EPA/540/AR-93/501
July 1993
perox-pure™ Chemical
Oxidation Technology
Peroxidation Systems, Inc.
Applications Analysis Report
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
Printed on Recycled Paper
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Notice
The information hi this document has been prepared for the U.S. Environmental Protection Agency
(EPA) Superfund Innovative Technology Evaluation (SITE) program under Contract No. 68-CO-0047.
This document has been subjected to EPA peer and administrative reviews and has been approved for
publication as an EPA document. Mention of trade names or commercial products does not constitute
an endorsement or recommendation for use.
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Foreword
The Superfund Innovative Technology Evaluation (SITE) program was authorized in the 1986
Superfund Amendments and Reauthorization Act. The program is a joint effort between the
U.S. Environmental Protection Agency's (EPA) Office of Research and Development and Office of
Solid Waste and Emergency Response. 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 site in Tracy,
California. The demonstration effort was directed 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) a Technology Evaluation Report, which describes field
activities and laboratory results, and (2) this Applications Analysis Report, which interprets the data and
discusses the potential applicability of the technology.
A limited number of copies of tlhis report will be available at no charge from EPA's Center for
Environmental Research Information, 26 West Martin Luther King Drive, Cincinnati, Ohio 45268.
Requests should include the EPA document number found on the report's cover. When the limited
supply is exhausted, additional copies 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
111
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Abstract
This report evaluates the perox-pure™ chemical oxidation technology's ability to remove volatile
organic compounds (VOC) and other organic contaminants present in liquid wastes. This 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 Systems, 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, California. Over a 3-week period in
September 1992, about 40,000 gallons of VOC-contaminated groundwater was treated in the perox-
pure'* system. For the SITE demonstration, the perox-pure™ system achieved trichloroethene (TCE)
and tetrachloroethene (PCE) average removal efficiencies of about 99.7 and 97.1 percent, respectively.
In general, the perox-pure™ system produced an effluent that contained (1) TCE, PCE, and
1,1-dichloroethane (DCA) below detection limits and (2) chloroform and 1,1,1-trichloroethane (TCA)
slightly above detection limits. The system also achieved chloroform, DCA, and TCA average removal
efficiencies of 93.1, 98.3, and 81.8 percent, respectively. 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.
The results from three case studies are also summarized in this report. All three case studies
represent full-scale, currently operating commercial installations of perox-pure™ chemical oxidation
systems. The contaminants of concern in these case studies include acetone, isopropyl alcohol (IPA),
TCE, and pentachlorophenol (PCP). In the first case study, the perox-pure™ system treated industrial
wastewater containing 20 milligrams per liter (mg/L) of acetone and IPA; the effluent met the discharge
limit of 0.5 mg/L for each compound. In the second case study, the perox-pure™ system treated
groundwater that was used as a municipal drinking water source. The groundwater initially contained
150 micrograms per liter (pg/L) of TCE. After treatment, the effluent TCE level was 0.5 /tg/L, well
below the TCE drinking water standard of 5 /ig/L. In the third case study, the perox-pure™ system
treated groundwater at a chemical manufacturing facility. The groundwater contained 15 mg/L of PCP;
after treatment the effluent achieved the target effluent PCP level of 0.1 mg/L.
Potential sites for applying this technology include Superfund and other hazardous waste sites where
groundwater or other liquid wastes are contaminated with organic compounds. Economic data indicate
that groundwater remediation costs for a 50-gallon per minute perox-pure™ system could range from
about $7 to $11 per 1,000 gallons, depending on contaminated groundwater characteristics. Of these,
perox-pure™ system direct treatment costs could range from about $3 to $5 per 1,000 gallons.
IV
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Contents
Notice ii
Foreword Jii
Abstract iv
Acronyms, Abbreviations, and Symbols : ix
Conversion Factors xi
Acknowledgements xii
1. Executive Summary 1
1.1 Introduction 1
1.2 Overview of the SITE Demonstration 1
1.3 Results from the SITE Demonstration 2
1.4 Results from Case Studies 3
1.5 Waste Applicability 3
1.6 Economics 3
2. Introduction 5
2.1 Purpose, History, and Goals of the SITE Program 5
2.2 Documentation of the SITE Demonstration Results 6
2.3 Purpose of the Applications Analysis Report 6
2.4 Technology Description 6
2.4.1 Treatment Technology 7
2.4.2 System Components and Function 8
2.4.3 Innovative Features of the Technology 8
2.5 Key Contacts 9
3. Technology Applications Analysis 11
3.1 Effectiveness of the perox-pure™ Technology 11
3.1.1 SITE Demonstration Results 11
3.1.2 Results of Other Case Studies 12
3.2 Factors Influencing Performance 13
3.2.1 Influent Characteristics 13
3.2.2 Operating Parameters ' 13
3.2.3 Maintenance Requirements 14
3.3 Site Characteristics 14
3.3.1 Support Systems 14
3.3.2 Site Area and Preparation 15
3.3.3 Site Access ' 15
3.3.4 Climate 15
3.3.5 Utilities 15
3.3.6 Services and Supplies 15
3.4 Material Handling Requirements 15
3.4.1 Pretreatment Materials 16
3.4.2 Treated Water 16
3.5 Personnel Requirements 16
3.6 Potential Community Exposures 16
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Contents (continued)
3.7 Potential Regulatory Requirements 17
3.7.1 Comprehensive Environmental Response, Compensation,
and Liability Act 17
3.7.2 Resource Conservation and Recovery Act 17
3.7.3 Clean Water Act 19
3.7.4 Safe Drinking Water Act 19
3.7.5 Toxic Substances Control Act 19
3.7.6 Mixed Waste Regulations 19
3.7.7 Federal Insecticide, Fungicide, and Rodenticide Act 19
3.7.8 Occupational Safety and Health Act 20
4. Economic Analysis 21
4.1 Basis of Economic Analysis 21
4.2 Cost Categories 24
4.2.1 Site Preparation Costs 25
4.2.2 Permitting and Regulatory Requirements Costs 25
4.2.3 Capital Equipment Costs 25
4.2.4 Startup Costs 27
4.2.5 Labor Costs 27
4.2.6 Consumables and Supplies Costs 27
4.2.7 Utilities Costs 28
4.2.8 Effluent Treatment and Disposal Costs 29
4.2.9 Residuals and Waste Shipping and Handling Costs 29
4.2.10 Analytical Services Costs 29
4.2.11 Maintenance and Modifications Costs 29
4.2.12 Demobilization Costs 30
5. References 31
Appendix A - Vendor Claims for the Technology 33
A.1 Introduction 33
A.2 Description of the perox-pure™ System 33
A.3 perox-pure™ Systems 34
A.4 Design Improvements 34
A.5 Pretreatment 36
A.6 perox-pure™ Applications 36
A.7 Advantages over Carbon Adsorption and Air Stripping Technologies 36
A.8 Other Advantages 38
A.9 Technology Combinations 38
Appendix B - SITE Demonstration Results 39
B.I Site Description 39
B.2 Site Contamination Characteristics 39
B.3 Review of SITE Demonstration 41
B.3.1 Site Preparation 41
B.3.2 Technology Demonstration 42
B.3.3 Site Demobilization 43
B.4 Experimental Design 43
B.4.1 Testing Approach 44
B.4.2 Sampling and Analytical Procedures 44
B.5 Review of Treatment Results 45
B.5.1 Summary of the Results for Critical Parameters 45
B.5.2 Summary of Results for Noncritical Parameters 56
B.6 Conclusions 58
B.7 References 58
VI
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Contents (continued)
Appendix C - Case Studies 59
C.1 Wastewater Treatment System, Florida 59
C.I.I Site Conditions 59
C.1.2 System Performance 59
C.1.3 Costs 59
C.2 Municipal Drinking Water System, Arizona 60
C.2.1 Site Conditions 60
C.2.2 System Performance 60
C.2.3 Costs 60
C.3 Chemical Manufacturing Company, Washington 60
C.3.1 Site Conditions 60
C.3.2 System Performance 60
C.3.3 Costs 61
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Figures
2-1 perox-pure™ Chemical Oxidation Treatment System 9
A-l Isometric Diagram of perox-pure™ Unit 35
B-l LLNL Site Location 40
B-2 perox-pure™ Chemical Oxidation Treatment System Sampling Locations 47
B-3 Comparison of VOC Concentrations at Different Influent pH Levels 49
B-4 Comparison of VOC Concentrations at Different Hydrogen Peroxide Levels 50
B-5 Comparison of VOC Concentrations at Different Flow Rates and Hydrogen
Peroxide Levels 51
B-6 Comparison of VOC Concentrations in Spiked and Unspiked Groundwater 52
B-7 VOC Removal Efficiencies in Reproducibility Runs 53
B-8 Comparison of 95 Percent UCLs for Effluent VOC Concentrations with Target Levels
in Reproducibility Runs 54
B-9 VOC Removal Efficiencies in Quartz Tube Cleaner Runs 55
B-10 Carbon Concentrations in Reproducibility Runs 57
Tables
2-1 Comparison of Technologies for Treating VOCs in Water 10
3-1 Regulations Summary 18
4-1 Costs Associated with the perox-pure™ Technology - Case 1 22
4-2 Costs Associated with the perox-pure™ Technology - Case 2 23
A-l Oxidation Potential of Oxidants 34
A-2 Partial List of perox-pure™ Technology Applications 37
B-l Experimental Matrix for perox-pure™ Technology Demonstration 45
B-2 Target Levels for VOCs in Effluent Samples 46
B-3 Analytical and Measurement Methods 48
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Acronyms, Abbreviations, and Symbols
AAR Applications Analysis Report
ACL Alternate concentration limit
AEA Atomic Energy Act
AOX Adsorbable organic halide
ARAR Applicable or relevant and appropriate requirement
BTEX Benzene, toluene, ethylbenzene, and xylene
BTX Benzene, toluene, and xylene
CC14 Carbon tetrachloride
CDEP Department of Environmental Protection, State of Connecticut
CERCLA Comprehensive Environmental Response, Compensation, and Liability Act
CFR Code of Federal Regulations
CWA Clean Water Act
DCA 1,1-dichloroethane
1,1-DCE 1,1-dichloroethene
1,2-DCE 1,2-dichloroethene
DIMP Diisopropyl methylphosphonate
DOE U.S. Department of Energy
EPA U.S. Environmental Protection Agency
FIFRA Federal Insecticide, Fungicide, and Rodenticide Act
FS Feasibility study
°F Degree Fahrenheit
GC Gas chromatography
gpd Gallons per day
gpm Gallons per minute
GSA General Services Area
H2O2 Hydrogen peroxide
hv Ultraviolet radiation
IPA Isopropyl alcohol
kW Kilowatt
kWh Kilowatt-hour
LLNL Lawrence Livermore National Laboratory
MCL Maximum contaminant level
MeCl Methylene chloride
MEK Methyl ethyl ketone
/xg/L Micrograms per liter
mg/L Milligrams per liter
MS Mass spectrometry
NPDES National Pollutant Discharge Elimination System
OH> Hydroxyl radical
O&M Operation and maintenance
ORD Office of Research and Development
OSHA Occupational Safety and Health Act
OSWER Office of Solid Waste and Emergency Response
PAH Polynuclear aromatic hydrocarbon
PCB Polychlorinated biphenyl
IX
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Acronyms, Abbreviations, and Symbols (continued)
PCE Tetrachloroethene
PCP PentacHorophenol
POC Purgeable organic carbon
POTW Publicly-owned treatment works
PPE Personal protective equipment
ppm Parts per million
PSI Peroxidation Systems, Inc.
QA/QC Quality assurance/quality control
RI Remedial investigation
RCRA Resource Conservation and Recovery Act
SARA Superfund Amendments and Reauthorization Act
SDWA Safe Drinking Water Act
SITE Superfund Innovative Technology Evaluation
SVOC Semivolatile organic compound
TC Total carbon
TCA 1,1,1-trichloroethane
TCE Trichloroethene
TER Technology Evaluation Report
TIC Tentatively identified compound
TOC Total organic carbon
TOX Total organic halide
TSCA Toxic Substances Control Act
UCL Upper confidence limit .
UV Ultraviolet
VOC Volatile organic compound
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Conversion Factors
To Convert From To
Multiply By
Length:
Area:
Volume:
inch
foot
mile
square foot
acre
gallon
cubic foot
centimeter
meter
kilometer
square meter
square meter
liter
cubic meter
2.54
0.305
1.61
0.0929
4,047
3.78
0.0283
Mass:
pound
kilogram
0.454
Energy:
kilowatt-hour
megajoule
3.60
Power:
kilowatt
horsepower
1.34
Temperature:
("Fahrenheit - 32) "Celsius
0.556
XI
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Acknowledgements
This report was prepared under the direction and coordination of Ms. Norma Lewis, U.S.
Environmental Protection Agency (EPA) Superfund Innovative Technology Evaluation (SITE) Project
Manager and Emerging Technology Section Chief in the Risk Reduction Engineering Laboratory
(RREL), Cincinnati, Ohio. Contributors and reviewers for this report were Messrs. Carl Chen, Gordon
Evans, John Ireland, and Ron Turner 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; Mr. Shyam Shukla of Lawrence Livermore National
Laboratory (LLNL), Livermore, California; and Mr. Geoffrey Germann of Engineering-Science, Inc.,
Fairfax; Virginia.
This report was prepared for EPA's SITE program by Dr. Kirankumar Topudurti, Mr. Michael
Keefe, Mr. Patrick Wooliever, Mr. Jeffrey Swano, and Ms. Carla Buriks 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. Carol Adams, Ms. Korreen Ball, Ms. Regina
Bergner, and Mr. Tobin Yager of PRC for their editorial, graphic, and production assistance during the
preparation of this report.
Xll
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Section 1
Executive Summary
1.1 Introduction
The perox-pure™ chemical oxidation technology,
developed by Peroxidation Systems, Inc. (PSI), was evaluated
under the U.S. Environmental Protection Agency 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 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 has
six reactors in series with one 5-kilowatt 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 are mounted on the quartz tubes to 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.
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.
The purpose of this report is to present information
from the SITE demonstration and several case studies 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,
describes the perox-pure™ technology, and lists key contacts.
Section 3 discusses information relevant to the technology's
application, including pretreatment and posttreatment
requirements, site characteristics, operating and maintenance
requirements, potential community exposures, and potentially
applicable environmental regulations. Section 4 summarizes
the costs associated with implementing the technology.
Section 5 includes a list of references. Appendices A
through C include the vendor claims for the technology, a
summary of the SITE demonstration results, and summaries
of three case studies, respectively.
1.2 Overview of the SITE Demonstration
Shallow groundwater at the LLNL site was selected as
the waste stream for evaluating the perox-pure™ chemical
oxidation technology. About 40,000 gallons of groundwater
contaminated with VOCs was treated during the
demonstration. The principal groundwater contaminants
were trichloroethene (TCE) and tetrachloroethene (PCE),
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which were present at concentrations of about 1,000 and 100
micrograms per liter (/xg/L), respectively. Groundwater was
pumped from two wells into a 7,500-gallon bladder tank to
minimize 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 tank. Treated groundwater was stored
in two 20,000-gallon steel tanks before being discharged.
The technology demonstration was conducted hi three
phases. 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 evaluate the effectiveness of quartz tube
cleaning. These phases are described below.
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
during Phase 1 to observe treatment system performance
under different operating conditions. Preferred operating
conditions, those under which the concentrations of spiked
groundwater effluent VOCs would be reduced to below
target levels, 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 quartz tube wipers
was evaluated by performing two runs using spiked
groundwater and 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, purgeable organic carbon (POC), total organic
halides (TOX), adsorbable organic halides (AOX), metals,
pH, alkalinity, turbidity, temperature, specific conductance,
hydrogen peroxide residual, and hardness, as applicable. In
addition, samples of influent to Reactor 1 and treatment
system effluent were collected and analyzed for acute toxicity
to freshwater organisms. In the bioassay tests,
Ceriodaphnia ditbia (water fleas) and Pimephales
promelas (fathead minnows) were used as the test
organisms. Hydrogen peroxide, acid, and base solutions
were also sampled and analyzed to verify concentrations.
1.3 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 /ig/L) and effluent
chloroform and TCA levels ranged from 15 to 30 /
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1.4 Results from Case Studies
1.5 Waste Applicability
Information on the perox-pure™ technology's
performance at three facilities was evaluated to provide
additional performance data. The three case studies
represent full-scale, currently operating commercial
installations of perox-pure™ systems. The contaminants of
concern in these case studies include acetone, isopropyl
alcohol (IPA), TCE, and pentachlorophenol (PCP). The
case studies are briefly summarized below.
The first case study involves wastewater treatment at the
Kennedy Space Center in Florida. At this facility, a liquid-
phase carbon adsorption system had originally been installed
to treat wastewater containing acetone and IPA at levels of
20 mg/L. The treatment facility discharge requirement for
both acetone and IPA is 0.5 mg/L. Because the carbon
adsorption system did not achieve the discharge requirement,
the perox-pure™ chemical oxidation technology was selected
to replace the carbon adsorption system. At this facility, the
perox-pure™ system initially treated wastewater in batches of
about 5,000 gallons. Later, the system was converted to a
flow-through mode. Currently, the system treats wastewater
at a flow rate of 5 gpm and produces an effluent that meets
the discharge standard.
The second case study involves treating groundwater
used as a municipal drinking water source in Arizona. In
1989, a municipal drinking water well in Arizona was found
to contain 50 to 400 |tg/L of TCE. The well, capable of
producing 2,000 gpm, was taken out of service wHle several
treatment options were evaluated. Because the well is
located on a city lot in the middle of a large residential area,
the city preferred using a low-visibility, quiet treatment
method that could consistently destroy TCE to
concentrations below the drinking water standard of 5 /tg/L.
Given these requirements, chemical oxidation using the
perox-pure™ system was selected. Currently, the system
treats groundwater at a flow rate of 135 gpm and produces
treated groundwater containing only 0.5 /ig/L of TCE.
The third case study deals with treatment of PCP-
contaminated groundwater at a chemical manufacturing
company in Washington. Groundwater at the site was found
to contain about 15 mg/L of PCP. In 1988, PSI installed a
perox-pure™ system at the site under a Full Service
Agreement. Because the groundwater was also found to
contain high levels of iron (200 mg/L) and carbonates that
could scale the quartz tubes and impair the treatment
efficiency, PSI recommended groundwater pretreatment.
Pretreatment consists of iron oxidation and removal,
followed by pH adjustment to about 5. Pretreated
groundwater is then treated by a perox-pure™ system
equipped with automatic quartz tube cleaners. Currently,
the perox-pure™ system treats groundwater at a flow rate of
70 gpm and produces an effluent that meets the discharge
standard of 0.1 mg/L.
Potential sites for applying the perox-pure™ technology
include 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, the perox-pure™ system was
combined with other treatment technologies for cost
effectiveness.
