide. However, the TOC data does not indicate whether the
organic carbon that was completely oxidized originated from the VOCs or from some other
compounds present in groundwater.
Effluent POC concentration was about 0.02 mg/L which is below the reporting limit of
0.035 mg/L. POC concentration data show that the average POC removal efficiency was about
93 percent. Assuming that the majority of organic carbon associated with VOCs could be
measured as POC, this indicates that about 93 percent of volatile organic carbon was converted to
either carbon dioxide or nonpurgeable organic carbon.
During Runs 10, 11, and 12, bioassay tests were performed to evaluate the acute toxicity
of influent to and effluent from the perox-pure" systems. Two freshwater test organisms, a water
flea (ceriodaphnia dubia) and a fathead minnow (pimcphalcs promelas), were used in the bioassay
tests. Toxicity was measured as the lethal concentration at which 50 percent of the organisms died
(LC50), and expressed as the percent of effluent (or influent) in the test water. One influent and
one effluent sample were tested in each run. One control sample was also tested to evaluate the
toxicity associated with hydrogen peroxide residual present in the effluent. The control sample
71
-------
Carbon Concentration, mg/L
0.01 0.1 I 10 100
Influent
Reactor 6
Run 10
0.01 0.1 I 10 100
Run II
0.01 0.1 1 10 100
\ " \
•.
-------
had about 10.5 mg/L of hydrogen peroxide (average effluent residual in Runs 10, II, and 12), and
had characteristics (alkalinity, hardness, and pH) similar to that of effluent in Runs 10, 11, and
12.
In general, the influent was not found to be acutely toxic to either test organism. The
effluent was found to be acutely toxic to both test organisms. The influent LC50 values for both
organisms indicated that in the undiluted influent sample more than 50 percent of the organisms
survived. However, LC50 values for the water flea were estimated to be 35, 13, and 26 percent
effluent in Runs 10, 11, and 12, respectively; and LCS0 values for the fathead minnow were
estimated to be 65 and 71 percent effluent in Runs 10 and 11, respectively. In Run 12, more than
50 percent of the fathead minnows survived in the undiluted effluent. The LC50 value for the
water flea was estimated to be 17.7 percent in the control sample, indicating that the sample
contained hydrogen peroxide at a concentration that was acutely toxic to water fleas. However,
more than 50 percent of the fathead minnows survived in the undiluted control sample indicating
hydrogen peroxide was not acutely toxic to fathead minnows at a concentration of 10.5 mg/L.
This observation, however, is not entirely consistent with observations made by the Connecticut
Department of Environmental Protection (CDEP). The CDEP Water Toxics Section of Water
Management Division reports LCS0 value of 18.2 mg/L of hydrogen peroxide with 95 percent
confidence limits of 10 mg/L and 25 mg/L (CDEP, 1993).
Comparison of the LC50 value of the control sample with LC50 values of effluent samples
for water fleas indicates the toxicity associated with the effluent samples is probably due to
hydrogen peroxide residual in the effluent. However, no conclusion can be drawn on the effluent
toxicity to fathead minnows because the control sample toxicity results from the SITE
demonstration data are not entirely consistent with the data collected by CDEP.
Iron and manganese were present at trace levels in the influent. In general, iron was
present at levels less than 45 ng/L, and manganese was present at an average level of 15 ng/L.
Significant removal of iron or manganese did not occur in the perox-pure™ system, because these
metals were present only at trace levels in the influent.
No changes in pH, alkalinity, hardness, or specific conductance were observed during
treatment.
73
-------
Average influent temperature was about 72 °F. Average effluent temperatures were about
90 °F and 76 °F, at influent flow rates of 10 gpm and 40 gpm, respectively. Because 10 gpm
corresponds to a hydraulic retention time of 1.5 minutes and 40 gpm corresponds to a retention
time of 0.4 minutes for the perox-pure~ system evaluated, the average temperature increase due
to 1 minute of UV radiation exposure in the perox-pure"" system is about 12 °F.
CONCLUSIONS
For the spiked groundwater, PSI determined the following preferred operating conditions:
(1) influent hydrogen peroxide concentration of 40 nig/L, (2) hydrogen peroxide concentration of
25 mg/L at the influent to Reactors 2 through 6, (3) influent pH of 5.0, and (4) flow rate of
10 gpm. At these conditions, the effluent TCE, PCE, and DCA levels were generally below
detection limit (5 ng/L) and effluent chloroform and TCA levels ranged from 15 to 30 /ig/L. The
average removal efficiencies for TCE, PCE, chloroform, DCA, and TCA were about 99.7, 97.1,
93.1, 98.3, and 81.8 percent, respectively.
For the unspiked groundwater, the effluent TCE and PCE levels were generally below
detection limit (1 pg/L) with corresponding removal efficiencies of about 99.9 and 99.7 percent.
The effluent TCA levels ranged from 1.4 to 6.7 ^g/L with corresponding removal efficiencies
ranging from 35 to 84 percent.
The perox-pure"* system effluent met California drinking water action levels and federal
drinking water MCLs for TCE, PCE, chloroform, DCA, and TCA at the 95 percent confidence
level.
The quartz tube wipers were effective in keeping the tubes clean, and they appear to
reduce the adverse effect scaling has on contaminant removal efficiencies.