1.6 Economics
Using information obtained from the SITE
demonstration, an economic analysis was performed to
examine 12 separate cost categories for perox-pure™ systems
treating about 260 million gallons of contaminated
groundwater at a Superfund site. This analysis examined two
cases based on groundwater characteristics. In Case 1, the
groundwater was assumed to have five contaminants, two of
which are easy to oxidize (TCE and PCE) and the remaining
three are difficult to oxidize (chloroform, DCA, and TCA).
In Case 2, the groundwater was assumed to have only two
contaminants that are easy to oxidize (TCE and PCE). For
each case, costs for three different flow rates (10, 50, and
100 gpm) were estimated. Detailed economic analysis for
the three flow rates of each case is included in Section 4.
Costs for the 50-gpm flow rate scenario for each case are
summarized below.
For Case 1, capital costs are estimated to be about
$906,000 of which the perox-pure™ system direct capital cost
is $185,000. Annual operation and maintenance (O&M)
costs are estimated to be about $188,000 of which
perox-pure™ system direct O&M costs are $125,000.
Groundwater remediation costs to treat 1,000 gallons of
contaminated water are estimated to be about $11 of which
perox-pure™ system direct treatment costs are $5.
For Case 2, capital costs are estimated to be about
$776,000 of which the perox-pure™ system direct capital cost
is $55,000. Annual O&M costs are estimated to be about
$111,000 of which perox-pure™ system direct O&M costs are
$61,000. Groundwater remediation costs to treat
1,000 gallons of contaminated water are estimated to be
about $7 of which perox-pure™ system direct treatment costs
are $3.
The case studies included in Appendix C have minimal
cost data. According to PSI, in the case studies, the total
O&M costs ranged from $0.28 to $3.90 per 1,000 gallons of
water treated.
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Section 2
Introduction
This section provides information about the Superfund
Innovative Technology Evaluation (SITE) program, discusses
the purpose of this report, and describes the perox-pure™
chemical oxidation technology developed by Peroxidation
Systems, Inc. (PSI), of Tucson, Arizona. The perox-pure™
technology is designed to treat waters contaminated with
organic compounds. For additional information about the
SITE program, the perox-pure™ technology, or the
demonstration site, key contacts are listed at the end of this
section.
2.1 Purpose, History, and Goals of the SITE
Program
The Superfund Amendments and Reauthorization Act
(SARA) of 1986 mandates that the U.S. Environmental
Protection Agency (EPA) select, to the maximum extent
practicable, remedial actions at Superfund sites that create
permanent solutions (as opposed to land-based disposal) for
contamination that affects human health and the
environment. In doing so, EPA is directed to use alternative
or resource recovery technologies. In response, EPA's
Office of Research and Development (ORD) and Office of
Solid Waste and Emergency Response (OSWER) established
three programs: (1) a program to accelerate the use of new
or innovative technologies to clean up Superfund sites
through field demonstrations; (2) a program to foster the
further research and development of treatment technologies
that are at the laboratory or pilot scale; and (3) a program
to demonstrate and evaluate new or innovative measurement
and monitoring technologies. Together, these three
components make up the SITE program.
The primary purpose of the SITE program is to enhance
the development and demonstration, and thereby establish
the commercial availability, of innovative technologies
applicable to Superfund sites. The SITE program has
established the following goals:
• Identify and remove impediments to the
development and commercial use of alternative
technologies
• Demonstrate promising innovative technologies to
establish reliable performance and cost information
for site characterization and remediation decisions
• Develop procedures and policies that encourage the
selection of alternative treatment remedies at
Superfund sites
• Develop a program that promotes and supports
emerging technologies
EPA recognizes that a number of forces inhibit the
expanded use of new and alternative technologies at
Superfund sites. The SITE program's goals are designed to
identify the most promising new technologies, develop
pertinent and useful data of known quality about them, and
make the data available to Superfund decision makers. An
additional goal is to promote the development of emerging
innovative technologies from the laboratory- or bench-scale
to the full-scale stage.
Implementation of the SITE program is a significant
ongoing effort involving ORD, OSWER, various EPA
Regions, and private sector business concerns, including
technology developers and parties responsible for site
remediation. The technology selection process and the
demonstration program together provide objective and
carefully controlled testing of field-ready technologies.
Through government publications, the SITE program
disseminates testing results to Superfund decision makers for
use in evaluating the applicability of technologies to site-
specific remediation efforts.
The demonstration process collects the following
information for Superfund decision makers to consider when
matching technologies with wastes, media, and sites requiring
remediation:
• The technology's effectiveness based on field
demonstration sampling and analytical data
collected during the demonstration
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• The potential need for pretreatment and
posttreatment of wastes
• The site-specific wastes and media to which the
technology can be applied
• Potential site-specific system operating problems as
well as possible solutions
• The approximate capital, operating, and
maintenance costs
• The projected long-term operation and maintenance
(O&M) costs
Innovative technologies chosen for a SITE demonstration
must be pilot- or full-scale applications and must offer some
advantage over existing technologies. Mobile technologies
are of particular interest. Each year the SITE program
sponsors demonstrations of approximately 10 technologies.
2.2 Documentation of the SITE Demonstration
Results
The results of each SITE demonstration are reported in
two documents: the Applications Analysis Report (AAR)
and the Technology Evaluation Report (TER). The AAR is
intended for decision makers responsible for implementing
specific remedial actions and is primarily used to assist in
screening the demonstrated technology as an option for a
particular cleanup situation. The purpose of the AAR is
discussed in the following section.
The TER is published separately from the AAR and
provides a comprehensive description of the demonstration
and its results. A likely audience for the TER includes
engineers responsible for evaluating the technology for
specific site and waste situations. These technical evaluators
seek to understand, in detail, the performance of the
technology during the demonstration, as well as advantages,
disadvantages, and costs of the technology for the given
application. This information is used to produce conceptual
designs in sufficient detail to enable preliminary cost
estimates for the demonstrated technology. If the candidate
technology appears to meet the needs of site engineers, a
more thorough analysis will be conducted based on the TER,
the AAR, and other site-specific information obtained from
remedial investigations.
2.3 Purpose of the Applications Analysis Report
Information presented in the AAR is intended to assist
Superfund decision makers in screening specific technologies
for a particular cleanup situation. The report discusses the
advantages, disadvantages, and limitations of the technology.
Costs of the technology for different applications are
estimated based on available data for pilot- and full-scale
applications. The report discusses factors that have a major
impact on cost and performance, such as site and waste
characteristics.
To encourage the general use of demonstrated
technologies, EPA will evaluate the applicability of each
technology for specific sites and wastes, other than those
already tested, and will study the estimated costs of the
applications. The results are presented in the AAR. This
AAR synthesizes available information on PSI's perox-pure™
chemical oxidation technology and draws reasonable
conclusions regarding its range of applicability. This AAR
will be useful to decision makers considering using the
perox-pure™ technology. It represents a critical step in the
development and commercialization of the treatment
technology.
Each SITE demonstration evaluates a technology's
performance hi treating an individual waste at a particular
site. To obtain data with broad applicability, priority is given
to technologies that treat wastes frequently found at
Superfund sites. However, in many cases, wastes at other
sites will differ in some way from the waste at the
demonstration site. Therefore, the successful demonstration
of a technology at one site does not ensure its success at
other sites. Data obtained from the demonstration may
require extrapolation to estimate total operating ranges over
which the technology performs satisfactorily. Any
extrapolation of demonstration data should also be based on
other available information from case studies about the
technology.
The amount of available data for the evaluation of an
innovative technology varies widely. Data may be limited to
laboratory tests on synthetic wastes or may include
performance data on actual wastes treated by pilot- or full-
scale treatment systems. In addition, only limited
conclusions regarding Superfund applications can be drawn
from a single field demonstration. A successful field
demonstration does not necessarily ensure that a technology
will be widely applicable or that it will be fully developed to
commercial scale.
2.4 Technology Description
In April 1991, EPA learned that PSI was contracted by
Lawrence Livermore National Laboratory (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-pure™ technology into the SITE
demonstration program. Through a cooperative effort
between EPA ORD, EPA Region IX, LLNL, and PSI, the
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perox-pure™ technology was demonstrated at the LLNL site
under the SITE program.
2.4.1 Treatment Technology
The perox-pure™ chemical oxidation treatment system
was developed by 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 (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 of an atom or group of atoms is always
accompanied by the reduction of another atom or group of
atoms. Reduction is 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, and 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, a
powerful oxidant 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 (H2O2)
through photolysis. The photolysis of hydrogen peroxide
occurs when UV radiation (hu) is applied, as shown in the
following reaction:
H2O2 + hu -* 2 OH»
Thus, photolysis of hydrogen peroxide results in a
quantum yield of two hydroxyl radicals (OH>) 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
10s 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.
The principal operating parameters for the perox-pure™
technology are hydrogen peroxide dose, influent pH, and
flow rate (which determines hydraulic retention tune).
Typically, during treatability studies, initial values of these
parameters are selected based on (1) the technology
developer's experience and (2) the anticipated effects of the
operating parameters on the treatment system's
performance. These operating parameters are discussed
briefly below. Their effects on the system's performance are
discussed in detail in Section 3.
Hydrogen peroxide dose is selected based on treatment
unit configuration, contaminated water chemistry, and
contaminant oxidation rates. Because hydrogen peroxide is
a hydroxyl radical scavenger, excess hydrogen peroxide can
result in a net decrease in treatment efficiency. However, if
the hydrogen peroxide dose is low, hydroxyl radical
formation will also be low, decreasing treatment efficiency.
Therefore, a balance must be maintained between excess and
low levels of hydrogen peroxide.
Influent pH level controls the carbonate chemistry, which
can affect treatment efficiency. Because carbonate and
bicarbonate ions will scavenge hydroxyl radicals, groundwater
pH may need to be adjusted before treatment to shift the
carbonate equilibrium to carbonic acid, which is not a
scavenger.
Flow rate through the treatment system will determine
hydraulic retention time. Increasing or decreasing the flow
rate will affect treatment efficiency by changing the tune
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available for hydroxyl radical formation and contaminant
destruction.
2,4.2 System Components and Function
The perox-pure™ chemical oxidation systems are typically
assembled from 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 mam system components, other equipment
is used to address site-specific conditions or requirements,
including contaminated water characteristics and effluent
discharge limits. For example, Figure 2-1 presents a
schematic diagram of the main and ancillary components of
the perox-pure™ chemical oxidation system used for the
SITE demonstration (Model SSB-30).
For the SITE demonstration, a skid-mounted acid feed
module and a base feed module were used to adjust pH of
water before and after treatment, 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 volatile
organic compounds (VOC) including trichloroethene (TCE)
and tctrachloroethene (PCE). A spiking solution feed
module was used to spike effluent from cartridge filters with
chloroform; 1,1-dichloroethane (DCA); and 1,1,1-
trichloroethane (TCA) for certain demonstration runs. A
7,500-gallon 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 has six reaction chambers, or
reactors, with one UV lamp in each reactor. Each UV lamp
has a power rating of 5 kilowatts (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 are
periodically used to remove any suspended particles that
have coated the quartz tubes. In a coating environment, this
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 oxidation unit;
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 milligrams per liter (mg/L).
Sodium hydroxide is then added to readjust the pH to meet
discharge requirements.
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™ unit. Hydrogen peroxide and acid injection are
activated by switches on the control panel and are monitored
with flow meters.
2.4.3 Innovative Features of the Technology
Common methods for treating groundwater
contaminated with solvents and other organic compounds
include air stripping, steam stripping, carbon adsorption,
chemical oxidation, and biological treatment. As regulatory
requirements for secondary wastes and treatment by-
products became more stringent and expensive to comply
with, oxidation technologies have been known to offer a
major advantage over other treatment techniques: chemical
oxidation technologies destroy contaminants rather than
transferring them to another medium, such as activated
carbon or the ambient air. Also, chemical oxidation
technologies offer faster reaction rates than other
technologies, such as some biological treatment processes.
However, the oxidation of organics by ozone, hydrogen
peroxide, or UV radiation alone has kinetic limitations,
restricting its applicability to a narrow range of
contaminants. As a result of these limitations, conventional
chemical oxidation technologies have been slow to become
cost-competitive treatment options.
The combined use of UV radiation and hydrogen
peroxide in the perox-pure™ system increases the destruction
efficiency of the treatment system and allows for the
treatment of a wider range of contaminants. Hydroxyl
radicals formed by UV photolysis of hydrogen peroxide
rapidly oxidize the contaminants and exhibit little
contaminant selectivity.
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GROUNDWATER FROM
SITE 300
*-TO DISPOSAL
UV LAMP
REACTOR
OXIDATION UNIT
SPIKING
SOLUTION
Figure 2-1 perox-pure"* Chemical Oxidation Treatment System
The perox-pure™ treatment system produces no air
emissions and generates no sludge or spent media that
require further processing, handling, or disposal. Ideally,
end products include water, carbon dioxide, halides, and in
some cases, organic acids. However, other oxidizable species
present in the water (including metals in reduced form,
cyanide, and nitrite) can also be oxidized in the process and
can exert an additional oxidant demand.
Hydrogen peroxide is inexpensive, easy to handle, and
readily available. As a result, its use with UV radiation in
the perox-pure™ system offers considerable advantages over
expensive and difficult to handle chemicals.
Table 2-1 compares several treatment options for water
contaminated with VOCs. Similar comparisons can be made
for semivolatile organic compounds (SVOC), polychlorinated
biphenyls (PCB), and pesticides, although air stripping is not
generally applicable to these types of contaminants.
2.5 Key Contacts
Additional information on the perox-pure™ chemical
oxidation technology, the SITE program, and Site 300 at
LLNL can be obtained from the following sources:
1. The perox-pure™ Technology
Chris Giggy
Process Engineering Manager
Peroxidation Systems, Inc.
5151 East Broadway, Suite 600
Tucson, Arizona 85711
(602) 790-8383
2. The SITE Program
Norma Lewis
Section Chief, EPA Project Manager
EPA SITE Program
26 West Martin Luther King Drive
Cincinnati, Ohio 45268
(513) 569-7665
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Tibia 2-1 Comparison of Technologies for Treating VOCs in Water
Technology Advantages
Disadvantages
Air stripping
Steam stripping
Effective at high concentrations;
mechanically simple; relatively
inexpensive
Effective at all concentrations
Alf stripping with carbon adsorption of Effective at high concentrations
vapors
Air stripping with carbon adsorption of Effective at high concentrations; no
vapors and spent carbon regeneration carbon disposal costs; can reclaim the
product
Carbon adsorption
Biological treatment
parox-pura'" technology
Low air emissions; effective at high
concentrations
Low air emissions; relatively
inexpensive
No air emissions; no secondary waste;
VOCs destroyed
Inefficient at low concentrations; VOCs
discharged to air
VOCs discharged to air; high energy
consumption
Inefficient at low concentrations;
requires disposal or regeneration of
spent carbon
Inefficient at low concentrations; high
energy consumption
Inefficient at low concentrations;
requires disposal or regeneration of
spent carbon; relatively expensive
Inefficient at high concentrations; slow
rates of removal; sludge treatment and
disposal required
High energy consumption; not cost-
effective at high concentrations
3. The Lawrence Livermore National Laboratory, Site 300
Albert Lamarre
Site 300 Section Leader
Lawrence Livermore National Laboratory
7000 East Avenue
P.O. Box 808, L-619
Livermore, California 94550
(510) 422-0757
Shyam Shukla
Project Manager, Site 300
Lawrence Livermore National Laboratory
7000 East Avenue
P.O. Box 808, L-528
Livermore, California 94550
(510) 422-3475
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Section 3
Technology Applications Analysis
This section addresses the applicability of the
perox-pure™ chemical oxidation technology to treat water
contaminated with organic compounds. The vendor claims
regarding the applicability and performance of the
perox-pure™ technology are included in Appendix A.
Because results from the SITE demonstration provided an
extensive data base, evaluation of the technology's
effectiveness and its potential applicability to contaminated
sites is mainly based on these results, which are presented in
Appendix B. The SITE demonstration results are
supplemented by results from other applications of the
perox-pure™ technology, which are presented in Appendix C.
This section summarizes the effectiveness of the
perox-pure™ chemical oxidation technology and discusses the
following topics in relation to the applicability of the
perox-pure™ technology: factors influencing performance,
site characteristics, material handling requirements,
personnel requirements, potential community exposures, and
potential regulatory requirements.
3.1 Effectiveness of the perox-pure™ Technology
This section discusses the effectiveness of the
perox-pure™ technology based on results from the SITE
demonstration and three other case studies.
3.1.1 SITE Demonstration Results
The SITE demonstration was conducted at LLNL Site
300 in Tracy, California, over a 3-week period in September
1992. During the demonstration, a perox-pure™ unit (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 micrograins per liter
(;ttg/L), respectively. Other VOCs (such as chloroform;
DCA; 1,1-dichloroethene; 1,2-dichloroethene; and TCA)
were present at average concentrations below 15 /xg/L.
Groundwater was pumped from two wells into a 7,500-gallon
bladder tank to minimize 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.
The perox-pure™ chemical oxidation technology
demonstration performed under the SITE program had the
following primary objectives:
• 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 the
treatment.
The technology demonstration was conducted in three
phases. 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 evaluate the effectiveness of quartz tube
cleaning. The three phases are described below.
The principal operating parameters for the perox-pure™
system are hydrogen peroxide dose, influent pH, and flow
rate. During Phase 1 of the demonstration, each of these
operating parameters was varied to observe treatment system
performance under different conditions. Preferred operating
conditions, those under which the concentrations of spiked
groundwater effluent VOCs would be reduced to below
target levels, were then determined for the system. The
target levels for the VOCs are given in Appendix B.
11
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During Phase 2, groundwater was spiked with known
concentrations of contaminants, and reproducibility tests
wore conducted. Spiked groundwater contained 200 to 300
ftg/L each of DCA, TCA, and chloroform. 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.
Phase 3 evaluated the effectiveness of the quartz tube
wipers by performing two runs using spiked groundwater and
scaled and clean quartz tubes.
During the demonstration, samples were collected at the
following locations: treatment system influent, effluent from
Reactor 1, effluent from Reactor 2, effluent from Reactor 3,
and treatment system effluent. Samples were analyzed for
VOCs, SVOCs, total organic carbon (TOC), total carbon,
purgeable organic carbon (POC), total organic halides
(TOX), adsorbable organic halides (AOX), metals, pH,
alkalinity, turbidity, temperature, specific conductance,
hydrogen peroxide residual, and hardness, as applicable. In
addition, samples of influent to Reactor 1 and treatment
system effluent were collected and analyzed for acute toxicity
to freshwater organisms. Hydrogen peroxide, acid, and base
solutions were also sampled and analyzed to verify
concentrations.
Appendix B summarizes information from the SITE
demonstration, including (1) site characteristics,
(2) contaminated groundwater characteristics,
(3) perox-purew system performance, and (4) technology
evaluation results. Key findings of the demonstration are as
follows:
• For the spiked groundwater, PSI determined the
following preferred operating conditions: (1)
influent hydrogen peroxide level of 40 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 the detection limit
(5 jtg/L) and effluent chloroform and TCA levels
ranged from 15 to 30 pgfL. The average overall
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 the detection
limit (1 Mg/L) with corresponding removal
efficiencies of about 99.9 and 99.7 percent. The
effluent TCA levels ranged from 1.4 to 6.7 jug/L
with 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 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 system achieved average removal efficiencies of
38 percent and greater than 93 percent for TOC
and POC, respectively.
• The temperature of groundwater increased at a rate
of 12 °F per minute of UV radiation exposure in
the perox-pure™ 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.
3.1.2 Results of Other Case Studies
The perox-pure™ technology has been used to treat
contaminated water at approximately 80 sites. Results from
three of these applications are discussed as case studies in
Appendix C. A brief summary of the effectiveness of the
perox-pure™ technology at the three sites chosen as case
studies is presented below.
All three case studies represent full-scale, currently
operating commercial installations of perox-pure™ chemical
oxidation systems. The contaminants of concern hi these
case studies include acetone, isopropyl alcohol (IPA), TCE,
and pentachlorophenol (PCP). In the first case study, the
perox-pure™ system treated industrial wastewater containing
20 mg/L of acetone and IPA; the effluent met the discharge
limit of 0.5 mg/L. In the second case study, the perox-pure™
system treated groundwater that was used as a municipal
drinking water source. The groundwater initially contained
an average concentration of 150 Mg/L TCE. After
treatment, the effluent TCE level was 0.5 /tg/L, well below
the TCE drinking water standard of 5 /tg/L. In the third
case study, the perox-pure™ system treated groundwater at
a chemical manufacturing facility. The groundwater
contained 15 mg/L of PCP; treatment achieved the target
effluent PCP level of 0.1 mg/L.
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3.2 Factors Influencing Performance
Several factors influence the effectiveness of the
perox-pure™ 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.
3.2.1 Influent Characteristics
The perox-pure™ chemical oxidation technology is
capable of treating water containing a variety of organic
contaminants, including VOCs, SVOCs, pesticides,
polynuclear aromatic hydrocarbons (PAH), PCBs, 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 back through
the oxidation unit to improve overall removal efficiency.
The perox-pure™ system uses a chemical oxidation
process to destroy organic contaminants; therefore, other
species in the influent that consume oxidants are considered
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 UV 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.
3.2.2 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 molecule of hydrogen peroxide results in a yield of 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 result in a net decrease in treatment
efficiency. According to PSI, the perox-pure™ system
overcomes these limitations by using medium-pressure UV
lamps.
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 to any of
the individual oxidation reactors. 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 some hydroxyl radicals will be present throughout the
oxidation unit.
Influent pH controls the equilibrium among carbonate,
bicarbonate, and carbonic acid. 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
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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. la 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
did not observe this phenomenon in the range of hydraulic
retention times provided by the perox-pure™ system.
3.2.3 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. A brief summary of the
maintenance requirements for the UV lamp assembly and
other miscellaneous components is presented below.
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 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 ulterior 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 and may reduce 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.
3.3 Site Characteristics
In addition to influent characteristics and effluent
discharge requirements, site characteristics are important
when considering the perox-pure™ technology. Site-specific
factors can impact the application of the perox-pure™
technology, and these effects should be considered before
selecting the technology for remediation of a specific site.
Site-specific factors include support systems, site area and
preparation, site access, climate, utilities, and services and
supplies. Tables 4-1 and 4-2 in Section 4 identify examples
of categories that are specific to the perox-pure™ system and
to a hazardous waste remediation site.
3.3.1 Support Systems
To clean up contaminated groundwater, extraction wells
and a groundwater collection and distribution system must
be installed to pump groundwater to a central facility where
the perox-pure™ system is located. Because the perox-pure™
system is normally operated as a continuous flow-through
system during site remediation, installation of several
extraction wells may be required to provide a continuous
supply of groundwater. An equalization tank may be
required if flow rates from the groundwater wells fluctuate
or if contaminant concentrations vary. When installing a
groundwater collection and distribution system, preventive
measures should be considered to reduce volatile
contaminant losses.
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Before choosing the perox-pure™ technology, the
location, design, and installation of tanks, piping, and other
equipment or chemicals associated with any pretreatment
systems should be considered. Pretreatment is often desired
to remove oil and grease, suspended solids, or metals. Any
tanks that are part of pretreatment or other support systems
should be equipped with vapor control devices (for example,
floating lids) to prevent VOC losses.
If on-site facilities are not available for office and
laboratory work, a small building or shed may be required
near the treatment system. The on-site building should be
equipped with electrical power to run laboratory equipment
and should be heated or air-conditioned, depending on the
climate. The on-site laboratory should contain equipment
needed to perform simple analyses of the physical and
chemical water characteristics required to monitor treatment
system performance. Such characteristics may include pH,
hydrogen peroxide dose, and temperature.
3.3.2 Site Area and Preparation
The perox-pure™ units are available in several sizes,
ranging in combined UV lamp power from 10 to 720 kW.
The perox-pure™ units have operated at flow rates between
5 and several thousand gpm, depending on the required
hydraulic retention time. During the SITE demonstration,
a 30-kW perox-pure™ unit with a total volume of 15 gallons
was used. A 10- by 20-foot area was adequate for the
perox-pure™ unit and associated chemical feed units. Larger
systems would require slightly larger areas. Areas required
for influent and effluent storage tanks, if needed, will depend
on the number and size of tanks. Also, a 20- by 15-foot area
may be required for an office or laboratory building.
The area containing the perox-pure™ unit and tanks
should be relatively level and should be paved or covered
with compacted soil or gravel.
3.3.3 Site Access
Site access requirements for treatment equipment are
minimal. The site must be accessible to tractor-trailer trucks
of standard size and weight. The roadbed must be able to
support such a vehicle delivering the perox-pure™ system and
tanks.
3.3.4 Climate
According to PSI, below-freezing temperatures and
heavy precipitation do not affect the operation of the
perox-pure™ system. The system is designed to withstand
rain and snow and does not require heating or insulation,
because the chemical oxidation process generates heat,
increasing the water temperature about 12 °F per minute of
contact time. However, if below-freezing temperatures are
expected for a long period of time, chemical and influent
storage tanks and associated plumbing should be insulated
or kept in a heated shelter, such as a building or shed.
Housing the system also facilitates regular system checks and
maintenance. The perox-pure™ unit requires a high-voltage
power supply, which should also be protected from heavy
precipitation.
3.3.5 Utilities
The perox-pure™ system requires potable water and
electricity. Potable water is required for a safety shower, an
eye wash station, personnel decontamination, and cleaning
field sampling equipment. The perox-pure™ unit requires
480-volt, 3-phase electrical service. Electrical power for the
chemical feed modules can be supplied through the
perox-pure™ unit. Additional 110-volt, single-phase electrical
service is needed to operate the groundwater extraction well
pumps, light the office and laboratory building, and operate
on-site laboratory and office equipment.
A telephone connection or cellular phone is required to
order supplies, contact emergency services, and provide
normal communications.
3.3.6 Services and Supplies
A number of services and supplies are required for the
perox-pure™ technology. Most of these services and supplies
can be readily obtained.
If UV lamps, pumps, flow meters, or piping
malfunctions, an adequate on-site supply of spare parts is
needed. If an on-site parts inventory is not an option, site
proximity to an industrial supply center is an important
consideration. In addition, an adequate supply of chemicals,
such as hydrogen peroxide, sulfuric acid, and sodium
hydroxide, or proximity to a supply center carrying these
chemicals is essential.
Complex laboratory services, such as VOC and SVOC
analyses, that cannot usually be performed in an on-site field
laboratory require contracting a local analytical laboratory
for an ongoing monitoring program.
3.4 Material Handling Requirements
The perox-pure™ system does not generate treatment
residuals, such as sludge or spent media, that require further
processing, handling, or disposal. The chemical oxidation
unit and other components of the system, such as the
chemical feed units, are air-tight and produce no air
emissions. Material handling requirements for the
perox-pure™ technology include those for (1) pretreatment
materials and (2) treated water. These are described below.
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3.4.1 Pretreatment Materials
3.4.2 Treated Water
In general, pretreatment requirements for contaminated
water entering the perox-pure™ system are minimal.
Depending on the influent characteristics, pretreatment
processing may involve one or more of the following: oil
and grease removal, suspended solids removal, metals
removal, or pH adjustment to reduce carbonate and
bicarbonate levels. These pretreatment requirements are
discussed below.
Water containing visible, free, or emulsified oil and
grease requires pretreatment to separate and remove the oil
and grease. If not treated, oil and grease will scale UV
lamps and reduce UV transmission, which makes the
oxidation process less effective. Separated oil and grease
should be containerized and analyzed to determine disposal
requirements.
Because suspended solids can also reduce UV
transmission, water containing more than 30 mg/L of
suspended solids should be pretreated. Depending on the
concentration, cartridge filters, sand filters, or settling tanks
may be used to remove suspended solids. Solids removed
from the influent by pretreatment precipitation, filtration, or
settling should be dewatered, containerized, and analyzed to
determine whether they should be disposed of as hazardous
or nonhazardous waste.
Pretreatment also may be necessary for water containing
dissolved metals, such as iron and manganese. These metals
are likely to be oxidized in the perox-pure™ unit and are less
soluble at higher oxidation states under alkaline pH
conditions. After oxidation, the metals will tend to
precipitate as suspended soh'ds in the perox-pure™ unit,
resulting in UV lamp scaling. Removing these metals is
often advised; however, removal may depend on the
concentration of oxidizable metals in the contaminated
water. The economics of metals removal should be
compared to (1) predicted decreases in contaminant removal
efficiency without metals removal and (2) the economics of
more frequent UV lamp cleaning or replacement. Metals
removed from the influent by precipitation should be
containerized and analyzed to determine whether the metals
should be disposed of as hazardous or nonhazardous waste.
If the contaminated water contains bicarbonate and
carbonate ions at levels greater than 400 mg/L as calcium
carbonate, pH adjustments are typically performed in-line.
Carbonate and bicarbonate ions act as oxidant scavengers
and present an additional load to the treatment system. The
only material handling associated with pH adjustment
involves handling chemicals such as acids and bases; pH
adjustment should not create any waste streams requiring
disposal.
Treated water can be disposed of either on or off site.
Examples of on-site disposal options for treated water
include groundwater recharge or temporary on-site storage
for sanitary usage. Examples of off-site disposal options
include discharge into surface water bodies, storm sewers,
and sanitary sewers. Bioassay tests may be required in
addition to routine chemical and physical analyses before
treated water is disposed of. Depending on permit
requirements and treatment unit operating conditions,
treated water may require pH adjustment before discharge.
3.5 Personnel Requirements
Personnel requirements for the perox-pure™ system are
minimal. Generally, one operator, trained by PSI, conducts
a daily 30-minute system check. The unit operator should be
capable of performing the following: (1) filling chemical
feed tanks and adjusting chemical flow rates to achieve
desired doses; (2) operating the control panel on the
chemical oxidation unit; (3) collecting liquid samples and
performing simple physical and chemical analyses and
measurements (for example, pH, hydrogen peroxide
concentration, temperature, and flow rate);
(4) troubleshooting minor operational problems; and
(5) collecting samples for off-site analyses. Analytical work
requiring more technical skills, such as VOC analyses, can be
performed by a local laboratory. The frequency of sample
collection and analysis will depend on site-specific permit
requirements.
The unit operator should also have completed an
Occupational Safety and Health Act (OSHA) initial 40-hour
health and safety training course and an annual 8-hour
refresher course, if applicable, before operating the
perox-pure™ system at hazardous waste sites. The operator
also should participate in a medical monitoring program as
specified under OSHA requirements.
For remote sites, where daily system checks by an
operator are not feasible, the perox-pure™ system can be
monitored remotely, or it can be remotely operated and
monitored. 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.
3.6 Potential Community Exposures
The perox-pure™ system generates no chemical or
particulate air emissions. Therefore, the potential for on-site
personnel or community exposure to airborne contaminants
is low. If a system malfunction occurs, alarms will sound,
and all components of the system will shut off automatically.
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Contaminated-water pumps can be hard-wired to the perox-
pure™ unit control panel so that alarm conditions
automatically stop flow through the unit, reducing the
potential for a contaminated water release.
Hydrogen peroxide solution, which is a reactive
substance, presents the greatest chemical hazard associated
with the system. However, when handled appropriately, the
potential for exposure to hydrogen peroxide by on-site
personnel is low. Acids, bases, and hydrogen peroxide
required for the perox-pure™ system are typically stored in
polyethylene totes housed in metal frames or cages. The
relatively small volumes of hydrogen peroxide used by the
system and secure chemical storage practices result hi a low
potential threat of community exposure to hydrogen
peroxide.
3.7 Potential Regulatory Requirements
This subsection discusses regulatory requirements
pertinent to site remediation using the perox-pure™
technology. Regulations applicable to a particular
application of this technology will depend on site-specific
remediation logistics and the type of contaminated water
being treated. Table 3-1 provides a summary of the
potentially applicable regulations discussed below.
Depending on the characteristics of the water to be
treated, pretreatment or posttreatment may be required for
the successful operation of the perox-pure™ system. For
example, solids may need to be prefiltered using cartridge
filters, sand filters, or settling tanks. Metals, such as iron
and manganese, may need to be removed by precipitation.
Each pretreatment or posttreatment process may have
additional regulatory requirements that need to be
determined prior to use. This subsection focuses on
regulations for the perox-pure™ system only.
3.7.1 Comprehensive Environmental Response,
Compensation, and Liability Act
The Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA), as amended by
SARA of 1986, authorizes the federal government to respond
to releases into the environment of hazardous substances,
pollutants, or contaminants that may present an imminent
and substantial danger to public health or welfare (Federal
Register, 1990a). Remedial alternatives that significantly
reduce the volume, toxicity, or mobility of hazardous
materials and provide long-term protection are preferred.
Selected remedies must also be cost effective and protective
of human health and the environment.
Contaminated water treatment using the perox-pure™
system will generally take place on site, while treated water
discharge may take place either on site or off site. On-site
actions must meet all substantive state and federal applicable
or relevant and appropriate requirements (ARAR).
Substantive requirements pertain directly to actions or
conditions in the environment (for example, effluent
standards). Off-site actions must comply with legally
applicable substantive and administrative requirements.
Administrative requirements, such as permitting, facilitate
the implementation of substantive requirements.
EPA allows an ARAR to be waived for on-site actions.
Six ARAR waivers are provided by CERCLA: (1) interim
measures waiver, (2) equivalent standard of performance
waiver, (3) greater risk to health and the environment
waiver, (4) technical impracticability waiver, (5) inconsistent
application of state standard waiver, and (6) fund-balancing
waiver. Justification for a waiver must be clearly
demonstrated (EPA, 1988). Off-site remediations are not
eligible for ARAR waivers, and all substantive and
administrative applicable requirements must be met.
Additional regulations pertinent to use of the perox-
pure™ system are discussed below. No air emissions or
residuals (such as sludge or spent filter media) are generated
by the perox-pure™ system. Therefore, only regulations
addressing contaminated water treatment and discharge are
presented.
3.7.2 Resource Conservation and Recovery Act
The Resource Conservation and Recovery Act (RCRA),
as amended by the Hazardous and Solid Waste Amendments
of 1984, regulates management and disposal of municipal
and industrial solid wastes. The EPA and RCRA-authorized
states [listed in 40 Code of Federal Regulations (CFR) Part
272] implement and enforce RCRA and state regulations.
The perox-pure™ system has been used to treat water
contaminated with a variety of organic materials, including
solvents, pesticides, PAHs, and petroleum hydrocarbons.
Contaminated water treated by the perox-pure™ technology
will most likely be hazardous or sufficiently similar to
hazardous waste so that RCRA standards will be
requirements. Criteria for identifying hazardous wastes are
included in 40 CFR Part 261. Pertinent RCRA
requirements are discussed below.
If the contaminated water to be treated is determined to
be a hazardous waste, RCRA requirements for storage and
treatment must be met. The perox-pure™ system may
include tank storage. Tank storage of contaminated and
treated water (if the waters are RCRA hazardous) must
meet tank storage requirements of 40 CFR Parts 264 or 265,
Subpart J. Although ah- emissions are not associated with
the perox-pure™ system, any fugitive emissions from storage
tank vents would be subject to forthcoming RCRA
regulations (see 40 CFR Part 269) on air emissions from
hazardous waste treatment, storage, and disposal facilities.
When promulgated, these requirements will include
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Tfb'0 3-1 R*gul*t!ora Summtry
fat
CERCLA
Applicability
Superfund sites
Application to perox-pure'" Chemical Oxidation
System
The Superfund program authorizes and regulates
Citation
40 CFR Part 300
RCRA
CWA
SDWA
TSCA
FIFRA
OSHA
Superfund and RCRA
sites
Discharges to surface
water bodies
Water discharges,
water reinjection, and
sole-source aquifer
and wellhead
protection
PCB contamination
AEA and RCRA Mixed wastes
Pesticides
AH remedial actions
the cleanup of environmental contamination. It
applies to all CERCLA site cleanups.
RCRA defines and regulates the treatment, storage,
and disposal of hazardous wastes. RCRA also
regulates corrective action at generator, treatment,
storage, and disposal facilities.
NPDES requirements of CWA apply to both
Superfund and RCRA sites where treated water is
discharged to surface water bodies. Pretreatment
standards apply to discharges to POTWs.
Maximum contaminant levels and contaminant level
goals should be considered when setting water
cleanup levels at RCRA corrective action and
Superfund sites. (Water cleanup levels are also
discussed under RCRA and CERCLA.) Reinjection
of treated water would be subject to underground
injection control program requirements, and sole
source and protected wellhead water sources
would be subject to their respective control
programs.
If PCB-contaminated wastes are treated, TSCA
requirements should be considered when
determining cleanup standards and disposal
requirements. RCRA also regulates solid waste
containing PCBs.
AEA and RCRA requirements apply to the treatment,
storage, and disposal of mixed waste containing
both hazardous and radioactive components.
OSWER and DOE directives provide guidance for
addressing mixed waste.
FIFRA regulates pesticide manufacturing and
labeling. However, if pesticide-contaminated water
is treated, RCRA regulations will generally apply.
OSHA regulates on-site construction activities and
the health and safety of workers at hazardous waste
sites. Installation and operation of the system at
Superfund or RCRA sites must meet OSHA
requirements.