TOX removal efficiencies ranged from 93 to 99 percent, AOX removal efficiencies
ranged from 95 to 99 percent.
For spiked groundwater, during reproducibility runs, the perox-purem system achieved
average removal efficiencies of 38 percent and about 93 percent for TOC and POC, respectively.
74
-------
The temperature of groundwater increased at a rate of 12 °F per minute of UV exposure
in the perox-purem system. Since the oxidation unit is exposed to the surrounding environment,
the temperature increase may vary depending upon the ambient temperature or other atmospheric
conditions.
FIELD OPERATIONAL AND EQUIPMENT PROBLEMS
The PRC SITE team experienced a few operational and equipment problems during the
demonstration. Some of these problems resulted in changes in the demonstration schedule, while
the others required making decisions in the field to solve the problems. These problems and
solutions include the following:
• Based on the 8-hour drawdown test performed in May 1992, LLNL
estimated that during the demonstration, contaminated groundwater could
be extracted from Wells W-7-0 and W-875-08 at approximately 9 gpm and
3 gpm, respectively. The demonstration tests were designed assuming that
the combined stream would be the influent to the perox-purem system.
However, based on the observations made in early September 1992, LLNL
informed the SITE team that the wells may not provide the estimated yield
throughout the demonstration. The SITE team resolved this issue by
reducing the extraction rates from both wells in the same proportion, so
that the influent characteristics would be approximately the same as those
estimated before the demonstration. The SITE team extracted groundwater
from Wells W-7-0 and W-875-08 at 6 gpm and 2 gpm, respectively. This
approach did not affect the demonstration schedule or the technology
evaluation.
• Flow rates through the perox-pure*" system for Runs 7 and 8 were planned
to be 50 gpm. In order to maintain the preferred influent pH conditions of
approximately five, the system flow rate was reduced to 40 gpm. PSI's acid
feed pumps were not capable of providing enough acid to the process flow
to increase the system flow rate. This deviation did not alter the selection
of preferred conditions from Phase 1 of the technology evaluation despite
the increased hydraulic retention time (inversely proportional to flow rate)
resulting from the change in flow rate.
• PSI requested that one of its operating facilities ship three scaled (coated)
and three clean (uncoated) quartz tubes to perform Phase 3 test runs.
However, of the six quartz tubes, one tube was broken in transit. PSI did
not have enough time to replace the broken tube. Therefore, Phase 3 tests
(Runs 13 and 14) were performed with only two UV lamps on, instead of
three. As a result, perox-pure" system performance with coated tubes and
uncoated tubes was compared based on the removals achieved in two
reactors, instead of those achieved in three reactors.
75
-------
• Late arrival of the perox-pure™ system (particularly the hydrogen peroxide
feed tank) and other auxiliary equipment (such as the bladder tank, pumps,
and other miscellaneous items) delayed the technology demonstration by 3
days. However, the PRC SITE team completed the demonstration on
schedule by working late evenings and weekends.
• At the beginning of the demonstration, while setting the operating
parameters, water inside the oxidation unit overheated and burned the
gaskets that maintain a water-tight seal in two of the reactors. As a result,
water leaked out of the treatment unit. PS1 collected this water in a 55-
gallon drum. PSI explained that because of its oversight, a few
pneumatically operated valves did not have an air supply, resulting in a
stagnant volume of water that overheated. PSI also stated that the
temperature sensor inside the unit, which is located in the top reactor, did
not detect the high water temperature because the unit was only partially
filled. Later, PSI connected an air compressor to the unit to avoid
reoccurrence of this situation. Replacement gaskets arrived the following
day, causing the demonstration to be postponed 1 day.
• During the initial stage of the demonstration due to improper operation of
valves downstream of the perox-pure'" system, the pressure inside the
perox-pure™ unit exceeded the design limit and the pressure relief gasket
gave way. PSI immediately collected the leaking water in a drum and shut
off the influent. Because PSI had a replacement gasket on site, this
operational problem did not cause a significant delay.
• Halfway through the demonstration, while one test run was in progress, the
sulfuric acid level in the acid feed tank decreased significantly. As a
result, the influent pH could not be lowered to the desired level, and the
PRC SITE team discontinued the run. The run was repeated after PSI
filled the acid feed tank with sulfuric acid.
• The PRC SITE team initially encountered problems measuring the effluent
pH at the sampling location downstream of sodium hydroxide addition
point. Because no static mixer was used, the sodium hydroxide added to
raise the effluent pH did not adequately mix with the effluent. Lack of
proper mixing caused problems in measuring the true effluent pH after
sodium hydroxide addition. The PRC SITE team resolved this issue by
installing another sampling port about 100 feet downstream, just before the
treated water entered the storage tanks. This modification significantly
reduced fluctuations in pH and provided a good measure of effluent pH.
76
-------
SECTION 7
COST OF DEMONSTRATION
The cost (rounded to the nearest $1,000) of conducting the EPA SITE demonstration of the
perox-pure*" chemical oxidation technology on the contaminated ground water at the LLNL site
was approximately $760,000. This cost includes site characterization and preparation,
demonstration planning and field work, chemical analyses, and report preparation. The PSI
portion of this cost was $11,000 and the balance of $749,000 was allocated to the SITE program.