40 CFR Parts 260 to 270,
Part 280
40 CFR Parts 122 to 125,
Part 403
40 CFR Part 141
40 CFR Part 761
AEA and RCRA
40 CFR Part 165
29 CFR Parts 1900 to
1926
29 CFR Part 1910.120
(hazardous waste and
emergency response
operations)
Note: Acronyms used in this table are defined in text.
standards for emissions from equipment leaks and process
vents. Treatment requirements included in 40 Part 265,
Subpart Q (Chemical, Physical, and Biological Treatment)
would also apply. This subpart includes requirements for
automatic influent shut-off, waste analysis, and trial tests.
The perox-pure'11' system could also be used to treat
contaminated water at RCRA-regulated facilities.
Requirements for corrective action at RCRA-regulated
facilities will be included in 40 CFR Part, 264 Subpart F
(Regulated Units) and Subpart S (Solid Waste Management
Units), as well as 40 CFR Part 280 (Underground Storage
Tanks); these subparts generally will apply to remediation at
Superfund sites. The regulations include requirements for
initiating and conducting RCRA corrective actions,
remediating groundwater, and ensuring that corrective
18
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actions comply with other environmental regulations
(Federal Register, 1990b).
Water quality standards included in RCRA (such as
groundwater monitoring and protection standards), the Clean
Water Act (CWA), and the Safe Drinking Water Act
(SDWA) would be appropriate cleanup standards and would
apply to discharges of treated water or reinjection of treated
groundwater (EPA, 1989). The CWA and SDWA are
discussed below.
3.7.3 Clean Water Act
The CWA is designed to restore and maintain the
chemical, physical, and biological quality of navigable surface
waters by establishing federal, state, and local discharge
standards. If treated water is discharged to surface water
bodies or publicly-owned treatment works (POTW), CWA
regulations will apply. On-site discharges to surface water
bodies must meet substantive National Pollutant Discharge
Elimination System (NPDES) requirements, but do not
require a NPDES permit. Off-site discharges to a surface
water body require a NPDES permit and must meet NPDES
permit limits. Discharge to a POTW is considered an off-
site activity, even if an on-site sewer is used. Therefore,
compliance with substantive and administrative requirements
of the national pretreatment program is required. General
pretreatment regulations are included in 40 CFR Part 403.
Any local or state requirements, such as state
antidegradation requirements, must also be identified and
satisfied.
3.7.4 Safe Drinking Water Act
The SDWA, as amended hi 1986, required EPA to
establish regulations to protect human health from
contaminants in drinking water. EPA has developed the
following programs to achieve this objective: (1) drinking
water standards program, (2) underground injection control
program, and (3) sole-source aquifer and wellhead
protection programs.
SDWA primary, or health-based, and secondary, or
aesthetic, MCLs will generally apply as cleanup standards for
water that is, or may be, used for drinking water supply. In
some cases, such as when multiple contaminants are present,
alternate concentration limits (ACL) may be used.
CERCLA and RCRA standards and guidance should be
used hi establishing ACLs (EPA, 1987a).
Water discharge through injection wells is regulated by
the underground injection control program. Injection wells
are categorized hi Class I through V, depending on their
construction and use. Reinjection of treated water involves
Class IV (reinjection) or Class V (recharge) wells and
should meet requirements for well construction, operation,
and closure.
The sole-source aquifer protection and wellhead
protection programs are designed to protect specific drinking
water supply sources. If such a source is to be remediated
using the perox-pure™ system, appropriate program officials
should be notified, and any potential regulatory requirements
should be identified. State groundwater antidegradation
requirements and water quality standards may also apply.
3.7.5 Toxic Substances Control Act
Testing, premanufacture notification, and record-keeping
requirements for toxic substances are regulated under the
Toxic Substances Control Act (TSCA). TSCA also includes
storage requirements for PCBs (see 40 CFR Part 761.65).
The perox-pure™ system may be used to treat water
contaminated with PCBs, and PCB storage requirements
would apply to pretreatment storage of PCB-contaminated
water. The SDWA MCL for PCBs is 0.05 /*g/L; this MCL
would generally be the treatment standard for groundwater
remediation at Superfund sites and RCRA corrective action
sites. RCRA land disposal requirements for PCBs (see 40
CFR Part 268) may also apply, depending on PCB
concentrations. For example, liquid hazardous waste
containing PCB concentrations between 50 and 499 ppm that
will be treated by incineration or an equivalent method will
meet the requirements of 40 CFR part 761.70.
3.7.6 Mixed Waste Regulations
Mixed waste contains both radioactive and hazardous
components, as defined by the Atomic Energy Act (AEA)
and RCRA, and is subject to the requirements of both acts.
When the application of both regulations results hi a
situation that is inconsistent with the AEA (for example, an
increased likelihood of radioactive exposure), ABA
requirements supersede RCRA requirements. Use of the
perox-pure™ system at sites with radioactive contamination
might involve the treatment or generation of mixed waste.
The EPA OSWER, hi conjunction with the Nuclear
Regulatory Commission, has issued several directives to
assist in the identification, treatment, and disposal of low-
level radioactive, mixed waste. Various OSWER directives
include guidance on defining, identifying, and disposing of
commercial, mixed, low-level radioactive and hazardous
waste (EPA, 1987b). If the perox-pure™ system is used to
treat low-level mixed wastes, these directives should be
considered. If high-level mixed waste or transuranic mixed
waste is treated, internal orders from the U.S. Department
of Energy (DOE) should be considered when developing a
protective remedy (DOE, 1988).
3.7.7 Federal Insecticide, Fungicide, and
Rodenticide Act
The perox-pure™ technology can treat water
contaminated with pesticides. EPA regulates pesticide
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product sale, distribution, and use through product licensing
or registration under the authority of the Federal Insecticide,
Fungicide, and Rodenticide Act (FIFRA) (see 40 CFR Part
165). Use of a pesticide product in a manner inconsistent
with its labeling violates FIFRA. Compliance with FIFRA
by following labeling directions may not be required at
Supcrfund or RCRA corrective action sites, because the
pesticide may be a RCRA hazardous waste at that point. In
such cases, requirements for hazardous wastes containing
pesticide constituents must be met.
3.7.8 Occupational Safety and Health Act
OSHA regulations, contained in 29 CFR Parts 1900
through 1926, are designed to protect worker health and
safety. Both Superfund and RCRA corrective actions must
meet OSHA requirements, particularly Part 1910.120,
Hazardous Waste Operations and Emergency Response.
Part 1926, Safety and Health Regulations for Construction,
applies to any on-site construction activities. For example,
electric utility hookups for the perox-pure™ system must
comply with Part 1926, Subpart K, Electrical. Product
chemicals, such as hydrogen peroxide, sulfuric acid, and
sodium hydroxide, used with the perox-pure™ system must be
managed in accordance with OSHA requirements (for
example, Part 1926, Subpart D, Occupational Health and
Environmental Controls, and Subpart H, Materials Handling,
Storage, and Disposal). Any more stringent state or local
requirements must also be met.
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Section 4
Economic Analysis
This section presents cost estimates for using the perox-
pure™ system to treat groundwater. Two cases, based on
groundwater characteristics, are presented. In Case 1, the
groundwater contains both contaminants that are difficult to
oxidize and contaminants that are easy to oxidize. In Case 2,
the groundwater contains only contaminants that are easy to
oxidize. In each case, treatment costs are compared at three
different flow rates: 10 gpm, 50 gpm, and 100 gpm.
Cost estimates presented in this section are based
primarily on data compiled during the SITE demonstration.
Costs have been placed in 12 categories applicable to typical
cleanup activities at Superfund and RCRA sites (Evans,
1990). Costs are presented hi April 1993 dollars and are
considered to be order-of-magnitude estimates with an
accuracy of plus 50 percent and minus 30 percent.
Table 4-1 presents a breakdown of costs for the 12
categories for Case 1, and Table 4-2 presents those costs for
Case 2. The tables also present total one-time costs and
total annual O&M costs; the total costs for a hypothetical,
long-term, groundwater remediation project; the net present
values of the long-term project; and the costs per 1,000
gallons of water treated. Both tables highlight in boldface
type the direct cost associated with using the perox-pure™
system. Each table concludes with a presentation of total
direct one-time costs, total direct annual O&M costs, and
the direct costs per 1,000 gallons of water treated.
4.1 Basis of Economic Analysis
A number of factors affect the estimated costs of
treating groundwater with the perox-pure™ chemical
oxidation system. Factors affecting costs generally include
flow rate, type and concentration of contaminants,
groundwater chemistry, physical site conditions, geographical
site location, contaminated groundwater plume size, and
treatment goals.
The perox-pure™ technology can treat several types of
liquid wastes, including contaminated groundwater, landfill
leachate, and industrial wastewater. Contaminated
groundwater was selected for this economic analysis because
it is commonly found at Superfund and RCRA corrective
action sites and because this waste treatment scenario
involves most of the cost categories. In addition, two
groundwater remediation cases based on groundwater
characteristics are analyzed. In Case 1, the groundwater
contains five contaminants, three of which are difficult to
oxidize and two of which are easy to oxidize. In Case 2, the
groundwater contains two contaminants that are easy to
oxidize. The following presents the assumptions and
conditions as they apply to each case. Next, the assumptions
and conditions used only for Case 1 are presented, and then
those used only for Case 2.
For each case, this analysis assumes that the
perox-pure™ system will treat contaminated groundwater on
a continuous flow cycle, 24 hours per day, 7 days per week.
Based on this assumption, during a 1-year period, the 10-
gpm unit will treat about 5.2 million gallons, the 50-gpm unit
will treat about 26 million gallons, and the 100-gpm unit will
treat about 52 million gallons. Because most groundwater
remediation projects are long-term, this analysis assumes
that a treatment project will last 50 years using the 10-gpm
flow rate, 10 years using the 50-gpm flow rate, and 5 years
at the 100-gpm flow rate. Treating groundwater at these
rates involves remediation of a contaminated groundwater
plume that contains approximately 260 million gallons of
water. While it is difficult in practice to determine both the
volume of groundwater to treat and the actual duration of a
project, these figures are used in order to perform this
economic analysis.
The total costs for a groundwater remediation project
for each case and each flow rate scenario are presented as
future values. Using the time, periods described above, this
analysis assumes a 5 percent inflation rate to estimate the
total costs. The future values are then presented as a net
present value using a discount rate of 5 percent. A higher
discount rate will make the initial costs weigh more heavily
in the calculation, and a lower discount rate will make the
future operating costs weigh more heavily. Because the costs
of demobilization will occur at the end of the project, the
appropriate future values of those costs presented in the
tables were used in calculating the final values. The costs
21
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Ttbta 4-1 Costs Associated with the perox-pure™ Technology - Case 1
Estimated Costs (1993 $)
Cost Categories
SHa Preparation (a)
Administrative
Trfftibility Study
System Design
Mobflizttion
Permitting and Regulatory Requirements (a)
Capital Equipment (a)
Extraction Wells, Pumps, and Piping
Shatter Building
Treatment Equipment
AuxiHary Equipment
Startup (a)
Labor (b)
Operations Stiff (c)
Health and Safety Refresher Course
Consumables and Supplies (b)
Hydrogen Peroxide
Suffurfc Add
Sodium Hydroxide
Cartridge Filters
Carbon Columns
PPE
Disposal Drums for PPE
UV Lamps
Sampling Supplies
Propane
Utilities (b)
Treatment System
Auxiliary Equipment
Effluent Treatment and Disposal (c)
Residuals and Waste Shipping and
Handling (b)
Analytical Services (b)
Maintenance and Modifications (b)
Treatment System
Auxiliary Equipment
Demobilization (a)
Trettment System
Alt Other
Total One-Time Costs
Total Annual O&M Costs
Qroundwatar Remediation:
Total Costs (d,e)
Net Present Value (0
Costs per 1,000 Gallons (g)
Tottt pef ox-pure" direct one-time costs
Total ptfox-pure*1 direct O&M costs
Costs per 1,000 Gallons—Direct Costs (g)
10gpm
$168,000
41,000
819,000
5,000
39,000
13,000
12,000
0
6,000
24,000
22,000
40,000
$1,073,000
$116,000
$25,776,000
$9,411,000
$36
$144,000
$64,000
$19
35,000
5,000
120,000
8,000
146,000
455,000
110,000
108,000
36,000
3,000
450
600
2,000
200
1,000
600
50
4,500
1,000
3,000
9,200
2,800
11,OOO
10,800
10,OOO
30,000
SOgpm
$171,000
45,000
906,000
5,000
39,000
30,000
60,000
0
6,000
24,000
29,000
40,000
$1,167,000
$188,000
$3,558,000
$2,747,000
$11
$227,000
$125,000
$5
35,000
5,000
123,000
8,000
158,000
455,000
185,000
108,000
36,000
3,000
2,200
3,000
10,000
200
1,000
600
50
9,000
1,000
3,000
45,900
13,800
18,500
10,800
10,000
30,000
100 gpm
$171,000
51,000
1,015,000
35,000
5,000
123,000
8,000
158,000
455,000
290,000
5,000
39,000
54,000
119,000
0
8,000
24,000
40,000
40,000
$1,283,000
$285,000
$2,863,000
$2,479,000
$10
$342,000
$205,000
$5
112,000
36,000
3,000
4,450
6,000
20,000
200
1,000
600
50
18,000
1,000
3,000
91,700
27,500
29,000
11,200
1O,000
30,000
Notes:
Hsms In bold denote pernx-pure™ system direct costs
a One-time costs
b Annual O&M costs
c See text for explanation of these costs
d Future value using annual inflation rate of 5 percent
0 To complete this project, it is assumed that the 10-gpm flow rate will take 50 years, the 50-gpm flow rate will take 10 years, and the
100-gpm flow rate w!H take 5 years to treat 260 million gallons total.
f Annual discount rate of 5 percent
g Presented as a net present value using the same assumptions used elsewhere in this table.
22
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Table 4-2 Costs Associated w/th the perox-puro"4 Technology - Case 2
Cost Categories
Site Preparation (a)
Administrative
Treatability Study
System Design
Mobilization
Permitting and Regulatory Requirements (a)
Capital Equipment (a)
Extraction Wells, Pumps, and Piping
Shelter Building
Treatment Equipment
Auxiliary Equipment
Startup (a)
Labor (b)
Operations Staff (c)
Health and Safety Refresher Course
Consumables and Supplies (b)
Hydrogen Peroxide
Sulfuric Acid
Sodium Hydroxide
Cartridge Filters
Carbon Columns
PPE
Disposal Drums for PPE
UV Lamps
Sampling Supplies
Propane
Utilities (b)
Treatment System
Auxiliary Equipment
Effluent Treatment and Disposal (c)
Residuals and Waste Shipping and
Handling (b)
Analytical Services (b)
Maintenance and Modifications (b)
Treatment System
Auxiliary Equipment
Demobilization (a)
Treatment System
All Other
Total One-Time Costs
Total Annual O&M Costs
Groundwater Remediation:
Total Costs (d,e)
Net Present Value (f)
Costs per 1,000 Gallons (g)
Total perox-purem direct one-time costs
Total perox-pure"' direct O&M costs
Costs per 1,000 Gallons-Direct Costs (g)
Wgpm
$168,000
38,000
764,000
5,000
39,000
10,000
4,000
0
6,000
24,000
16,000
40,000
$1,015,000
$99,000
$25,159,000
$8,091,000
$31
$84,000
$49,OOO
$15
Estimated Costs
35,000
5,000
120,000
8,000
146,000
455,000
55,OOO
108,000
36,000
3,000
3OO
600
2,000
200
1,000
600
50
1,500
1,000
3,000
3,100
900
5,500
10,800
10,000
30,000
(1993 $)
500pm
$171,000
39,000
776,000
5,000
39,000
22,000
4,000
0
6,000
24,000
16,000
40,000
$1,032,000
$111,000
$2,453,000
$1,894,000
$7
684,000
$61,000
$3
35,000
5,OOO
123,000
8,000
158,000
455,000
55,000
108,000
36,000
3,000
1,600
3,OOO
10,000
200
1,000
600
50
1,50O
1,000
3,000
3,100
900
5,500
10,800
10,000
30,000
100 gpm
$171,000
39,000
780,000
5,000
39,000
38,000
8,000
0
8,000
24,000
17,000
40,000
$1,036,000
$134,000
$1,787,000
$1,547,000
$6
$84,OOO
$80,000
$2
35,000
5,000
123,000
8,000
158,000
455,000
55,000
112,000
36,000
3,000
3,100
6,000
20,000
200
1,000
600
50
3,OOO
1,000
3,000
6,100
1,800
5,500
11,200
10,000
30,000
Hems in bold denote perox-pure™ system direct costs
a One-time costs
b Annual O&M costs
See text for explanation of these costs
Future value using annual inflation rate of 5 percent
To complete this project, it is assumed that the 10-gpm flow rate will take 50 years, the 50-gpm flow rate will take 10 years, and the
100-gpm flow rate will take 5 years to treat 260 million gallons total.
Annual discount rate of 5 percent
Presented as a net present value using the same assumptions used elsewhere in this table.
23
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per 1,000 gallons treated are derived from the net present
values. Capital equipment is not depreciated in this
economic analysis.
Further assumptions about groundwater conditions and
treatment for each case include the following:
• Any suspended solids present in groundwater are
removed before entering the perox-pure™ system.
• Alkalinity is about 250 mg/L as calcium carbonate.
• The influent has a pH of 8 that is lowered to 5.5 via
pretreatment.
• The treated effluent has a pH between 4 and 5 that
is adjusted to between 6.5 and 8.5 via posttreatment
to meet discharge standards.
This analysis assumes that treated water for each case
will be discharged to surface water, and MCLs specified in
the SDWA are the treatment target levels. Based on results
of the SITE demonstration, the perox-pure™ system should
achieve these levels.
The following assumptions were also made for each case
in this analysis:
• The site is a Superfund site located in a rural area
of the Midwest.
• Contaminated water is located in a shallow aquifer.
• The groundwater contains negligible amounts of
iron and manganese and will not require
pretreatment for metals.
• Suitable site access roads exist.
• Utility lines, such as electricity and telephone lines,
exist overhead on site.
• A 4,000-square-foot building will be needed to
house the treatment system and auxiliary equipment
for all three flow rate scenarios.
• The treatment system operates automatically.
• One technician will be required to operate the
equipment, collect all required samples, and
perform equipment maintenance and minor repairs.
• One treated water sample and one untreated water
sample will be collected daily to monitor system
performance.
• Treated and untreated water samples will be
collected monthly and analyzed off site for VOCs.
• Labor costs associated with major repairs are not
included.
• PSI will dispose of spent UV lamps from the perox-
pure™ system at no cost.