EPA SITE CONTRACTOR COSTS
Each SITE project is divided into two phases: planning (Phase I) and demonstration (Phase
II). Costs (rounded to the nearest $1,000) for each phase are presented below along with a list of
the activities performed during each phase. Phase I costs are actual costs previously incurred;
Phase II costs include actual costs plus estimates for labor to complete the Technology Evaluation
Report (TER), Applications Analysis Report (AAR), and technology demonstration videotape.
Phase I: Planning
Phase I activities included the following:
• Chemical oxidation technology literature review
• Ground water sampling and testing
• Sampling and analysis plan development
• Demonstration plan development
Costs for Phase I are summarized below by cost category:
Labor
Equipment and supplies
Travel
Chemical analyses
TOTAL
$80,000
5,000
4,000
5,000
$94,000
77
-------
Phase IT: Demonstration
Phase II activities included the following:
• Site preparation, mobilization, and demobilization
• Sample collection and field oversight
• Chemical analyses (field and off-site)
• Support for the U.S.-German bilateral program
• TER, AAR, and videotape preparation
Costs for Phase II are summarized below by cost category:
Labor
Sampling equipment and supplies
Travel/transportation
Chemical analyses
Subcontractors (including rental of tanks,
pumps, trailer, and enclosure and
waste disposal)
TOTAL
DEVELOPER COSTS
Developer costs are the actual costs incurred by PS1 in preparing for and conducting the
SITE demonstration.
PSI's costs (rounded to the nearest $1,000) are presented below:
Labor S 3,000
Laboratory 1,000
Travel 2,000
Equipment (using retail rate) 5.000
TOTAL $ 11,000
$300,000
30,000
25,000
200,000
100.000
$655,000
78
-------
SECTION 8
CONCLUSIONS AND RECOMMENDATIONS
CONCLUSIONS
For the spiked groundwater, PSI determined the following preferred operating conditions:
(1) influent hydrogen peroxide concentration of 40 mg/L, (2) hydrogen peroxide concentration of
25 mg/L at the influent to Reactors 2 through 6, (3) influent pH of 5.0, and (4) flow rate of
10 gpm. At these conditions, the effluent TCE, PCE, and DCA levels were generally below
detection limit (5 ng/L) and effluent chloroform and TCA levels ranged from 15 to 30 ng/L. The
average removal efficiencies for TCE, PCE, chloroform, DCA, and TCA were about 99.7, 97.1,
93.1, 98.3, and 81.8 percent, respectively.
For the unspiked groundwater, the effluent TCE and PCE levels were generally below
detection limit (1 jtg/L) with corresponding removal efficiencies of about 99.9 and 99.7 percent.
The effluent TCA levels ranged from 1.4 to 6.7 ^g/L with corresponding removal efficiencies
ranging from 35 to 84 percent.
The perox-pure1" system effluent met California drinking water action levels and federal
drinking water MCLs for TCE, PCE, chloroform, DCA, and TCA at the 95 percent confidence
level.
The quartz tube wipers were effective in keeping the tubes clean, and they appear to
reduce the adverse effect scaling has on contaminant removal efficiencies.
TOX removal efficiencies ranged from 93 to 99 percent. AOX removal efficiencies
ranged from 95 to 99 percent.
For spiked groundwater, during reproducibility runs, the perox-pure"" system achieved
average removal efficiencies of 38 percent and about 93 percent for TOC and POC, respectively.
The temperature of groundwater increased at a rate of 12 °F per minute of UV exposure
in the perox-purem system. Since the oxidation unit is exposed to the surrounding environment,
the temperature increase may vary depending upon the ambient temperature or other atmospheric
conditions.
79
-------
RECOMMENDATIONS
The following recommendations are made based on the SITE demonstration results. These
recommendations should be taken into account when the perox-purem chemical oxidation system
is considered for treating contaminated liquid wastes.
During the SITE demonstration, although the effluent VOC levels were well below the
target levels (federal drinking water MCLs and California drinking water action levels), bioassay
test indicated that the effluent was toxic while the influent was not toxic to freshwater test
organisms (Ceriodaphnia duhia and Pimcphales promclas). However, these bioassay tests were
inconclusive regarding whether the toxicity was because of hydrogen peroxide residual or the
perox-pure"" treatment. Because hydrogen peroxide appears to be toxic to certain aquatic
organisms at levels greater than 10 mg/L, it is recommended that the effluent hydrogen peroxide
residual be kept well below 10 mg/L. After this, in addition to performing physicochemical
analyses, the bioassay tests should be performed on the effluent to determine if the effluent can
be discharged to aquatic bodies.
80
-------
REFERENCES
APHA, AWWA, and WPCF, 1989, Standard Methods for the Examination of Water and
Wastewater, 17th Edition
Boltz, D.F., and J.A. Howell, 1979, Colorimetric Determination of Non-Metals. John Wiley &
Sons, New York, New York
Connecticut Department of Environmental Protection (CDEP), 1993, Personnel communication
from A. Iqcobucci to the U.S. Environmental Protection Agency (EPA) on the acute
toxicity of hydrogen peroxide to freshwater organisms.
Glaze, W., and others, 1987, The Chemistry of Water Treatment Processes Involving Ozone,
Hydrogen Peroxide, and Ultraviolet Radiation. Ozone Science and Engineering.