For Case 1, the chemical feed rates and the hydraulic
retention time required to meet treatment goals listed in
Appendix B were estimated based on the perox-pure™
system performance during Runs 10,11, and 12 of the SITE
demonstration. Based on the demonstration, VOC levels in
the groundwater, and perox-pure™ system operating
conditions assumed for Case 1 include the following:
• Chloroform at 200
• DCA at 150
• TCA at 130
• TCE at 700
• PCE at 100 |tg/L
• Hydrogen peroxide dose of 85 mg/L
• Hydraulic retention time of 0.75 minute
For Case 2, the chemical feed rates and hydraulic
retention time required to meet treatment goals listed in
Appendix B were estimated based on the perox-pure™
system performance during Run 8. Based on the
demonstration, the VOC levels in the groundwater, and
perox-pure™ system operations include the following:
• TCE at 1,070 /ig/L
• PCE at 108
• Hydrogen peroxide dose of 60 mg/L
• Hydraulic retention time of 0.05 minute
4.2 Cost Categories
Cost data associated with the perox-pure™ technology
have been assigned to the following 12 categories: (1) site
preparation; (2) permitting and regulatory requirements; (3)
capital equipment; (4) startup; (5) labor; (6) consumables
and supplies; (7) utilities; (8) effluent treatment and disposal;
(9) residuals and waste shipping and handling; (10) analytical
services; (11) maintenance and modifications; and (12)
demobilization. Costs associated with each category are
presented in the sections that follow. Each section presents
24
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the costs that are identical for each case. If applicable,
differences between the costs of Case 1 and Case 2 are then
discussed. Some categories end with a summary of the
significant costs within the category. All direct costs
associated with operating the perox-pure™ system are
identified as perox-pure™ direct costs; all costs associated
with the hypothetical remediation and auxiliary equipment
are identified as groundwater remediation costs.
4.2.1 Site Preparation Costs
Site preparation costs include administrative, treatability
study, system design, and mobilization costs. For this
analysis, administrative costs, such as legal searches, access
rights, and other site planning activities, are associated with
a groundwater remediation project and are estimated to be
$35,000.
A treatability study will need to be performed to
determine the appropriate specifications of the perox-pure™
system for the site as well as the amounts of chemicals and
reagents needed for optimal performance. PSI estimates the
cost for this study, which is directly associated with operating
the perox-pure™ treatment system, to be about $5,000.
System design costs include designing the site layout and
the treatment system operations and are associated with a
groundwater remediation project. Design costs are typically
20 percent of the total construction costs. Construction costs
include constructing a shelter building for the treatment and
auxiliary equipment and installing extraction wells and piping
(see Capital Equipment Costs). Construction costs are
about $600,000 for the 10-gpm flow rate scenario and about
$613,000 for the 50- and 100-gpm flow rate scenarios.
Therefore, design costs would be about $120,000 for the 10-
gpm flow rate scenario and about $123,000 for the 50- and
100-gpm flow rate scenarios.
Mobilization involves transporting all equipment to the
site, assembling it, performing optimization and shakedown
activities, and operator training. Transportation costs are
site-specific and will depend on the location of the site in
relation to all equipment vendors. The skid-mounted
perox-pure™ system is delivered to each site hi one
semitrailer from Tucson, Arizona. PSI will position the
system and perform optimization and shakedown activities as
part of the mobilization. Initial operator training is needed
to ensure safe, economical, and efficient operation of the
system. PSI estimates mobilization costs to be about $8,000
and to take about 1 week to complete.
For each case, total site preparation costs are estimated
to be $168,000 for the 10-gpm flow rate scenario and
$171,000 for the 50- and 100-gpm flow rate scenarios.
System design constitutes about 71 percent of the total site
preparation costs, and administrative costs make up about 20
percent. As such, about 7 percent of the site preparation
costs are associated with the perox-pure™ treatment system.
4.2.2 Permitting and Regulatory Requirements
Costs
Permitting and regulatory costs depend on whether
treatment is performed at a Superfund or a RCRA
corrective action site and on how treated effluent and any
solid wastes generated are disposed of. Superfund sites
require remedial actions to be consistent with ARARs of
environmental laws, ordinances, regulations, and statutes,
including federal, state, and local standards and criteria. In
general, ARARs must be determined on a site-specific basis.
RCRA corrective action sites require additional monitoring
records and sampling protocols, which can increase the
permitting and regulatory costs by an additional 5 percent.
Permitting and regulatory costs are associated with a
groundwater remediation project and are assumed to be
about 5 percent of the total capital equipment costs for a
treatment operation that is part of a Superfund site
remediation project. This estimate does not include annual
discharge permit costs, which may vary significantly
depending on state and local requirements.
For Case 1, permitting and regulatory costs are
estimated to be $41,000 for the 10-gpm flow rate scenario;
$45,000 for the 50-gpm flow rate scenario; and $51,000 for
the 100-gpm flow rate scenario. For Case 2, these costs are
estimated to be $38,000 for the 10-gpm, and $39,000 for the
50- and 100-gpm flow rate scenarios. The costs hi Case 2
are similar because total capital equipment costs are nearly
the same for each flow rate. The difference in costs between
the two cases is due to the lower perox-pure™ system capital
equipment costs associated with Case 2.
4.2.3 Capital Equipment Costs
Capital equipment costs include installing extraction
wells; constructing a building to shelter the treatment and
auxiliary equipment; and purchasing and installing all
treatment equipment, including auxiliary equipment and
monitoring equipment.
Extraction well installation costs are associated with a
groundwater remediation project and include installing the
well and pump and connecting the pumps, piping, and valves
from the wells to the perox-pure™ system. This analysis
assumes that four, 150-foot extraction wells will be required
to maintain the flow rate in each scenario. Extraction wells
can be installed at about $150 per foot per well. Total well
construction costs for each case will be about $90,000.
Pumps, piping, and valve connection costs are associated
with a groundwater remediation project and will depend on
the following factors: the number of extraction wells needed,
25
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the flow rate, the distance of the extraction wells from the
treatment system, and the climate of the area. This analysis
assumes that four extraction wells are located about 200 feet
from the pcrox-pure™ system. Four 2.5-gpm pumps will be
required to maintain a 10-gpm flow rate. The total cost for
these four pumps is about $8,000. Four 12.5-gpm pumps will
be required to maintain a 50-gpm flow rate, at a total cost
of about $20,000. Four 25-gpm pumps will be required to
maintain a 100-gpm flow rate, at a total cost of about
$20,000. Piping and valve connection costs are about $60 per
foot, including underground installation. Therefore, total
piping costs will be an additional $48,000.
A building will need to be constructed to shelter the
perox-pure™ system and all auxiliary equipment, because the
site is assumed to be located in the Midwest, and
remediation will likely be conducted in adverse weather
conditions. The building will require about 4,000 square feet
and will cost about $100 per square foot, including
construction and materials, for a total cost of $400,000.
Costs associated with designing the building are included in
the system design costs (see Site Preparation Costs).
Heating costs included in this analysis assume that the
building site is remote and will require a propane or liquid
petroleum gas heating system with a 3,000-gallon tank and
fuel delivery service. The propane tank, heating unit, and
duct work will cost about $25,000 to install. Finally, utility
connections to the building are estimated to cost $30,000.
Total building costs for each case will be about $455,000 for
each flow rate scenario and are associated with a
groundwater remediation project.
Treatment equipment typically consists of chemical feed
modules and the skid-mounted components of the
perox-pure™ system. The cost of the perox-pure™ unit will
vary depending on the size of the unit needed. PSI identifies
unit sizes by their kW usage. To meet the treatment goals
for Case 1, PSI estimates that the 10-gpm unit will require
15 kW, the 50-gpm unit will require 75 kW, and the 100-gpm
unit will require 150 kW. However, the nearest
commercially available perox-pure™ units PSI offers are 30
kW, 90 kW, and 180 kW respectively. These will cost
$100,000, $175,000, and $280,000 respectively. PSI
recommends turning off any lamps in excess of the necessary
electrical power.
To meet the treatment goals of Case 2, PSI estimates
that the 10-gpm unit will require 1 kW, the 50-gpm unit will
require 5 kW, and the 100-gpm unit will require 10 kW.
However, the nearest commercially available unit PSI offers
is 10 kW. Therefore, perox-pure™ unit cost will be $45,000
for each flow rate scenario of Case 2.
This analysis assumes that the site treatment scenarios
for each case will include acid feed and base feed modules.
The chemical feed modules consist of one 2,000-gallon
hydrogen peroxide tank and two feed pumps, one 500-gallon
acid storage tank and two feed pumps, and one 500-gallon
base storage tank and two feed pumps. The total additional
cost for all three chemical feed modules for each case will be
about $10,000.
Auxiliary equipment considered in this analysis is
associated with a groundwater remediation project and
includes one sedimentation tank, two equalization tanks, two
cartridge filters, one filter press, and monitoring equipment.
One 2,000-gallon sedimentation tank will be located
downstream of the extraction wells and upstream of the
cartridge filters to allow solids to settle out before treatment.
This tank costs about $5,000. Two 5,000-gallon equalization
tanks are needed to minimize fluctuations in VOC
concentrations. While one tank is being filled, the other will
be emptied. These tanks will be located downstream of the
cartridge filters. Both equalization tanks will cost a total of
about $14,000. All tanks used during the remediation are
assumed to have closed tops with vents. A venting system
that includes duct work and carbon columns will be needed
to eliminate fugitive emissions from the tanks. This venting
system will cost about $25,000.
Filtration will be required to remove any suspended
solids from the sedimentation tank effluent. Two cartridge
filters will be installed on the perox-pure™ feed line.
Cartridges cost about $2,000 each for the 10- and 50-gpm
flow rate scenarios, for a total cost of $4,000. Cartridges
cost about $4,000 each for the 100-gpm flow rate scenario,
for a total cost of $8,000. The costs of replacement filters
are included in Consumables and Supplies Costs.
A filter press will be needed to dewater the sediment
collected in the sedimentation tank and any other tanks that
may accumulate sediment. The size of the filter press will
be determined after a bench-scale study is performed. This
analysis assumes that a 4-cubic-foot filter press will be used,
at a cost of about $50,000.
Monitoring equipment includes a spectrophotometer to
measure hydrogen peroxide concentration, a pH meter, a
thermometer, and other as needed. This equipment can be
purchased for about $10,000.
Total auxiliary equipment costs, including venting duct
work, for the 10- and 50-gpm flow rate scenarios will be
about $108,000. The total auxiliary equipment costs for the
100-gpm flow rate scenario will be about $112,000.
For Case 1, total capital costs will be about $819,000 for
the 10-gpm flow rate scenario; $906,000 for the 50-gpm flow
rate scenario; and $1,015,000 for the 100-gpm flow rate
scenario. Of these costs, only the perox-pure™ and feed
modules are associated with operating the perox-pure™
system. The costs of these components account for about 13
percent of total capital costs for the 10-gpm flow rate
scenario, 20 percent for the 50-gpm flow rate scenario, and
26
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19 percent for the 100-gpm flow rate scenario. In addition,
the shelter building accounts for about 56 percent of the
total capital costs for the 10-gpm flow rate scenario, about
50 percent for the 50-gpm flow rate scenario, and about 45
percent for the 100-gpm flow rate scenario.
For Case 2, total capital costs will be about $764,000 for
the 10-gpm flow rate scenario; $776,000 for the 50-gpm flow
rate scenario; and $780,000 for the 100-gpm flow rate
scenario. Of these costs, only the perox-pure™ system and
feed modules are associated with operating the perox-pure™
system. The costs of these components account for about 7
percent of total capital costs for the each flow rate scenario.
In addition, the shelter building accounts for about 60
percent of the total capital costs for the 10-gpm flow rate
scenario, about 59 percent for the 50-gpm flow rate scenario,
and about 58 percent for the 100-gpm flow rate scenario.
The cost differences between the two cases are due to lower
system costs associated with Case 2.
4.2.4 Startup Costs
Startup costs include the cost of developing a health and
safety program. For each case, developing a health and
safety program will also include providing a 40-hour health
and safety training course. This cost is associated with a
groundwater remediation project and is estimated to cost
about $5,000.
4.2.5 Labor Costs
Labor costs include the total staff needed for operating
and maintaining the perox-pure™ system, conducting an
annual health and safety refresher course, and medical
monitoring. The labor wage 'rates provided in this analysis
do not include overhead or fringe benefits. Once the system
is functioning, it is assumed to operate continuously at the
designed flow rate, except during routine maintenance. One
operator will monitor the equipment, make any required
hydrogen peroxide dose and pH adjustments, perform
routine maintenance, and perform routine monitoring and
sample analysis. PSI estimates that under normal operating
conditions, an operator will be required to work only 3.5
hours per week. However, because finding a person willing
to work for this short period of time may be difficult; this
analysis assumes that the operator will work 8 hours during
the weekdays, and 2 hours, at time and one-half, during each
day of the weekend. Annual staff costs for each case will be
about $36,000. The annual health and safely refresher
course and medical monitoring are associated with a
groundwater remediation project and will cost about $3,000
per person.
For each case, total annual labor costs will be about
$39,000. Of these costs, about 92 percent is associated with
operating the perox-pure™ treatment system.
4.2.6 Consumables and Supplies Costs
Consumables. and supplies costs include hydrogen
peroxide, sulfuric acid and sodium hydroxide solutions for
pH adjustment, cartridge filters, activated carbon columns,
disposable personal protective equipment (PPE) and PPE
disposal drums, UV lamps, sampling supplies, and propane.
Costs of these items are discussed below.
Hydrogen peroxide is commercially available in solutions
of 30 to 50 percent by weight. It can be purchased hi bulk,
delivered to the site when needed, and stored in a 2,000-
gallon tank (see Capital Equipment Costs). Hydrogen
peroxide has a shelf life of over 1 year and a density of
about 10 pounds per gallon. A 50 percent solution can be
purchased for about $0.12 per pound including delivery; this
cost is associated with operating the perox-pure™ treatment
system. The quantities of hydrogen peroxide consumed
depend on the system flow rate and the waste characteristics.
Based on the SITE demonstration, the annual hydrogen
peroxide costs for the 10-gpm flow rate scenario would be
about $450 for Case 1 and $300 for Case 2. Annual
hydrogen peroxide costs for the 50-gpm flow rate scenario
would be about $2,200 for Case 1 and $1,600 for Case 2. For
the 100-gpm flow rate scenario, annual hydrogen peroxide
costs would be about $4,450 for Case 1 and $3,100 for
Case 2.
This analysis assumes sulfuric acid will be used to adjust
pH before treatment, and sodium hydroxide will be used to
adjust pH after treatment. In addition, this analysis assumes
that a 93 percent solution of sulfuric acid can be purchased
in bulk, delivered to the site when needed, and stored in a
500-gallon tank (see Capital Equipment Costs). Sulfuric acid
has a shelf life of over 1 year and a density of 15 pounds per
gallon. It can be purchased for about $0.09 per pound. The
quantities of sulfuric acid consumed depend on the flow rate
and the initial pH of the contaminated groundwater. Based
on the SITE demonstration, annual sulfuric acid costs for the
10-gpm flow rate scenario would be about $600 for each
case. Annual acid costs for the 50-gpm flow rate scenario
would be about $3,000 for each case. For the 100-gpm flow
rate scenario, annual acid costs would be about $6,000 for
each case.
Sodium hydroxide solution has a shelf life of over 1 year
and a density of 15 pounds per gallon. A 50 percent solution
of sodium hydroxide can be purchased for about $0.10 per
pound. Based on the SITE demonstration, annual sodium
hydroxide costs for the 10-gpm flow rate scenario would be
about $2,000 for each case. Annual sodium hydroxide costs
for the 50-gpm flow rate scenario would be about $10,000 for
each case. For the 100-gpm flow rate scenario, the annual
sodium hydroxide costs would be about $20,000 for each
case.
27
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This analysis assumes two cartridge filters capable of
screening material larger than 3 micrometers will be installed
upstream of the perox-pure™ unit and downstream of the
sedimentation tank. These filters should remove any
suspended solids in the sedimentation tank effluent.
Replacement frequency depends on the quality of the
groundwater to be treated and the flow rate. However, this
analysis assumes one filter will need to be changed every 3
months and is associated with a groundwater remediation
project. The dual filter system allows one filter to be used
while the other is replaced. For each case, replacement
filters will cost about $50 each or $200 per year.
Activated carbon columns on the venting system for the
sedimentation and equalization tanks are assumed to be
replaced every 6 months and are associated with a
groundwatcr remediation project. For each case,
replacement columns cost about $500 each, for a total of
$1,000 per year. The actual rate at which these carbon
columns will need replacement depends on the
concentrations of VOCs in the water being treated.
PPE is associated with a groundwater remediation
project and typically consists of nondisposable and disposable
equipment. Nondisposable equipment consists of steel-toe
boots and a full-face air respirator. For each case,
disposable PPE includes latex inner gloves, nitrile outer
gloves, and safety glasses. Disposable PPE for each case is
assumed to cost about $600 per year for the one operator,
regardless of flow rate. Disposable PPE is assumed to be
hazardous and will need to be disposed of in 24-gallon fiber
drums. Any potentially hazardous wastes will also be
disposed of in these drums. One drum is assumed to be
filled every 3 months. Drums cost about $12 each. For each
case, total annual drum costs will be about $50.
UV lamp usage is associated with operating the perox-
pure™ treatment system. PSI warranties its UV lamps for
3,000 hours of use. At this rate, the lamps will need to be
changed three times per year. Five-kW lamps cost about
$500 each and 15-kW lamps cost about $600. For Case 1,
three 5-kW lamps are used during treatment in the 10-gpm
unit for a total annual cost of $4,500. Five 15-kW lamps are
used in the 50-gpm unit for a total annual cost of $9,000.
Ten 15-kW lamps are used in the 100-gpm unit for a total
annual cost of $18,000. For Case 2, one 5-kW lamp is used
during treatment in the 10- and 50-gpm units for a total
annual cost of $1,500. Two 5-kW lamps are used in the 100-
gpm unit for a total annual cost of $3,000. PSI will dispose
of used UV lamps at no cost.
Sampling supplies are associated with a groundwater
remediation project and consist of sampling bottles and
containers, ice, labels, shipping containers, and laboratory
forms for off-site analyses. For routine monitoring,
laboratory glassware will also be needed. The number and
types of sampling supplies will be based on the analyses to
be performed. Costs for laboratory analyses are presented
in the Analytical Services Costs section. For each case, these
costs are assumed to be $1,000 per year.
Propane use is associated with a groundwater
remediation project and will be needed to heat the shelter
building during the colder months of the year. Annual
propane usage will be based on the square footage of the
shelter building, number of cold days, building materials, and
other variables. For each case, propane is assumed to be
$3,000 per year.
For Case 1, total consumables and supplies costs are
estimated to be $13,000 for the 10-gpm flow rate scenario;
$30,000 for the 50-gpm flow rate scenario; and $54,000 for
100-gpm flow rate scenario. Of these costs, feed chemicals
and the UV lamps are direct costs of operating the perox-
pure™ system. These costs account for about 58 percent of
the total consumables and supplies costs for the 10-gpm flow
rate scenario, about 81 percent for the 50-gpm flow rate
scenario, and about 90 percent for the 100-gpm flow rate
scenario. UV lamps account for between 30 and 35 percent
of the total consumables and supplies costs. Feed chemicals
account for between 23 and 56 percent of the total
consumables and supplies costs.