LLNL, 1990, Remedial Investigation of the General Services Area, Lawrence Livermore National
Laboratory, Site 300 (May)
PRC Environmental Management, Inc. (PRC), 1992, Demonstration Plan for the PSI perox-pure™
Ultraviolet/Oxidation System. Final Report, submitted to EPA ORD, Cincinnati, Ohio
Steffans, K., 1992, Personal communication with EPA on the analytical procedure for AOX
measurement
EPA, 1983, Methods for Chemical Analysis of Water and Wastes. EPA-600/4-79-020,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio, and subsequent
EPA-600/4 Technical Additions
EPA, 1985, Methods for Measuring Acute Toxicity of Effluent to Fresh Water and Marine
Organisms. EPA/600/4-85/013, Third Edition
EPA, 1986, Test Methods for Evaluating Solid Waste. Volumes IA-IC: Laboratory Manual,
Physical/Chemical Methods, and Volume II: Field Manual, Physical/Chemical Methods,
SW-846, Third Edition, Office of Solid Waste and Emergency Response, Washington, D.C.
EPA, 1993, Applications Analysis Report for the perox-pure™ Treatment Technology [prepared
for EPA Risk Reduction Engineering Laboratory, Cincinnati, Ohio]
81
-------
APPENDIX A
ANALYTICAL DATA FOR REPRODUCIBILITY RUNS
82
-------
TABLE A-1
ANALYTICAL DATA FOR VOCs BY GC ANALYSIS IN RUN 10
VOC**
Unit
Influent
Reactor 1 - Effluent
Reactor 2 - Effluent
Reactor 3 - Effluent
Reactor 6 - Effluent
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Chloroform
m/L
140
8.16
84.0*
9.5*
NA
NA
43.0
7.07
10.4
3.7
1,1-DichIoroethane
mn-
163
20.6
26.3*
5.5*
NA
NA
2.9
0.85
2.9
0.85
Tetrachloroethene
m/l
92
7.93
3.0
1.41
NA
NA
2.4
0.48
2.4
0.48
1,1,1 -T richloroethane
miL
114
21.4
90.7*
4.9*
NA
NA
59.5
10.2
25.8
4,7
Trichloroethene
m/l
1020*
76.4*
6.1
7.26
NA
NA
2.4
0.48
2.4
0.48
Notes: * Mean and standard deviation were calculated using data for three of four replicates.
** VOCs present above detection limit.
TABLE A-2
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 10
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before HjS04
Influent - After
h2scs4
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Alkalinity
mg/L as CaC03
NA
280
88
NA
112
NA
Bioassay, IX50
NA
NA
NA
NA
NA
NA
NA
Ceriodaphnia dubia
% Sample
NA
NA
>100
NA
17
NA
Pimephales promelas
% Sample
NA
NA
>100
NA
65
NA
Electricity Consumption*
kW
NA
NA
NA
NA
NA
NA
-------
TABLE A-2
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 10 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
h2so4
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Flow Rate
NA
NA
NA
NA
NA
NA
NA
Ground Water Flow Rate
gpm
NA
NA
10
NA
NA
NA
H202 Flow Rate
ml/min
9.1
NA
NA
NA
NA
NA
Acid Flow Rate
mL/min
3.2
NA
NA
NA
NA
NA
Base Flow Rate
mt/min
10.3
NA
NA
NA
NA
NA
Hardness
mg/L as CaC03
NA
310
315
NA
310
NA
Hydrogen Peroxide
mg/L
598,000
NA
NA
NA
13.1
NA
Iron
/>g/L
NA
<46.0
NA
NA
<46.0
NA
Manganese
m n.
NA
15.7
NA
NA
16.5
NA
pHb, Mean
pH Units
NA
7.47
5.58
NA
5.76
7.65
pH*, Range
pH Units
NA
7.47-7.47
5.39-5.76
NA
5.62-5,90
6.37-8.93
Purgeable Organic Carbon
mg/L
NA
0.34
NA
NA
0.04
NA
Semivolatile Organic Compounds'1
NA
NA
NA
NA
NA
NA
NA
Hexathiepane (14.80-14.82)
//g/L
NA
8.8
NA
NA
ND
NA
Pentanoic acid (4.73)
m/L
NA
ND
NA
NA
ND
NA
Unknown (3.64-7.68)
Mfl/L
NA
18
NA
NA
ND
NA
Unknown (5.01)
ml l
NA
NO
NA
NA
ND
NA
Unknown (16.90-16.91)
m n-
NA
66
NA
NA
ND
NA
Unknown (17.59-17.62)
Jffl/L
NA
ND
NA
NA
ND
NA
-------
TABLE A-2
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 10 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
H2S04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Unknown (19.98-19.99)
^g/L
NA
66
NA
NA
ND
NA
Unknown (21.00-21.04)
^g/L
NA
ND
NA
NA
ND
NA
Unknown (21.93-21.94)
^9/L
NA
ND
NA
NA
ND
NA
Sodium Hydroxide Concentration
N
18.4
NA
NA
NA
NA
NA
Specific Conductance
//m ho/cm
NA
NA
1740
NA
1770
NA
Sulfuric Acid Concentration
N
33.4
NA
NA
NA
NA
NA
Total Carbon
mg/L
NA
74
NA
NA
51
NA
Total Organic Carbon
mg/L
NA
1.7
NA
NA
1.0
NA
Temperature
°C
NA
21.8
NA
NA
31.5
NA
Total Organic Halides
#/g/L
NA
1200
NA
NA
8.9
NA
Turbidity
NTU
NA
NA
0,35
NA
.20
NA
Volatile Organic Compounds (GC/MS)
NA
NA
NA
NA
NA
NA
NA
Target Analytes
NA
NA
NA
NA
NA
NA
NA
Acetone
//g/L
NA
3
NA
NA
9
NA
2-Butanone
miL
NA
ND
NA
NA
ND
NA
Chloroform
A»9/L
NA
180
NA
NA
10
NA
1,1 -Dichloroethane
//g/L
NA
190
NA
NA
ND
NA
1,1-Dichloroethene
mfi-
NA
15
NA
NA
ND
NA
1,2-Dichloroethene (total)
//g/t
NA
13
NA
NA
ND
NA
-------
TABLE A-2
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 10 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2SO,
Influent - After
H2S04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
T etrachloroethene
M9/L
NA
120
NA
NA
ND
NA
Toluene
Afg/L
NA
6
NA
NA
ND
NA
1,1,1 -T richloroethane
/ug/L
NA
170
NA
NA
21
NA
T richloroethene
pg/L
NA
810
NA
NA
ND
NA
Tentatively Identified Compound
(retention time, minutes)
NA
NA
NA
NA
NA
NA
NA
Tetrahydrofuran (14.36-14.46)
liglL
NA
7
NA
NA
ND
NA
Notes:
" The mean electricity consumption was 32.19 kW.