For Case 2, total consumables and supplies costs are
estimated to be $10,000 for the 10-gpm flow rate scenario;
$22,000 for the 50-gpm flow rate scenario; and $38,000 for
100-gpm flow rate scenario. Of these costs, feed chemicals
and the UV lamps are direct costs of operating the perox-
pure™ treatment system. These costs account for about 44
percent of the total consumables and supplies costs for the
10-gpm flow rate scenario, and about 73 percent for the 50-
gpm flow rate scenario and about 84 percent for the 100-
gpm flow rate scenario. Feed chemicals account for between
29 and 77 percent of the total consumables and supplies
costs. UV lamps account for between 8 and 15 percent of
the total consumables and supplies costs.
The difference hi costs between the two cases is
attributable to the higher power requirements and, hence,
the higher number of UV lamps needed to treat the
groundwater characteristics of Case 1.
4.2.7 Utilities Costs
Total utility costs are based on the electrical power used
to operate the entire treatment system and all auxiliary
equipment including the shelter building. The mercury-
vapor UV lamps, which are associated with operating the
perox-pure1* unit, draw significant electricity. This analysis
assumes that electricity costs about $0.07 per kilowatt-hour
(kWh), inclusive of usage and demand charges. In addition,
this analysis assumes that all auxiliary equipment, which is
associated with a groundwater remediation project, will draw
28
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an additional 30 percent of the total electrical power of the
perox-pure™ system.
For Case 1, the 10-gpm unit annually draws about
131,000 kWh, the 50-gpm unit draws about 655,200 kWh, and
the 100-gpm unit draws about 1,310,400 kWh. Total annual
utility costs for operating the lamps only will be about
$9,200, $45,900, and $91,700 for the 10-, 50-, and 100-gpm
flow rate scenarios, respectively. Auxiliary equipment usage
will cost an additional $2,800, $13,800, and $27,500 for the
respective three flow rate scenarios. Operating the perox-
pure™ system accounts for about 77 percent of total utility
costs for all three flow rate scenarios.
For Case 2, the 10- and 50-gpm units annually draw
about 43,680 kWh, and the 100-gpm unit draws about 87,360
kWh. Total annual utility costs for operating the lamps only
will be about $3,100 for the 10- and 50-gpm flow rate
scenarios, and $6,100 for the 100-gpm flow rate scenario.
Auxiliary equipment usage will cost an additional $900 for
the 10- and 50-gpm flow rate scenarios, and $1,800 for the
100-gpm flow rate scenario. Operating the treatment system
accounts for about 77 percent of total utility costs for all
three flow rate scenarios.
The difference in costs between the two cases is
attributable to the higher power requirement to operate the
UV lamps, needed for treating the groundwater in Case 1.
Electrical costs can vary by as much as 50 percent
depending on the geographical location and local utility
rates. A diesel gas-powered generator can also be used as
a backup or alternate source of electric power, but it will
cost considerably more than similar power supplied by local
utilities.
4.2.8 Effluent Treatment and Disposal Costs
The perox-pure™ system does not generate sludge or
spent carbon that requires further processing, handling, or
disposal. Ideally, the end products of the process are water,
carbon dioxide, halides, and sometimes organic acids.
Effluent monitoring will be conducted routinely by the
operator (see Labor Costs). The effluent can be discharged
directly to a nearby surface water body, provided the
appropriate permits have been obtained (see Permitting and
Regulatory Requirements Costs).
4.2.9 Residuals and Waste Shipping and Handling
Costs
Spent cartridge filters and PPE drums are associated
with a groundwater remediation project. These wastes are
considered hazardous and will require disposal at a
permitted facility. For each case, this analysis assumes that
about six drums will be disposed of annually for the 10- and
50-gpm flow rate scenarios, and eight drums will be disposed
of for the 100-gpm flow rate scenario. The cost of shipping,
handling, and transporting drums to a hazardous waste
disposal facility are assumed to be $1,000 per drum. Total
drum disposal costs for each case will be about $6,000 for
the 10- and 50-gpm flow rate scenarios and $8,000 for the
100-gpm flow rate scenario.
In addition, filter cake from the filter press is considered
hazardous waste and will require disposal at a permitted
facility. Because the amount of filter cake generated will
vary greatly from site to site, this analysis does not present
the costs of filter cake disposal. PSI will dispose of used UV
lamps at no cost.
4.2.10 Analytical Services Costs
Analytical costs are associated with a groundwater
remediation project and include laboratory analyses, data
reduction and tabulation, quality assurance/quality control
(QA/QC), and reporting. For each case, this analysis
assumes that one sample of untreated water and one sample
of treated water will be analyzed for VOCs each month,
along with trip blank, duplicate, and matrix spike/matrix
spike duplicate samples. Monthly laboratory analyses will
cost about $1,250; data reduction, tabulation, QA/QC, and
reporting is estimated to cost about $750 per month. Total
annual analytical services costs for each case are estimated
to be about $24,000 per year.
4.2.11 Maintenance and Modifications Costs
Annual repair and maintenance costs apply to all
equipment involved in every aspect of groundwater
remediation with the perox-pure™ system. No modification
costs are assumed to be incurred. Total annual maintenance
costs are estimated to be about 10 percent of capital
equipment costs. For Case 1, total annual maintenance costs
for the perox-pure™ system are estimated to be about
$11,000 for a 10-gpm unit; $18,500 for a 50-gpm unit; and
$29,000 for a 100-gpm unit. Total annual maintenance costs
for the auxiliary equipment are estimated to be about
$10,800 for the 10- and 50-gpm units, and $11,200 for a 100-
gpm unit.
For Case 2, total annual maintenance costs for the
perox-pure™ treatment system are estimated to be about
$5,500 for each flow rate scenario. Total annual
maintenance costs for the auxiliary equipment are estimated
to be about $10,800 for the 10- and 50-gpm units, and
$11,200 for a 100-gpm unit.
The difference in costs between the two cases is
attributable to the higher capital equipment costs in Case 1.
These costs are higher because more power is required to
achieve treatment goals.
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4.2.12 Demobilization Costs
Site demobilization includes shutdown, disassembly,
transportation, and disposal of perox-pure™ equipment and
auxiliary equipment at a licensed hazardous waste disposal
facility. This analysis assumes the perox-pure™ system will
have no salvage value at the end of the project. Site cleanup
and restoration are also included in demobilization costs.
For each case, this analysis assumes the costs from shutdown
to disposal for all activities associated with a groundwater
remediation project will be about $30,000, including site
cleanup, restoration, and building decontamination. This
analysis assumes the shelter building will remain standing at
the site. All disposal activities associated with operating the
pcrox-pure™ system are estimated to be about $10,000. For
each case, demobilization is estimated to take about 1 week
to complete and will cost a total of about $40,000.
The costs of demobilization, however, will occur at the
end of the remediation project. To complete the project,
this analysis assumes that the 10-gpm unit will be used for 50
years, the 50-gpm unit will be used for 10 years, and the 100-
gpm unit will be used for 5 years. Therefore, based on the
annual inflation rate of 5 percent, the net future values of
this cost for 10-gpm, 50-gpm, and 100-gpm units are
estimated to be about $459,000; $65,000; and $51,000,
respectively. These figures were used to calculate the total
costs for a groundwater remediation project presented in
Tables 4-1 and 4-2.
30
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Section 5
References
Evans, G., 1990, Estimating Innovative Technology Costs for
the SITE Program. Journal of Air and Waste
Management Association. Volume 40, No. 7 (July).
Federal Register, 1990a, U.S. Environmental Protection
Agency (EPA), National Oil and Hazardous Substances
Pollution Contingency Plan; Final Rule. Volume 55, No.
46 (March 8).
Federal Register, 1990b, EPA Proposed Rules for Corrective
Action for Solid Waste Management Units at Hazardous
Waste Management Facilities. Volume 55, No. 145 (July
27).
Glaze, W., and others, 1987, The Chemistry of Water
Treatment Processes Involving Ozone, Hydrogen
Peroxide, and Ultraviolet Radiation. Ozone Science and
Engineering.
U.S. Department of Energy (DOE), 1988, Radioactive
Waste Management Order. DOE Order 5820.2A
(September 26).
U.S. Environmental Protection Agency (EPA), 1987a,
Alternate Concentration Limit (ACL) Guidance. Part
1: ACL Policy and Information Requirements,
EPA/530/SW-87/017.
EPA, 1987b, Joint EPA-Nuclear Regulatory Agency
Guidance on Mixed Low-Level Radioactive and
Hazardous Waste. OSWER Directives 9480.00-14 (June
29), 9432.00-2 (January 8), and 9487.00-8 (August 3).
EPA, 1988, CERCLA Compliance with Other
Environmental Laws: Interim Final, Office of Solid
Waste and Emergency Response (OSWER).
EPA/540/G-89/006.
EPA, 1989, EPA Memorandum from OSWER to Waste
Management Division and Office of Regional Counsel,
Applicability of Land Disposal Restrictions to RCRA
and CERCLA Groundwater Treatment Reinjection.
Superfund Management Review: Recommendation No.
26 (December 27).
31
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Appendix A
Vendor Claims for the Technology
A.I Introduction
Because 50 percent of U.S. drinking water is obtained
from groundwater resources, the removal of contaminants
from polluted groundwater has become a major
environmental priority. Increasing groundwater pollution has
been caused by leaking underground fuel and chemical
storage tanks, accumulations of pesticides and herbicides,
landfill leachates, and improper handling and disposal of
industrial chemicals and wastewater effluent. Contaminants
often migrate through soil into municipal water wells,
aquifers, and other water resources. The U.S.
Environmental Protection Agency has identified 129 priority
organic contaminants; with such diversity in molecular
structure and chemical properties, these contaminants
present a challenge to traditional treatment technologies.
The perox-pure™ advanced chemical oxidation system,
developed by Peroxidation Systems, Inc. (PSI), of Tucson,
Arizona, provides an on-site treatment process that destroys
contaminants in groundwater and wastewater. The patented
system design has been used to meet the most stringent
federal and state groundwater cleanup regulations.
Since it entered the market in 1987, the perox-pure™
system has been used on site to treat organic contamination
in groundwater at approximately 80 locations in the United
States, Canada, Puerto Rico, and Europe. The perox-pure™
system has been used to treat groundwater, wastewater,
leachate, dredge water, bioeffiuent, and municipal water
contaminated with volatile organic compounds, semivolatile
organic compounds, aromatic compounds, polynuclear
aromatic hydrocarbons, phenols, petroleum hydrocarbons,
and a number of other organic compounds.
A.2 Description of the perox-pure™ System
The perox-pure™ system rapidly breaks the bonds
between atoms in organic molecules, thereby allowing the
atoms to form simpler, nontoxic compounds, such as carbon
dioxide and water. In the perox-pure™ system, water
pumped from a contaminated source is combined with
hydrogen peroxide, a chemical oxidant. Hydrogen peroxide
is preferred to ozone as a chemical oxidant, because ozone
is not very soluble in water, which results in long oxidation
times. The higher solubility of hydrogen peroxide in water
greatly simplifies the reactor design in terms of oxidant
addition, mixing of reactants, and reduction of toxic gas
emissions. Hydrogen peroxide is commercially available in
solutions of 30 to 50 percent by weight. Systems using
hydrogen peroxide also require significantly less storage and
feed equipment and are less expensive relative to those using
ozone, because ozone must be generated on site. Finally,
because ozone is a toxic gas, it requires a special gas phase
decomposition system and an air discharge permit.
The mixture of contaminated water and hydrogen
peroxide passes through a series of reactor chambers that
expose it to high intensity ultraviolet (UV) lamps mounted
inside protective quartz tubes. Inside each of the UV lamp
chambers, a photochemical reaction occurs that forms highly
reactive hydroxyl radicals (OH») from hydrogen peroxide
(see Table A-l). Energy from the UV lamps absorbed by
the target compounds also increases the compounds'
oxidation rate.
Hydrogen peroxide injection points at the inlet of each
lamp section allow hydrogen peroxide to be added to each
reactor separately. This arrangement, called the splitter, aids
the operator hi maintaining the ideal balance of hydroxyl
radicals.
Hydroxyl radicals destroy the bonds hi organic
contaminants between carbon and the attached groups of
atoms, forming simpler, nontoxic chemical compounds. The
treated water exits the system at the top of the reactor
chambers. The only additive to the system, hydrogen
peroxide, is consumed in the process, and the system
generates no ah- emissions or by-products that require
disposal.
The perox-pure™ system is effective in treating a variety
of organic compounds present in contaminated waters and
is not limited by mass transfer, as are liquid-phase carbon
adsorption and air stripping.
33
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T*b!a A-1 Oxftfttion Potential of Oxidants
Relative Oxidation
Power Chlorine = 1.00
2.23
2.06
1.78
1.52
1.31
1.25
1.24
1.17
1.15
1.10
1.07
1.00
0.80
0.54
Oxidative Species
Fluorine
Hydroxyl Radical
Atomic Oxygen
Ozone
Hydrogen Peroxide
Perhydroxyl Radical
Permanganate
Hypobromous Acid
Chlorine Dioxide
Hypochlorous Acid
Hypoiodous Acid
Chlorine
Bromine
Iodine
Potential (Volts)
3.03
2.80
2.42
2.07
1.78
1.70
1.69
1.59
1.56
1.50
1.46
1.36
1.09
0.73
A.3 perox-pure™ Systems
The perox-pure™ systems are compact and designed to
operate unattended on a continuous basis. The skid-
mounted unit consists of a control panel, lamp drive
enclosures, and a reactor chamber. An accompanying
hydrogen peroxide module is also skid-mounted and provides
storage, feed pumps, and an eye wash station and safety
shower. For sites where pH adjustment of influent
wastewater or effluent is necessary, a skid-mounted acid feed
module or base feed module is used in addition to the
equipment listed above.
The combined use of UV lamps and hydrogen peroxide
results in improved reaction rates. Moreover, a smaller,
simpler design is possible, which reduces space requirements,
the number of potential replacement parts, and
corresponding maintenance costs.
PSI can supply perox-pure™ units in various sizes. PSI
has designed, built, and installed systems capable of treating
flow rates varying from 5 gallons per minute to thousands of
gallons per minute. The unit size required for a particular
application is determined through laboratory treatability
studies and on-site tests.
A diagram of the perox-pure™ unit is shown in Figure A-
1. The perox-pure™ oxidation unit consists of multiple
horizontal sections connected hi series. Inside each section,
one high intensity, medium-pressure UV lamp is mounted
inside a quartz tube. The lamp and tube assembly are
positioned perpendicular to the side walls of the chamber.
A.4 Design Improvements
The advanced design of current perox-pure™ systems
decreased the costs of earlier systems by 50 percent or more.
Improvements include an innovative reactor design,
anticorrosion lining in the reactors, better conversion
efficiencies from electrical power to UV energy, and
unproved methods for sequential hydrogen peroxide
addition. Engineering design improvements also make it
easier to adjust such parameters as flow rate, pH, UV
energy, and the addition of hydrogen peroxide to individual
reactor chambers to maximize destruction rates. An
optional programmable logic controller can be installed to
integrate the system into a fully automated remote treatment
system.
Advanced perox-pure™ systems include a patented,
automated, self-cleaning mechanism for the UV lamps that
virtually eliminates the scaling of the quartz tubes. The
cleaning mechanism consists of a wiper that fits in the
annular space between the quartz tube and the oxidation
chamber wall. Propelled by water being treated in the
system, the wiper regularly removes deposits from the quartz
tubes. As a result, costs associated with unscheduled
maintenance to the system have been substantially reduced.
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^ft* WMefln E*s*g^ssga
Figure A-1 Isometric Diagram of perox-pure"* Unit
35
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These engineering improvements have transformed the
perox-pure™ system into an efficient, low maintenance, and
highly reliable advanced oxidation system that is cost
competitive with carbon adsorption and air stripping
technologies.
A.5 Pretreatment
A prctreatment system is sometimes needed to reduce
the levels of certain inorganic species in the water. If high
levels of suspended solids or turbidity are present, filtration
and clarification may be required to provide optimum
treatment. Acid can also be added to increase treatment
efficiency by shifting the equilibrium from carbonate and
bicarbonate species to carbonic acid.
A.6"perox-pure™ Applications
Although a broad spectrum of aqueous wastes can be
treated with the perox-pure™ technology, the most common
application is for water containing less than 500 milligrams
per liter of organic compounds. Higher concentrations can
be treated; however, the longer oxidation times needed to
treat higher concentrations may require batch or partial
recycle treatment. In addition, treated water may need to be
cooled to keep it from overheating the system. A partial list
of applications of the perox-pure™ technology is shown in
Table A-2.
While the chemistry of the perox-pure™ technology has
a number of complex interactions which depend on the
characteristics of the water, a large database is available
from which initial predictions can be made.
To determine if the perox-pure™ system is applicable to
a specific contamination problem, a team of application
specialists is available at the PSI corporate headquarters in
Tucson, Arizona (800-552-8064). After gathering the
information available from the potential user, the application
specialists can assess the general applicability of the
perox-pure™ technology and, in most cases, provide an
estimate of the capital and operating costs for perox-pure™
technology. If requested, written estimates are prepared
which document the figures and provide information on the
available perox-pure™ systems and services.
PSI requires the following information to evaluate the
application of the perox-pure™ technology:
• Contaminated water flow rate or production rate
• Identities and concentrations of organic
contaminants
• Treatment objectives
Other information that allows PSI to provide a more
reliable estimate of treatment includes the following:
• Source of contaminated water
• Identity and concentrations of inorganics such as
iron, chloride, and nitrate
• Levels of total organic carbon, chemical oxygen
demand, pH, alkalinity, dissolved solids, turbidity,
color, and suspended solids
• Current treatment and pretreatment systems in use
The estimates provided by PSI are intended to be used
to determine if the perox-pure™ technology is an
economically feasible method of treatment compared with
the costs of other potential treatment processes. Since the
water quality has such a significant impact on the
perox-pure™ system performance, a process assessment at
the PSI Testing Laboratory, or in the field, with an actual
sample of the water is necessary to provide definitive
treatment cost projections.
A.7 Advantages over Carbon Adsorption and Air
Stripping Technologies
The perox-pure™ advanced chemical oxidation
technology has demonstrated major advantages over carbon
adsorption and air stripping technologies. From a regulatory
perspective, the major advantage of the perox-pure™
technology is that it creates no secondary pollutants to treat
or haul away. This benefit has become more important as
federal, state, and local regulations become more stringent
regarding the allowable contaminant concentrations of air
emissions generated using air stripping as well as the
disposal of secondary pollutants such as spent carbon. These
regulations have increased the costs of monitoring and
disposal as well as the risk of legal liability associated with
treatment technologies. The perox-pure™ technology greatly
reduces the risk of future liability associated with the
creation of secondary pollutants.