b Readings were taken 2 or 3 times for pH measurement. Range of readings is also listed.
c None of the semivolatile organic target analytes were detected. Only tentatively identified compounds (TIC) are given in this table. Retention time in minutes
for each TIC is given in parentheses.
d The flow rate was monitored throughout the run, and the volume remained constant.
NA Not applicable
ND Not detected
°C Degree Celsius
gpm Gallons per minute
GC/MS Gas chromatography and mass spectrometry
kW Kilowatts
^g/L Micrograms per liter
^/mho/cm Micromhos per centimeter
mg/L Milligrams per liter
ml/min Milliliters per minute
NTU Nephelometric Turbidity Unit
N Normal (equivalents per liter! solution
-------
TABLE A-3
ANALYTICAL DATA FOR VOCS BY GC ANALYSIS IN RUN 11
voc**
Unit
Influent
Reactor 1 - Effluent
Reactor 2 - Effluent
Reactor 3 - Effluent
Reactor 6 - Effluent
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Chloroform
fj g/L
147*
5.8*
107*
8.5*
NA
NA
34.8
5.97
9.4*
2.9*
1,1-Dichloroethane
//g/L
167*
5.8*
47.5*
7.6*
NA
NA
2.4
0.48
2.1
0.94
T etrachloroethene
m' L
66
3.86
3.8
1.56
NA
NA
2.4
0.48
2.1
0,94
1,1,1 -T richloroethane
^9/L
130
24.5
107
19.0
NA
NA
53,0
8.12
16.0*
1.7*
Trichloroethene
Aig/L
730
11.6
3.8
1.56
NA
NA
2.4
0.48
2.1
0.94
Notes: * Mean and standard deviation were calculated using data for three of four replicates,
** VOCs present above detection limit.
TABLE A-4
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 11
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2SQ4
Influent - After
H2S04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Alkalinity
mg/L as CaC03
NA
270
17
NA
18
NA
Bioassay, LC50
NA
NA
NA
NA
NA
NA
NA
Ceriodaphnia dubia
% Sample
NA
NA
>100
NA
13
NA
Pimephales prometas
% Sample
NA
NA
>100
NA
71
NA
Electricity Consumption*
kW
NA
NA
NA
NA
NA
NA
-------
TABLE A-4
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN II (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
H2S04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Flow Rate
NA
NA
NA
NA
NA
NA
NA
Ground Water Flow Rate
gpm
NA
NA
10
NA
NA
NA
H202 Flow Rate
mL/min
9.7
NA
NA
NA
NA
NA
Acid Flow Rate
mL/min
3.2
NA
NA
NA
NA
NA
Base Flow Rate
mL/min
10.3
NA
NA
NA
NA
NA
Hardness
mg/L as CaC03
NA
320
315
NA
315
NA
Hydrogen Peroxide
mg/L
644,000
NA
NA
NA
12.0
NA
Iron
^g/L
NA
<46.0
NA
NA
51.7
NA
Manganese
//g/L
NA
15.8
NA
NA
16.4
NA
pH6, Mean
pH Units
NA
7.46
5.05
NA
5.33
7.16
pHb, Range
pH Units
NA
7.45-7.47
4.75-5.34
NA
5.07-5.51
6.86-7.45
Purgeable Organic Carbon
mg/L
NA
0.27
NA
NA
0.04
NA
Semivolatile Organic Compounds0
NA
NA
NA
NA
NA
NA
NA
Hexathiepane (14.80-14.82)
A*g/L
NA
4.0
NA
NA
ND
NA
Pentanoic acid (4.73)
^g/L
NA
30
NA
NA
ND
NA
Unknown (3.64-7.68)
//g/L
NA
ND
NA
NA
ND
NA
Unknown (5.01)
pg/L
NA
ND
NA
NA
ND
NA
Unknown (16.90-16.91)
^g/L
NA
ND
NA
NA
ND
NA
Unknown (17.59-17.62)
/jg/L
NA
28
NA
NA
ND
NA
-------
TABLE A-4