The perox-pure™ technology is advantageous for treating
contaminated groundwater hi residential neighborhoods and
highly technical industrial complexes because the system
offers a low-profile, on-site treatment that produces minimal
noise. In addition, the perox-pure™ systems are very
compact and can be positioned among existing equipment.
As a result, public relations problems are minimized.
The perox-pure™ technology is ideal for those
applications where carbon adsorption and air stripping are
not viable. For example, some priority pollutants, such as
methyl-tert-butyl ether, vinyl chloride, and methylene
chloride, are not readily adsorbed by carbon. Many common
organic contaminants, such as isopropyl alcohol and acetone,
36
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Table A-2 Partial List of perox-pure'" Technology Applications
Waste Stream
Principal Contaminants"
Site Location
Bioeffluent
Dredge Water
Effluent
Groundwater
Chlorobenzene
Polychlorinated Biphenyls
BTX
Phenol
MeCI, Phenol, PAH
Nitrated Esters
Phenol
Phenols, Nitmphenols
IPA, TOG, TCA, DCE, MEK
Acrylic Acid, Butyl Acrylate
BTEX
TCE
BTX
BTX
TCA, Freon, MeCI, BTX
TCA, TCE
TCE
TCE, PCE, BTX, TCA
TCE, PCE, DCE, TCA, MeCI, Chloroform
TCE, PCE, TCA, DCE
TCE, TCA, CO, MeCI
TCE, TCA, PCE, DCE
Tetrahydrofuran
BTX.
TCE, PAHs
TCE, PCE, TCA, DCE
BTX
MeCI, TCA
TCE, DCE, PCE, MeCI
TCE, DCE, PCE, TCA
Pentachlorophenol
Connecticut
Massachusetts
California
New Jersey
North Carolina
Pennsylvania
Pennsylvania
Texas
Utah
Arizona
Arizona
Arizona
California
California
California
California
California
California
California
California
California
California
California
Colorado
Louisiana
Maryland
Massachusetts
Massachusetts
New Jersey
New York
Washington
37
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T*bl» A-2 Ptrtltl List of perox-pur»M Technology Applications (continued)
Waste Stream
Leachato
Municipal Water
Recycle
Miscellaneous
Principal Contaminants*
Mixed Organic Acids, Ketones, and VOCs
Humic Acid/Color Control
Chemical Oxygen Demand
Bacteria, Phenol, Formaldehyde
Hydrazine
Hydrazine, DIMP
Site Location
New Hampshire
California
Arizona
Ohio
Colorado
Colorado
Notes:
* Acronyms used In this table are defined as follows:
BTEX Benzene, toluene, ethylbenzene, and xylene
B7X Benzene, toluene, and xylene
CCI4 Carbon tetrachloride
DCE Dlchloroethene
DIMP Dllsopropyl methylphosphonate
IPA Isopropyl alcohol
MeCI Methylene chloride
MEK Methyl ethyl ketone
PAH Polynuclear aromatic hydrocarbon
PCE Tetrachloroethene
TOC Total organic carbon
TCE Trichloroathene
TCA Trichloroethane
VOC Volatile organic compound
arc not removed by air stripping. The perox-pure™
technology provides reliable, consistent destruction of these
contaminants.
A.8 Other Advantages
To minimize capital investment and avoid an
unreasonably long-term commitment to the treatment
process, PSI offers a 5-year plan in which equipment,
maintenance, technical services, and hydrogen peroxide are
provided in one monthly fee. This plan allows customers to
accurately budget costs over the life cycle of the project, and
it allows PSI to respond to changing regulations on behalf of
the client and initiate process changes and improvements as
needed. In some cases, the monthly fee has been reduced
as the process or water quality has improved.
A.9 Technology Combinations
In many water treatment systems, the perox-pure™
technology has been paired with carbon adsorption, air
stripping, or biological treatment. Depending on the water
quality and treatment objectives, the perox-pure™ technology
can be combined with other technologies to produce a more
cost-effective solution than is achieved with any single
process.
38
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Appendix B
SITE Demonstration Results
In April 1991, the U.S. Environmental Protection Agency
(EPA) learned that Peroxidation Systems, Inc. (PSI), was
contracted by Lawrence Livermore National Laboratory
(LLNL) to perform pilot-scale chemical oxidation studies as
part of remediation activities at the LLNL site. At that time,
EPA and PSI discussed the possibility of PSI participating in
the Superfund Innovative Technology Evaluation (SITE)
program to demonstrate how PSI's perox-pure™ chemical
oxidation technology could be used to treat contaminated
groundwater at LLNL Site 300 in Tracy, California. EPA
subsequently accepted the perox-pure™ technology into the
SITE demonstration program. Through a cooperative effort
between the EPA Office of Research and Development
(ORD), EPA Region IX, LLNL, and PSI, the perox-pure™
technology was demonstrated at the LLNL site under the
SITE program. This appendix briefly describes the LLNL
site and summarizes the SITE demonstration activities and
demonstration results.
B.I Site Description
LLNL is a 640-acre research facility about 45 miles east
of San Francisco and 3 miles east of Livermore, California
(see Figure B-l). 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 volatile organic compounds (VOC), metals, and
tritium were used and released at the site.
The SITE demonstration was conducted at Site 300,
which is operated by LLNL but is located separately from
the LLNL main campus (see Figure B-l). LLNL established
Site 300 as a high-explosives test area in 1955. Site 300
occupies 11 square miles in the Altamont Hills about
15 miles southeast of Livermore and 8.5 miles southwest of
Tracy, California. Site 300 operations consist of four
activities: (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 the following: photo laboratory 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 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.
B.2 Site Contamination Characteristics
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. Data from the RI report (LLNL, 1990) were
used to select the shallow aquifer at the site 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, semivolatile organic compounds (SVOC), metals,
39
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0 5 10 15 20
Kilomatirs
Figure B-1 LLNL Site Location
40
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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 of 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, trichloroethene (TCE);
tetrachloroethene (PCE); 1,1-dichloroethene (1,1-DCE); 1,2-
dichloroethene (1,2-DCE); and 1,1,1-trichloroethane (TCA)
were present at 1,200 micrograms per liter (/tg/L), 95 /ig/L,
7.1 /*g/L, 8.7 /ig/L, and 7.5 /ig/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 milligrams per liter
(mg/L) as calcium carbonate; (3) the concentration of total
dissolved solids was 930 mg/L; (4) the concentration of iron
was 10 /*g/L, and (5) the concentration of manganese was 20
B.3 Review of SITE Demonstration
The SITE demonstration was divided into three phases:
(1) site preparation; (2) technology demonstration; and (3)
site demobilization. These activities and a review of
technology and perox-pure™ system performance during the
phases are described below.
B.3.1. Site Preparation
Approximately 10,000 square feet of relatively flat
ground surface was used for the perox-pure™ chemical
oxidation system and support equipment and facilities, such
as 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 enclosure covering approximately one-fourth of
the demonstration area was erected to provide shelter for
the perox-pure™ system during inclement weather. Site
preparation included setting up major support equipment,
on-site support services, and utilities. These activities are
discussed below.
Major 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 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 water
and decontamination rinse water, a dumpster, a forklift with
operator, pumps, sampling equipment, health- and safety-
related gear, and a van. 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; the drum was equipped
with a floating lid and a mixing device. During the
demonstration, a spiking solution containing
chloroform; 1,1-dichloroethane (DCA); and TCA
was added inline 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 to store untreated
groundwater and minimize VOC losses during
storage. The tank was used (1) as an equalization
tank and (2) as a storage tank for a few
demonstration runs performed at flow rates greater
than the groundwater yield.
One pump for transferring contaminated water from
the bladder tank to the perox-pure™ system and one
pump for adding spiking solution inline 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 to adjust the
pH of the effluent from the perox-pure™ system;
PSI provided the module, which consisted of a 55-
gallon base feed drum, two pumps, and flow
measuring devices.
One solid waste dumpster 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
41
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Analytical equipment for measuring
parameters at the demonstration site
field
• 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 and protective coveralls, latex or similar
inner gloves, nitrile outer gloves, steel-toe boots and
disposable overboots, safety glasses, and a hard hat
• A van to transport oversight personnel and supplies
On-Site Support Services
On-site laboratory analyses were conducted in a field
trailer measuring 12 by 44 feet. The field trailer also 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. Water was required for
equipment and personnel decontamination, for field
laboratory use, and for drinking purposes. 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-pure™ system, the
office trailer, and the laboratory equipment. The perox-
purc™ 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. LLNL provided most of the support
required to arrange utilities for the demonstration.
B.3.2 Technology Demonstration
This section discusses (1) operational/equipment
problems and (2) health and safety considerations associated
with the SITE demonstration.
Operational/Equipment Problems
The SITE team, consisting of EPA's contractors,
experienced a few operational/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-O and W-875-08 at
approximately 9 gallons per minute (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 SITE team
that the wells might 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-O and W-875-08 at 6 gpm and 2 gpm,
respectively. This approach did not affect the
demonstration schedule or the technology
evaluation.
• PSI requested that one of its operating facilities ship
three scaled and three clean 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 ultraviolet (UV)
lamps, instead of three. As a result, perox-pure™
system performance with scaled tubes and clean
tubes was compared based on the removals
achieved in two reactors, instead of those achieved
in three reactors.
• 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
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,
42
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which PSI collected 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 hi progress, the sulfuric acid level hi the
acid feed tank decreased significantly. As a result,
the influent pH could not be lowered to the desired
level, and the SITE team discontinued the run. The
run was repeated after PSI filled the acid feed tank
.with sulfuric acid.
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 of
approximately 5, the system flow rate was reduced
to 40 gpm. PSI's acid feed pumps were riot 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.
The SITE team initially encountered problems
measuring the effluent pH at the sampling location
downstream of the sodium hydroxide addition point.
Because no static mixer was used, 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 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.
Health and Safety Considerations
In general, potential health hazards associated with the
demonstration resulted from the possibility of exposure to
contaminated groundwater and process chemicals, including
hydrogen peroxide, sulfuric acid, and sodium hydroxide
solutions. Although the treatment system was entirely
closed, potential routes of exposure during the
demonstration included inhalation, ingestion, and skin and
eye contact from possible splashes or spills during sample
collection.
All personnel working hi the demonstration area had, at
a minimum, 40 hours of health and safety training and were
under routine medical surveillance. Personnel were required
to wear protective equipment appropriate for the activity
being performed. Steel-toe boots were required hi the
exclusion zone. Personnel working in direct contact with
contaminated groundwater and process chemicals wore
modified Level D protective equipment, including safety
shoes, latex inner gloves, nitrile outer gloves, and safety
glasses.
B.3.3 Site Demobilization
After the demonstration was completed and on-site
equipment was disassembled and decontaminated, equipment
and site demobilization activities began. Equipment
demobilization 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. The treated water
collected during the demonstration was tested, and the
results were provided to LLNL. LLNL disposed of this
water appropriately. LLNL also disposed of all hazardous
wastes at a permitted landfill. All nonhazardous wastes were
routinely disposed of along with similar wastes generated by
LLNL.
B.4 Experimental Design
The technology demonstration had the following primary
objectives: (1) determine VOC removal efficiencies hi the
treatment system under different operating conditions, (2)
determine whether treated water 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 preliminary information on the type of by-
products formed during the treatment. To accomplish these
objectives, the following test approach and sampling and
analytical procedures were used.
43
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B.4.1 Testing Approach
The perox-pure™ chemical oxidation technology was
demonstrated over a 3-week period in September 1992.
During the demonstration the perox-pure™ unit 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 /tg/L, respectively. Groundwater was pumped
from two wells into a 7,500-gallon bladder tank to minimize
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.
The technology demonstration was conducted in three
phases (see Table B-l). 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 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 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 below target levels (see
Table B-2) for spiked groundwater. 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 to 300 jtg/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
maybe contaminated with VOCs that are difficult to oxidize.
Phase 2 was also designed to evaluate the reproducibility of
perox-pure™ system performance at the preferred operating
conditions determined in Phase 1. Specifically, Runs 10,11,
and 12 were performed at Run 3 conditions to evaluate the
reproducibility of 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 tests were obtained from a
hazardous waste site where the water hardness and iron
content caused scaling on the quartz tubes. PSI obtained
two sets of quartz tubes for Phase 3 tests. 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
only two tubes of each type (scaled and clean) were
available, 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 used.
B.4.2 Sampling and Analytical Procedures
Liquid samples were collected from the perox-pure™
treatment system at the locations shown in Figure B-2.
Table B-3 lists analytical and measurement methods used
during the demonstration. Total organic halides (TOX) and
adsorbable organic halides (AOX) listed in Table B-3 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. The following
parameters were considered critical for evaluating the perox-
pure™ technology: (1) VOC, hydrogen peroxide, and acid
concentrations; and (2) flow rate and pH. VOCs were
measured by both gas chromatography (GC) and GC/mass
spectrometry (MS) methods. Only GC measurement of
VOCs was considered critical, because GC data were
planned for quantitative use; GC/MS data were planned for
qualitative use.
Because the perox-pure™ technology was developed to
treat organics, and because VOCs were the principal
contaminants in groundwater, four replicate samples were
collected for GC analysis of VOCs. For other analytes, the
number of samples was based on (1) the intended use of the
data, (2) analytical costs, (3) sampling time, and (4) the
discretion of analytical laboratory. EPA-approved sampling,
analytical, quality assurance, and quality control (QA/QC)
procedures were followed to obtain reliable data. Details on
QA/QC procedures are presented in the demonstration plan
(PRC, 1992).
44
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Table B-1 Experimental Matrix for perox-pure'" Technology Demonstration
Run Number Influent pH
Hydrogen Peroxide at Influent Hydrogen Peroxide at Influent
to Reactor 1 (mg/L) to Reactors 2 to 6 (mg/L)
Flow Rate
Phase 1 (Raw Groundwater Runs)
1 8.0
2 6.5
3 5.0
4 5.0
5 5.0
6 5.0
7 5.0
8 5.0
40
40
40
70
30
240
240
60
25
25
25
50
15
Hydrogen Peroxide
was added at Influent
to Reactor 1 only
10
10
10
10
10
10
40
40
Phase 2 (Soiked Groundwater and Reoroducibilitv Runs)
9 5.0
10 5.0
11 5.0
12 5.0
13 5.0
14 5.0
70
40
40
40
Phase 3 (Quartz Tube
40
40
50
25
25
25
Cleaner Runs)
25
25
10
10
10
10
10
10
B.5 Review of Treatment Results
This section summarizes the results of both critical and
noncritical parameters for the perox-pure™ chemical
oxidation system demonstration, and it evaluates 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 tunes the
detection limit were used as estimated concentrations for the
first, second, third, and fourth replicate samples, respectively.
Throughout this appendix, the terms "Reactor 6 effluent,"
"perox-pure™ effluent," and "effluent" are used synonymously.
B.5.1 Summary
Parameters
of the Results for Critical
Results for the critical parameters are presented below
for each phase of the demonstration.
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 present above
detection limits 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, because effluent samples did not require
dilution, the TCA concentration could be measured in
treated groundwater. In general, TCA was present in the
effluent from the perox-pure™ system. Phase 1 VOC
concentration data are presented for TCE and PCE in
Figures B-3 through B-5. TCA concentrations are not
shown in figures because TCA levels in the influent could
not be measured.
45
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TMa B-2 Target Level* for VOCs in Effluent Samples
VOC
Target
Level
Chloroform
1,1-DIchloroethane (DCA)
1,1-Dichloroethene (1,1-DCE)
1,2-Dichloroethene (1,2-DCE)
1,1,1-Trichloroethane (TCA)
Trichloroethene (TCE)
Tetrachloroethene (PCE)
100
5
6
6
200
5
5
Figure B-3 presents TCE and PCE concentrations in the
influent and Reactors 1, 3, and 6 effluent 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 level of 5 /ig/L
and below the detection limit of 1 /*g/L. Figure B-3 shows
that the perox-pure™ system performed best in Run 1, when
the influent pH was 8 (the unadjusted pH of groundwater).
In this run, the Reactor 1 effluent had lower levels of TCE
and PCE than in Runs 2 and 3, and it had the same levels
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 jttg/L (Reactor 6 effluent TCA
concentrations in Runs 1 and 2 were 6.7 and 3.1 jtg/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 B-4 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 show that
Reactor 1 effluent TCE and PCE concentrations were the
lowest in Run 4 (with the highest hydrogen peroxide level)
and in Run 5 (with the lowest hydrogen peroxide level).
Higher levels of TCE and PCE in the Reactor 1 effluent at
intermediate hydrogen peroxide levels cannot be explained.
The Reactor 6 effluent TCA concentrations in Runs 3, 4,
and 5 were 1.4,1.8, and 2.1 |tg/L, respectively. No definite
trend can be identified based on TCE, PCE, and TCA data
in Runs 3, 4, and 5.
Figure B-5 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, the same total amount of hydrogen peroxide was 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 levels 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 levels in treated groundwater were
below the detection limit of 1.0 jtg/L. However, effluent
TCA levels in Runs 4 and 6 were 1.8 and 3.0 jtg/L,
respectively. Based on this data, adding hydrogen peroxide
at multiple points in the perox-pure™ system appears to
enhance the system's performance.
A comparison of TCE and PCE levels in Runs 6 and 7
shows that both TCE and PCE concentrations in Reactor 1
effluent were higher hi Run 7 than in Run 6. Similarly, the
effluent TCA level in Run 7 (3.9 /tg/L) was higher than in
Run 6 (3.0 /tg/L)- These observations are consistent with
the operating conditions, because contaminated groundwater
had a much longer UV exposure tune in Run 6 than hi Run
7. UV exposure tunes were 1.5 and 0.4 minutes in Runs 6
and 7, respectively.
A comparison of TCE and PCE levels 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
levels were about the same in both runs (3.9 and 4.0 /ig/L
in Runs 7 and 8, respectively). The higher Reactor 1
effluent TCE level hi Run 7 may be attributed to higher
influent TCE levels in that run. Reactor 1 effluent TCE
levels correspond to 99.5 and 99.9 percent TCE removal hi
Runs 7 and 8, respectively. Similarly, the Reactor 1 effluent
PCE levels correspond to 92.9 and 99.2 percent PCE
removal in Runs 7 and 8. These data seem to indicate that
higher doses of hydrogen peroxide may have scavenged
hydroxyl radicals or excess hydrogen peroxide reduced UV
46
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GROUNDWATER FROM
SITE 300
•TO DISPOSAL
UV LAMP
REACTOR
OXIDATION UNIT
SPIKING
SOLUTION
LEGEND
• SAMPLING LOCATION
Figure B-2 perox-pure"* Chemical Oxidation Treatment System Sampling Locations
transmittance through water, which resulted 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 the preferred operating conditions for spiked
groundwater. As a result, Runs 10 through 14 were
performed using Run 3 operating conditions.