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 11 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
h2so4
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Unknown (19-98-19.99)
fJQtt-
NA
ND
NA
NA
ND
NA
Unknown (21,00-21.04)
/^g/L
NA
30
NA
NA
ND
NA
Unknown (21.93-21.94)
M/L
NA
ND
NA
NA
ND
NA
Sodium Hydroxide Concentration
N
18.6
NA
NA
NA
NA
NA
Specific Conductance
/^mho/cm
NA
NA
1750 "
NA
1760
NA
Sulfuric Acid Concentration
N
35.2
NA
NA
NA
NA
NA
Total Carbon
mg/L
NA
75
NA
NA
55
NA
Total Organic Carbon
mg/L
NA
1.9
NA
NA
0.8
NA
Temperature
°C
NA
22.6
NA
NA
NA
NA
Total Organic Halides
mlL
NA
800
NA
NA
29
NA
Turbidity
NTU
NA
NA
0.20
NA
.15
NA
Volatile Organic Compounds (GC/MS)
NA
NA
NA
NA
NA
NA
NA
Target Analytes
NA
NA
NA
NA
NA
NA
NA
Acetone
fjgO-
NA
4
NA
NA
19
NA
2-Butanone
^g/L
NA
ND
NA
NA
ND
NA
Chloroform
pgfL
NA
160
NA
NA
10
NA
1,1 -Dichloroethane
m/l
NA
180
NA
NA
ND
NA
1,1 -Dichloroethene
^9/L
NA
11
NA
NA
ND
NA
1,2-Dichloroethene (total)
ml l
NA
10
NA
NA
ND
NA
-------
TABLE A-4
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 11 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before HjSO,
Influent - After
h2so4
Reactor 2
Effluent
Reactor 6
Effluent
Effluent • After
NaOH
T etrachl oroethene
mb/l
NA
79
NA
NA
ND
NA
Toluene
pg'L
NA
4
NA
NA
ND
NA
1,1,1-T richloroethane
mR-
NA
140
NA
NA
16
NA
Trichloroethene
mi i-
NA
670
NA
NA
ND
NA
Tentatively Identified Compound
(retention time, minutes)
NA
NA
NA
NA
NA
NA
NA
Tetrahydrofuran (14.36 14.46)
W'L
NA
5
NA
NA
ND
NA
yŁ>
NOTES:
" The mean electricity consumption was 32,19 kW.
" Readings were taken 2 or 3 times for pH measurement. Range of readings is also listed.
c None of the semivolatile organic target analytes were detected. Only tentatively identified compounds (TIC) are given in this table. Retention time in minutes
for each TIC is given in parentheses.
4 The flow rate was monitored throughout the run, and the volume remained constant.
NA Not applicable
ND Not detected
°C Degree Celsius
gpm Gallons per minute
GC/MS Gas chromatography and mass spectrometry
kW Kilowatts
pg/L Micrograms per liter
//mho/cm Micromhos per centimeter
mg/L Milligrams per liter
mL/min Milliliters per minute
NTU Nephelometric Turbidity Unit
N Normal (equivalents per liter) solution
-------
TABLE A-S
ANALYTICAL DATA FOR VOCS BY GC ANALYSIS IN RUN 12
voc,#
Unit
Influent
Reactor 1 - Effluent
Reactor 2 - Effluent
Reactor 3 - Effluent
Reactor 6 - Effluent
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Chloroform
pg/L
243
9.57
106
15.2
56.5
5.92
29.5
7.94
17.0
13.4
1,1 -Dichloroethane
pg/l
119
72.2
66.5
22.4
4,1
3.28
2.8
1.71
2.1
0.85
Tetrachloroethene
pg/L
72
11.6
2.4
0.48
2.4
0.48
2.8
1.71
2.1
0.85
1,1,1-T richloroethane
130
8.16
112
23.7
69.0
4.90
40.0*
5.0"
25.8
6.65
Trichloroethene
/fg/L
680
49.7
2.4
0.48
2.4
0.48
2.8
1.71
2.1
0.85
Notes: * Mean and standard deviation were calculated using data for three of four replicates.
* * VOCs present above detection limit.