Phase 2 Results
Phase 2 (Runs 9 through 12) results for VOC removal
in the perox-pure™ system are presented in Figures B-6
through B-8. A comparison of the perox-pure™ system's
performance in treating spiked groundwater (Run 9) and
unspiked groundwater (Run 4) is presented in Figure B-6.
Figure B-6 shows that TCE and PCE levels 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
levels plotted in Figure B-6 are estimated concentrations.
Because the detection limit for TCE and PCE in Run 9 was
5 Mg/L and in Run 4 was 1 |*g/L, and because TCE and
PCE were present at nondetectable 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 /*g/L. VOC removal
efficiencies in reproducibility runs are plotted in Figure B-7.
Figure B-7 shows that for TCE and PCE, which are easy to
oxidize, 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-pure™ system. However, for chloroform,
DCA, and TCA, which are difficult to oxidize, considerable
removal occurred beyond Reactor 1. 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. After Reactor
6, overall removal efficiencies for TCE, PCE, chloroform,
DCA, and TCA increased to 99.7, 97.1, 93.1, 98.3, and 81.8,
respectively. The overall removal efficiencies of the perox-
pure™ system were reproducible for all VOCs. However, for
47
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T»b!a B-3 Analytical and Measurement Methods
Parameter
Acid
Alkalinity
AOX
Base
Btoassay
Electricity
consumption
Flow rate
Hardness
Hydrogen peroxide
Metals
(Iron and manganese)
pH
Purgosble organic
carbon (POC)
SVOCs
Specific conductance
Total carbon (TC) and
Total organic carbon
(TOG)
Temperature
TOX
Turbidity
VOCs(GC)
VOCs (GG/MS)
Notes:
* EPA, 1983.
6 Stoffans, 1992.
" EPA, 1985.
d EPA, 1986.
* APHA, AWWA, a
Method Type
Field
Laboratory
Laboratory
Field
Laboratory
Laboratory
Field
Field
Laboratory
Field
Laboratory
Field
Laboratory
Laboratory
Field
Laboratory
Field
Laboratory
Laboratory
Laboratory
Laboratory
nd WPCF, 1989.
Method Source
Acid-base titration
MCAWW 310.1"
DIN 38409 H14b
Acid-base titration
EPA/600/4-85/01 3°
EPA/600/4-85/013c
None
None
MCAWW 730.2"
BoHz and Howell, 1979
SW-846 3010/601 Od
MCAWW 150.1"
SM 53708*
SW-846 3510/3640/8270d
SW-846 9050"
SM 5310C"
MCAWW 170.1*
SW-846 9020d
MCAWW 180.1"
SW-846 5030/8010"
SW-846 8240"
Name of Method
Titration with sodium hydroxide
Alkalinity (titrimetric)
Adsorbable organic halide measurement
Titration with sulfuric acid
48-hour static acute toxicity test (definitive)
using Ceriodaohnia dubia
96-hour static acute toxicity test (definitive)
using Pimephales oromelas
Electricity consumption
Flow rate measurement using monitoring
equipment on the treatment system
Hardness
Color/metric method for hydrogen peroxide
measurement
Metals by inductively coupled plasma-atomic
emission spectroscopy
pH electrometric measurement
Carbon measurement by combustion-
infrared method
GC/MS for SVOCs: capillary column
technique
Specific conductance
Carbon measurement by persulfate-
ultraviolet oxidation method
Temperature
Total organic halide measurement
Turbidity (nephelometric)
Halogenated VOCs by GC: purge and trap
VOCs by GC/MS: capillary column
technique
48
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TCE
PCE
VOC Concentration, jjg/L
10 100 1,000
Run /
Influent pH = 8.0
10,000
Influent
Reactor I
Reactor 3
Reactor 6
1,000 10,000
TCE
PCE
TCE
PCE
1,000 10,000
Figure B-3 Comparison of VOC Concentrations at Different Influent pH Levels
(Hydrogen Peroxide Level at Reactor 1 = 40 mg/L; Hydrogen Peroxide Level at
Reactors 2 through 6 = 25 mg/L; Flow Rate = 10 gpm)
49
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VOC Concentration, yg/L
10 100 1,000
TCE
PCE
Run 3
(Hydrogen Peroxide Level
at Reactor I = 40 mgIL;
at Reactors 2 through 6 = 25 mgIL)
10,000
Influent
Reactor I
Reactor 3
Reactor 6
1,000 10,000
TCE
PCE
Run 4
(Hydrogen Peroxide Level
at Reactor I = 70 mgIL;
at Reactors 2 through 6 = SO mgIL)
1,000 10,000
TCE
PCE
Run 5
(Hydrogen Peroxide Level
at Reactor I = 30 mgIL;
at Reactors 2 through 6=15 mgIL)
Flguta B-4 Comparison of VOC Concentrations at Different Hydrogen Peroxide Levels
(Influent pH * 5.0; Flow Rate = 10gpm)
50
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O.I
VOC Concentration, jig/L
10 100 1,000
10,000
TCE
PCE
110 Run 4
(Hydrogen Peroxide Level
at Reactor I =70 mgIL;
at Reactors 2 through 6 = SO mgIL;
Flow Rate = 10 gpm)
O.I
10
100 1,000 10,000
TCE
PCE
1,000 10,000
TCE
PCE
TCE
PCE
120
Run 6
(Hydrogen Peroxide Level
at Reactor I = 240 mgIL;
Flow Rate = 10 gpm)
Run 7
(Hydrogen Peroxide Level
at Reactor I = 240 mgIL;
Flow Rate = 40 gpm)
(Hydrogen Peroxide Level
at Reactor I =60 mgIL;
Flow Rate = 40 gpm)
1,000 10,000
Influent
Reactor I
Reactor 3
Reactor 6
Figure B-5 Comparison of VOC Concentrations at Different Flow Kates and Hydrogen Peroxide Levels
(Influent pH = 5.0)
51
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r
TCE
PCE
Chloroform
DCA
TCA
TCE
PCE
VOC Concentration, pg/L
! 10
100
Phase 2 — Run 9
Spiked
Phase / — Run 4
Unspiked
Figure B-6 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)
1,000
1,000
1980
Influent
Reactor /
Reactor 3
Reactor 6
52
-------
Percent Removal
Percent Removal
Percent Removal
n n n
a a a
a a a
o o o
-n -I -t
Ox Lo —.
-------
1,000
100
_
o
D
«Ł
in
10
TL=IOO
Target Level
: lk=J
2.9
3.2
l3.1l
2.9
3.2
TL = 5
4.9
32
311)
x'
113
Run 10
Run 11
Run 12
TCE
PCE Chloroform DCA
TCA
Figure B.8 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)
certain compounds, the removal efficiencies after Reactor 1
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 B-8 compares the 95 percent upper confidence
limits (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 chloroform, the most stringent limit is the
California drinking water action level. For chloroform,, the
most stringent limit is the maximum contaminant level
(MCL) specified in the Safe Drinking Water Act. Figure B-
8 shows that perox-pure"1 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 B-9 presents VOC concentrations in Runs 12,13,
and 14, which were 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, but they 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
consistently less 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, the removal efficiencies will likely decrease hi
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 removal efficiency in Run 14. Because the quartz
tubes used hi Run 12 had little coating, it was expected that
the removal efficiencies in Run 12 would be higher than
those hi 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; this inconsistency cannot be explained.
54
-------
Percent Removal
Percent Removal
Percent Removal
-------
B.5.2 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.
GC/MS analysis of influent and effluent samples for
SVOCs showed that target SVOCs were not present at
detectable levels. However, several unknown TICs were
present in both the influent and effluent samples.
Average influent TOX and AOX levels were 800 jig/L
and 730 /xg/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 hi influent and
effluent samples in Runs 10, 11, and 12 are presented in
Figure B-10. 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-pure™ system may
be due to the loss of dissolved carbon dioxide that occurred
as a result of the turbulent movement of contaminated
groundwater in the perox-pure™ system.
Figure B-10 shows a decrease in TOC 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 do not indicate whether
the organic carbon that was completely oxidized had
originated from the VOCs present hi groundwater or from
some other compounds present hi 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 dubid) and a
fathead minnow (Pimephales promelas), were used in the
bioassay tests. Toxicity was measured as the lethal
concentration at which 50 percent of the organisms died
(LCso), and expressed as the percent of effluent (or influent)
in the test water. One influent and one effluent sample were
tested hi each run. One control sample was also tested to
evaluate the toxicity associated with hydrogen peroxide
residual present hi the effluent. The control sample had
about 10.5 mg/L of hydrogen peroxide (average effluent
residual hi Runs 10, 11, and 12), and had characteristics
(alkalinity, hardness, and pH) similar to that of effluent hi
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 LC^, values for
both organisms indicated that hi the undiluted influent
sample more than 50 percent of the organisms survived.
However, LCj,, values for the water flea were estimated to be
35, 13, and 26 percent effluent in Runs 10, 11, and 12,
respectively; and LC50 values for the fathead minnow were
estimated to be 65 and 71 percent effluent hi Runs 10 and
11, respectively. In Run 12, more than 50 percent of the
fathead minnows survived hi the undiluted effluent. The
LC50 value for the water flea was estimated to be
17.7 percent hi 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 hi 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 Department of Environmental
Protection, State of Connecticut (CDEP). The CDEP Water
Toxics Section of Water Management Division reports LCSO
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 LC^ value of the control sample with
LC^ values of effluent samples for water fleas indicates the
toxicity associated with the effluent samples is probably due
to hydrogen peroxide residual hi 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 hi the
influent. In general, iron was present at levels less than 45
jtg/L, and manganese was present at an average level of 15
/tg/L. Removal of iron or manganese did not occur hi the
perox-pure™ system, because these metals were present only
at trace levels hi the influent.
No changes hi pH, alkalinity, hardness, or specific
conductance were observed during treatment.
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.
56
-------
0.01
TC
TOC
POC
0.01
TC
TOC
POC
0.01
TC
TOC
POC
Carbon Concentration, mg/L
O.I I 10
Run 10
Run //
Run 12
Figure B-10 Carbon Concentrations 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)
Influent
Reactor 6
57
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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, the average temperature increase due to 1
minute of UV radiation exposure in the perox-pure™ system
is about 12 °F.
B.6 Conclusions
For the spiked groundwater, PSI determined the
following preferred operating conditions: (1) influent
hydrogen peroxide level of 40 mg/L, (2) hydrogen peroxide
level of 25 mg/L in 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 jtg/L) and TCA levels
ranged from 15 to 30 pg/I-. The average removal
efficiencies for TCE, PCE, chloroform, DCA, and TCA were
about 99.7, 97.1, 93.1, 983, and 81.8 percent, respectively.
For the unspiked groundwater, the effluent TCE and
PCE levels were generally below the detection limit
(1 /
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Appendix C
Case Studies
This appendix summarizes three case studies on the use
of the perox-pure™ chemical oxidation system developed by
Peroxidation Systems, Inc. (PSI). The perox-pure™ system
has proven to be a technically and economically viable
alternative to conventional technologies. It should be
evaluated in cases requiring treatment of water contaminated
with organic contaminants. All three case studies represent
full-scale, currently operating commercial installations. The
contaminants of concern in these case studies include
acetone, isopropyl alcohol (IPA), trichloroethene (TCE), and
pentachlorophenol (PCP). The scope of the case studies is
limited to basic information concerning the following topics:
site conditions, system performance, and costs. The
following case studies are discussed in this appendix:
• Wastewater Treatment System, Kennedy Space
Center, Florida
• Municipal Drinking Water System, Arizona
• Chemical Manufacturing Company, Washington
C.I Wastewater Treatment System, Florida
This case study describes the performance and treatment
costs of the perox-pure™ system treating industrial
wastewater containing acetone and IPA at the Kennedy
Space Center site in Florida.
C.1.1 Site Conditions
Effluent from the existing wastewater treatment system
at the Kennedy Space Center in Florida frequently exceeded
the permitted levels for discharges of acetone and IPA.
Discharges were reported at levels up to 20 milligrams per
liter (mg/L) for both compounds. The treatment facility
discharge requirement for both acetone and IPA is 0.5
mg/L. A liquid-phase carbon adsorption system had
originally been installed as part of the treatment system, but
was found to be inadequate. Subsequently, perox-pure™
chemical oxidation technology was selected as the new
method of treatment.
After selecting the perox-pure™ chemical oxidation
technology, the facility contractor installed a perox-pure™
Model SSB-30R in the fall of 1992. The system was used to
treat 5,000- to 6,000-gallon batches of contaminated water.
A demineralization system operated by another contractor
received effluent from the perox-pure™ unit. Facility
requirements specified a maximum treatment time of 24
hours for each batch.
C.I.2 System Performance
The perox-pure™ unit is currently treating maximum
levels of acetone and IPA (both 20 mg/L) to less than 0.5
mg/L for each compound. The treatment objectives were
easily met, even when the wastewater contained twice the
maximum expected acetone and IPA concentrations.
Treatment objectives were achieved for each batch in less
than the specified 24-hour maximum treatment time. In
addition, effluent from the perox-pure™ unit met the
demineralization discharge standards, making treatment by
the demineralization system unnecessary.
Due to the efficiency of treatment, the contractor was
able to treat wastewater in a flow-through mode rather than
in batches. The resulting flow rate of 5 gallons per minute
(gpm) for a period of 20 hours per day requires 10 kilowatts
(kW) to power the ultraviolet (UV) radiation lamps. The
additional capacity of the perox-pure™ unit will be used in
contaminant spill situations, which would produce much
higher acetone and IPA concentrations. The influent
hydrogen peroxide dosage for flow-through operation was
100 mg/L.
C.1.3 Costs
The operation and maintenance (O&M) costs for flow-
through operation of the perox-pure™ unit include electricity,
chemicals (hydrogen peroxide), and general maintenance.
The following items are used at the indicated rate for each
1,000 gallons treated: electricity at $0.06 per kilowatt-hour
(kWh) costs $2.00; 50 percent hydrogen peroxide at $0.35
per pound costs $0.60; and estimated maintenance
59
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requirements cost $1.00. The total O&M cost per 1,000
gallons treated is $3.60.
C.2 Municipal Drinking Water System, Arizona
This case study describes the performance and treatment
costs of the perox-pure™ system treating groundwater
containing TCE. The groundwater was a source of
municipal drinking water in Arizona.
C.2.1 Site Conditions
In 1989, a municipal groundwater well in Arizona used
for drinking water was found to contain 50 to 400
micrograms per liter (/tg/L) of TCE. The well, capable of
producing 2,000 gpm, was taken out of service while
treatment options were considered. Because the well is
located on a city lot in the middle of a large residential area,
the city preferred using a low-visibility, quiet treatment
method that could consistently destroy TCE to
concentrations below the drinking water standard of 5 /tg/L.
Moreover, treatment to below the drinking water standard
was desirable because of the high profile of the site
remediation. Given these requirements, the perox-pure™
chemical oxidation technology was selected.
An on-site performance evaluation was initiated in
December 1989 using a perox-pure™ pilot system to treat
contaminated groundwater pumped from the well at a flow
rate of 135 gpm. Testing showed that TCE could be
destroyed to below the analytical detection limit of 0.5 /*g/L.
C.2.2 System Performance
A perox-pure™ Model SSB-30R is currently hi operation
at the site, treating organic contamination to below
detectable levels at a flow rate of 135 gpm. Treatment is
accomplished with only 15 kW of power, one-half the
capacity of the unit. The average influent concentration of
TCE is 150 /tg/L, and the effluent TCE concentration is less
than 0.5
C.2.3 Costs
O&M costs for continuous operation of the perox-pure™
system at a flow rate of 135 gpm include electricity,
chemicals (hydrogen peroxide), and general maintenance.
The following items are consumed at the indicated rate for
each 1,000 gallons treated: electricity at $0.06 per kWh costs
$0.11; 50 percent hydrogen peroxide at $0.35 per pound costs
$0.12; and estimated maintenance requirements cost $0.05.
The total O&M cost per 1,000 gallons treated is $0.28.
C3 Chemical Manufacturing Company,
Washington
This case study describes the performance and treatment
costs of the perox-pure™ system treating groundwater
containing PCP at a chemical manufacturing facility hi
Washington.
C.3.1 Site Conditions
PCP contamination was discovered hi local groundwater
surrounding a chemical manufacturing company hi
Washington. The company had produced PCP for more
than 30 years. Because of the site geology, the groundwater
was brackish and contained high concentrations of iron and
calcium carbonate. The chemical company initiated a
remediation effort that included a pump-and-treat process.
After bench-scale testing, the perox-pure™ chemical
oxidation system was selected to destroy PCP to below a
target level of 0.1 mg/L.
A full-scale perox-pure™ system was installed hi 1988
under a Full Service Agreement with PSI. When the
remediation effort began, groundwater was contaminated
with PCP at levels of up to 15 mg/L, three tunes higher than
expected. Iron was detected at levels of up to 200 mg/L, 20
tunes higher than expected. PSI made pretreatment
recommendations and assisted with the selection of an iron
oxidation and removal system, which included clarification
and multimedia filtration. Treatment with the perox-pure™
system reduced iron concentrations hi the groundwater to
acceptable levels. The groundwater was stabilized and the
scaling tendency was reduced by adding acid to lower the
groundwater pH to approximately 5.
The original perox-pure™ unit did not have enough
capacity to treat the unexpectedly high PCP levels.
However, as part of the Full Service Agreement, a perox-
pure™ Model CEBX-360R was installed to replace the
original unit. The new model incorporated the latest
improvements hi the 'perox-pure™ unit, including an
automatic tube cleaning device.
C.3.2 System Performance
The groundwater is being successfully treated at a flow
rate of about 70 gpm, and a power requirement of 180 kW.
The pH of the influent groundwater is adjusted to 5 by
adding acid, and hydrogen peroxide is added to the influent
to achieve a concentration of 150 mg/L. The perox-pure™
system is currently treating maximum influent PCP
concentrations of 15 mg/L to average effluent concentration
of 0.1 mg/L.
60
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C.3.3 Costs
O&M costs for continuous operation of the perox-pure™
system at a flow rate of 70 gpm include electricity, chemicals
(hydrogen peroxide and acid), and general maintenance.
The following items are used at the indicated rate for each
1,000 gallons treated: electricity at $0.06 per kWh costs
$2.57; 50 percent hydrogen peroxide at $0.35 per pound costs
$0.87; acid at $0.085 per pound costs $0.03; and estimated
maintenance requirements cost $0.43. The total O&M cost
per 1,000 gallons treated is $3.90.
61
•ft U.S. GOVERNMENT PRINTING OFFICE: 1995—651-569
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