TABLE A-6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
H2S04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Alkalinity
mg/L as CaC03
NA
270
25
51
26
NA
Bioassay, LCS0
NA
NA
NA
NA
NA
NA
NA
Ceriodaphnia dub/a
% Sample
NA
NA
>100
NA
26
NA
Pimephales promelas
% Sample
NA
NA
>100
NA
>100
NA
Electricity Consumption8
kW
NA
NA
NA
NA
NA
NA
-------
TABLE A-6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
H2SO<
Reactor 2
Effluent
Reactor 6
Effluent
Effluent • After
NaOH
Flow Rate
NA
NA
NA
NA
NA
NA
NA
Ground Water Flow Rate
gpm
NA
NA
10
NA
NA
NA
H202 Flow Rate
mL/min
9.5
NA
NA
NA
NA
NA
Acid Flow Rate
mL/min
3.2
NA
NA
NA
NA
NA
Base Flow Rate
mL/min
10.3
NA
NA
NA
NA
NA
Hardness
mg/L as CaC03
NA
320
320
320
320
NA
Hydrogen Peroxide
mg/L
615,000
NA
NA
22.0
7.4
NA
Iron
«J/L
NA
<46.0
NA
NA
<46.0
NA
Manganese
pg/i
NA
15.1
NA
NA
15.4
NA
pH", Mean
pH Units
NA
7.48
5.12
5.36
5.34
7.22
pH", Range
pH Units
NA
7.46-7.49
5.11-5.13
5.35-5.36
5.34-5.34
7.19-7.25
Purgeable Organic Carbon
mg/L
NA
0.24
NA
NA
0.04
NA
Semivolatile Organic Compounds0
NA
NA
NA
NA
NA
NA
NA
Hexathiepane (14.80-14.82)
v q/l
NA
ND
NA
NA
ND
NA
Pentanoic acid (4.73)
//g/L
NA
ND
NA
NA
ND
NA
Unknown (3.64-7.68)
pg/L
NA
ND
NA
NA
ND
NA
Unknown (5.01)
//g/L
NA
ND
NA
NA
12
NA
Unknown (16.90-16.91)
mn-
NA
20
NA
NA
ND
NA
Unknown (17.59-17.62)
VQ/l
NA
ND
NA
NA
ND
NA
-------
TABLE A-6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2SO,
Influent - After
H2S04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Unknown (19.98-19.99)
^g/L
NA
ND
NA
NA
ND
NA
Unknown (21.00-21.04)
fjgli
NA
ND
NA
NA
ND
NA
Unknown (21.93-21.94)
mft-
NA
23
NA
NA
ND
NA
Sodium Hydroxide Concentration
N
18.5
NA
NA
NA
NA
NA
Specific Conductance
//mho/cm
NA
NA
1700
NA
1640
NA
Sulfuric Acid Concentration
N
34.2
NA
NA
NA
NA
NA
Total Carbon
mg/L
NA
76
NA
NA
59
NA
Total Organic Carbon
mg/L
NA
1.9
NA
NA
1.6
NA
Temperature
°c
NA
23.8
NA
28.4
33.8
NA
Total Organic Halides
fJQll
NA
740
NA
160
24
NA
Turbidity
NTU
NA
NA
<0.1
NA
<0.1
NA
Volatile Organic Compounds (GC/MS)
NA
NA
NA
NA
NA
NA
NA
Target Analytes
NA
NA
NA
NA
NA
NA
NA
Acetone
m/L
NA
49
NA
NA
7
NA
2-Butanone
mft-
NA
ND
NA
NA
ND
NA
Chloroform
A/g/L
NA
180
NA
NA
13
NA
1,1-Dichloroethane
m/L
NA
190
NA
NA
ND
NA
1,1-Dichloroethene
m'L
NA
9
NA
NA
ND
NA
1,2-Dichloroethene (total)
fjgit-
NA
8
NA
NA
ND
NA
-------
TABLE A-6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
HjS04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Tetrachloroethene
^g/L
NA
71
NA
NA
ND
NA
Toluene
NA
2
NA
NA
ND
NA
1,1,1 -T richloroethane
mft-
NA
150
NA
NA
19
NA
Trichloroethene
fjg/t
NA
430
NA
NA
ND
NA
Tentatively Identified Compound
(retention time, minutes)
NA
NA
NA
NA
NA
NA
NA
Tetrahydrofuran (14.36-14.46)
vq/l
NA
2
NA
NA
ND
NA
Notes:
* The mean electricity consumption was 32.19 kW.
b Readings were taken 2 or 3 times for pH measurement. Range of readings is also listed.
c None of the semivolatile organic target analytes were detected. Only tentatively identified compounds (TIC) are given in this table. Retention time in minutes
for each TIC is given in parentheses.
a The flow rate was monitored throughout the run, and the volume remained constant.
NA Not applicable
ND Not detected
°C Degree Celsius
gpm Gallons per minute
GC/MS Gas chromatography and mass spectrometry
kW Kilowatts
fjg/L Micrograms per liter
j/mho/cm Micromhos per centimeter
mg/L Milligrams per liter
mL/min Milliliters per minute
NTU Nephelometric Turbidity Unit
N Normal (equivalents per liter) solution
-------
TABLE A-5
ANALYTICAL DATA FOR VOCS BY GC ANALYSIS IN RUN 12
voc#*
Unit
Influent
Reactor 1 - Effluent
Reactor 2 - Effluent
Reactor 3 ¦ Effluent
Reactor 6 - Effluent
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Mean
Standard
Deviation
Chloroform
fjg/i
243
9.57
106
15.2
56.5
5.92
29.5
7.94
17.0
13.4
1,1 -Dichloroethane
fjg/L
119
72.2
66.5
22.4
4.1
3.28
2.8
1.71
2.1
0.85
T etrachloroethene
m't
72
11.6
2.4
0.48
2.4
0.48
2.8
1.71
2.1
0.85
1,1,1-Trichloroethane
pgll
130
8.16
112
23.7
69.0
4.90
40.0-
5.0*
25.8
6.65
Trichloroethene
mi L
680
49.7
2.4
0.48
2.4
0.48
2.8
1.71
2.1
0.85
Notes: * Mean and standard deviation were calculated using data for three of four replicates.
** VOCs present above detection limit.
01
TABLE A-6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
H2S04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Alkalinity
mg/L as CaC03
NA
270
25
51
26
NA
Bioassay, LC50
NA
NA
NA
NA
NA
NA
NA
Ceriodaphnia dub/a
% Sample
NA
NA
>100
NA
26
NA
Pimepha/es promelas
% Sample
NA
NA
>100
NA
>100
NA
Electricity Consumption*
kW
NA
NA
NA
NA
NA
NA
-------
TABLE A-6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H,S04
Influent - After
h2so4
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Flow Rate
NA
NA
NA
NA
NA
NA
NA
Ground Water Flow Rate
gpm
NA
NA
10
NA
NA
NA
Hj02 Flow Rate
mL/min
9.5
NA
NA
NA
NA
NA
Acid Flow Rate
mL/min
3.2
NA
NA
NA
NA
NA
Base Flow Rate
mL/min
10.3
NA
NA
NA
NA
NA
Hardness
mg/L as CaC03
NA
320
320
320
320
NA
Hydrogen Peroxide
mg/L
615,000
NA
NA
22.0
7.4
NA
Iron
//g/L
NA
<46.0
NA
NA
<46.0
NA
Manganese
m/L
NA
15.1
NA
NA
15.4
NA
pH", Mean
pH Units
NA
7.48
5.12
5.36
5.34
7.22
pHb, Range
pH Units
NA
7.46-7.49
5.11-5.13
5.35-5.36
5.34-5.34
7.19-7.25
Purgeable Organic Carbon
mg/L
NA
0.24
NA
NA
0.04
NA
Semivolatile Organic Compounds'
NA
NA
NA
NA
NA
NA
NA
Hexathiepane (14.80-14.82)
m/L
NA
NO
NA
NA
ND
NA
Pentanoic acid (4.73)
/jg/L
NA
NO
NA
NA
ND
NA
Unknown (3.64-7.68)
/rg/L
NA
ND
NA
NA
ND
NA
Unknown (5.01)
pg/L
NA
NO
NA
NA
12
NA
Unknown (16.90-16.91)
m/l
NA
20
NA
NA
ND
NA
Unknown (17.59-17.62)
m/l
NA
ND
NA
NA
ND
NA
-------
TABLE A-6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2S04
Influent - After
HaS04
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Unknown (19.98-19.99)
^g/L
NA
NO
NA
NA
ND
NA
Unknown (21,00-21.04)
//g/L
NA
ND
NA
NA
ND
NA
Unknown (21.93-21.94)
//g/L
NA
23
NA
NA
ND
NA
Sodium Hydroxide Concentration
N
18,5
NA
NA
NA
NA
NA
Specific Conductance
^/mho/cm
NA
NA
1700
NA
1640
NA
Sulfuric Acid Concentration
N
34.2
NA
NA
NA
NA
NA
Total Carbon
mg/L
NA
76
NA
NA
59
NA
Total Organic Carbon
mg/L
NA
1.9
NA
NA
1.6
NA
Temperature
°C
NA
23.8
NA
28.4
33.8
NA
Total Organic Halides
//g/L
NA
740
NA
160
24
NA
T urbidity
NTU
NA
NA
<0,1
NA
<0.1
NA
Volatile Organic Compounds (GC/MS)
NA
NA
NA
NA
NA
NA
NA
Target Analytes
NA
NA
NA
NA
NA
NA
NA
Acetone
vg/L
NA
49
NA
NA
7
NA
2-Butanone
pg/L
NA
NO
NA
NA
ND
NA
Chloroform
(ig/L
NA
180
NA
NA
13
NA
1,1 -Dichloroethane
//g/L
NA
190
NA
NA
ND
NA
1,1-Dichloroethene
//g/L
NA
9
NA
NA
ND
NA
1,2-Dichloroethene (total!
//g/L
NA
8
NA
NA
ND
NA
-------
XABLE A"6
ANALYTICAL AND MEASUREMENT DATA FOR MISCELLANEOUS PARAMETERS IN RUN 12 (Continued)
Parameter
Unit
Sampling/Measurement Locations
Chemical Feed
Tank
Influent -
Before H2SO,
Influent - After
h2so4
Reactor 2
Effluent
Reactor 6
Effluent
Effluent - After
NaOH
Tetrachloroethene
/>g/L
NA
71
NA
NA
ND
NA
Toluene
^g/L
NA
2
NA
NA
ND
NA
1,1,1 -T richloroethane
//g/L
NA
1 §0
NA
NA
19
NA
Trichloroethene
miL
NA
430
NA
NA
ND
NA
Tentatively Identified Compound
(retention time, minutes)
NA
NA
NA
NA
NA
NA
NA
Tetrahydrofuran (14.36-14.46)
pg/L
NA
2
NA
NA
ND
NA
Notes:
* The mean electricity consumption was 32.19 kW.
b Readings were taken 2 or 3 times for pH measurement. Range of readings is also listed.
c None of the semivolatile organic target analytes were detected. Only tentatively identified compounds (TIC! are given in this table. Retention time in minutes
for each TIC is given in parentheses.
" The flow rate was monitored throughout the run, and the volume remained constant.
NA Not applicable
ND Not detected
°C Degree Celsius
gpm Gallons per minute
GC/MS Gas chromatography and mass spectrometry
kW Kilowatts
fjg/L Micrograms per liter
//mho/cm Micromhos per centimeter
mg/L Milligrams per liter
ml/min Milliliters per minute
NTU Nephelometric Turbidity Unit
N Normal {equivalents per liter) solution
------- |